JPH11171877A - Herbicidal azole derivative and its intermediate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound scarcely manifesting phytotoxicity to paddy rice and capable of manifesting herbicidal activity against Echinochloa oryzicola Vasing. which is a strongly damaging weed of a paddy field with a small dose. SOLUTION: This compound is represented by formula I [Z<1> is a (substituted) heterocyclic ring or the like which contains at least one oxygen, sulfur or nitrogen atom and 3-7 carbon atoms of the ring and may be condensed with the benzene ring; R<1> is a 1-6C alkyl or the like; (n) is 0-14; R<2> and R<3> are each H or a 1-6C alkyl; X is benzothiazole or the like; A is O or S], e.g. 2-[4-(1- methyl-5-methylthio-1H-[1,2,4]triazol-3-yl)phenoxymethyl]benzothiazole. The compound represented by formula I is obtained by condensing a phenol compound or a thiophenol compound represented by formula II with an azole compound represented by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel azole derivative having excellent herbicidal activity, a salt thereof, or an intermediate for producing the same.

[0002]

2. Description of the Related Art There has been a demand for a herbicide that selectively kills only harmful weeds without causing phytotoxicity to crops.
As a result of various studies, many selective herbicides have been published, but the emergence of even better herbicides is desired.

On the other hand, as a compound similar to the present compound,
ownnal of Medicinal Chemi
story, 1987, 30 , 2087-2093 and also Journal of Medicinal C
hemistry, 1992, 35 , 1200-120.
9, a substituted phenyloxy derivative is described, but differs from the compound of the present invention represented by the general formula (I) in the chemical structure such as the substitution position of the substituent. In addition, all of them describe the use as a leukotriene D4 antagonist, but there is no description or suggestion about the use as an agrochemical.

[0004]

SUMMARY OF THE INVENTION The inventor of the present invention has conducted intensive studies on the synthesis and biological activity of azole derivatives over many years, and as a result, a novel azole derivative having a structure different from that of known compounds has been obtained. The present invention has been found to show little herbicidal activity against rice, and to show excellent herbicidal activity at a low dose in the rice field, which is a highly damaging weed. completed.

[0005]

The azole compounds having excellent herbicidal activity of the present invention are represented by the general formula (I):

[0006]

Embedded image[Wherein, Z¹Is at least one oxygen, sulfur or
Containing 3 to 7 ring atoms including a nitrogen atom and
A heterocyclic group which may be condensed with a ring (the heterocyclic group is
1 to 3 identical or selected from the group consisting of
It may be substituted by different substituents. ), Formula-
C (R⁶) = NR⁷[Wherein, R⁶Is a hydrogen atom, C1-C
6 alkyl group or formula -NR⁸R⁹中 where R⁸And R⁹Is
Same or different, hydrogen atom, C1-C6 alkyl group
(The alkyl group may be one to four identical or different
A halogen atom or one C1-C6 alkoxy group
It may be exchanged. ), C2-C6 alkenyl groups, C2-
A C6 alkynyl group, a C2-C7 alkylcarbonyl group,
C2-C7 alkoxycarbonyl group or phenyl group (this
The phenyl group is selected from the following substituent groups b.
May be substituted with 5 identical or different substituents
No. ).基 represents a group represented by
⁷Is a C1-C6 alkyl group (the alkyl group is
Up to four identical or different halogen atoms or one ferrite
It may be substituted by a nyl group. ), C1-C6 alcohol
A xy group (the alkoxy group may be 1 to 4 identical or different
Substituted by one halogen atom or one phenyl group
C2 -C6 alkenyloxy group, C3-
C6 alkynyloxy group, hydroxyl group or formula -NR^8aR
^9a中 where R^8aAnd R^9aIs the aforementioned R⁸And R⁹Equivalent to
Is shown. Represents a group represented by｝. A group represented by the formula:
NH-C (R^Ten) = G ｛where R^TenIs C1-C6 al
Kill group, C1-C6 alkoxy group, C1-C6 alkyl
A thio group or an amino group (the amino group is one or two identical
Or even if substituted by a different C1-C3 alkyl group
Good. G is the formula = CHNO_TwoThe base represented by
Represents a group represented by the formula = N-CN. The base represented by｝
Is the formula -N = J where J is the formula = S (CH_Three)_TwoRepresented by
Group or formula = C (R¹¹) Q ^a-R¹²中 where R¹¹Is C
1-C6 alkyl group, C1-C6 alkoxy group, C1-
C6 alkylthio group, amino group (the amino group is 1 or
Two identical or different C1-C3 alkyl groups
It may be exchanged. ) Or a cyano group; ¹²Is C1
-C6 alkyl group (where the alkyl group is a C2-C7 alkyl group)
Even if substituted by a oxycarbonyl group or a phenyl group
Good. ) Or a C2-C6 alkynyl group;^aIs
Indicates an oxygen atom or a sulfur atom. Indicates a group represented by｝
You. And R¹Is a C1-C6 alkyl group (the a
The alkyl group is one to four identical or different halogen atoms.
, Or one C1-C6 alkoxy group, C1-C6
Alkylthio group, C2-C7 alkylcarbonyl group, C
2-C7 alkoxycarbonyl group, hydroxyl group, mercapto
Group, formyl group or carboxyl group
Good. ), C1-C6 alkoxy groups (the said alkoxy groups
Represents 1 to 4 identical or different halogen atoms or 1
Of C1-C6 alkoxy groups.
No. ), C1-C6 alkylthio group, C2-C7 alkyl
Carbonyl group, C2-C7 alkoxycarbonyl group,
Halogen atom, nitro group, formyl group or carboxyl
And n represents 0, 1, 2, 3 or 4;^TwoPassing
And R^ThreeAre the same or different and represent a hydrogen atom or C1-C6
X represents an alkyl group;

[0007]

Embedded image In the formula, p represents 0, 1 or 2, and R ⁴ represents C 1 to C
6 alkyl groups (the alkyl groups may be substituted by 1 to 4 identical or different halogen atoms or 1 C1 to C6 alkoxy group), C2 to C6 alkenyl groups, C2 to C6 alkynyl groups, C1-C6 alkoxy groups (the alkoxy groups may be substituted by 1 to 4 identical or different halogen atoms), C1 to C6
6 alkylthio group, C2-C7 alkylcarbonyl group,
C2 to C7 alkoxycarbonyl group, phenyl group (the phenyl group is 1 to 5 selected from the following substituent group b)
May be substituted by the same or different substituents. ), A phenyloxy group (the phenyloxy group is
It may be substituted by 1 to 5 identical or different substituents selected from the following substituent group b. ), A phenylthio group (the phenylthio group may be substituted by 1 to 5 identical or different substituents selected from the following substituent group b), a halogen atom, a hydroxyl group, a nitro group,
A cyano group, a formyl group or a carboxyl group; or when p is 2, two R ⁴ 's together form C3
~ C4 alkylene group may be formed, and q is 0, 1,
Represents 2, 3 or 4, wherein R ⁵ is a C1 to C6 alkyl group (the alkyl group may be substituted by 1 to 4 identical or different halogen atoms or one C1 to C6 alkoxy group). ), C2-C6 alkenyl groups, C2-
C6 alkynyl group, C1-C6 alkoxy group (the alkoxy group may be substituted by 1 to 4 same or different halogen atoms), C1-C6 alkylthio group, C2-C7 alkylcarbonyl group, C2- A C7 alkoxycarbonyl group, a phenyl group (the phenyl group may be substituted with 1 to 5 identical or different substituents selected from the following substituent group b), a phenyloxy group (the phenyloxy group) May be substituted with 1 to 5 identical or different substituents selected from the following substituent group b), phenylthio group (the phenylthio group is 1 to 5 selected from the following substituent group b) 5
May be substituted by the same or different substituents. ), Halogen atom, hydroxyl group, nitro group, cyano group,
It represents a formyl group or a carboxyl group, and Q represents an oxygen or sulfur atom. A represents an oxygen or sulfur atom; Substituent group a is a C1-C6 alkyl group (the alkyl group is one to four identical or different halogen atoms or one May be substituted by a C1-C6 alkoxy group.), C2-C6 alkenyl group, C2-
A C6 alkynyl group, a C1-C6 alkoxy group (the alkoxy group may be substituted by 1 to 4 identical or different halogen atoms), a phenyl group (the phenyl group is selected from the following substituent group b) Selected from 1 to 5 same or different substituents),
A phenyloxy group (the phenyloxy group may be substituted by 1 to 5 identical or different substituents selected from the following substituent group b), a phenylthio group (the phenylthio group is 1 selected from group b
It may be substituted by up to 5 identical or different substituents. ), A phenylsulfonyl group (the phenylsulfonyl group may be substituted by 1 to 5 identical or different substituents selected from the following substituent group b),
Formyl group, carboxyl group, C2-C7 alkylcarbonyl group, C2-C7 alkoxycarbonyl group, C1-
A C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a halogen atom,
Hydroxyl group, nitro group, amino group (the amino group is
C6 alkyl group, C2-C7 alkylcarbonyl group, C
It may be substituted by a 2-C7 alkoxycarbonyl group or a formyl group. ), A cyano group, a di (C1-C6 alkyl) carbamoyl group and a di (C1-C6 alkyl) sulfamoyl group, and the substituent group b is a halogen atom, a nitro group, a cyano group, a C1-C6 alkyl group. (The alkyl group may be substituted by 1 to 4 identical or different halogen atoms.) And C1 to C6.
A group consisting of an alkoxy group is shown. And an important synthetic intermediate of the compound (I) of the present invention is represented by the general formula (II):

[0008]

Embedded image Wherein Z ² is a halogen atom, a cyano group, a formula —COR
¹³ wherein R ¹³ is a hydrogen atom, a C1-C6 alkyl group {the alkyl group is one to four identical or different halogen atoms or one amino group (the amino group is one or two The same or different, a C1-C6 alkyl group, C
It may be substituted by a 1-C6 alkoxy group or a phenyl group, or may form a quaternary ammonium salt. ). {C1-C6 alkenyl group} The alkenyl group has 1 to 4 identical or different halogen atoms or 1
Amino groups (the amino groups may be substituted with one or two identical or different C1-C6 alkyl groups, C1-C6 alkoxy groups or phenyl groups, and form a quaternary ammonium salt May be shown). ｝, Hydroxyl group,
C 1 -C ⁶ alkoxy group, formula —NR ⁸ R ⁹ } wherein R ⁸ and R ⁹ are the same or different and are a hydrogen atom, a C 1 -C 6 alkyl group (the alkyl group is 1 to 4 same or different May be substituted by a halogen atom or one C1-C6 alkoxy group), a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C2-C7 alkylcarbonyl group, a C2-C7 alkoxycarbonyl group or a phenyl group ( The phenyl group may be substituted with 1 to 5 identical or different substituents selected from the following substituent group b). A group represented by｝,
Formula —NH—NR ⁸ R ⁹ } wherein R ⁸ and R ⁹ are as defined above. Represents a group represented by｝, a fluorine atom, a chlorine atom or a bromine atom. Or a thiocarbamoyl group;
¹ is a C1 to C6 alkyl group (the alkyl group is 1 to 4 identical or different halogen atoms, or 1 C1 to C6 alkoxy group, C1 to C6 alkylthio group,
It may be substituted by a C2-C7 alkylcarbonyl group, a C2-C7 alkoxycarbonyl group, a hydroxyl group, a mercapto group, a formyl group or a carboxyl group. ), C1
C6 alkoxy group (the alkoxy group may be substituted by 1 to 4 identical or different halogen atoms or 1 C1 to C6 alkoxy group), C1 to C6 alkylthio (the alkylthio group is 1 to 4 May be substituted by four identical or different halogen atoms.), A C2-C7 alkylcarbonyl group, a C2-C7
Represents an alkoxycarbonyl group, a halogen atom, a nitro group, a formyl group or a carboxyl group, and n is 0, 1,
2, 3 or 4; R ² and R ³ are the same or different and each represent a hydrogen atom or a C1-C6 alkyl group;
formula

[0009]

Embedded image In the formula, p represents 0, 1 or 2, and R ⁴ represents C 1 to C
6 alkyl groups (the alkyl groups may be substituted by 1 to 4 identical or different halogen atoms or 1 C1 to C6 alkoxy group), C2 to C6 alkenyl groups, C2 to C6 alkynyl groups, C1-C6 alkoxy groups (the alkoxy groups may be substituted by 1 to 4 identical or different halogen atoms), C1 to C6
6 alkylthio group, C2-C7 alkylcarbonyl group,
C2 to C7 alkoxycarbonyl group, phenyl group (the phenyl group is 1 to 5 selected from the following substituent group b)
May be substituted by the same or different substituents. ), A phenyloxy group (the phenyloxy group is
It may be substituted by 1 to 5 identical or different substituents selected from the following substituent group b. ), A phenylthio group (the phenylthio group may be substituted by 1 to 5 identical or different substituents selected from the following substituent group b), a halogen atom, a hydroxyl group, a nitro group,
A cyano group, a formyl group or a carboxyl group; or when p is 2, two R ⁴ 's together form C3
~ C4 alkylene group may be formed, and q is 0, 1,
Represents 2, 3 or 4, wherein R ⁵ is a C1 to C6 alkyl group (the alkyl group may be substituted by 1 to 4 identical or different halogen atoms or one C1 to C6 alkoxy group). ), C2-C6 alkenyl groups, C2-
C6 alkynyl group, C1-C6 alkoxy group (the alkoxy group may be substituted by 1 to 4 same or different halogen atoms), C1-C6 alkylthio group, C2-C7 alkylcarbonyl group, C2- A C7 alkoxycarbonyl group, a phenyl group (the phenyl group may be substituted with 1 to 5 identical or different substituents selected from the following substituent group b), a phenyloxy group (the phenyloxy group) May be substituted with 1 to 5 identical or different substituents selected from the following substituent group b), phenylthio group (the phenylthio group is 1 to 5 selected from the following substituent group b) 5
May be substituted by the same or different substituents. ), Halogen atom, hydroxyl group, nitro group, cyano group,
It represents a formyl group or a carboxyl group, and Q represents an oxygen or sulfur atom. A represents an oxygen or sulfur atom; Substituent group b represents a halogen atom, a nitro group, a cyano group, a C1 to C6 alkyl group (the alkyl group has 1 to 4 And the same or different halogen atoms may be substituted) and C1-C6 alkoxy groups. ] Or a salt thereof.

In the present specification, "C1-C6 alkyl" means, for example, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, pentyl, isopentyl, 2 -Methylbutyl, neopentyl, 1-ethylpropyl, cyclopentyl, hexyl, 4-methylpentyl, 3-
Methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2, It is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms such as 3-dimethylbutyl, 2-ethylbutyl and cyclohexyl, preferably a linear or branched alkyl group having 1 to 4 carbon atoms. A branched alkyl group, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms (C1 to C3 alkyl group), further preferably a methyl group or an ethyl group, and most preferably Is a methyl group.

In the present specification, the "C1-C6 alkoxy group" is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentoxy, isopentoxy, 2-methylbutoxy, Neopentoxy, 1-ethylpropoxy,
Hexyloxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1-methylpentoxy, 3,3-
1 to 1 carbon atoms such as dimethylbutoxy, 2,2-dimethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy, 2-ethylbutoxy 6 straight-chain or branched-chain alkoxy groups, preferably a straight-chain or branched-chain alkoxy group having 1 to 3 carbon atoms (C1-C3 alkoxy group), more preferably a methoxy group or an ethoxy group Group, more preferably,
It is a methoxy group.

In the present specification, "C1-C6 alkyl group substituted by one C1-C6 alkoxy group" means, for example, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, s-butoxymethyl, t- One such C1 to C6 alkoxy group, such as butoxymethyl, pentyloxymethyl, hexyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, "C1
To C6 alkyl group ", preferably an alkyl group having 1 to 3 carbon atoms substituted by one alkoxy group having 1 to 3 carbon atoms, more preferably methoxyethyl Or an ethoxymethyl group.

In the present specification, the “halogen atom” is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. It is.

In the present specification, the "C1-C6 alkylthio group" is, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, s-butylthio, t-butylthio, pentylthio, isopentylthio, Methylbutylthio, neopentylthio, 1-ethylpropylthio, hexylthio, 4-methylpentylthio, 3-methylpentylthio, 2-methylpentylthio, 1-methylpentylthio, 3,3-dimethylbutylthio, 2, 1-carbon such as 2-dimethylbutylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,3-dimethylbutylthio, and 2-ethylbutylthio A straight-chain or branched alkylthio group having 1 to 3 carbon atoms, preferably a straight-chain or branched alkylthio group having 1 to 3 carbon atoms (C1 to C3 alkylthio group). A group),
More preferably, it is a methylthio group or an ethylthio group.

In the present specification, "C2-C6 alkenyl group" means, for example, vinyl, 2-propenyl, 1-methyl
2-propenyl, 2-methyl-2-propenyl, 2-ethyl-2-
Propenyl, 2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-ethyl-2-butenyl, 3-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 1-
Ethyl-3-butenyl, 2-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 4-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-
A straight-chain or branched alkenyl group having 2 to 6 carbon atoms, such as hexenyl, preferably a straight-chain or branched alkenyl group having 3 to 5 carbon atoms (C3-C5 alkenyl group);
And more preferably, 2-propenyl, 1-methyl-
It is a 2-propenyl or 2-butenyl group, more preferably a 2-propenyl group.

In the present specification, "C2-C6 alkynyl group" means, for example, ethynyl, 2-propynyl, 1-methyl-2-propynyl, 2-butynyl, 1-methyl-2-butynyl, 1-ethyl- 2-butynyl, 3-butynyl, 1-methyl-3-
Butynyl, 2-methyl-3-butynyl, 1-ethyl-3-butynyl, 2-pentynyl, 1-methyl-2-pentynyl, 3-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 4-pentynyl, 1-methyl-4-pentynyl, 2-methyl
-4-A straight-chain or branched alkynyl group having 2 to 6 carbon atoms, such as pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl and 5-hexynyl, preferably having 3 to 5 carbon atoms. Linear or branched alkynyl groups (C2-C5 alkynyl groups), more preferably a 2-propynyl group.

In the present specification, "C2-C6 alkenyloxy group" means, for example, allyloxy, 1-methyl-2
-Propenyloxy, 2-methyl-2-propenyloxy, 2-
Ethyl-2-propenyloxyoxy, 2-butenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 1-ethyl-2-butenyloxy, 3-butenyloxy, 1-methyl-3-butenyloxy, 2- Methyl-3-butenyloxy, 1-ethyl-3-butenyloxy, 2-pentenyloxy, 1-methyl-2-pentenyloxy, 2-methyl-2
-Pentenyloxy, 3-pentenyloxy, 1-methyl-3
-Pentenyloxy, 2-methyl-3-pentenyloxy,
4-pentenyloxy, 1-methyl-4-pentenyloxy,
2-methyl-4-pentenyloxy, 2-hexenyloxy,
A straight-chain or branched alkenyloxy group having 2 to 6 carbon atoms, such as 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, preferably a straight-chain or branched alkenyloxy group having 2 to 5 carbon atoms; It is a branched alkenyloxy group (C2-C5 alkenyloxy group), and more preferably an allyloxy group.

In the present specification, "C3-C6 alkynyloxy group" means, for example, 2-propynyloxy, 1-methyl-2-propynyloxy, 2-ethyl-2-propynyloxy, 2-butynyloxy, Methyl-2-butynyloxy,
2-methyl-2-butynyloxy, 1-ethyl-2-butynyloxy, 3-butynyloxy, 1-methyl-3-butynyloxy, 2-methyl-3-butynyloxy, 1-ethyl-3-butynyloxy, 2-pentynyloxy, 1-methyl-2-pentynyloxy, 2-methyl-2-pentynyloxy, 3-pentynyloxy, 1-methyl-3-pentynyloxy, 2-methyl-3
-Pentynyloxy, 4-pentynyloxy, 1-methyl-4
-Pentynyloxy, 2-methyl-4-pentynyloxy,
A straight-chain or branched-chain alkynyl group having 3 to 6 carbon atoms, such as 2-hexynyloxy, 3-hexynyloxy, 4-hexynyloxy and 5-hexynyloxy, preferably a straight-chain or branched alkynyl group having 3 to 5 carbon atoms; A branched alkynyl group (C3-
C5 alkynyl group), and more preferably a 2-propynyloxy group.

As used herein, the term "C1-C6 alkyl group substituted by 1 to 4 halogen atoms" includes, for example, chloromethyl, dichloromethyl, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 1-chloropropyl, 3-chloropropyl, 1-chlorobutyl, 4-chlorobutyl, 2,2,2-trichloroethyl, fluoromethyl,
Difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, fluorochloromethyl, bromomethyl, 1-bromoethyl, 2-bromoethyl, 1,1,1,2-
The same or different “halogen atoms” such as tetrachloroethyl, 1,1,2,2, -tetrafluoroethyl
And 4 groups bonded to the “C1-C6 alkyl group”, preferably, for example, chloromethyl, dichloromethyl, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 1-chloropropyl, 3-chloropropyl, fluoro C substituted by one to three halogen atoms, such as methyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, fluorochloromethyl, bromomethyl, 1-bromoethyl, 2-bromoethyl
It is a 1-C3 alkyl group, more preferably a fluoromethyl group, a chloromethyl group or a trifluoromethyl group.

In the present specification, “C 1 -C 6 alkoxy group substituted by 1 to 4 halogen atoms” means
For example, chloromethoxy, dichloromethoxy, trichloromethoxy, 1-chloroethoxy, 2-chloroethoxy, 1-chloroethoxy
Chlorpropoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-fluoroethoxy, 2-
The same or different “halogen atom” is 1 to 4 such as fluoroethoxy, fluorochloromethoxy, bromomethoxy, 1,1,1,2-tetrachloroethoxy, 1,1,2,2, -tetrafluoroethoxy; A group bonded to four “C1-C6 alkoxy groups”, preferably an alkoxy group having 1 to 3 carbon atoms substituted by 1 to 4 halogen atoms, more preferably a fluoro group Methoxy group,
A chloromethoxy group and a trifluoromethoxy group, more preferably a trifluoromethoxy group.

In the present specification, "a C1 to C6 alkoxy group substituted by one C1 to C6 alkoxy group" means that one "C1 to C6 alkoxy group" is the same as the "C1 to C6 alkoxy group".
~ C6 alkoxy group ", preferably,
A methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group or an ethoxyethoxy group.

In the present specification, "a phenyl group substituted by 1 to 5 identical or different substituents selected from the above-mentioned substituent group b" means, for example, 2-methylphenyl, 3-ethylphenyl, -Propylphenyl, 2-
Ethoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-chloromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-chlorophenyl, 3-bromophenyl, 4-fluorophenyl, 2-nitro Phenyl, 3-nitrophenyl, 4-nitrophenyl, 2-cyanophenyl, 3-
Cyanophenyl, 4-cyanophenyl, 2,3,4
The "halogen atom", a nitro group, a cyano group, the "C1-C6 alkyl group", the "C1-C6 alkyl group substituted by 1 to 4 halogen atoms" such as 5,6-pentafluorophenyl A group in which 1 to 5 identical or different substituents selected from the group consisting of the above-mentioned "C1-C6 alkoxy group" are bonded to a phenyl group,
Preferably, one or two identical or different alkyl groups having 1 to 3 carbon atoms are bonded to a phenyl group, more preferably a methylphenyl group.

As used herein, the term "amino group substituted by one or two identical or different C1 to C3 alkyl groups" means that the above "C1 to C3 alkyl group" is 1 or 2
It is an amino group bonded individually, and is preferably a dimethylamino group.

In the present specification, “an amino group substituted by a C1 to C6 alkyl group, a C2 to C7 alkylcarbonyl group, a C2 to C7 alkoxycarbonyl group or a formyl group” means the above “C1 to C6 alkyl group”; The “C2-C7 alkylcarbonyl group” and the “C2-C7
A 7-alkoxycarbonyl group "or an amino group to which one or two same or different substituents selected from the group consisting of formyl groups are bonded, and preferably the above-mentioned" 1 or 2 same or different C1 to C1 An amino group substituted by a C3 alkyl group ", and more preferably a dimethylamino group.

In the present specification, "phenyloxy group substituted by 1 to 5 identical or different substituents selected from the above-mentioned substituent group b" means, for example, 2-methylphenyloxy, 3-ethylphenyl Oxy, 4-propylphenyloxy, 2-ethoxyphenyloxy, 3-
Methoxyphenyloxy, 4-methoxyphenyloxy, 2-chloromethylphenyloxy, 3-trifluoromethylphenyloxy, 4-trifluoromethylphenyloxy, 2-chlorophenyloxy, 3-bromophenyloxy, 4-fluorophenyloxy, 2-nitrophenyloxy, 3-nitrophenyloxy, 4-nitrophenyloxy, 2-cyanophenyloxy, 3-
Cyanophenyloxy, 4-cyanophenyloxy,
The aforementioned “halogen atom”, such as 2,3,4,5,6-pentafluorophenyloxy, a nitro group, a cyano group,
The "C1-C6 alkyl group", the "C1-C6 alkyl group substituted by 1 to 4 halogen atoms",
A group in which 1 to 5 identical or different substituents selected from the group consisting of the aforementioned “C1 to C6 alkoxy groups” are bonded to a phenyloxy group, and preferably 1 or 2 identical or different carbon atoms; A group in which several to three alkyl groups are bonded to a phenyloxy group, more preferably a methylphenyloxy group.

As used herein, the term "phenylthio group substituted by 1 to 5 identical or different substituents selected from the above-mentioned substituent group b" means, for example, 2-methylphenylthio, 3-ethylphenylthio , 4-propylphenylthio, 2-ethoxyphenylthio, 3-methoxyphenylthio, 4-methoxyphenylthio, 2-chloromethylphenylthio, 3-trifluoromethylphenylthio, 4-trifluoromethylphenylthio, 2- Chlorophenylthio, 3-bromophenylthio, 4-fluorophenylthio, 2-nitrophenylthio, 3-nitrophenylthio, 4-nitrophenylthio, 2-cyanophenylthio, 3-cyanophenylthio, 4-cyanophenylthio Like 2,3,4,5,6-pentafluorophenylthio, "Halogen atom", a nitro group, a cyano group, the "C1~C6 alkyl group", the "1 to 4
C1 to C6 alkyl groups substituted by two halogen atoms "and 1 to 5 identical or different substituents selected from the group consisting of the above" C1 to C6 alkoxy groups "are bonded to a phenylthio group. Preferably, one or two identical or different alkyl groups having 1 to 3 carbon atoms are bonded to a phenylthio group, more preferably a methylphenylthio group.

As used herein, the term "C2-C7 alkoxycarbonyl group" means, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, s-butoxycarbonyl, t-butoxycarbonyl, The above-mentioned "C1-C6 alkoxy group" such as pentylcarbonyl and hexylcarbonyl is a group bonded to a carbonyl group, preferably a straight-chain or branched-chain alkoxycarbonyl group having 2 to 4 carbon atoms (C2- C4 alkoxycarbonyl group), and more preferably a methoxycarbonyl group or an ethoxycarbonyl group.

As used herein, the term "C2-C7 alkylcarbonyl group" means, for example, acetyl, propionyl,
A group in which the above “C1 to C6 alkyl group” is bonded to a carbonyl group, such as butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, and heptanoyl, preferably a straight or branched chain having 2 to 4 carbon atoms An alkylcarbonyl group (C2-C4 alkylcarbonyl group), more preferably an acetyl group or a propionyl group.

In the present specification, "C1-C6 alkylsulfonyl group" means, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, t-
A group in which the above “C1 to C6 alkyl group” is bonded to a sulfonyl group, such as butylsulfonyl, n-pentylsulfonyl, and hexylsulfonyl, preferably a linear or branched alkylsulfonyl having 1 to 3 carbon atoms. Group (C1-C
3 alkylsulfonyl group), and more preferably a methylsulfonyl group.

In the present specification, the “C1-C6 alkylsulfinyl group” includes, for example, methylsulfinyl,
The above-mentioned “C1-C1, such as ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, t-butylsulfinyl, pentylsulfinyl, and hexylsulfinyl,
6 alkyl group "is a group bonded to a sulfinyl group,
Preferably, it is a linear or branched alkylsulfinyl group having 1 to 3 carbon atoms (C1 to C3 alkylsulfinyl group), more preferably a methyl group sulfinyl group.

In the present specification, "phenylsulfonyl group substituted by 1 to 5 identical or different substituents selected from the above-mentioned substituent group b" means, for example, 2-methylphenylsulfonyl, 3-ethylphenyl Sulfonyl, 4-propylphenylsulfonyl, 2-ethoxyphenylsulfonyl, 3-methoxyphenylsulfonyl,
4-methoxyphenylsulfonyl, 2-chloromethylphenylsulfonyl, 3-trifluoromethylphenylsulfonyl, 4-trifluoromethylphenylsulfonyl, 2-chlorophenylsulfonyl, 3-bromophenylsulfonyl, 4-fluorophenylsulfonyl, 2-
Nitrophenylsulfonyl, 3-nitrophenylsulfonyl, 4-nitrophenylsulfonyl, 2-cyanophenylsulfonyl, 3-cyanophenylsulfonyl, 4-
The “halogen atom”, the nitro group, the cyano group, the “C1 to C6 alkyl group”, the “1 to 4”, such as cyanophenylsulfonyl and 2,3,4,5,6-pentafluorophenylsulfonyl. A C1-C6 alkyl group substituted by a halogen atom ", and a group in which 1 to 5 identical or different substituents selected from the group consisting of the" C1 to C6 alkoxy group "are bonded to a phenylsulfonyl group. Is a group in which one or two identical or different alkyl groups having 1 to 3 carbon atoms are bonded to a phenylsulfonyl group, more preferably a methylphenylsulfonyl group.

In the present specification, "di (C1-C6 alkyl) carbamoyl group" means, for example, dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, N-cyclohexyl-N-methylcarbamoyl, dibutylcarbamoyl, dipentylcarbamoyl And the aforementioned “C1-C6 alkyl group” such as dihexylcarbamoyl is a carbamoyl group bonded to two nitrogen atoms.
Preferably, it is a carbamoyl group in which a straight-chain alkyl group having 1 to 3 carbon atoms is bonded to two nitrogen atoms, more preferably, a dimethylcarbamoyl group or a diethylcarbamoyl group, and further preferably, dimethylcarbamoyl. Group.

In the present specification, "di (C1-C6 alkyl) sulfamoyl group" means, for example, dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, dipentylsulfamoyl, dihexyl The “C1-C6 alkyl group” is a sulfamoyl group having two nitrogen atoms bonded, such as sulfamoyl. Preferably, a linear alkyl group having 1 to 3 carbon atoms is a sulfamoyl group bonded to two nitrogen atoms, more preferably, a dimethylsulfamoyl group or a diethylsulfamoyl group. Is
It is a dimethylsulfamoyl group.

In the present specification, the “C1-C6 alkyl group substituted by one phenyl group” includes, for example,
Benzyl, phenethyl, α-methylbenzyl, α, α-
A group in which one phenyl group is bonded to the above-mentioned "C1-C6 alkyl group", such as dimethylbenzyl and α-pentylbenzyl, and preferably one phenyl group is the above-mentioned "C1-C6 alkyl group".
A "C3 alkyl" linked group, more preferably a benzyl group.

As used herein, the term "C1 to C6 alkyl group substituted by one C1 to C6 alkylthio group" includes, for example, methylthiomethyl, ethylthiomethyl, propylthiomethyl, butylthiomethyl, pentyloxymethyl , Hexylthiomethyl, methylthioethyl, ethylthioethyl, propylthioethyl, butylthioethyl, methylthiopropyl, methylthiobutyl, etc., one of the "C1-C6 alkylthio groups"
1 to C6 alkyl group ", and preferably,
An alkyl group having 1 to 3 carbon atoms substituted by one alkylthio group having 1 to 3 carbon atoms, and more preferably a methylthiomethyl group.

In the present specification, "a C1-C6 alkyl group substituted by one C2-C7 alkylcarbonyl group" means, for example, 2-propanoyl, 2-butanoyl, 3-butanoyl, 2-pentanoyl, 3-pentanoyl, Pentanoyl, 4-pentanoyl, 3-hexanoyl, 4-hexanoyl, 5-hexanoyl, 4-heptanoyl, 5-
The aforementioned “C2” such as heptanoyl, 5-octanoyl
To C7 alkylcarbonyl group ”is one of the above“ C1 to C6 ”.
An alkyl group having 2 to 4 carbon atoms, such as 2-propanoyl, 2-butanoyl, 3-butanoyl, 2-pentanoyl, 3-pentanoyl, and 4-pentanoyl. It is an alkyl group having 1 to 3 carbon atoms substituted by one group, more preferably a 2-propanoyl group.

As used herein, "C1-C6 alkyl group substituted by one C2-C7 alkoxycarbonyl group" includes, for example, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl,
1- (methoxycarbonyl) ethyl, 2- (methoxycarbonyl) ethyl, 1- (ethoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 1- (propoxycarbonyl) ethyl, 2- (propoxycarbonyl) ethyl, 1- (Methoxycarbonyl) propyl, 2
-(Methoxycarbonyl) propyl, 3- (methoxycarbonyl) propyl, 1- (ethoxycarbonyl) propyl, 2- (ethoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl, 1- (propoxycarbonyl) propyl, 2- ( Such as propoxycarbonyl) propyl, 3- (propoxycarbonyl) propyl,
One of the “C2 to C7 alkoxycarbonyl groups” is a group bonded to the “C1 to C6 alkyl group”, preferably, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl And an alkyl group having 1 to 3 carbon atoms substituted by one alkoxycarbonyl group having 2 to 4 carbon atoms, such as, 2- (ethoxycarbonyl) ethyl and 3- (methoxycarbonyl) propyl. Is a methoxycarbonylmethyl group.

In the present specification, "C1-C6 alkyl group substituted by one hydroxyl group" means, for example, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl , 3-hydroxypropyl, 1-methyl-2-hydroxyethyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 1-methyl-3-
One hydroxyl group, such as hydroxypropyl, has the aforementioned “C1
~ C6 alkyl group ". Preferably, it is a C1-C3 alkyl group substituted by a hydroxyl group such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, and more preferably, a hydroxymethyl group or a 2-hydroxyl group. It is an ethyl group.

In the present specification, "C1-C6 alkyl group substituted by one mercapto group" means, for example, mercaptomethyl, 1-mercaptoethyl, 2-mercaptoethyl, 1-mercaptopropyl, 2-mercaptopropyl Propyl, 3-mercaptopropyl, 1-methyl-
Mercapto groups 1 such as 2-mercaptoethyl, 4-mercaptobutyl, 5-mercaptopentyl, 6-mercaptohexyl, 1-methyl-3-mercaptopropyl
Is a group bonded to the “C1-C6 alkyl group”. Preferably, C1-C3 substituted by one mercapto group, such as mercaptomethyl, 1-mercaptoethyl, 2-mercaptoethyl, 3-mercaptopropyl
It is an alkyl group, more preferably a 2-mercaptoethyl group.

In the present specification, the “C1-C6 alkyl group substituted by one formyl group” includes, for example,
Formylmethyl, 1-formylethyl, 2-formylethyl, 1-formylpropyl, 2-formylpropyl,
One formyl group such as 3-formylpropyl, 4-formylbutyl, 5-formylpentyl, and 6-formylhexyl is a group in which one formyl group is bonded to the “C1-C6 alkyl group”. Preferably it is a C1-C3 alkyl group substituted by one formyl group, such as formylmethyl, 1-formylethyl, 2-formylethyl, 3-formylpropyl, more preferably a formylmethyl group. is there.

As used herein, the term "C1-C6 alkyl group substituted by one carboxyl group" means, for example, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 1-carboxypropyl, 2-carboxypropyl One carboxyl group such as propyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl is the same as the above “C1-C
6 alkyl group ". Preferably, it is a C1-C3 alkyl group substituted by a carboxyl group, such as carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 3-carboxypropyl, and more preferably a carboxymethyl group.

As used herein, the term “having at least one oxygen atom, sulfur atom or nitrogen atom and having 3 ring atoms.
And a heterocyclic group which may be further condensed with a benzene ring, for example, include oxiranyl, oxetanyl, aziridinyl, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,
Oxazolinyl, furazanyl, imidazolyl, pyrazolyl, pyranyl, pyridyl, oxopyridinyl, dioxopiperidinyl, dioxooxazolidinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolinyl, pyrrolidinyl, pyrrolidinyl, pyrrolidonyl, piperidinyl,
Imidazolyl, imidazolidinyl, pyrazolinyl, pyrazolidinyl, piperidinyl, piperazinyl, azepanonyl, morpholinyl, oxadiazolyl, triazolyl,
Triazinyl, tetrazolyl, oxazolinonyl, thiazolinonyl, pyrazolinonyl, imidazolinonyl, triazolinonyl, triazolidinonyl, tetrazolinonyl, tetrazolidinonyl, tetrazolidinonyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, benzothiophenyl, quinolyl, indazolyl Unsaturated or partially or completely saturated, such as oxazolinyl, oxazolidinonyl, benzoxazolyl, benzothiazolyl and dioxoimidazolidinyl, which is a 3- to 7-membered ring which may be further condensed with a benzene ring Heterocyclic group. Preferably, Z ¹ is furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxazolidinyl, imidazolyl, pyrazolyl, pyranyl, pyridyl, oxopyridinyl, dioxopiperidinyl, dioxooxazolidinyl, pyridazinyl, pyrimidinyl, Pyrazinyl, pyrrolinyl, pyrrolidinyl, pyrrolidinonyl, pyrrolidonyl,
Piperidonyl, imidazolyl, imidazolidinyl, pyrazolidinyl, piperidinyl, piperazinyl, azepanonyl, morpholinyl, oxadiazolyl, triazolyl,
Triazinyl, tetrazolyl, oxazolinonyl, thiazolinonyl, pyrazolinonyl, imidazolinonyl, triazolinonyl, triazolidinonyl, tetrazolinonyl, tetrazolidinonyl, indolyl, benzofuranyl, benzothiophenyl, quinolyl, indazolyl, isoxazolinyl, oxazolidinonyl, A 5- to 7-membered ring such as benzoxazolyl, benzothiazolyl and dioxoimidazolidinyl, which may be further condensed with a benzene ring;

[0043]

Embedded image [In the formula, m is 1, 2 or 3, and D and D ′ are the same or different and each represent a hydrogen atom, a C1-C6 alkyl group, a di (C1-C6 alkyl) carbamoyl group or a di (C1-
A C6 alkyl) sulfamoyl group, wherein E, E 'and E "are a hydrogen atom, a C1-C6 alkyl group (the alkyl group may be substituted by 1 to 4 identical or different halogen atoms) , C1-C6 alkoxy groups (the alkoxy groups may be substituted by 1 to 4 identical or different halogen atoms), C1 to C6
It is an alkylthio group, a C1-C6 alkylsulfonyl group or a halogen atom. And most preferably a group represented by the formula

[0044]

Embedded image Wherein m is 1 or 2, D is a hydrogen atom or C
1 to C3 alkyl groups, E, E 'and E "are the same or different and each are a hydrogen atom, a C1 to C4 alkyl group (the alkyl group may be substituted by 1 to 3 identical halogen atoms, A C1 to C3 alkoxy group or a halogen atom.].

The compound (I) of the present invention can be converted into salts such as, for example, sulfates, hydrochlorides, nitrates and phosphates. As long as they can be used as agricultural and horticultural herbicides, they are included in the present invention.

The compounds of the present invention include compounds having an asymmetric carbon, and in this case, the present invention also includes a mixture of one kind of optically active substance and several kinds of optically active substances at an arbitrary ratio. .

The hydrate of the compound of the present invention is also included in the present invention.
It is what is done. (A) In the general formula (I), Z¹Is preferably
A ring containing at least one oxygen, sulfur or nitrogen atom
It has 5 to 7 atoms and may be further condensed with a benzene ring
A heterocyclic group (the heterocyclic group is selected from the following substituent group a1).
Substituted by 1 to 3 identical or different substituents
May be done. ), Formula -C (R⁶) = NR⁷[Wherein, R⁶
Is a hydrogen atom, a C1-C6 alkyl group or a formula -NR⁸R⁹
(Where R⁸And R⁹Are the same or different and are a hydrogen atom,
C1-C6 alkyl group, C2-C7 alkylcarbonyl
Group, C2-C7 alkoxycarbonyl group or phenyl group
Is shown. ) Represents a group represented by⁷Are C1-C6
Alkoxy group, C2-C6 alkenyloxy group, hydroxyl group or
Is the formula -NR^8aR^9a(Where R^8aAnd R^9aIs the aforementioned R⁸
And R⁹Is equivalent to ). 〕so
A group represented by the formula -NH-C (R^Ten) = G ｛where R
^TenIs a C1-C6 alkyl group, a C1-C6 alkoxy
Group, C1-C6 alkylthio group or amino group (the amino group
Groups are one or two identical or different C1-C3 alkyls;
May be substituted by a phenyl group. ) Where G is the formula = C
HNO_TwoOr a group represented by the formula = N-CN
Show. A group represented by｝ or a formula -N = J wherein J is a group represented by the formula
= S (CH_Three)_TwoOr a group represented by the formula = C (R¹¹) Q ^a−
R¹²中 where R¹¹Is a C1-C6 alkyl group, C1-C6
6 alkoxy group, C1-C6 alkylthio group, amino group
(The amino group is one or two identical or different C1 to C1
It may be substituted by a C3 alkyl group. ) Or cyano
A group represented by R ¹²Is a C1-C6 alkyl group (such as
The kill group is a C2-C7 alkoxycarbonyl group or phenyl.
May be substituted by a phenyl group. ) Or C2-C6 alk
Represents a nyl group, or Q^aRepresents an oxygen atom or a sulfur atom
You. And the substituent group a1 is a group represented by C1 to C
6 alkyl groups (the alkyl groups may be 1 to 4 identical or
May be substituted by different halogen atoms. ),
C1 to C6 alkoxy group (the alkoxy group is 1 to
Substituted by four identical or different halogen atoms
Is also good. ), Phenyl group, formyl group, amino group (
The amino group is a C1-C6 alkyl group, a C2-C7 alkyl group.
Carbonyl group C2-C7 alkoxycarbonyl group or
It may be substituted by a formyl group. ), C1-C6
Alkylthio group, C1-C6 alkylsulfonyl group, halo
Gen atom, di (C1-C6 alkyl) carbamoyl group and
And di (C1-C6 alkyl) sulfamoyl groups
Group, more preferably furyl, thienyl, pylori
Oxazolyl, isoxazolyl, thiazolyl, i
Sothiazolyl, oxazolidinyl, imidazolyl, pyra
Zolyl, pyranyl, pyridyl, oxopyridinyl, geo
Oxopiperidinyl, dioxooxazolidinyl, pyrida
Dinyl, pyrimidinyl, pyrazinyl, pyrrolinyl, pyro
Lysinyl, pyrrolidinonyl, pyrrolidonyl, piperidoni
, Imidazolyl, imidazolidinyl, pyrazolidini
, Piperidinyl, piperazinyl, azepanonyl, mole
Folinyl, oxadiazolyl, triazolyl, triazi
Nil, tetrazolyl, oxazolinonyl, thiazolinoni
, Pyrazolinonyl, imidazolinonyl, triazolino
Nil, triazolidinonyl, tetrazolinonyl, tetra
Zolidinonyl, indolyl, benzofuranyl, benzothi
Ophenyl, quinolyl, indazolyl, isoxazoly
Nil, oxazolidinonyl, benzoxazolyl, ben
Group consisting of zothiazolyl and dioxoimidazolidinyl
A heterocyclic group selected from the group consisting of the following substituent groups
1 to 3 identical or different substituents selected from a1
May be substituted by ), Formula -C (R⁶) = NR
⁷[Wherein, R⁶Represents a hydrogen atom or a C1-C6 alkyl group
And R⁷Is a C1-C6 alkoxy group, a C2-C6
Lucenyloxy group or formula -NR⁸R⁹(Where R⁸And R⁹
Are the same or different and are a C1-C6 alkyl group, C1-
C6 alkylcarbonyl group or C1-C6 alkoxyca
Represents a rubonyl group. ). ]
A group of the formula -NH-C (R^Ten) = G ｛where R^TenIs C1
-C3 alkyl group, C1-C3 alkoxy group, C1-C
3 alkylthio group or amino group (the amino group is 1 or
Two identical or different C1-C3 alkyl groups
It may be exchanged. G is the formula = CHNO_TwoIn table
Or a group represented by the formula = N-CN. Table with｝
Or a group represented by the formula -N = J [wherein J is a group represented by the formula = S (C
H_Three)_TwoOr a group represented by the formula = C (R¹¹) Q ^a-R¹²{formula
Medium, R¹¹Is a C1-C3 alkyl group, a C1-C3 alcohol
Xy group, C1-C3 alkylthio group, dimethylamino group
Or a cyano group;¹²Is a C1-C3 alkyl group
(The alkyl group is a C2-C4 alkoxycarbonyl
Group or a phenyl group. ) Or C2
C4 alkynyl group; ^aIs an oxygen atom or sulfur
Indicates an atom. Represents a group represented by｝. A group represented by
And the substituent group a1 includes a C1 to C6 alkyl group (the
The kill group is 1 to 4 identical or different halogen atoms
May be substituted by ), C1-C6 alkoxy group
(The alkoxy group may be 1 to 4 identical or different
It may be substituted by a halogen atom. ), Phenyl
Group, formyl group, amino group (the amino group is
6 alkyl groups, C2-C7 alkylcarbonyl groups C2-
Substituted by C7 alkoxycarbonyl group or formyl group
May be done. ), C1-C6 alkylthio group, C1-C6
C6 alkylsulfonyl group, halogen atom, di (C1-
C6 alkyl) carbamoyl group and di (C1-C6
Kill) a sulfamoyl group, more preferably
Is the expression

[0048]

Embedded image [In the formula, m represents 1, 2 or 3, and D and D ′ are the same or different and are each a hydrogen atom, a C1-C6 alkyl group, a di (C1-C6 alkyl) carbamoyl group or a di (C1-
C6 alkyl) sulfamoyl group, E, E ′ and E ″ are the same or different and are each a hydrogen atom, a C1-C6 alkyl group (the alkyl group is substituted by 1 to 4 same or different halogen atoms, And C1 to C1.
C6 alkoxy (the alkoxy group may be substituted by 1 to 4 same or different halogen atoms), phenyl group, formyl group, amino group (the amino group is a C1-C6 alkyl group, a C2- A C7 alkylcarbonyl group, which may be substituted by a C2 to C7 alkoxycarbonyl group or a formyl group), a C1 to C6 alkylthio group, a C1 to C6 alkylsulfonyl group, or a halogen atom. Groups represented by] the formula -C (R ⁶⁾ = NR ⁷
[Wherein, R ⁶ represents a hydrogen atom or a C1-C6 alkyl group, and R ⁷ represents a C1-C6 alkoxy group, a C2-C6 alkenyloxy group or a formula —NR ⁸ R ⁹ (wherein, R ⁸ and R ⁹
Are the same or different and are C1-C6 alkyl groups, C2-
It represents a C7 alkylcarbonyl group or a C2-C7 alkoxycarbonyl group. ). ], Formula -N
^{H-C (R 10) =} G { wherein, R ¹⁰ is, C1 to C3 alkyl group, C1 to C3 alkoxy group, C1 to C3 alkylthio group or an amino group (said amino group one or two identical or different may be substituted by C1~C3 alkyl group.) indicates, G represents a group represented by the group or the formula = N-CN formula = CHNO _2. Or a group represented by the formula -N = J [wherein J is a group represented by the formula = S (CH ₃ ) ₂ or a formula = C (R ¹¹ ) Q ^a -R ¹² } ¹¹ is C1
-C3 alkyl group, C1-C3 alkoxy group, C1-C
3 represents an alkylthio group, a dimethylamino group or a cyano group, and R ¹² represents a C1 to C3 alkyl group (the alkyl group may be substituted by a C2 to C4 alkoxycarbonyl group or a phenyl group) or a C2 to C4 alkynyl. And Q ^a represents an oxygen atom or a sulfur atom. Represents a group represented by｝. Is most preferably a group represented by the formula

[0049]

Embedded image[In the formula, m represents 1 or 2, D represents a hydrogen atom or C
1-C3 alkyl group, wherein E, E 'and E "are the same or
Is different from a hydrogen atom, a C1-C4 alkyl group
Alkyl groups are substituted by one to three identical halogen atoms.
It may be exchanged. ), C1-C3 alkoxy group, holmi
A halogen group or a halogen atom. A group represented by the formula -C
(R⁶) = NR⁷(Where R⁶Is a C1-C3 alkyl group
And R⁷Represents a C1-C3 alkoxy group. )so
A group represented by the formula -NH-C (R^Ten) = G (where R
^TenIs a C1-C3 alkyl group, a C1-C3 alkoxy group
And G represents the formula = N-CN. )
Is the formula -N = J where J is the formula = S (CH_Three)_TwoRepresented by
Group or formula = C (R¹¹) Q ^a-R¹²中 where R¹¹Is C
Represents a 1-C3 alkyl group or a C1-C3 alkoxy group
Then R¹²Is a C1-C3 alkyl group (the alkyl group
Represents a C2-C4 alkoxycarbonyl group or a phenyl group
It may be more substituted. ) And Q^aIs an oxygen atom or
Represents a sulfur atom. Represents a group represented by｝. ]
Group. (B) In the general formula (I), R¹Is preferably
A C1-C6 alkyl group or a halogen atom, more preferably
Suitably, it is a C1-C3 alkyl group. (C) In the general formula (I), n is preferably 0
Or 1. (D) In the general formula (I), R^TwoAnd R^ThreeIs suitable
Are both hydrogen atoms. (E) In the general formula (I), X is preferably 2
-With a benzothiazolyl group or a 2-benzoxazolyl group
And more preferably a 2-benzothiazolyl group. (F) In the general formula (I), A is preferably an acid
Elementary atom. (1) In the general formula (I), preferably, (1a)
Z¹Preferably has at least one oxygen, sulfur or
Has a nitrogen atom and has 5 to 7 ring atoms, and
A heterocyclic group which may be condensed with a heterocyclic group (the heterocyclic group is
1 to 3 identical or different members selected from substituent group a1
May be substituted by a substituent. ), Formula -C (R⁶)
= NR⁷[Wherein, R⁶Is a hydrogen atom, C1-C6 alkyl
Group or formula -NR⁸R⁹(Where R⁸And R⁹Are the same or different
A hydrogen atom, a C1-C6 alkyl group, C2-C7
Alkylcarbonyl group, C2-C7 alkoxy carbonyl
A phenyl group or a phenyl group. ) Represents a group represented by
⁷Is a C1-C6 alkoxy group, a C2-C6 alkenyl
Oxy group, hydroxyl group or formula -NR^8aR^9a(Where R^8aas well as
R^9aIs the aforementioned R⁸And R⁹Is equivalent to )
Group. A group represented by the formula -NH-C (R^Ten) =
G ｛where R^TenIs a C1-C6 alkyl group, C1-C6
Alkoxy group, C1-C6 alkylthio group or amino group
(The amino group is one or two identical or different C1 to C1
It may be substituted by a C3 alkyl group. ) And G
Is the formula = CHNO_TwoOr a group represented by the formula = N-CN
Shows the group to be formed. A group represented by｝ or a formula -N = J [formula
Where J is the formula = S (CH_Three)_TwoOr a group represented by the formula:
(R¹¹) Q ^a-R¹²中 where R¹¹Is C1-C6 alk
Group, C1-C6 alkoxy group, C1-C6 alkylthio
O group, amino group (the amino group is one or two identical or
May be substituted by different C1-C3 alkyl groups
No. ) Or a cyano group; ¹²Is C1-C6 alk
(The alkyl group is a C2-C7 alkoxycarbo group
It may be substituted by a nyl group or a phenyl group. ) Or
Represents a C2-C6 alkynyl group, or Q^aIs an oxygen atom
Or a sulfur atom. A group represented by the formula:
a1 is a C1-C6 alkyl group (the alkyl group is 1
From 4 to 4 identical or different halogen atoms
It may be. ), A C1-C6 alkoxy group (the alcohol
The xy group is one to four identical or different halogen atoms.
May be substituted by ), Phenyl group, formyl
Group, amino group (the amino group is a C1-C6 alkyl
Group, C2-C7 alkylcarbonyl group C2-C7 alcohol
May be substituted by a xycarbonyl group or a formyl group
No. ), C1-C6 alkylthio group, C1-C6 alkyl
Rusulfonyl group, halogen atom, di (C1-C6 alkyl
B) carbamoyl group and di (C1-C6 alkyl) sulfur
A group consisting of a famoyl group, (1b) R¹Is C1
-C6 alkyl group or halogen atom, and (1c) n
Is 0 or 1, and (1d) R^TwoAnd R^ThreeAre both hydrogen
(1e) X is a 2-benzothiazolyl group or
Is a 2-benzoxazolyl group, and (1f) A is an acid
(2) More preferably (2a) Z¹Is
formula

[0050]

Embedded image [In the formula, m represents 1, 2 or 3, and D and D ′ are the same or different and are each a hydrogen atom, a C1-C6 alkyl group, a di (C1-C6 alkyl) carbamoyl group or a di (C1-
C6 alkyl) sulfamoyl group, E, E ′ and E ″ are the same or different and are each a hydrogen atom, a C1-C6 alkyl group (the alkyl group is substituted by 1 to 4 same or different halogen atoms, And C1 to C1.
C6 alkoxy (the alkoxy group may be substituted by 1 to 4 same or different halogen atoms), phenyl group, formyl group, amino group (the amino group is a C1-C6 alkyl group, a C2- A C7 alkylcarbonyl group, which may be substituted by a C2 to C7 alkoxycarbonyl group or a formyl group), a C1 to C6 alkylthio group, a C1 to C6 alkylsulfonyl group, or a halogen atom. Groups represented by] the formula -C (R ⁶⁾ = NR ⁷
[Wherein, R ⁶ represents a hydrogen atom or a C1-C6 alkyl group, and R ⁷ represents a C1-C6 alkoxy group, a C2-C6 alkenyloxy group or a formula —NR ⁸ R ⁹ (wherein, R ⁸ and R ⁹
Are the same or different and are C1-C6 alkyl groups, C2-
It represents a C7 alkylcarbonyl group or a C2-C7 alkoxycarbonyl group. ). ], Formula -N
^{H-C (R 10) =} G { wherein, R ¹⁰ is, C1 to C3 alkyl group, C1 to C3 alkoxy group, C1 to C3 alkylthio group or an amino group (said amino group one or two identical or different may be substituted by C1~C3 alkyl group.) indicates, G represents a group represented by the group or the formula = N-CN formula = CHNO _2. Or a group represented by the formula -N = J [wherein J is a group represented by the formula = S (CH ₃ ) ₂ or a formula = C (R ¹¹ ) Q ^a -R ¹² } ¹¹ is C1
-C3 alkyl group, C1-C3 alkoxy group, C1-C
3 represents an alkylthio group, a dimethylamino group or a cyano group, and R ¹² represents a C1 to C3 alkyl group (the alkyl group may be substituted by a C2 to C4 alkoxycarbonyl group or a phenyl group) or a C2 to C4 alkynyl. And Q ^a represents an oxygen atom or a sulfur atom. Represents a group represented by｝. And (2b) R ¹
Is a C1-C3 alkyl group, (2c) n is 0 or 1, (2d) R ² and R ³ are both hydrogen atoms, and (2e) X is a 2-benzothiazolyl group or 2 (2f) A is an oxygen atom, and (3) more preferably (3a) Z ¹ is a group represented by the formula:

[0051]

Embedded image[In the formula, m represents 1 or 2, D represents a hydrogen atom or C
1-C3 alkyl group, wherein E, E 'and E "are the same or
Is different from a hydrogen atom, a C1-C4 alkyl group
Alkyl groups are substituted by one to three identical halogen atoms.
It may be exchanged. ), C1-C3 alkoxy group, holmi
A halogen group or a halogen atom. A group represented by the formula -C
(R⁶) = NR⁷(Where R⁶Is a C1-C3 alkyl group
And R⁷Represents a C1-C3 alkoxy group. )so
A group represented by the formula -NH-C (R^Ten) = G (where R
^TenIs a C1-C3 alkyl group, a C1-C3 alkoxy group
And G represents the formula = N-CN. )
Is the formula -N = J where J is the formula = S (CH_Three)_TwoRepresented by
Group or formula = C (R¹¹) Q ^a-R¹²中 where R¹¹Is C
Represents a 1-C3 alkyl group or a C1-C3 alkoxy group
Then R¹²Is a C1-C3 alkyl group (the alkyl group
Represents a C2-C4 alkoxycarbonyl group or a phenyl group
It may be more substituted. ) And Q^aIs an oxygen atom or
Represents a sulfur atom. Represents a group represented by｝. ]
(3b) R¹Is a C1-C3 alkyl group
And (3c) n is 0 or 1, and (3d) R^TwoPassing
And R^ThreeAre both hydrogen atoms, and (3e) X is
Benzothiazolyl group or 2-benzoxazolyl group
You. (3f) A is an oxygen atom.

The representative compounds of the present invention are shown in the following Tables 1 and 2, but the present invention is not limited to these compounds.

In the following, “Me” represents a methyl group and “Et”
Is an ethyl group, `` Pr '' is a propyl group, `` iPr '' is an isopropyl group, `` tBu '' is a t-butyl group, `` Ph '' is a phenyl group, `` 2,6-Cl ₂ '' is 2, Each represents a 6-dichloro group.

In the table, Z-1 to Z-47 represent the following formulas:

[0055]

Embedded image And a heterocyclic group represented by X-1 to X-4 are
The following formula

[0056]

Embedded image And a heterocyclic group represented by

In the table, in the parentheses after X, the above heterocyclic X
-1 to X-4, a substituent (R ^Four)_pOr (R^Five)_qIndicates
ing.

In the table, "H" for (R ¹ ) _n , (R ⁴ ) _p and (R ⁵ ) _q indicates the case where n, p and q are 0, respectively.

[0059]

[Table 1]

[0060]

Embedded image 化合物 Compound Z ¹ (R ¹ ) _n R ² R ³ AX [( R ⁴ ) _p or (R ⁵ ) _q ] number ─────────────────────────────────── 1.1 Z- 1 [D = H] HHHO X-2 [H] 1.2 Z-1 [D = H] HHHO X-2 [5-Cl] 1.3 Z-1 [D = H] HHHO X-2 [4,5-Cl ₂ ] 1.4 Z-1 [D = H] HHHO X-2 [4-Me] 1.5 Z-1 [D = H] HHHO X-4 [H] 1.6 Z-1 [D = H] HHHO X-3 [ H] 1.7 Z-1 [D = Me] HHHO X-4 [H] 1.8 Z-1 [D = Me] HHHO X-2 [H] 1.9 Z-1 [D = Me] HHHO X-2 [4- Ph] 1.10 Z-1 [D = Me] HHHO X-2 [4-CF ₃ ] 1.11 Z-1 [D = Me] HHHO X-2 [4,5-Cl ₂ ] 1.12 Z-1 [D = Et ] HHHO X-4 [H] 1.13 Z-1 [D = H] 3-Me HHO X-4 [H] 1.14 Z-1 [D = H] 3-Me HHO X-2 [H] 1.15 Z-1 [D = H] 3-Me HHO X-1 [H] 1.16 Z-1 [D = Me] 3-Me HHO X-2 [H] 1.17 Z-1 [D = Me] 2-Me HHO X-4 [H] 1.18 Z-1 [D = Me] 3-Me HHO X-4 [H] 1.19 Z-1 [D = Me] 2-Cl HHO X-4 [H] 1.20 Z-1 [D = Me] 3-Cl HHO X-4 [H] 1.21 Z-1 [D = Me] 2-FHHO X-4 [H] 1.22 Z-1 [D = Me] 3-FHHO X-4 [H] 1.23 Z-1 [D = Me] 2-OMe HHO X-4 [H] 1.24 Z-1 [D = Me] 3-OMe HHO X-4 [H] 1.25 Z-1 [D = Me] 2-NO ₂ HHO X-4 [H] 1.26 Z-1 [D = Me] 3-NO ₂ HHO X-4 [H] 1.27 Z-1 [D = Me] 2-SMe HHO X-4 [H] 1.28 Z-1 [D = Me] 3-SMe HHO X-4 [H] 1.29 Z-1 [D = Me] 3-Me HHO X-3 [H] 1.30 Z-1 [D = Me] 3-Me HHO X-2 [4,5-Cl ₂ ] 1.31 Z-1 [D = Et] 3-Me HHO X-4 [H] 1.32 Z-1 [D = Et] 3-Me HHO X-3 [H] 1.33 Z-1 [D = tBu] 3-Me HHO X-4 [H] 2.1 Z-2 [D = Me] HHHO X-4 [H] 2.2 Z-2 [D = Et] HHHO X-4 [H ] 2.3 Z-2 [D = Me] 3-Me HHO X-4 [H] 2.4 Z-2 [D = Me] 3-Me HHO X-4 [5-F] 2.5 Z-2 [D = Me] 3-Me HHO X-4 [5-F] 2.6 Z-2 [D = Me] 3-Me HHS X-4 [5-F] 2.7 Z-2 [D = Me] 3-Me HHO X-4 [ 5-Cl] 2.8 Z-2 [D = Me] 3-Me HHO X-4 [5-OMe] 2.9 Z-2 [D = Me] 3-Me HHO X-4 [5-Me] 2.10 Z-2 [D = Me] 3-Me HHO X-4 [6-F] 2.11 Z-2 [D = Me] 3-Me HHO X-3 [6-F] 2.12 Z-2 [D = Me] 3-Me HHS X-4 [6-F] 2.13 Z-2 [D = Me] 3-Me Me HO X-4 [H] 2.14 Z-2 [D = Me] 3-Me Et HO X-4 [H] 2.15 Z-2 [D = Me] 3-Me Me Me O X-4 [H] 2.16 Z-2 [D = Me] 3-Me Et Et O X-4 [H] 2.17 Z-2 [D = Me] 3-Me HHO X-2 [H] 2.18 Z-2 [D = Me] 3-Me HHS X-2 [H] 2.19 Z-2 [D = Me] 3-Me HHO X-1 [H] 2.20 Z -2 [D = Me] 3-Me HHO X-2 [4,5-Cl ₂ ] 2.21 Z-2 [D = Me] 3-Me HHS X-2 [4,5-Cl ₂ ] 2.22 Z-2 [D = Me] 3-Me HHO X-1 [4,5-Cl ₂ ] 2.23 Z-2 [D = Me] 3-Me HHO X-2 [4-CF ₃ ] 2.24 Z-2 [D = Me] 3-Me HHO X-1 [4-CF ₃ ] 2.25 Z-2 [ D = Et] 3-Me HHO X-4 [H] 2.26 Z-2 [D = Et] 3-Me HHO X-3 [H] 2.27 Z-2 [D = tBu] 3-Me HHO X-4 [ H] 2.28 Z-2 [D = COMe] 3-Me HHS X-4 [H] 2.29 Z-2 [D = COOMe] 3-Me HHO X-4 [H] 2.30 Z-2 [D = CON (Me ) 3-Me HHO X-4 [H] 2.31 Z-2 [D = CON (Et) ₂ ] 3-Me HHO X-4 [H] 2.32 Z-2 [D = SO ₂ Me] 3-Me HHO X -4 [H] 2.33 Z-2 [D = SO ₂ Ph] 3-Me HHO X-4 [H] 2.34 Z-2 [D = SO ₂ N (Me) ₂ ] 3-Me HHO X-4 [H ] 3.1 Z-3 [D = H] HHHO X-2 [H] 3.2 Z-3 [D = H] HHHO X-1 [H] 3.3 Z-3 [D = H] HHHO X-4 [H] 3.4 Z-3 [D = H] HHHO X-3 [H] 3.5 Z-3 [D = Me] HHHO X-4 [H] 3.6 Z-3 [D = Me] HHHO X-3 [H] 3.7 Z- 3 [D = Et] HHHO X-4 [H] 3.8 Z-3 [D = iPr] HHHO X-4 [H] 3.9 Z-3 [D = Me] 3-Me HHO X-2 [4,5- Cl ₂ ] 3.10 Z-3 [D = Me] 3-Me HHO X-4 [H] 3.11 Z-3 [D = Me] 3-Me HHO X-3 [H] 3.12 Z-3 [D = Et] 3-Me HHO X-4 [H] 3.13 Z-3 [D = Et] 3-Me HHO X-3 [H] 4.1 Z-4 [D = Me] HHHO X-2 [H] 4.2 Z-4 [ D = Me] HHHO X-1 [H] 4.3 Z-4 [D = Me] HHHO X-4 [H] 4.4 Z-4 [D = Et] HHHO X-4 [H] 4.5 Z-4 [D = iPr] HHHO X-4 [H] 4.6 Z-4 [D = Me] 3-Me HHO X-2 [H] 4.7 Z-4 [D = Me] 3-Me HHO X-4 [H] 4.8 Z- 4 [D = Me] 3-M e HHO X-3 [H] 4.9 Z-4 [D = Et] 3-Me HHO X-4 [H] 4.10 Z-4 [D = Et] 3-Me HHO X-3 [H] 5.1 Z-5 [m = 1] HHHO X-2 [H] 5.2 Z-5 [m = 1] HHHO X-4 [H] 5.3 Z-5 [m = 1] HHHO X-3 [H] 5.4 Z-5 [m = 1] HHHS X-4 [H] 5.5 Z-5 [m = 1] 3-Me HHO X-2 [H] 5.6 Z-5 [m = 1] 3-Me HHO X-4 [H] 5.7 Z -5 [m = 1] 3-Me HHO X-3 [H] 5.8 Z-5 [m = 2] HHHO X-2 [H] 5.9 Z-5 [m = 2] HHHO X-4 [H] 5.10 Z-5 [m = 2] 3-Me HHO X-2 [H] 5.11 Z-5 [m = 2] 3-Me HHO X-4 [H] 5.12 Z-5 [m = 2] 3-Me HHS X-4 [H] 5.13 Z-5 [m = 3] HHHO X-3 [H] 5.14 Z-5 [m = 3] HHHO X-3 [H] 6.1 Z-6 [D = Me] HHHO X- 2 [H] 6.2 Z-6 [D = Me] HHHO X-1 [H] 6.3 Z-6 [D = Me] HHHO X-4 [H] 6.4 Z-6 [D = Me] HHHO X-3 [ H] 6.5 Z-6 [D = Et] HHHO X-4 [H] 6.6 Z-6 [D = Et] HHHO X-3 [H] 6.7 Z-6 [D = Pr] HHHO X-4 [H] 6.8 Z-6 [D = Pr] HHHO X-3 [H] 6.9 Z-6 [D = iPr] HHHO X-4 [H] 6.10 Z-6 [D = iPr] HHHO X-3 [H] 6.11 Z -6 [D = Me] 3-Me HHO X-2 [H] 6.12 Z-6 [D = Me] 3-Me HHO X-4 [H] 6.13 Z-6 [D = Me] 3-Me HHO X -3 [H] 6.14 Z-6 [D = Et] 3-Me HHO X-4 [H] 6.15 Z-6 [D = Pr] 3-Me HHO X-4 [H] 6.16 Z-6 [D = iPr] 3-Me HHO X-4 [H] 7.1 Z-7 [E = H] HHHO X-2 [H] 7.2 Z-7 [E = H] HHHO X-4 [H] 7.3 Z-7 [E = H] HHHO X-3 [H] 7.4 Z-7 [E = H] 3-Me HHO X-4 [H] 7.5 Z-7 [E = H] 2,6-Cl ₂ HHO X-4 [H] 7.6 Z-7 [E = OMe] HHHO X-2 [H] 7.7 Z-7 [E = OMe] HHHO X-4 [H] 7.8 Z-7 [E = OMe] HHHO X-3 [H] 8.1 Z-8 [D = Me, E = SMe] HHHO X-2 [H] 8.2 Z-8 [D = Me, E = SMe] HHHO X-4 [H] 8.3 Z-8 [D = Me, E = SMe] HHHO X-3 [H] 8.4 Z-8 [D = Me, E = SO ₂ Me ] HHHO X-4 [H] 8.5 Z-8 [D = Me, E = SO ₂ Me] HHHO X-3 [H] 8.6 Z-8 [D = Me, E = OMe] HHHO X-4 [H] 8.7 Z-8 [D = Me, E = OMe] HHHO X-3 [H] 8.8 Z-8 [D = Me, E = OCH ₂ CF ₃ ] HHHO X-4 [H] 9.1 Z-9 [D = Me, E = CF ₃ ] HHHO X-2 [H] 9.2 Z-9 [D = Me, E = CF ₃ ] HHHO X-4 [H] 9.3 Z-9 [D = Me, E = CF ₃ ] HHHO X-3 [H] 9.4 Z-9 [D = Me, E = CF ₃ ] 3-Me HHO X-2 [H] 9.5 Z-9 [D = Me, E = CF ₃ ] 3-Me HHO X- 4 [H] 9.6 Z-9 [D = Me, E = CF ₃ ] 3-Me HHO X-3 [H] 10.1 Z-10 [D = Me, D '= H] HHHO X-2 [H] 10.2 Z-10 [D = Me, D '= H] HHHO X-4 [H] 10.3 Z-10 [D = Me, D' = H] HHHO X-3 [H] 10.4 Z-10 [D = Me, D '= H] 3-Me HHO X-2 [H] 10.5 Z-10 [D = Me, D' = H] 3-Me HHO X-4 [H] 10.6 Z-10 [D = Me, D ' = H] 3-Me HHO X-3 [H] 11.1 Z-11 [D = E = Me] HHHO X-2 [H] 11.2 Z-11 [D = E = Me] HHHO X-4 [H] 11.3 Z-11 [D = E = Me] HHHO X-3 [H] 11.4 Z-11 [D = E = Me] 3-Me HHO X-2 [H] 11.5 Z-11 [D = E = Me] 3 -Me HHO X-4 [H] 11.6 Z-11 [D = E = Me] 3-Me HHO X-3 [H] 12.1 Z-12 [E = Me] HHHO X-4 [H] 12.2 Z-12 [E = CF ₃ ] HHHO X-4 [H] 12.3 Z-12 [E = Me] 3 -Me HHO X-4 [H] 12.4 Z-12 [E = CF ₃ ] 3-Me HHO X-4 [H] 13.1 Z-13 [E = Me] HHHO X-4 [H] 13.2 Z-13 [ E = Me] HHHO X-3 [H] 13.3 Z-13 [E = Me] 3-Me HHO X-4 [H] 13.4 Z-13 [E = Me] 3-Me HHO X-3 [H] 14.1 Z-14 [E = E '= E''= H] HHHO X-3 [H] 14.2 Z-14 [E = E' = E '' = H] HHHO X-4 [H] 14.3 Z-14 [ E = OEt, E '= E''= H] HHHO X-2 [H] 14.4 Z-14 [E = OEt, E' = E '' = H] HHHO X-4 [H] 14.5 Z-14 [ E = OEt, E '= E''= H] HHHO X-3 [H] 14.6 Z-14 [E = OEt, E' = Me, E '' = H] HHHO X-4 [H] 14.7 Z- 14 [E = OEt, E '= Me, E''= H] HHHO X-3 [H] 14.8 Z-14 [E = E''= H, E' = CF ₃ ] HHHO X-4 [H] 14.9 Z-14 [E = E '' = H, E '= CF ₃ ] HHHO X-3 [H] 14.10 Z-14 [E = E' = H, E '' = Cl] HHHO X-4 [H ] 14.11 Z-14 [E = E '= H, E''= Cl] HHHO X-3 [H] 14.12 Z-14 [E = E' = E '' = H] 3-Me HHO X-3 [ H] 14.13 Z-14 [E = E '= E''= H] 3-Me HHO X-4 [H] 14.14 Z-14 [E = E''= H, E' = Me] HHHO X-4 [H] 14.15 Z-14 [E = E '' = H, E '= Me] HHHO X-3 [H] 14.16 Z-14 [E = E' = Me, E '' = H] HHHO X-4 [H] 14.17 Z-14 [E = E '= Me, E''= H] HHHO X-3 [H] 14.18 Z-14 [E = E' = H, E '' = Me] HHHO X-4 [H] 14.19 Z-14 [E = E '= H, E''= Me] HHHO X-3 [H] 14.20 Z-14 [E = E' = M e, E '' = H] 3-Me HHO X-4 [H] 14.21 Z-14 [E = E '= Me, E''= H] 3-Me HHO X-3 [H] 14.22 Z-14 [E = E '= tBu, E''= H] HHHO X-4 [H] 14.23 Z-14 [E = E' = tBu, E '' = H] HHHO X-3 [H] 14.24 Z-14 [E = E '= E''= Me] HHHO X-4 [H] 14.25 Z-14 [E = E' = E '' = Me] HHHO X-3 [H] 14.26 Z-14 [E = E '= Et, E''= H] HHHO X-4 [H] 14.27 Z-14 [E = E' = Et, E '' = H] HHHO X-3 [H] 14.28 Z-14 [E = Me , E '= E''= H] HHHO X-4 [H] 14.29 Z-14 [E = Me, E' = E '' = H] HHHO X-3 [H] 14.30 Z-14 [E = Cl , E '= Me, E''= H] HHHO X-3 [H] 14.31 Z-14 [E = CHO, E' = E '' = H] HHHO X-4 [H] 14.32 Z-14 [E = CHO, E '= E''= H] HHHO X-3 [H] 14.33 Z-14 [E = OMe, E' = E '' = H] HHHO X-4 [H] 14.34 Z-14 [E = OMe, E '= E''= H] HHHO X-3 [H] 14.35 Z-14 [E = E' = Ph, E '' = H] HHHO X-4 [H] 14.36 Z-14 [E = E '= Ph, E''= H] HHHO X-3 [H] 15.1 Z-15 HHHO X-2 [H] 15.2 Z-15 HHHO X-1 [H] 15.3 Z-15 HHHO X-4 [ H] 15.4 Z-15 HHHO X-3 [H] 15.5 Z-15 3-Me HHO X-2 [H] 15.6 Z-15 3-Me HHO X-1 [H] 15.7 Z-15 3-Me HHO X -4 [H] 15.8 Z-15 3-Me HHO X-3 [H] 16.1 Z-16 HHHO X-2 [H] 16.2 Z-16 HHHO X-4 [H] 16.3 Z-16 3-Me HHO X -2 [H] 16.4 Z-16 3-Me HHO X-4 [H] 17.1 Z-17 [E = Me] HHHO X-2 [H] 17.2 Z-17 [E = Me] HHHO X-4 [H ] 17.3 Z-17 [E = Me ] HHHO X-3 [H] 17.4 Z-17 [E = Me] 3-Me HHO X-2 [H] 17.5 Z-17 [E = Me] 3-Me HHO X-4 [H] 18.1 Z-18 [E = Me, E '= CH ₂ Cl] HHHO X-2 [H] 18.2 Z-18 [E = Me, E' = CH ₂ Cl] HHHO X-1 [H] 18.3 Z-18 [E = Me , E '= CH ₂ Cl] HHHO X-4 [H] 18.4 Z-18 [E = Me, E' = CH ₂ Cl] HHHO X-3 [H] 18.5 Z-18 [E = Me, E '= CH ₂ Cl] 3-Me HHO X-2 [H] 18.6 Z-18 [E = Me, E '= CH ₂ Cl] 3-Me HHO X-4 [H] 18.7 Z-18 [E = Me, E '= CH ₂ Cl] 3-Me HHS X-4 [H] 18.8 Z-18 [E = Me, E' = CH ₂ Cl] 3-Me HHO X-3 [H] 19.1 Z-19 [E = Me ] HHHO X-2 [H] 19.2 Z-19 [E = Me] HHHO X-1 [H] 19.3 Z-19 [E = Me] HHHO X-4 [H] 19.4 Z-19 [E = Me] HHHO X-3 [H] 19.5 Z-19 [E = Me] 3-Me HHO X-4 [H] 19.6 Z-19 [E = Me] 3-Me HHO X-3 [H] 20.1 Z-20 [D = Me, E = Cl] HHHO X-2 [H] 20.2 Z-20 [D = Me, E = Cl] HHHO X-4 [H] 20.3 Z-20 [D = Me, E = Cl] HHHO X- 3 [H] 20.4 Z-20 [D = Me, E = Cl] 3-Me HHO X-2 [H] 20.5 Z-20 [D = Me, E = Cl] 3-Me HHO X-4 [H] 20.6 Z-20 [D = Me, E = Cl] 3-Me HHO X-3 [H] 21.1 Z-21 [E = tBu, E '= H] HHHO X-2 [H] 21.2 Z-21 [E = tBu, E '= H] HHHO X-4 [H] 21.3 Z-21 [E = tBu, E' = Cl] HHHO X-4 [H] 21.4 Z-21 [E = tBu, E '= Cl] 3-Me HHO X-2 [H] 21.5 Z-21 [E = tBu, E '= Cl] 3-Me HHO X-4 [H] 21.6 Z-21 [E = tBu, E' = Cl] 3- Me HHO X-3 [H] 22.1 Z-22 [E = E '= H] HHHO X-2 [H] 22.2 Z-22 [E = E' = H] HHHO X-1 [H] 22.3 Z-22 [ E = E '= H] HHHO X-4 [H] 22.4 Z-22 [E = E' = H] HHHO X-3 [H] 22.5 Z-22 [E = E '= H] 3-Me HHO X -2 [H] 22.6 Z-22 [E = E '= H] 3-Me HHO X-2 [4,5-Cl ₂ ] 22.7 Z-22 [E = E' = H] 3-Me HHO X- 2 [4-Me] 22.8 Z-22 [E = E '= H] 3-Me HHO X-1 [H] 22.9 Z-22 [E = E' = H] 3-Me HHO X-4 [H] 22.10 Z-22 [E = E '= H] 3-Me HHO X-3 [H] 23.1 Z-23 [E = E' = H] HHHO X-2 [H] 23.2 Z-23 [E = E ' = H] HHHO X-1 [H] 23.3 Z-23 [E = E '= H] HHHO X-4 [H] 23.4 Z-23 [E = E' = H] HHHO X-3 [H] 23.5 Z -23 [E = E '= H] 3-Me HHO X-2 [H] 23.6 Z-23 [E = E' = H] 3-Me HHO X-2 [4,5-Cl ₂ ] 23.7 Z- 23 [E = E '= H] 3-Me HHO X-2 [4-Me] 23.8 Z-23 [E = E' = H] 3-Me HHO X-1 [H] 23.9 Z-23 [E = E '= H] 3-Me HHO X-4 [H] 23.10 Z-23 [E = E' = H] 3-Me HHO X-3 [H] 23.11 Z-23 [E = E '= Me] HHHO X-4 [H] 23.12 Z-23 [E = E '= Me] HHHO X-3 [H] 24.1 Z-24 [E = E' = E '' = H] HHHO X-2 [H] 24.2 Z -24 [E = E '= E''= H] HHHO X-1 [H] 24.3 Z-24 [E = E' = E '' = H] HHHO X-4 [H] 24.4 Z-24 [E = E '= E''= H] HHHO X-3 [H] 24.5 Z-24 [E = E' = E '' = H] 3-Me HHO X-2 [H] 24.6 Z-24 [E = E '= E''= H] 3-Me HHO X-2 [4,5-Cl ₂ ] 24.7 Z-24 [E = E' = E '' = H] 3-Me HHO X -2 [4-Me] 24.8 Z-24 [E = E '= E''= H] 3-Me HHO X-1 [H] 24.9 Z-24 [E = E' = E '' = H] 3 -Me HHO X-4 [H] 24.10 Z-24 [E = E '= E''= H] 3-Me HHO X-3 [H] 24.11 Z-24 [E = E''= Cl, E' = H] HHHO X-4 [H] 24.12 Z-24 [E = E '' = Cl, E '= H] HHHO X-3 [H] 24.13 Z-24 [E = Cl, E' = E '' = H] HHHO X-4 [H] 24.14 Z-24 [E = Cl, E '= E''= H] HHHO X-3 [H] 24.15 Z-24 [E = E' = Cl, E '' = H] HHHO X-4 [H] 24.16 Z-24 [E = E '= Cl, E''= H] HHHO X-3 [H] 25.1 Z-25 [D = D' = E = H] HHHO X-2 [H] 25.2 Z-25 [D = D '= E = H] HHHO X-1 [H] 25.3 Z-25 [D = D' = E = H] HHHO X-4 [H] 25.4 Z -25 [D = D '= E = H] HHHO X-3 [H] 25.5 Z-25 [D = D' = E = H] 3-Me HHO X-2 [H] 25.6 Z-25 [D = D '= E = H] 3-Me HHO X-2 [4,5-Cl ₂ ] 25.7 Z-25 [D = D' = E = H] 3-Me HHO X-2 [4-Me] 25.8 Z -25 [D = D '= E = Me] HHHO X-1 [H] 25.9 Z-25 [D = D' = E = Me] HHHO X-4 [H] 25.10 Z-25 [D = D '= E = Me] HHHO X-3 [H] 25.11 Z-25 [D = D '= E = Me] 3-Me HHO X-1 [H] 25.12 Z-25 [D = D' = E = Me] 3 -Me HHO X-4 [H] 25.13 Z-25 [D = D '= E = Me] 3-Me HHO X-3 [H] 26.1 Z-26 HHHO X-2 [H] 26.2 Z-26 HHHO X -1 [H] 26.3 Z-26 HHHO X-4 [H] 26.4 Z-26 HHHO X-3 [H] 26.5 Z-26 3-Me HHO X-2 [H] 26.6 Z-26 3-Me HHO X -1 [H] 26.7 Z-26 3-Me HHO X-4 [H] 26.8 Z-26 3-Me HHO X- 3 [H] 27.1 Z-27 [D = Me, E = OMe] HHHO X-2 [H] 27.2 Z-27 [D = Me, E = OMe] HHHO X-4 [H] 27.3 Z-27 [D = Me, E = OMe] HHHO X-3 [H] 27.4 Z-27 [D = Me, E = OMe] 3-Me HHO X-2 [H] 27.5 Z-27 [D = Me, E = OMe] 3-Me HHO X-4 [H] 27.6 Z-27 [D = Me, E = OMe] 3-Me HHO X-3 [H] 27.7 Z-27 [D = Me, E = OCH ₂ CF ₃ ] HHHO X-2 [H] 27.8 Z-27 [D = Me, E = OCH ₂ CF ₃ ] HHHO X-4 [H] 27.9 Z-27 [D = Me, E = OCH ₂ CF ₃ ] HHHO X-3 [ H] 27.10 Z-27 [D = Me, E = OCH ₂ CF ₃ ] 3-Me HHO X-2 [H] 27.11 Z-27 [D = Me, E = OCH ₂ CF ₃ ] 3-Me HHO X- 4 [H] 27.12 Z-27 [D = Me, E = OCH ₂ CF ₃ ] 3-Me HHO X-3 [H] 28.1 MeNH-N = CH HHHO X-4 [H] 28.2 MeNH-N = CH HHHO X-3 [H] 28.3 EtNH-N = CH HHHO X-4 [H] 28.4 EtNH-N = CH HHHO X-3 [H] 28.5 Me ₂ NN = CH HHHO X-4 [H] 28.6 Me ₂ NN = CH HHHO X-3 [H] 28.7 PhNH-N = CH HHHO X-4 [H] 28.8 MeCONH-N = CH HHHO X-4 [H] 28.9 MeCONH-N = CH HHHO X-3 [H] 28.10 MeO ₂ CNH-N = CH HHHO X-4 [H] 28.11 MeO ₂ CNH-N = CH HHHO X-3 [H] 28.12 MeO-N = CH HHHO X-4 [H] 28.13 MeO-N = CMe HHHO X-2 [H] 28.14 MeO-N = CMe HHHO X-4 [H] 28.15 MeO-N = CMe HHHO X-3 [H] 28.16 MeO-N = CMe 3-Me HHO X-2 [H] 28.17 MeO-N = CMe 3-Me HHO X-1 [H] 28.18 MeO-N = CMe 3-Me H HO X-4 [H] 28.19 MeO-N = CMe 3-Me HHO X-3 [H] 28.20 HO-N = CMe 3-Me HHO X-4 [H] 28.21 CH ₂ = CHCH ₂ ON = CMe HHHO X -4 [H] 28.22 EtO-N = CMe HHHO X-4 [H] 28.23 EtO-N = CMe 3-Me HHO X-4 [H] 28.24 EtO-N = CMe 3-Me HHO X-2 [H] 28.25 tBuO-N = CMe HHHO X-4 [H] 28.26 iPrO-N = CMe HHHO X-4 [H] 28.27 PhCH ₂ ON = CMe HHHO X-4 [H] 28.28 HO-N = C (NH ₂ ) HHHO X-4 [H] 29.1 Z-28 [D = E '= H, E = CF ₃ ] HHHO X-4 [H] 29.2 Z-28 [D = E' = H, E = CF ₃ ] 3-Me HHO X-4 [H] 29.3 Z-28 [D = Me, E = CF ₃ , E '= H] HHHO X-2 [H] 29.4 Z-28 [D = Me, E = CF ₃ , E' = H] HHHO X-4 [H] 29.5 Z-28 [D = Me, E = CF ₃ , E '= H] HHHO X-3 [H] 29.6 Z-28 [D = Me, E = CF ₃ , E '= H] 3-Me HHO X-2 [H] 29.7 Z-28 [D = Me, E = CF ₃ , E' = H] 3-Me HHO X-4 [H] 29.8 Z-28 [D = E '= Me, E = CF ₃ ] HHHO X-2 [H] 29.9 Z-28 [D = E' = Me, E = CF ₃ ] 3-Me HHO X-4 [H] 30.1 Z-29 [E = E '= H] HHHO X-2 [H] 30.2 Z-29 [E = E' = H] 3-Me HHO X-2 [H] 30.3 Z-29 [E = E '= H] HHHO X- 4 [H] 30.4 Z-29 [E = E '= H] 3-Me HHO X-4 [H] 30.5 Z-29 [E = Me, E' = H] HHHO X-2 [H] 30.6 Z- 29 [E = Me, E '= H] 3-Me HHO X-2 [H] 30.7 Z-29 [E = E' = Me] HHHO X-4 [H] 30.8 Z-29 [E = E '= Me] 3-Me HHO X-4 [H] 51.1 Z-30 3-Me HHO X-4 [H] 32.1 Z-31 3-Me HHO X-4 [H] 33.1 Z-32 [E = E '= Me] HHHO X-3 [H] 33.2 Z-32 [E = E' = Me] HHHO X-4 [H] 33.3 Z -32 [E = E '= H] HHHO X-3 [H] 33.4 Z-32 [E = E' = H] HHHO X-4 [H] 33.5 Z-32 [E = Cl, E '= H] HHHO X-3 [H] 33.6 Z-32 [E = Cl, E '= H] HHHO X-4 [H] 34.1 Z-33 [D = Me] HHHO X-4 [H] 34.2 Z-33 [D = Me] 3-Me HHO X-4 [H] 35.1 Z-34 HHHO X-3 [H] 35.2 Z-34 HHHO X-4 [H] 36.1 Z-35 HHHO X-3 [H] 36.2 Z-35 HHHO X-4 [H] 37.1 Z-36 HHHO X-3 [H] 37.2 Z-36 HHHO X-4 [H] 38.1 Z-37 [E = Me, E '= H] HHHO X-4 [H] 38.2 Z-37 [E = Me, E '= H] 3-Me HHO X-4 [H] 38.3 Z-37 [E = NH ₂ , E' = H] HHHO X-4 [H] 38.4 Z-37 [E = NH ₂ , E '= H] 3-Me HHO X-4 [H] 38.5 Z-37 [E = NHCOMe, E' = H] HHHO X-4 [H] 38.6 Z-37 [E = NHCOMe , E '= H] 3-Me HHO X-4 [H] 38.7 Z-37 [E = NHCOOMe, E' = H] HHHO X-4 [H] 38.8 Z-37 [E = NHCOOMe, E '= H ] 3-Me HHO X-4 [H] 38.9 Z-37 [E = NHCHO, E '= H] HHHO X-4 [H] 38.10 Z-37 [E = NHCHO, E' = H] 3-Me HHO X-4 [H] 38.11 Z-37 [E = NH2, E '= Cl] 3-Me HHO X-4 [H] 38.12 Z-37 [E = Et, E' = Me] HHHO X-4 [H ] 38.13 Z-37 [E = Et, E '= H] HHHO X-4 [H] 38.14 Z-37 [E = Cl, E' = H] HHHO X-4 [H] 38.15 Z-37 [E = E '= H] HHHO X-4 [H] 39.1 Z-38 [D = CF ₃ , E = Me] HHHO X-3 [H] 39.2 Z-38 [D = C F ₃ , E = Me] HHHO X-4 [H] 40.1 Z-39 [E = Me, E '= H] HHHO X-3 [H] 40.2 Z-39 [E = Me, E' = H] HHHO X-4 [H] 40.3 Z-39 [E = H, E '= Me] HHHO X-3 [H] 40.4 Z-39 [E = H, E' = Me] HHHO X-4 [H] 40.5 Z -39 [E = E '= H] HHHO X-3 [H] 40.6 Z-39 [E = E' = H] HHHO X-4 [H] 41.1 Z-40 [E = E '= H] HHHO X -3 [H] 41.2 Z-40 [E = E '= H] HHHO X-4 [H] 42.1 Z-41 HHHO X-3 [H] 42.2 Z-41 HHHO X-4 [H] 43.1 Z-42 HHHO X-3 [H] 43.2 Z-42 HHHO X-4 [H] 44.1 Z-43 [E = H, E '= SMe] HHHO X-4 [H] 44.2 Z-43 [E = H, E' = Cl] HHHO X-4 [H] 44.3 Z-43 [E = E '= Me] HHHO X-3 [H] 44.4 Z-43 [E = E' = Me] HHHO X-4 [H] 45.1 Z -44 [E = E '= Me] HHHO X-3 [H] 45.2 Z-44 [E = E' = Me] HHHO X-4 [H] 46.1 Z-45 [E = E '= OMe] HHHO X -3 [H] 46.2 Z-45 [E = E '= OMe] HHHO X-4 [H] 47.1 Z-46 [E = Me] HHHO X-3 [H] 47.2 Z-46 [E = Me] HHHO X-4 [H] 48.1 Z-47 [D = H, E = Me] HHHO X-3 [H] 48.2 Z-47 [D = H, E = Me] HHHO X-4 [H] 49.1 MeSC (= CHNO ₂ ) NH 3-Me HHO X-4 [H] 49.2 MeNHC (= CHNO ₂ ) NH 3-Me HHO X-4 [H] 49.3 Me2NC (= CHNO ₂ ) NH 3-Me HHO X-4 [H] 49.4 MeSC (= NCN) NH 3-Me HHO X-4 [H] 49.5 MeOC (= NCN) NH 3-Me HHO X-4 [H] 49.6 MeNHC (= NCN) NH 3-Me HHO X-4 [H ] 49.7 Me2NC (= NCN) NH 3-Me HHO X-4 [H] 49.8 MeC (= NCN) NH 3-Me HHO X-4 [H] 50.1 MeSC (SMe) = N 3-Me HHO X-4 [H] 50.2 MeSC (OMe) = N 3-Me HHO X-4 [H] 50.3 MeOC (SCH ₂ Ph) = N 3-Me HHO X-4 [H] 50.4 MeSC (SEt) = N 3-Me HHO X-4 [H] 50.5 MeSC (NMe ₂ ) = N 3-Me HHO X-4 [H] 50.6 Me ₂ NC (SCH ₂ C≡CH) = N 3-Me HHO X-4 [H] 50.7 MeOC (SCH ₂ COOEt) = N 3-Me HHO X-4 [H] 50.8 EtOC (Me) = N 3-Me HHO X-4 [H] 50.9 EtOC (Me) = NHHHO X-4 [H] 50.10 MeSC (CN) = N 3-Me HHO X-4 [H] 50.11 MeS (Me) = NHHHO X -4 [H] ───────────────────────────────────

[0061]

[Table 2]

[0062]

Embedded image 化合物 Compound Z ¹ (R ¹ ) _n R ² R ³ AX [( R ⁴ ) _p or (R ⁵ ) _q ] number ─────────────────────────────────── 31.1 Me ₂ N-CH = CHCO HHHO X-2 [5-Cl] 31.2 Me ₂ N-CH = CHCO HHHO X-2 [4,5-Cl ₂ ] 31.3 Me ₂ N-CH = CHCO HHHO X-2 [4-Me ] 31.4 Me ₂ N-CH = CHCO HHHO X-2 [4-Ph] 31.5 Me ₂ N-CH = CHCO HHHO X-2 [4-CF ₃ ] 31.6 Me ₂ N-CH = CHCO HHHO X-2 [H ] 31.7 Me ₂ N-CH = CHCO HHHO X-1 [H] 31.8 Me ₂ N-CH = CHCO HHHO X-4 [H] 31.9 Me ₂ N-CH = CHCO H Me HO X-4 [H] 31.10 Me ₂ N-CH = CHCO H Me Me O X-4 [H] 31.11 Me ₂ N-CH = CHCO HHHO X-3 [H] 31.12 Me ₂ N-CH = CHCO HHHO X-4 [5-F] 31.13 Me ₂ N-CH = CHCO HHHO X-4 [6-F] 31.14 Me ₂ N-CH = CHCO HHHO X-4 [5-OMe] 31.15 Me ₂ N-CH = CHCO HHHO X-4 [5-Cl] 31.16 Me ₂ N-CH = CHCO HHHS X-4 [H] 31.17 Me ₂ N-CH = CHCO 3-Me HHO X-4 [H] 31.18 Me ₂ N-CH = CHCO 3-Me HHO X-3 [H] 31.19 Me ₂ N-CH = CHCO 3-Me HHO X-4 [5-F] 31.20 Me ₂ N-CH = CHCO 3-Me HHS X-4 [H] 31.21 Me ₂ N-CH = CHCO 2-Cl HHO X-4 [H] 31.22 Me ₂ N-CH = CHCO 3-Cl HHO X-4 [H] 31.23 Me ₂ N-CH = CHCO 3-FHHO X-4 [H] 31.24 Me ₂ N-CH = CHCO 3-OMe HHO X-4 [H] 31.25 Me ₂ N-CH = CHCO 3-SMe HHO X-4 [H] 31.26 Me ₂ N-CH = CHCO 3-NO ₂ HHO X -4 [H] 31.27 EtO ₂ CHHHO X-2 [H] 31.28 EtO ₂ CHHHO X-1 [H] 31.29 EtO ₂ CHHHO X-4 [H] 31.30 EtO ₂ CHHHO X-3 [H] 31.31 EtO ₂ C 3 -Me HHO X-4 [H] 31.32 EtO ₂ C 3-Me HHO X-3 [H] 31.33 HO ₂ CHHHO X-4 [H] 31.34 HO ₂ C 3-Me HHO X-4 [H] 31.35 MeCO HHHO X-2 [H] 31.36 MeCO HHHO X-4 [H] 31.37 MeCO HHHO X-3 [H] 31.38 MeCO 3-Me HHO X-2 [H] 31.39 MeCO 3-Me HHO X-4 [H] 31.40 MeCO 3-Me HHO X-3 [H] 31.41 H ₂ NCO HHHO X-4 [H] 31.42 H ₂ NCO 3-Me HHO X-4 [H] 31.43 MeO-NHCO HHHO X-4 [H] 31.44 EtO-NHCO HHHO X-4 [H] 31.45 MeNHCO HHHO X-4 [H] 31.46 Me ₂ NCO HHHO X-4 [H] 31.47 OHC HHHO X-2 [H] 31.48 OHC HHHO X-4 [H] 31.49 OHC HHHO X- 3 [H] 31.50 N≡CHHHO X-2 [H] 31.51 N≡CHHHO X-4 [H] 31.52 N≡C 3-Me HHO X-3 [H] 31.53 H ₂ NCS HHHO X-2 [H] 31.54 H ₂ NCS HHHO X-4 [H] 31.55 H ₂ NCS HHHO X-3 [H] 31.56 H ₂ N-NHCO HHHO X-4 [H] 31.57 PhNHCO HH HO X-4 [H] 31.58 FHHHO X-4 [H] 31.59 FHHHO X-3 [H] 31.60 Cl HHHO X-4 [H] 31.61 Cl HHHO X-3 [H] 31.62 Br HHHO X-2 [H] 31.63 Br HHHO X-1 [H] 31.64 Br HHHO X-4 [H] 31.65 Br HHHO X-3 [H] 31.66 Br 3-Me HHO X-4 [H] 31.67 Br 3-Me HHO X-3 [H ] ─────────────────────────────────── Among the above exemplified compounds, preferred are: 5,
1.7, 1.12, 1.13, 1.17, 1.29,
1.31, 1.32, 1.33, 2.1, 2.2, 2..
3, 2.25, 2.26, 2.30, 2.31, 2.3
4, 3.1, 3.5, 3.7, 3.9, 4.3, 4.
4, 4.5, 5.2, 5.9, 5.13, 6.3, 6.
4, 6.5, 6.6, 6.7, 6.8, 6.9, 6.1
0, 6.12, 6.13, 7.2, 7.3, 7.5,
7.7, 7.8, 8.2, 8.4, 8.6, 8.8,
9.2, 9.3, 9.5, 9.6, 10.2, 11.
2, 12.1, 12.2, 13.1, 14.1, 14.
2, 14.6, 14.8, 14.9, 14.10, 1
4.11, 14.12, 14.13, 14.14, 1
4.15, 14.16, 14.17, 14.18, 1
4.19, 14.20, 14.21, 14.22, 1
4.23, 14.24, 14.25, 14.26, 1
4.27, 14.28, 14.29, 14.30, 1
4.31, 14.33, 14.35, 14.36, 1
5.3, 15.7, 16.2, 17.2, 18.3, 1
9.3, 20.2, 20.3, 21.2, 21.3, 2
2.3, 23.3, 23.4, 23.11, 23.1
2, 24.3, 24.4, 24.11, 24.12, 2
4.13, 24.14, 24.15, 24.16, 2
5.9, 26.7, 27.2, 27.3, 27.8, 2
7.9, 28.1, 28.2, 28.3, 28.4, 2
8.5, 28.6, 28.7, 28.9, 28.10,
28.11, 28.12, 28.14, 28.18, 2
8.19, 28.20, 28.21, 28.22, 2
8.23, 28.24, 28.25, 28.26, 2
8.27, 28.28, 29.1, 29.2, 29.
4, 29.7, 29.9, 30.3, 30.4, 51.
1, 32.1, 33.1, 33.2, 33.3, 33.
4, 33.5, 33.6, 34.1, 35.1, 35.
2, 36.2, 37.2, 38.1, 38.2, 38.
4, 38.6, 38.8, 38.10, 38.11, 3
8.12, 38.13, 38.14, 38.15, 3
9.1, 39.2, 40.1, 40.2, 40.3, 4
0.4, 40.5, 40.6, 41.1, 14.2, 4
2.2, 43.2, 44.1, 44.2, 44.3, 4
4.4, 45.1, 45.2, 46.2, 47.2, 4
8.2, 49.1, 49.2, 49.3, 49.4, 4
9.5, 49.6, 49.7, 49.8, 50.1, 5
0.2, 50.3, 50.4, 50.5, 50.6, 5
0.7, 50.8, 50.9, 50.10 and 50.1
No. 1 is more preferable.
7, 1.12, 1.13, 2.1, 2.2, 2.3,
2.25, 2.26, 2.30, 2.31, 3.5,
3.7, 4.4, 4.5, 5.2, 5.9, 6.3,
6.4, 6.5, 6.6, 6.7, 6.8, 6.9,
6.10, 6.12, 6.13, 7.2, 7.3, 7.
5, 9.2, 9.3, 11.2, 12.1, 14.1,
14.2, 14.11, 14.12, 14.13, 1
4.14, 14.16, 14.17, 14.18, 1
4.20, 14.23, 14.24, 14.26, 1
4.28, 14.29, 14.30, 14.31, 1
4.33, 16.2, 17.2, 21.2, 21.3,
22.3, 23.3, 23.4, 23.11, 24.
3, 24.11, 24.13, 24.15, 28.2,
28.5, 28.6, 28.8, 28.10, 28.1
1, 28.14, 28.18, 28.20, 28.2
1, 28.22, 28.23, 28.26, 28.2
8, 30.3, 30.4, 32.1, 33.1, 33.
2, 33.3, 33.4, 33.5, 33.6, 34.
1, 37.2, 38.1, 38.2, 38.4, 38.
15, 39.2, 40.1, 40.2, 40.6, 4
1.2, 42.2, 43.2, 44.2, 44.3, 4
9.1, 49.2, 49.3, 49.4, 49.5, 4
9.6, 49.7, 49.8, 50.1, 50.2, 5
0.3, 50.4, 50.6, 50.7, 50.8, 5
0.9 and 50.11, the most preferred being 1.7, 2.1, 2.2, 2.3, 3,.
5, 5.2, 5.9, 6.3, 6.4, 6.12, 6.
13, 9.2, 11.2, 14.2, 14.12, 1
4.13, 14.14, 14.16, 14.17, 1
4.28, 14.29, 14.30, 14.31, 1
4.33, 16.2, 21.2, 21.3, 22.3,
22.4, 24.3, 24.15, 28.14, 28.
22, 30.3, 30.4, 33.1, 33.2, 3
3.3, 33.4, 33.6, 34.1, 37.2, 3
8.1, 38.2, 38.15, 40.2, 42.2,
44.2, 49.5, 49.8, 50.2, 50.3,
50.6, 50.7, 50.8, 50.9 and 50.1
1 can be mentioned.

The azole derivative of the present invention can be produced by the method described below. (Step A)

[0064]

Embedded image In the above process, R ¹ , R ² , R ³ , X, A, Q, Z ¹ , Z ² and n have the same meanings as described above, and R ²⁰ is a compound represented by the formula L ¹ (wherein
L ¹ represents a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom. Or a group represented by the formula O
L ² (wherein, L ² represents an alkylsulfonyl group such as methanesulfonyl; a substituted phenylsulfonyl group such as p-toluenesulfonyl; or a phosphate group such as dimethyl phosphate or diethyl phosphate). Group.

[0065] Step A is as factories to produce the compound (I) of the present invention a phenolic compound or a thiophenol compound (III) or (V) and the azole compound (IV) as the starting material. Step A-1 Step A-1 comprises a phenol compound or thiophenol compound (III) produced by the following step B and an azole compound (I) produced by the following steps C and D.
V) to obtain the compound (I) of the present invention.

This step is performed in the presence of a solvent, if necessary, in the presence of a base.

The base used is, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate, potassium carbonate or cesium carbonate; sodium methoxide or sodium ethoxy. Metal alkoxides such as potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; 1,4-diazabicyclo [ 2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-
Aliphatic cyclic tertiary amines such as ene (DBU); pyridines such as pyridine, collidine, 4- (N, N-dimethylamino) pyridine; butyllithium, s-butyllithium, lithium diisopropylamide, sodium bis Organometallic bases such as trimethylsilylamide and lithium bistrimethylsilylamide can be mentioned.
Preferably, an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; an alkali metal carbonate such as sodium carbonate, potassium carbonate and cesium carbonate; an alkali metal hydride such as sodium hydride and potassium hydride It is. More preferably, they are sodium hydroxide, potassium hydroxide, and sodium hydride.

The solvent used is not particularly limited as long as it does not hinder the reaction and dissolves the starting materials to some extent. Examples thereof include water; alcohols such as methanol, ethanol and t-butanol; Ketones such as methyl isobutyl ketone; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane Aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; and mixed solvents thereof. Preferably, water; ketones such as acetone and methyl isobutyl ketone; dimethylformamide;
Amides such as dimethylacetamide; sulfoxides such as dimethylsulfoxide; and mixed solvents thereof. More preferably, it is dimethylformamide.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 15 minutes to 6 hours
Time. Step A-2 Step A-2 is a step of converting Z ² of compound (II) of the present invention produced by the following step A-3 to Z ¹ to obtain compound (I) of the present invention. .

This step is performed, for example, in a COMPREHENSIVE HETERO
CYCLIC CHEMISTRY (Ed. By Alan R. KatritzkyY and Cha
rles W. Rees) PERGAMON (1984) and COMPREHENSIVE HET
EROCYCLIC CHEMISTRY II (Ed. By Alan R. KatritzkyY,
Eric FV Scriven, andCharles W. Rees) PERGAMON
(1996). Step A-3 Step A-3 is a step of condensing a phenol compound or a thiophenol compound (V) with an azole compound (IV) produced by the following steps C and D to give a compound (II) of the present invention. This is the step of obtaining.

This step is performed according to step A-1. (Step B)

[0073]

Embedded imageDuring the above process, R¹, Z¹, A and n are as defined above.
Then R^{twenty one}Represents a C1-C6 group such as a methyl group or an ethyl group.
Alkyl group; ethoxycarbonyl group, phenyloxycar
A C2-C7 alkoxycarbonyl group such as a bonyl group;
C2-C7 alkylthio such as ethylthiocarbonyl
C2- such as carbonyl group, ethyldithiocarbonyl
A C7 alkyldithiocarbonyl group; or a benzyl group
And Z ^ThreeIs Z^Two(Z^TwoHas the same significance as described above. )or
Represents an amino group.

Step B is a step of preparing compound (III) which is a starting material of the above step A. Step B-1 Step B-1 is a step of producing compound (VI) by converting Z ³ of compound (VII) to Z ¹ .

This step is performed according to step A-2. Step B-2 Step B-2 is a step of preparing the compound (V
This is a step of converting the substituent R ²¹ of I) into a hydrogen atom to obtain a phenol compound or a thiophenol compound (III).

In this step, a plurality of reaction means can be used. An example is shown below. (1) This step is carried out by performing hydrolysis and deprotection in the presence of a solvent in the presence of a base.

The base to be used is not particularly limited as long as it is used for ordinary hydrolysis.
Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate are preferred. Is preferably sodium hydroxide or potassium hydroxide.

The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but is preferably water; methanol, ethanol, t-
Alcohols such as butanol; diethyl ether;
Ethers such as tetrahydrofuran and dioxane;
Examples thereof include aromatic hydrocarbons such as toluene, and a mixed solvent thereof. Preferably, water, methanol, dioxane and a mixed solvent thereof are used.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -50 to 100 ° C.

The reaction time mainly depends on the reaction temperature, starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 30 minutes to 1 hour
2 hours. (2) In this step, deprotection can be performed using a Lewis acid in the presence or absence of a solvent.

The Lewis acid to be used is not particularly limited as long as it is used for deprotection without using a usual nucleophile. Compounds; or silicon compounds such as tristrimethylsilane iodide. Preferably, it is boron tribromide.

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent. Examples thereof include halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Examples thereof include aromatic hydrocarbons such as toluene and a mixed solvent thereof. Preferably, it is methylene dichloroethane chloride.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 15 minutes to 6 hours
Time. (3) In this step, deprotection can be performed using a nucleophile in the presence or absence of a solvent and in the presence of a Lewis acid.

The Lewis acid used is not particularly limited as long as it is used for deprotection using a usual nucleophile. For example, an aluminum halide such as aluminum trichloride or aluminum tribromide may be used. Compounds. Preferably, it is aluminum trichloride.

The nucleophile to be used is not particularly limited as long as it is used for ordinary deprotection. Examples thereof include alkylthiols such as ethanethiol and propanethiol. Preferably, it is ethanethiol.

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent. Examples thereof include halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ,
Examples thereof include aromatic hydrocarbons such as toluene and a mixed solvent thereof. Preferably, they are methylene chloride and dichloroethane.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 15 minutes to 6 hours
Time. Or (4) In this step, deprotection can be performed according to a method of hydrogenation in the presence of a catalyst.

This step is performed in the presence or absence of a solvent.

The catalyst to be used is not particularly limited as long as it is one used in a usual hydrogenation reaction, and examples thereof include palladium-carbon (Pd-C) and platinum-carbon. , Palladium-carbon (Pd-C)
It is.

The solvent used is not particularly limited as long as it does not inhibit the reaction, but is preferably water; alcohols such as methanol, ethanol and t-butyl alcohol; and esters such as ethyl acetate. Ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide;
Sulfoxides such as dimethyl sulfoxide can be mentioned. Preferably, it is water, methanol, ethanol, ethyl acetate or tetrahydrofuran.

The reaction temperature is usually -90 ° C to 200 ° C, preferably -50 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 48 hours, preferably 30 minutes to 2 hours
4 hours. (Step C)

[0095]

Embedded image In the above process, X is as defined above, and R ¹⁹ is a group represented by the formula L
¹ [wherein L ¹ represents a chlorine atom, a bromine atom or an iodine atom. And L ³ represents a chlorine atom or a bromine atom.

Step C is a step for producing a compound (IVa) in which R ² and R ³ are hydrogen atoms among the compound (IV) which is the starting material of the above step A. Step C-1 Step C-1 is a step of converting a compound (VIII) having L ³ at the 2-position of the azole ring into a compound (IX) having a methylsulfide group at the 2-position of the azole ring.

This step is carried out in the presence or absence of a solvent, using methanethiol and a base, or using an alkali metal salt of methanethiol.

Examples of the base used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; sodium methoxide, sodium ethoxide, Metal alkoxides such as potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; 1,4-diazabicyclo [2.2. 2] Octane (DABC
O), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU)
Aliphatic tertiary amines such as pyridine; pyridine, collidine, pyridines such as 4- (N, N-dimethylamino) pyridine; butyllithium, s-butyllithium, lithium diisopropylamide, sodium bistrimethylsilylamide, lithium Organometallic bases such as bistrimethylsilylamide can be mentioned. Preferably,
It is an alkali metal hydroxide or alkali metal hydride, more preferably sodium hydroxide, potassium hydroxide or sodium hydride.

Examples of the alkali metal salt of methanethiol include, for example, sodium salt of methanethiol,
Examples thereof include a potassium salt and an aqueous solution thereof, preferably an aqueous solution of a sodium salt of methanethiol.

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent. Preferably, the solvent is water; methanol, ethanol, t-
Alcohols such as butanol; ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; diethyl ether Ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; and mixed solvents thereof. Preferably, they are alcohols or amides, and more preferably, methanol, ethanol, or dimethylformamide.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 15 minutes to 1 hour
2 hours.

Among the starting materials in this step, compound (VII)
I) can be produced, for example, according to the methods described in JP-A-1-121280 and JP-A-2-45477.

The target compound (IVa) in this step was obtained by
trahedron, 44 (7), 2021 (1988), J. Am. Chem. Soc., 53 ,
1470 (1931) and J. Med. Chem., 35 , 3792 (1992). Step C-2 Step C-2 comprises oxidizing the compound (IX) having a methyl sulfide group at the 2-position of the azole ring produced in the step C-1 to thereby form a methanesulfonyl group at the 2-position of the azole ring. This is a step of producing a compound (X).

This step is a step of oxidizing a sulfide group to a sulfinyl group or a sulfonyl group according to a conventional method.

This step can be performed using, for example, an organic or inorganic peroxide such as meta-chloroperbenzoic acid and aqueous hydrogen peroxide.

This step is performed in the presence or absence of a solvent.

The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; Hydrogens; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; and mixed solvents thereof. Preferably, it is water, methylene chloride, chloroform, dichloroethane. More preferably, it is water or dichloroethane.

The reaction temperature is usually -90 ° C to 200 ° C, preferably -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 15 minutes to 6 hours
Time. Step C-3 Step C-3 is a step of reacting compound (X) having a methanesulfonyl group at the 2-position of the azole ring, produced in step C-2, with a Grignard reagent having a methyl group to give compound (XI) ).

The Grignard reagent used has the formula MeM
gL ⁴ [wherein L ⁴ represents a chlorine atom, a bromine atom or an iodine atom. ] It is a commercially available compound represented by these.

This step can be performed according to a usual Grignard reaction method.

The target compound (XI) in this step was COMP
REHENSIVE HETEROCYCLIC CHE MISTRY Vol.6 (Ed. By Al
an R. KatritzkyY and Charles W. Rees) PERGAMON (19
84) p.293-321, THIAZOLE AND ITS DERIVATIVES Part
One (Ed. By Jacques V. Metzger) JOHN WILEY & SONS
(1979), J.Org.Chem., 39 , 3277 (1974), J.Org.Chem., 4
3 , 2296 (1978) and J. Chem. Soc. Perkin Trans 2, 1582
It can also be produced according to the method described in (1972). Step C-4 Step C-4 is a step of producing a compound (IVa) having a halomethyl group at the 2-position of the azole ring by halogenating the compound (XI) having a methyl group at the 2-position of the azole ring. is there.

In this step, the compound (XI) is converted into a compound (XI) in the presence or absence of a solvent, and optionally in the presence of a radical initiator.
It is carried out by reacting with a halogenating agent.

Examples of the halogenating agent used include halogen gas such as chlorine molecule and bromine molecule; N-chlorosuccinimide, N-bromosuccinimide,
N-halogenosuccinimides such as iodosuccinimide can be mentioned. Preferably, they are N-chlorosuccinimide and N-bromosuccinimide.

Examples of the radical initiator used include dibenzoyl peroxide (BPO) and azobisisobutyronitrile (AIBN).

The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. Examples thereof include water; halogens such as carbon tetrachloride, methylene chloride, chloroform and dichloroethane. Hydrocarbon; acetic acid; dimethylformamide. Preferably, they are halogenated hydrocarbons, and more preferably, carbon tetrachloride.

The reaction temperature is usually -90 ° C to 200 ° C, preferably -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, starting compound,
Depending on the type of reaction reagent and solvent used,
It is usually from 10 minutes to 150 hours, preferably from 30 minutes to 80 hours.

The target compound (IVa) in this step was obtained by
trahedron 44 (7), 2021 (1988), J. Am. Chem. Soc. 53 ,
1470 (1931), Liebigs Ann. Chem. 623 (1981), J. Me
d.Chem., 35 , 3792 (1992), Synthetic Communications,
19 , 2921 (1989), J. Med.Chem., 35 , 457 (1992) and Sy
nthesis, 102 (1979). (Step D)

[0121]

Embedded image In the above steps, X, R ² and R ³ are as defined above,
R ²⁰ represents a group represented by the formula OL ² (wherein L ² has the same meaning as described above), R ²² represents a C1 to C6 alkyl group, and R ¹⁴ represents a benzoyl group. And R ^2a and R
^3a is the same or different and represents a C1 to C6 alkyl group.

Step D is a step of producing compound (IV) which is a starting material of the above step A. Step D-1 In step D-1, the compound (XII) having a cyano group at the 2-position of the azole ring is hydrolyzed in the presence of an alcohol to obtain a compound (XIII) having an alkoxycarbonyl group at the 2-position of the azole ring. ).

In this step, R ²² OH [where R ²² is as defined above. By subjecting compound (XII) to hydrolysis in the presence of an alcohol and an acid represented by the formula:

The alcohol used is, for example, a linear or branched alcohol having 1 to 6 carbon atoms such as methanol, ethanol, butanol, pentanol and hexanol, and is preferably methanol or ethanol. is there.

Examples of the acid used include inorganic acids such as hydrochloric acid and sulfuric acid; and organic acids such as p-toluenesulfonic acid. Preferably, it is hydrochloric acid.

The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. Examples thereof include alcohols such as methanol, ethanol and t-butanol; Halogenated hydrocarbons such as chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene;
And a mixed solvent thereof. Preferably, they are alcohols or ethers, and more preferably, methanol, ethanol, tetrahydrofuran or dioxane.

The reaction temperature is generally -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 1 minute to 12 hours, preferably 2 minutes to 6 hours.

The azole compound (XII) having a cyano group at the 2-position, which is a starting material in this step, is prepared by the method described in Helv. Chim.
a., 40 , 554 (1957) and J. Heterocyclic Chem., 29 , 639
It can be produced according to the method described in (1992).

The target compound (XIII) in this step is
Synthetic Communication, 14 , 947 (1984), Tetrahedron
Letters, 645 (1973), Helv. Chim. Acta, 28 , 924 (1
945), JP-A-6-298748 and Heterocycle.
s, 9 , 1271 (1978). Step D-2 Step D-2 is a step of preparing a compound (X
This is a step of producing a compound (XIVa) in which the 2-position of the azole ring is a hydroxymethyl group by reducing the alkoxycarbonyl group at the 2-position of the azole ring in III).

In this step, the ester can be reduced to a primary alcohol using a reducing agent according to a conventional method.

The reducing agent to be used is not particularly limited as long as it is used for ordinary reduction of ester groups. For example, alkali metal borohydride compounds such as sodium borohydride and lithium borohydride are used. Can be given. Preferably, it is sodium borohydride or lithium borohydride.

The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, and examples thereof include alcohols such as methanol and ethanol. Preferably, it is methanol or ethanol.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -20 ° C to 80 ° C.

The reaction time mainly depends on the reaction temperature, starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 10 minutes to 1 hour
2 hours.

The target compound (XIVa) in this step is
It can also be produced according to the method described in Helvetica Chimica Acta, 55 , 1782 (1972). Step D-3 In step D-3, the compound (XV) having a benzoyloxymethyl group at the 2-position of the azole ring is hydrolyzed to give a compound (XIV) having a hydroxymethyl group at the 2-position of the azole ring.
This is the step of manufacturing a).

This step can be performed in the presence or absence of a solvent and in the presence of a base.

Examples of the base used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium methoxide, sodium ethoxide and potassium Metal alkoxides such as t-butoxide and the like can be mentioned. Preferably, they are sodium hydroxide and potassium hydroxide.

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but is preferably water; methanol, ethanol, t Alcohols such as -butanol; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; and mixed solvents thereof. Preferably, water, methanol, dioxane and a mixed solvent thereof are used.

The reaction temperature is usually -90 ° C to 200 ° C, preferably -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 48 hours, preferably 10 minutes to 2 hours
4 hours.

Compound (XV) which is a starting material in this step
Can be produced according to the method described in CA 49 8923f (1955). Step D-4 Step D-4 is a step of oxidizing the compound (XIVa) having a hydroxymethyl group produced by steps D-2 and D-3 to obtain a compound (XVI) having a formyl group.

This step can be performed according to a conventional method for oxidizing a hydroxymethyl group to a formyl group, such as Swern oxidation, Jones oxidation, or oxidation using manganese dioxide. Step D-5 Step D-5 comprises converting a compound having a formyl group (XVI) produced by Step D-4 into a compound of the formula R ^2a MgL ⁵ [wherein:
R ^2a has the same meaning as described above, and L ⁵ represents a chlorine atom, a bromine atom or an iodine atom. The compound (XIVb) is produced by reacting with a Grignard reagent represented by the formula

This step can be carried out according to step C-3. Step D-6 Step D-6 is a step of producing compound (XIVc) by reacting compound (XIII) having an alkoxycarbonyl group at the 2-position of the azole ring with a Grignard reagent.

This step can be carried out according to step D-5.

The Grignard reagent used is R
^2aAnd R^3aAre the same, the formula R^3aMgL^Five[Wherein, R^3a
And L^FiveHas the same significance as described above. ] The compound represented by
Is used in an amount of 2 equivalents or more based on the starting material. Also, R^2aAnd R
^3aAre different, the formula R^2aMgL^Five[Wherein, R^2aAnd L^Five
Has the same significance as described above. And a compound represented by the formula R
^3aMgL^Five[Wherein, R^3aAnd L^FiveHas the same meaning as above.
You. With respect to the starting material
Use 1 equivalent or more.Step D-7 Step D-7 includes Step D-2, Step D-3, Step D-5, and the like.
(XIVa) produced by steps D-6 and D-6,
Using (XIVb) and (XIVc) as raw materials,
General formula L2 L^Five[Wherein L is a compound represented by the formula:^TwoIs the same as above
Show meaning, L^FiveIs a leaving group (where the leaving group is a chlorine atom
Represents a bromine atom or a bromine atom. ). ]
From the sulfonate or phosphonate hydroxyl group
The leaving group R²⁰[Wherein, R²⁰Is
Show the same significance. (IV) having a group represented by the formula:
This is the step of manufacturing.

This step is performed in the presence of a solvent, if necessary, in the presence of a base.

The base to be used includes, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; sodium methoxide and sodium ethoxy. Metal alkoxides such as potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; 1,4-diazabicyclo [ 2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-
Aliphatic cyclic tertiary amines such as ene (DBU); pyridines such as pyridine, collidine, 4- (N, N-dimethylamino) pyridine; butyllithium, s-butyllithium, lithium diisopropylamide, sodium bis Organometallic bases such as trimethylsilylamide and lithium bistrimethylsilylamide can be mentioned.
Preferably, alkali metal hydroxide, alkali metal hydride or aliphatic tertiary amines, more preferably sodium hydroxide, potassium hydroxide, sodium hydride, triethylamine, more preferably, Triethylamine.

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. Examples thereof include water; ketones such as acetone and methyl isobutyl ketone; and acetonitrile. Nitriles; esters such as ethyl acetate; methylene chloride;
Halogenated hydrocarbons such as chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; and mixed solvents thereof. Preferably, it is a halogenated hydrocarbon, and more preferably, methylene chloride.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 15 minutes to 6 hours
Time. (Step E)

[0152]

Embedded imageDuring the above process, R¹, R^Two, R^Three, X, A, Z¹And n are before
Has the same meaning as ¹'Is the Z¹Alkylated, halo
Genation, alkoxylation, oxidation, carbamoylation, sulf
Shows an amoylated group.

Step E is a step in which the compound (I) of the present invention produced in Step A-1 or Step A-2 is further subjected to alkylation, halogenation, alkoxylation, oxidation, carbamoylation or sulfamoylation. . 1) Alkylation, carbamoylation, and sulfamoylation This step is a step for performing alkylation, carbamoylation, and sulfamoylation.

This step can be performed according to step A-1. 2) Halogenation This step is a step of performing halogenation.

This step can be carried out according to step C-4. 3) Alkoxylation This step is a step of performing alkoxylation.

[0156] This step is a Z ^1, and the leaving group (wherein the leaving group, for example, a halogen atom such as chlorine atom, alkyl such as methane sulfinyl group, alkyl sulfonyl group such as methanesulfonyl group Or an alkylthio group such as a methylthio group.
A chlorine atom, a methanesulfonyl group, a methanesulfinyl group or a methylthio group, more preferably a methanesulfonyl group. ) Is a step of substituting the compound having the formula (1) with an alkoxy group.

This step is performed in the presence of a solvent, if necessary, in the presence of a base.

As the base used, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; sodium methoxide, sodium ethoxy Metal alkoxides such as potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; 1,4-diazabicyclo [ 2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-
Aliphatic cyclic tertiary amines such as ene (DBU); pyridines such as pyridine, collidine, 4- (N, N-dimethylamino) pyridine; butyllithium, s-butyllithium, lithium diisopropylamide, sodium bis Organometallic bases such as trimethylsilylamide and lithium bistrimethylsilylamide can be mentioned.
Preferred are sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride and potassium hydride. More preferably, it is sodium hydride.

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent. Examples thereof include water; alcohols such as methanol, ethanol and t-butanol; acetone. Ketones such as methyl isobutyl ketone; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane Aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; and mixed solvents thereof. Preferably, water; ketones such as acetone and methyl isobutyl ketone; dimethylformamide;
Amides such as dimethylacetamide; sulfoxides such as dimethylsulfoxide; and mixed solvents thereof. More preferably, it is dimethylformamide.

The reaction temperature is generally -90 ° C to 200 ° C, preferably -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 15 minutes to 6 hours
Time. 4) Oxidation This step is an oxidation step.

This step is a step of oxidizing a sulfide group to a sulfinyl group or a sulfonyl group according to a conventional method.

This step can be carried out according to step C-2. (Step F)

[0164]

Embedded image In the above process, R ¹ , A and n have the same meanings as described above,
Y is a group represented by the formula R ²¹ wherein R ²¹ is as defined above. ]
Group or formula represented by

[0165]

Embedded image [Wherein, R ² , R ³ and X have the same meaning as described above. And Z ^2a represents a halogen atom, a cyano group or a formula —COR.
¹³ wherein R ¹³ is a hydrogen atom, a C1-C6 alkyl group [the alkyl group is one to four identical or different halogen atoms or one amino group (the amino group is one or two The same or different, a C1-C6 alkyl group, C
It may be substituted by a 1-C6 alkoxy group or a phenyl group, or may form a quaternary ammonium salt. ). Or a C1-C6 alkoxy group. Wherein Z ^2b is a group represented by the formula (—COR ¹³ ) wherein R ¹³ is
C2 to C6 alkenyl group [The alkenyl group is 1 to 4 identical or different halogen atoms or 1 amino group (the amino group is 1 or 2 identical or different C1 to C6 alkyl groups, Which may be substituted with a C1 to C6 alkoxy group or a phenyl group, or may form a quaternary ammonium salt). ], Hydroxyl group, formula -NR ⁸
R ⁹ wherein R ⁸ and R ⁹ are as defined above. A group represented by the formula —NHNR ⁸ R ^{9 wherein} R ⁸ and R ⁹ are
The meaning is as defined above. ], A fluorine atom, a chlorine atom or a bromine atom. Or a thiocarbamoyl group.

In the step F, the compound (II) having Z ^2a produced in the step A-3 is further subjected to alkenylation, halogenation, amidation, thioamidation or hydrolysis to convert Z ^2b . This is a step of producing the compound (II) of the present invention. (1) Alkenylation In this step, when alkenylating Z ^2a , an α, β unsaturated carbonyl compound can be synthesized by, for example, a condensation reaction such as aldol condensation or a dehydration reaction thereof.

This step is carried out under basic conditions such as sodium methoxide, sodium hydroxide and potassium hydroxide, under acidic conditions such as formic acid and acetic acid or under hot conditions at high temperatures.

This step is performed in the presence or absence of a solvent.

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent. Examples thereof include water; alcohols such as methanol, ethanol and t-butanol; Halogenated hydrocarbons such as methylene, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene and toluene; and mixed solvents thereof. Preferably, water; alcohols such as methanol, ethanol and t-butanol can be mentioned.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 15 minutes to 6 hours
Time. (2) Halogenation In this step, Z ^2a can be halogenated to form an acid halide. The halogenation in this step is, for example, benzoic acid or benzoic acid such as thionyl chloride, oxalyl chloride, phosphoryl chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus tribromide, chlorine, N-chlorosuccinimide or N-bromosuccinimide. It can be carried out according to a conventional method of converting benzaldehyde into an acid halide. (3) Amidation In this step, Z ^2a can be amidated. (I) The amidation in this step is carried out by reacting the acid halide produced in the above (2) with an amino compound after purification or in an unpurified state to convert the acid halide into an amide compound in a conventional manner. be able to. (II) In the amidation in this step, an acid anhydride is produced according to a conventional method of converting benzoic acid into a mixed acid anhydride such as acetyl chloride, propionyl chloride, methyl chloroformate or ethyl chloroformate. By reacting this with an amino compound after purification or in an unpurified state,
It can be carried out according to a conventional method for converting an acid anhydride into an amide compound. (4) Hydrolysis In this step, Z ^2a is ^converted to, for example, hydrochloric acid, sulfuric acid, acetic acid,
In a conventional manner, a benzoic acid ester or benznitrile is hydrolyzed to benzoic acid using a mineral acid such as formic acid, sodium hydroxide, potassium hydroxide or boron trifluoride, an organic acid, a Lewis acid or an alkali. Therefore, it can be converted. (5) Thioamidation In this step, compound (II) of the present invention can be produced by subjecting Z ^2a to, for example, hydrogen sulfide or thioacetamide to exchange benznitrile with thioamide.

This step is performed according to C.I. A. 49 8923f
(1955). Or, J. Am. Chem. So
c. , 82 2656 (1960).

After completion of each of the above reaction steps, the target compound of each step can be collected from the reaction mixture according to a conventional method. For example, it can be obtained by appropriately neutralizing the reaction mixture, removing any insoluble matter by filtration, adding an organic solvent immiscible with water, washing with water, and distilling off the solvent. If necessary, the obtained target compound can be further purified by a conventional method, for example, recrystallization, reprecipitation or chromatography.

The compound of the present invention may be mixed with a carrier and, if necessary, other adjuvants to prepare a preparation usually used as a herbicide, for example, powder, coarse powder, granule, granule, wettable powder,
It is prepared and used in aqueous solvents, emulsions, solutions and the like. A carrier as used herein refers to a synthetic or natural inorganic or organic substance that is mixed into a herbicide to help the active ingredient compound reach plants or to facilitate storage, transportation or handling of the active ingredient. means.

Suitable solid carriers include, for example, clays represented by kaolinite group, montmorillonite group, attapulgite group, etc., talc, mica, phyllite, pumice, vermiculite, gypsum, dolomite, diatomaceous earth, magnesium Lime, phosphorous lime, zeolite, silicic anhydride, synthetic calcium silicate, kaolin, bentonite,
Inorganic substances such as calcium carbonate, soybean flour, tobacco flour, walnut flour, flour, wood flour, starch, vegetable organic substances such as crystalline cellulose, coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone Synthetic or natural polymer compounds such as resin, ester gum, copal gum, dammar gum, etc .; waxes such as carnauba wax, paraffin wax and beeswax; urea;

Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and methylnaphthalene; Carbon tetrachloride, chloroform,
Chlorinated hydrocarbons such as trichloroethylene, monochlorobenzene, chlorotoluene, ethers such as dioxane and tetrahydrofuran, acetone, methyl ethyl ketone,
Ketones such as diisobutyl ketone, cyclohexanone, acetophenone and isophorone, esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate and diethyl succinate, methanol, n-hexanol, ethylene glycol, diethylene glycol and cyclo Hexanol, alcohols such as benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether,
Examples thereof include ether alcohols such as diethylene glycol butyl ether, polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Surfactants used for the purpose of emulsification, dispersion, wetting, spreading, binding, control of disintegration, stabilization of active ingredients, improvement of fluidity, rust prevention, promotion of absorption into plants, etc. may be ionic. It may be non-ionic.

Suitable nonionic surfactants include, for example, sucrose esters of fatty acids, ethylene oxide polymerization adducts of higher aliphatic alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol, and alkylphenols such as isooctylphenol and nonylphenol. Polymerized adducts of ethylene oxide, ethylene oxide adducts of alkyl naphthols such as butyl naphthol and octyl naphthol, ethylene oxide polymer adducts of higher fatty acids such as palmitic acid, stearic acid, and oleic acid; Polymerized ethylene oxide adducts of phosphoric acid, ethylene oxide adducts of higher aliphatic amines such as dodecylamine and stearamide, higher fatty acid esters of polyhydric alcohols such as sorbitan, and their oxidized oxides Copolymers of emissions polymerization adducts and ethylene oxide and propylene oxide can be cited.

Suitable anionic surfactants include, for example, alkyl sulfates such as sodium lauryl sulfate and amine salt of oleyl alcohol sulfate, and fatty acid salts such as sodium dioctyl sulfosuccinate, sodium oleate and sodium stearate. ,
Examples thereof include alkylaryl sulfonates such as sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate, and sodium dodecylbenzenesulfonate.

Suitable cationic surfactants include, for example, higher aliphatic amines, quaternary ammonium salts, alkylpyridinium salts and the like.

The herbicide of the present invention may further contain, for example, gelatin, gum arabic, casein, albumin, glue, sodium alginate, polyvinyl alcohol, and the like, for the purpose of improving the properties of the preparation and enhancing the biological effect. Carboxymethylcellulose, methylcellulose,
It may contain a high molecular compound such as hydroxymethylcellulose, a thixotropic agent such as sodium polyphosphate and bentonite, and other auxiliary agents.

The above carriers and various auxiliaries are used singly or in combination depending on the purpose, depending on the purpose of application of the dosage form of the preparation.

Dusts usually contain 2 to 10 parts by weight of an active ingredient compound, and the remainder is a solid carrier.

The wettable powder usually contains 10 to 80 parts by weight of the active ingredient, and the balance is a solid carrier and a dispersing wetting agent. If necessary, a protective colloid agent, a thixotropic agent, an antifoaming agent and the like are added.

Granules generally contain the active ingredient compound in an amount of 0.1 to 1%.
It contains 0 parts by weight, and the balance is mostly solid carrier. The active ingredient compound is uniformly mixed with the solid carrier or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm.

The emulsion usually contains 1 to 50 parts by weight of the active ingredient, and contains about 5 to 20 parts by weight of the emulsion, the remainder being a liquid carrier, and if necessary, a rust inhibitor is added. .

When the compound of the present invention thus prepared in various dosage forms is subjected to soil treatment before or after germination of a weed in a paddy field, for example, 1 g to 1000 g, preferably 10 g to 10 g as an active ingredient per 10 a is obtained. 300
By treating g, weeds can be effectively controlled.

The method of treating the compound of the present invention is usually formulated as described above, and the compound is prepared about one before or after emergence of the weed.
Perform soil treatment, foliage treatment or flooding treatment within a month. Soil treatment includes soil surface treatment, soil admixture treatment, and the like, and foliage treatment includes, in addition to treatment from above the plant, extreme treatment that treats only weeds so that they do not adhere to crops.
The flooding treatment includes spraying of granules and flowables and irrigation treatment on the water surface.

It is preferable that other herbicides are added to the herbicide of the present invention in order to broaden the herbicidal spectrum. In some cases, a synergistic effect can be expected.

The herbicide of the present invention can of course be used in admixture with other plant growth regulators, fungicides, insecticides, acaricides, nematicides or fertilizers.

Examples of the herbicide of the present invention, Reference Examples, Formulation Examples and Test Examples will be specifically described below, but the present invention is not limited thereto.

[0192]

【Example】

[0193]

Example 1 2- [4- (1-methyl-5-methylthio-1H- [1,2,4]
Triazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 8.2) (1) 3- (4-methoxyphenyl) -1-methyl-5-methylthio
-1H- [1,2,4] triazole (Step B-1) 4-methoxybenzoic acid (2.0 g, 13.1 mmol) was added to thionyl chloride
(1.91 mL) and heated in benzene (30 mL) at 90 ° C. for 1 hour. The reaction solution was concentrated under reduced pressure, diluted with methylene chloride (3 mL), and added dropwise to a solution of 2-methyl-3-thiosemicarbazide (2.07 g) in pyridine (20 mL) cooled to 0 ° C.
Stirred for days. Water was poured into the reaction mixture, and a solid precipitated. The precipitated solid was filtered, dried under reduced pressure, dissolved in a 10% aqueous sodium hydroxide solution (20 mL), and heated at 100 ° C. for 5 hours. The reaction was cooled to room temperature and acidified using concentrated hydrochloric acid, and a solid precipitated. The precipitated solid was filtered and dried under reduced pressure, and the obtained solid (2.23 g) was dissolved in a mixed solvent of 5% aqueous sodium hydroxide (10 mL) and ethanol (10 mL). Methyl chloride (2 mL) was added, and the mixture was stirred at room temperature for 1 day. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, and the extract was dried over anhydrous sodium sulfate.
After filtration of the drying agent, the solvent was distilled off, and the residue was purified by silica gel chromatography to give the title compound 3- (4-methoxyphenyl) -1-methyl-5-methylthio-1H- [1,2,4 ] 2.21 g of triazole were obtained. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.06-8.
00 (3H, m), 7.98-7.89 (1H, m), 7.55-7.36 (2H, m),
7.08 (2H, d, J = 8.8 Hz), 5.53 (2H, s), 3.79

(3H, s), 2.74 (3H, s). (2) 3- (4-hydroxyphenyl) -1-methyl-5-methylthio-1H- [1,2,4] triazole (B-2 Step) 3- (4-methoxyphenyl) -1 obtained by the method of (1) above
-Methyl-5-methylthio-1H- [1,2,4] triazole (1.78
g, 7.57 mmol) in methylene chloride (35 mL) at 0 ° C. was added with boron trisulfide (1M in methylene chloride, 11.35 mL), and the mixture was stirred at 0 ° C. for 10 minutes and at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into water and extracted with methylene chloride. The extract was washed with water and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off to obtain 0.35 g of the title compound, 3- (4-hydroxyphenyl) -1-methyl-5-methylthio-1H- [1,2,4] triazole. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.98 (2
H, d, J = 9.0 Hz), 6.93 (2H, d, J = 9.0 Hz), 3.83
(3H, s), 3.78 (3H, s), 2.72 (3H, s). (3) 2- [4- (1-methyl-5-methylthio-1H- [1,2,4] triazole-3- Yl) phenoxymethyl] benzothiazole (Step A-1) 3- (4-hydroxyphenyl) obtained by the method of (2) above
1-methyl-5-methylthio-1H- [1,2,4] triazole (1.84
g, 8.3 mmol) in dimethylformamide (30 mL).
° C, and at the same temperature, sodium hydride (60% in oi
l, 0.40 mg) and 2-iodomethylbenzothiazole (3.44 mg
g) was added and the mixture was stirred at 0 ° C. for 1 hour and at room temperature for 1 hour. After the completion of the reaction, the reaction solution was poured into water to precipitate crystals. The precipitated crystals were filtered and washed with a mixed solution of hexane-ethyl acetate to obtain 0.27 g of the title compound. Melting point: 159-160 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.94 (2
H, d, J = 8.7 Hz), 6.86 (2H, d, J = 8.7 Hz), 5.24-
5.20 (1H, m), 3.80 (3H, s), 2.74 (3H, s).

[0195]

Example 2 4- [4- (benzothiazol-2-ylmethoxy)
Phenyl] -2-methyl-5-trifluoromethyl-2,4-dihydro [1,2,4] triazol-3-one (Compound No. 9.2) The title compound according to the method of Example 1 (3). Was synthesized. Melting point: 151-154 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 7.8 Hz), 7.92 (1H, dd, J = 7.8, 1.5 Hz),
7.56-7.38 (2H, m), 7.29 (2H, d, J = 9.0 Hz), 7.16
(2H, d, J = 9.0 Hz), 5.52 (2H, s), 3.59 (3H, s).

[0196]

Example 3 4- [4- (benzoxazol-2-ylmethoxy) phenyl] -2-methyl-5-trifluoromethyl-2,4-dihydro [1,2,4] triazol-3-one (compound Number 9.
3) The title compound was synthesized according to the method of Example 1 (3). Melting point: 148-150 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.80-7.
75 (1H, m), 7.61-7.56 (1H, m), 7.41-7.36 (2H, m),
7.29 (2H, d, J = 9.2 Hz), 7.18 (2H, d, J = 9.2 H
z), 5.37 (2H, s), 3.59 (3H, s).

[0197]

Example 4 2- [4- (benzothiazol-2-ylmethoxy)
Phenyl] -4,5-dimethyl-2,4-dihydro [1,2,4] triazol-3-one (Compound No. 11.2) The title compound was synthesized according to the method of Example 1 (3). Melting point: 226-229 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05-7.
84 (4H, m) 7.55-7.36 (2H, m), 7.11-7.06 (2H, m),
5.50 (2H, s), 3.29 (3H, s), 2.30 (3H, s).

[0198]

Example 5 3- [4- (benzothiazol-2-ylmethoxy)
Phenyl] -6-trifluoromethyl-1H-pyrimidine-2,4-
Dione (Compound No. 29.1) The title compound was synthesized according to the method of Example 1 (3). Melting point:> 280 ° C ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 12.45
(1H, br.s), 8.15 (1H, d, J = 7.8Hz), 8.06 (1H, d,
J = 7.4Hz), 7.60-7.44 (2H, m), 7.29-7.15 (4H, m),
6.34 (1H, s), 5.68 (2H, s).

[0199]

Example 6 3- [4- (benzothiazol-2-ylmethoxy)
2-Methylphenyl] -6-trifluoromethyl-1H-pyrimidine-2,4-dione (Compound No. 29.2) The title compound was synthesized according to the method of Example 1 (3). Physical properties: amorphous ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.7Hz), 7.91 (1H, d, J = 7.7Hz), 7.54-7.3
8 (3H, m), 7.05-6.93 (3H, m), 6.23 (1H, s), 5.48 (2
H, s), 2.11 (3H, s).

[0200]

Example 7 3- [4- (benzothiazol-2-ylmethoxy)
[Phenyl] -1-methyl-6-trifluoromethyl-1H-pyrimidine-2,4-dione (Compound No. 29.4) The title compound was synthesized according to the method of Example 1 (3). Melting point: 226-228 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.07-7.
89 (2H, m), 7.56-7.38 (2H, m), 7.16 (4H, s), 6.37
(1H, s), 5.52 (2H, s), 3.54 (3H, s).

[0201]

Example 8 3- [4- (benzothiazol-2-ylmethoxy)
-2-methylphenyl] -1-methyl-6-trifluoromethyl-1
H-pyrimidine-2,4-dione (Compound No. 29.7) The title compound was synthesized according to the method of Example 1 (3). Physical properties: amorphous ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 8.2Hz), 7.91 (1H, dd, J = 7.6, 1.6Hz), 7.
55-7.37 (2H, m), 7.07-6.96 (3H, m), 6.37 (1H, s),
5.50 (2H, s), 3.55 (3H, d, J = 1.2Hz), 2.11 (3H,
s).

[0202]

Example 9 3- [4- (benzothiazol-2-ylmethoxy)
2-Methylphenyl] -1,5-dimethyl-6-trifluoromethyl-1H-pyrimidine-2,4-dione (Compound No. 29.9) The title compound was synthesized according to the method of Example 1 (3). did. Physical properties: amorphous ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.3Hz), 7.91 (1H, dd, J = 7.9, 1.1Hz), 7.
55-7.37 (2H, m), 7.05-6.98 (3H, m), 5.50 (2H, s),
3.55 (3H, d, J = 2.0Hz), 2.24 (3H, m), 2.10 (3H,
s).

[0203]

Example 10 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] pyrrolidine-2,5-dione (Compound No. 3)
0.3) The title compound was synthesized according to the method of Example 1 (3). Melting point: 244-245 ° C. ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 8.14
(1H, dd, J = 7.2, 1.6Hz), 8.05 (1H, dd, J = 7.3,
1.4 Hz), 7.61-7.45 (2H, m), 5.67 (2H, s), 2.77 (4
H, s).

[0204]

Example 11 1- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] pyrrolidine-2,5-dione (Compound No. 30.4) Titled according to the method of Example 1 (3). Compounds were synthesized. Melting point: 166-169 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.2Hz), 7.91 (1H, d, J = 7.5Hz), 7.55-7.3
7 (2H, m), 7.04-6.94 (3H, m), 5.48 (2H, s), 2.90 (4
H, s), 2.12 (3H, s).

[0205]

Example 12 2- [4- (Benzothiazol-2-ylmethoxy) phenyl] isoindole-1,3-dione (Compound No. 15.3) The title compound was synthesized according to the method of Example 1 (3). did. Melting point: 274-276 ° C ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 8.06-
7.77 (6H, m), 7.56-7.36 (4H, m), 7.19-7.15 (2H,
m), 5.54 (2H, s).

[0206]

Example 13 2- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] isoindole-1,3-dione (Compound No. 15.7) According to the method of Example 1 (3) The title compound was synthesized. Melting point: 158-160 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 7.7Hz), 7.98-7.90 (3H, m), 7.82-7.77 (2
H, m), 7.55-7.42 (2H, m), 7.15 (1H, d, J = 8.8Hz),
7.06-6.96 (2H, m), 5.52 (2H, s), 2.19 (3H, s).

[0207]

Example 14 2- [4- (5-Methanesulfonyl-1-methyl-1H)
-[1,2,4] Triazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 8.4) (Step E) 2- [4- (1-methyl-5-methylthio) obtained in Example 1 above -
A solution of 1H- [1,2,4] triazol-3-yl) phenoxymethyl] benzothiazole (1.88 g, 5.1 mmol) and m-chloroperbenzoic acid (70%, 3.14 g) in 1,2-dichloroethane (40 mL) was stirred at room temperature for 5 hours. After completion of the reaction, the reaction solution was poured into an aqueous solution of sodium hydrogen carbonate, extracted with ethyl acetate, and the extract was dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off to obtain crystals. The obtained crystals were washed with a mixed solvent of hexane-ethyl acetate-methylene chloride to obtain 2.0 g of the title compound. Melting point: 191-193 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.07-8.
00 (3H, m), 7.99-7.89 (1H, m), 7.56-7.37 (2H, m),
7.11 (2H, d, J = 8.8 Hz), 5.55 (2H, s), 4.22 (3H,
s), 3.47 (3H, s).

[0208]

Example 15 2- [4- (5-methoxy-1-methyl-1H- [1,2,4]
Triazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 8.6) (Step E) 2- [4- (5-methanesulfonyl-1) obtained in Example 14 above
To 1-methyl-1H- [1,2,4] triazol-3-yl) phenoxymethyl] benzothiazole (0.31 g, 0.77 mmol) was added sodium methoxide (10% methanol solution, 7 mL), and the reaction mixture was added to 90 mL. The mixture was stirred for 3 hours while heating to ° C. After the completion of the reaction, the reaction solution was poured into water, and the precipitated crystals were filtered. The obtained crystals were washed with water, heated and dried under reduced pressure to obtain 0.16 g of the title compound. Melting point: 194-195 ° C. ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 8.17-
8.12 (1H, m), 8.07-8.03 (1H, m), 7.89 (2H, d, J =
8.9 Hz), 7.61-7.44 (2H, m), 7.18 (2H, d, J = 8.9 H
z), 5.66 (2H, s), 4.10 (3H, s), 3.60 (3H, s).

[0209]

Example 16 2- [4- [1-Methyl-5- (2,2,2-trifluoroethoxy) -1H- [1,2,4] triazol-3-yl] phenoxymethyl] benzothiazole ( Compound No. 8.8) The title compound was synthesized according to the method of Example 15. Melting point: 190-191 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.15 (1
H, dd, J = 7.6, 0.8 Hz), 8.05 (1H, dd, J = 8.0, 1.
0 Hz), 7.89 (2H, d, J = 8.3 Hz), 7.60-7.44 (2H,
m), 7.20 (2H, d, J = 8.3 Hz), 5.67 (2H, s), 5.19
(2H, q, J = 9.0 Hz), 3.66 (3H, s).

[0210]

Example 17 5- [4- (Benzothiazol-2-ylmethoxy) phenyl] -2-methyl-2,4-dihydro [1,2,4] triazol-3-one (Compound No. 10.2) The title compound was synthesized according to the method of Example 15. Melting point:> 250 ° C. ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 12.11
(1H, s), 8.15 (1H, dd, J = 7.9, 1.1 Hz), 8.05 (1
H, dd, J = 7.5, 1.1 Hz), 7.76 (2H, d, J = 8.9Hz),
7.61-7.44 (2H, m), 7.23 (2H, d J = 8.9 Hz), 5.69
(2H, s), 3.35 (3H, s).

[0211]

Example 18 4- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -2-methyl-5-trifluoromethyl-2,4-dihydro [1,2,4] triazole-3 -One (Compound No. 9.5) (1) 4- (4-methoxy-2-methylphenyl) -5-trifluoromethyl-2,4-dihydro [1,2,4] triazol-3-one (B Step 1) Carbon tetrachloride (17.59 mL) and trifluoroacetic acid (2.81 mL) were added to a solution of triphenylphosphine (28.68 g) in 1,2-dichloroethane (50 mL), and the mixture was cooled to 0 ° C and cooled at the same temperature. Then, triethylamine (6.1 mL) was added to the reaction solution, and the mixture was stirred for 10 minutes.
g, 36.45 mmol) in 1,2-dichloroethane (10 mL) and heated at 90 ° C. for 2 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, the solvent was distilled off, the obtained residue was diluted with hexane, and insolubles were removed by filtration using Celite.
The filtrate was concentrated, and the obtained residue was purified by silica gel chromatography to give 2,2,2-trifluoro-N- (4-methoxy-2
7.29 g of -methylphenyl) acetimidoyl chloride were obtained. Physical properties: Oil ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 7.18
(1H, d, J = 8.4Hz), 6.83-6.75 (2H, m), 3.83 (3H, s),
2.24 (3H, s). The obtained 2,2,2-trifluoro-N- (4-methoxy-2-methylphenyl) acetimidoyl chloride (5.0 g, 19.87 m
mol) was dissolved in 1,4-dioxane (50 mL), methyl carbazate (3.58 g) was added to this solution, and the mixture was heated at 100 ° C. for 2 hours. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure.
An 8% aqueous sodium hydroxide solution (40 mL) was added to the obtained residue, and the mixture was stirred at 100 ° C for 2 hours. The reaction solution was acidified using 6N hydrochloric acid, and extracted with ethyl acetate. The extract was washed with water and brine, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to give the title compound 4- (4-
(Methoxy-2-methylphenyl) -5-trifluoromethyl-2,
1.79 g of 4-dihydro [1,2,4] triazol-3-one was obtained. ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 10.60
-10.59 (1H, m), 7.15 (1H, d, J = 8.4Hz), 6.88-6.81 (2H,
m), 3.85 (3H, s), 2.18 (3H, s). (2) 4- (4-methoxy-2-methylphenyl) -2-methyl-5-
Trifluoromethyl-2,4-dihydro [1,2,4] triazole
-3-one (Step B-1) 4- (4-methoxy-2-methylphenyl) -5-trifluoromethyl-2,4-dihydro [1,2,4] obtained by the method of the above (1). Triazol-3-one (1.79 g, 6.85 mmol) was dissolved in dimethylformamide (15 mL), and sodium hydride (60% inoil, 0.41 g) and methane iodide (2.13 m
L) was added and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the residue was purified by silica gel chromatography to give the title compound, 4- (4-methoxy-2-methylphenyl) -2-methyl-5-trifluoromethyl-2. 0.76 g of 1,4-dihydro [1,2,4] triazol-3-one was obtained. Physical properties: Oil ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 7.11
(1H, d, J = 8.4Hz), 6.84-6.80 (2H, m), 3.83 (3H, s),
3.61 (3H, s), 2.15 (3H, s). (3) 4- (4-hydroxy-2-methylphenyl) -2-methyl-5
-Trifluoromethyl-2,4-dihydro [1,2,4] triazol-3-one (Step B-2) 4- (4-methoxy-2-methylphenyl)-obtained by the method of (2) above. 2-methyl-5-trifluoromethyl-2,4-dihydro
[1,2,4] Triazol-3-one (0.80 g, 2.79 mmol) was dissolved in methylene chloride (10 mL), and to this solution was added boron trisulfide (1 M in methylene chloride, 5.58 mL) at 0 ° C. Plus 0
The mixture was stirred at 20 ° C for 20 minutes and at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into water and extracted with methylene chloride. The extract was washed with water and dried over anhydrous sodium sulfate. After filtration of the drying agent, the solvent was distilled off, and the title compound, 4- (4-hydroxy-
2-methylphenyl) -2-methyl-5-trifluoromethyl-2,
0.74 g of 4-dihydro [1,2,4] triazol-3-one was obtained. Physical properties: Solid-state ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 6.91
(1H, d, J = 9.2Hz), 6.53-6.49 (2H, m), 3.66 (3H, s),
2.03 (3H, s). (4) 4- [4- (benzothiazol-2-ylmethoxy) -2-methylphenyl] -2-methyl-5-trifluoromethyl-2,4-dihydro [1,2, 4] Triazol-3-one (Step A-1) 4- (4-hydroxy-2-methylphenyl) -2-methyl-5-trifluoromethyl-2,4-dihydro obtained by the method of the above (3) [1,2,4] Triazol-3-one (0.20 g, 0.73 mmol) was dissolved in dimethylformamide (8 mL), and the solution was cooled to 0 ° C, and then sodium hydride (60% in oil, 35 mg) And 2-
Add iodomethylbenzothiazole (0.24 g) and add 9
Stirred for 0 minutes. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent is distilled off,
The residue was purified by silica gel chromatography to obtain 0.27 g of the title compound. Melting point: 134-136 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 8.1Hz), 7.93 (1H, dd, J = 6.8, 0.9Hz), 7.56-7.
38 (2H, m), 7.15 (1H, d, J = 8.8Hz), 7.03 (1H, d, J = 2.9H
z), 6.96 (1H, dd, J = 8.8, 2.9Hz), 5.50 (2H, s), 3.61
(3H, s), 2.16 (3H, s).

[0212]

Example 19 4- [4- (benzoxazol-2-ylmethoxy) -2-methylphenyl] -2-methyl-5-trifluoromethyl-2,4-dihydro [1,2,4] triazole-3 -On (Compound No. 9.6) The title compound was synthesized according to the method of Example 18. Melting point: 114-115 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.80-7.7
5 (1H, m), 7.60-7.56 (1H, m), 7.44-7.37 (2H, m), 7.15
(1H, d, J = 8.8Hz), 7.05 (1H, d, J = 2.2Hz), 6.99 (1H, d
d, J = 8.8, 2.2Hz), 5.35 (2H, s), 3.60 (3H, s), 2.16 (3
H, s).

[0213]

Example 20 2- [4- (5-methoxy-4-methyl-4H- [1,2,4]
Triazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 27.2) The title compound was synthesized according to the method of Example 18. Melting point: 191-193 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.79-7.7
4 (1H, m), 7.59 (2H, d, J = 9.0Hz), 7.59-7.55 (1H, m),
7.40-7.36 (2H, m), 7.17 (2H, d, J = 9.0Hz), 5.38 (2H,
s), 4.19 (3H, s), 3.43 (3H, s).

[0214]

Example 21 2- [4- (5-methoxy-4-methyl-4H- [1,2,4]
Triazol-3-yl) phenoxymethyl] benzoxazole (Compound No. 27.3) The title compound was synthesized according to the method of Example 18. Melting point: 125-127 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1H,
d, J = 8.5Hz), 7.92 (1H, dd, J = 6.9, 1.1Hz), 7.59 (2H,
d, J = 8.9Hz), 7.57-7.41 (2H, m), 7.15 (2H, d, J = 8.9H
z), 5.54 (2H, s), 4.19 (3H, s), 3.44 (3H, s).

[0215]

Example 22 2- [4- (5-Trifluoroethoxy-4-methyl-4H- [1,2,4] triazol-3-yl) phenoxymethyl]
Benzothiazole (Compound No. 27.8) The title compound was synthesized according to the method of Example 18. Melting point: 204-206 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.06 (1H,
d, J = 8.1Hz), 7.92 (1H, d, J = 8.1Hz), 7.60 (1H, d, J =
9.0Hz), 7.56-7.43 (2H, m), 7.17 (2H, d, J = 9.0Hz), 5.
56 (2H, s), 4.90 (2H, q, J = 8.3Hz), 3.51 (3H, s).

[0216]

Example 23 2- [4- (5-Trifluoroethoxy-4-methyl-4H- [1,2,4] triazol-3-yl) phenoxymethyl]
Benzoxazole (Compound No. 27.9) The title compound was synthesized according to the method of Example 18. Melting point: 192-193 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.80-7.7
6 (1H, m), 7.63-7.56 (1H, m), 7.60-7.56 (1H, m), 7.60
(2H, d, J = 8.7Hz), 7.41-7.37 (2H, m), 7.19 (2H, d, J =
8.7Hz), 5.40 (2H, s), 4.90 (2H, w, J = 8.1Hz), 3.15 (3
H, s).

[0219]

Example 24 2- (4-Imidazol-1-ylphenoxymethyl) benzoxazole (Compound No. 24.4) The title compound was synthesized according to the method of Example 18. Melting point: 120-123 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.80-7.6
0 (2H, m), 7.60-7.56 (1H, m), 7.44-7.32 (2H, m), 7.34
(2H, d, J = 9.1Hz), 7.17 (2H, d, J = 9.1Hz), 7.20-7.16
(2H, m), 5.38 (2H, s).

[0218]

Example 25 2- (4-Imidazol-1-ylphenoxymethyl) benzothiazole (Compound No. 24.3) The title compound was synthesized according to the method of Example 18. Melting point: 177-179 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1H,
d, J = 7.5Hz), 7.92 (1H, dd, J = 6.8, 0.9Hz), 7.76 (1H,
br.s), 7.56-7.38 (2H, m), 7.33 (2H, d, J = 9.1Hz), 7.2
0-7.18 (2H, m), 7.14 (2H, d, J = 9.1Hz), 5.54 (2H, s).

[0219]

Example 26 2- [4- (2,5-Dichloro-imidazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 2
4.11) The title compound was synthesized according to the method of Example 18. Melting point: 162-165 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1H,
d, J = 8.1Hz), 7.92 (1H, dd, J = 6.8, 1.0Hz), 7.59-7.42
(2H, m), 7.31 (2H, d, J = 9.0Hz), 7.14 (2H, d, J = 9.0H
z), 7.04 (1H, s), 5.54 (2H, s).

[0220]

Example 27 2- [4- (2,5-Dichloro-imidazol-1-yl) phenoxymethyl] benzoxazole (Compound No. 24.12) The title compound was synthesized according to the method of Example 18. Melting point: 141-143 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.81-7.7
6 (1H, m), 7.60-7.56 (1H, m), 7.41-7.37 (2H, m), 7.32
(2H, d, J = 9.0Hz), 7.17 (2H, d, J = 9.0Hz), 7.05 (1H,
s), 5.39 (2H, s).

[0221]

Example 28 2- [4- (5-Chloro-imidazol-1-yl)
[Phenoxymethyl] benzothiazole (Compound No. 2
4.13) The title compound was synthesized according to the method of Example 18. Melting point: 181-182 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1H,
dd, J = 8.6, 1.3Hz), 7.92 (1H, dd, J = 8.0, 1.1Hz), 7.
57 (1H, s), 7.56-7.42 (2H, m), 7.30 (2H, d, J = 9.0Hz),
7.16 (2H, d, J = 9.0Hz), 7.05 (1H, s), 5.55 (2H, s).

[0222]

Example 29 2- [4- (5-Chloro-imidazol-1-yl)
Phenoxymethyl] benzoxazole (Compound No. 2
4.14) The title compound was synthesized according to the method of Example 18. Melting point: 118-120 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.81-7.7
6 (1H, m), 7.61-7.56 (1H, m), 7.58 (1H, d, J = 1.1Hz),
7.44-7.37 (2H, m), 7.31 (2H, d, J = 9.1Hz), 7.06 (1H,
d, J = 1.0Hz), 5.39 (2H, s).

[0223]

Example 30 2- (4- [1,2,4] triazol-1-ylphenoxymethyl) benzoxazole (Compound No. 23.
4) The title compound was synthesized according to the method of Example 18. Melting point: 134-136 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.45 (1H,
s), 8.08 (1H, s), 7.80-7.75 (1H, m), 7.60-7.55 (1H,
m), 7.61 (2H, d, J = 9.1Hz), 7.41-7.37 (2H, m), 7.20 (2
(H, d, J = 9.1Hz), 5.39 (2H, s).

[0224]

Example 31 2- (4- [1,2,4] triazol-1-ylphenoxymethyl) benzothiazole (Compound No. 23.
3) The title compound was synthesized according to the method of Example 18. Melting point: 192-195 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.45 (1H,
s), 8.08 (1H, s), 8.05 (1H, d, J = 7.6Hz), 7.91 (1H, d
d, J = 6.8, 0.9Hz), 7.61 (2H, d, J = 9.1Hz), 7.56-7.42
(2H, m), 7.17 (2H, d, J = 9.1Hz), 5.55 (2H, s).

[0225]

Example 32 2- [4- (3-trifluoromethylpyrazole)
1-yl) phenoxymethyl] benzoxazole (Compound No. 14.9) The title compound was synthesized according to the method of Example 18. Melting point: 88-91 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.85 (1H,
s), 7.80-7.74 (1H, m), 7.59-7.55 (1H, m), 7.64 (2H,
d, J = 9.1Hz), 7.44-7.34 (2H, m), 7.17 (2H, d, J = 9.1H
z), 6.70 (1H, d, J = 1.9Hz), 5.38 (2H, s).

[0226]

Example 33 2- [4- (3-trifluoromethylpyrazole)
1-yl) phenoxymethyl] benzothiazole (Compound No. 14.8) The title compound was synthesized according to the method of Example 18. Melting point: 155-157 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1H,
d, J = 8.1Hz), 7.91 (1H, d, J = 8.4Hz), 7.85 (1H, d, J =
0.9Hz), 7.63 (1H, d, J = 9.0Hz), 7.59-7.38 (2H, m), 7.1
4 (2H, d, J = 9.0Hz), 6.70 (1H, d, J = 2.1Hz), 5.54 (2H,
s).

[0227]

Example 34 5- [4- (Benzothiazol-2-yl-methoxy) phenyl] -1,3,5-trimethylimidazolidine-2,4-
Dione (Compound No. 25.9) Melting point: 161-164 ° C. (1) 5- (4-methoxyphenyl) imidazolidin-2,4-dione (Step B-1) 4-methoxybenzaldehyde (9.93 g, 72.9 mmol) , Potassium cyanide (9.5 g) and ammonium carbonate (35.0 g)
Was added to methanol (50 mL) -water (50 mL), and 8
Heated at 0 ° C. for 3 hours. After completion of the reaction, the reaction solution was carefully acidified, and the precipitated solid was filtered and dried by heating under reduced pressure to obtain 8.88 g of the title compound, 5- (4-methoxyphenyl) imidazolidine-2,4-dione. Was. ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 10.75
(1H, s), 8.35 (1H, s), 7.25 (2H, d, J = 8.6 Hz),
6.97 (2H, d, J = 8.6 Hz), 5.10 (1H, s), 3.77

(3H, s). (2) a) 5- (4-methoxyphenyl) -1,3,5-trimethylimidazolidine-2,4-dione and b) 5- (4-methoxyphenyl)- 1,3-dimethylimidazolidine-2,4-dione (B-
One step) 5- (4-methoxyphenyl) imidazolidin-2,4-dione (0.51 g, 2.45 mmol) and methane iodide (0.76 mL) obtained by the method of the above (1) are added to a dimethylformamide solution (10 mL). )
, The solution was cooled to 0 ° C., and sodium hydride (60% in oil, 0.22 g) was added to the reaction solution at the same temperature.
Stirred at room temperature for 1 day. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. The solvent was distilled off after filtering the drying agent, and the obtained residue was purified by silica gel chromatography to give the title compound a) 5- (4-methoxyphenyl) -1,3,5
0.25 g of -trimethylimidazolidine-2,4-dione and 0.25 g of the title compound b) 5- (4-methoxyphenyl) -1,3-dimethylimidazolidine-2,4-dione were obtained. a) ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.1
6 (2H, d, J = 8.9 Hz),

6.89 (2H, d, J = 8.9 Hz), 3.77 (3H,
s), 3.02 (3H, s), 2.80 (3H, s), 1.75 (3H, s) .b) ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.1
6 (2H, d, J = 8.7 Hz), 6.93 (2H, d, J = 8.7 Hz), 4.
74 (1H, s), 3.80 (3H, s), 3.06 (3H, s), 2.87 (3H,
s). (3) 5- [4- (benzothiazol-2-ylmethoxy) phenyl] -1,3,5-trimethylimidazolidine-2,4-dione (B
-2 step) 5- (4-methoxyphenyl)-obtained by the method of the above (2)
1,3,5-trimethylimidazolidine-2,4-dione (a)
(0.25 g, 1.1 mmol) in methylene chloride (10 mL),
Aluminum chloride (0.42 g) and ethanethiol (0.39 mL) were added to this solution at 0 ° C., and the mixture was stirred at room temperature for 70 minutes. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off to obtain 0.23 g of a solid. The obtained solid was dissolved in dimethylformamide (5 mL), cooled to 0 ° C., and sodium hydride (60% in oil, 47 mg) and 2-
Add iodomethylbenzothiazole (0.32 g) and add
Stirred for 90 minutes. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography.
0.37 g of the title compound was obtained. Melting point: 161-164 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.2 Hz), 7.90 (1H, d, J = 6.8 Hz), 7.55-
7.37 (2H, m), 7.22 (2H, d.J = 9.0 Hz), 7.05 (2H, m
d, J = 9.0 Hz), 5.49 (2H, s), 3.05 (3H, s), 2.82
(3H, s), 1.78 (3H, s).

[0230]

Example 35 2- [4- (1H-tetrazol-5-yl) phenoxymethyl] benzothiazole (Compound No. 3.1)
(Step A-2) Trimethylaluminum (1.5 M hexane solution, 12.6 mL)
Trimethylsilyl azide (2.5 mL) at 0 ° C, followed by 4- (benzothiazol-2-ylmethoxy) benzonitrile (0.50 g, 1.88 mmol), heated to 80 ° C, and stirred at the same temperature for 12 hours. did. After completion of the reaction, the reaction solution was poured into diluted hydrochloric acid, extracted with ethyl acetate, and the extract was dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained crystals were washed with isopropyl ether to give the title compound 0.58.
g was obtained. Melting point: 235-238 ° C ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 8.17-
8.04 (2H, m), 7.70 (4H, ABq, J = 8.8 Hz), 7.62-7.4
5 (2H, m), 5.74 (2H, s).

[0231]

Example 36 a) 2- [4- (1-Methyl-1H-tetrazole-5)
-Yl) phenoxymethyl] benzothiazole (Compound No. 3.5) and b) 2- [4- (2-methyl-2H-tetrazole-5)
-Yl) phenoxymethyl] benzothiazole (Compound No. 4.1) (Step E) 2- [4- (1H-tetrazol-5-yl) phenoxymethyl] benzothiazole obtained from Example 35 (99.2 mg, 0.32 mmol)
l) in dimethylformamide (4 mL), and methane iodide (0.06 mL) and sodium hydride were added to this solution at room temperature.
(60% in oil, 15 mg) and stirred for 90 minutes. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. The solvent was distilled off after filtering the drying agent, and the obtained residue was purified by silica gel chromatography to give the title compound a) 2- [4-
(2-methyl-2H-tetrazol-5-yl) phenoxymethyl]
69 mg of benzothiazole and 18 mg of the title compound b) 2- [4- (1-methyl-1H-tetrazol-5-yl) phenoxymethyl] benzothiazole were obtained. a) Melting point: 200-203 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.06 (1
H, d, J = 8.1 Hz), 7.92 (1H, dd, J = 8.7, 1.5 Hz),
7.48 (4H, ABq, J = 8.5 Hz), 7.53-7.43 (2H, m), 5.5
8) (2H, s), 4.16 (3H, s). B) Melting point: 183-185 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.08-7.
89 (2H, m), 7.63 (4H, ABq, J = 8.9 Hz), 7.55-7.41
(2H, m), 5.56 (2H.s), 4.38 (3H, s).

[0232]

Example 37 2- [4- (1-Ethyl-1H-tetrazol-5-yl) phenoxymethyl] benzothiazole (Compound No. 3.7) The title compound was synthesized according to the method of Example 36. Melting point: 150-151 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.06 (1
H, d, J = 8.8 Hz), 7.92 (1H, dd, J = 7.0, 1.0 Hz),
7.56-7.43 (2H, m), 7.44 (4H, ABq, J = 8.8 Hz), 5.
58 (2H, s), 4.46 (2H, q, J = 7.2 Hz), 1.58 (3H, t,
J = 7.2 Hz).

[0233]

Working Example 38 2- [4- (1-isopropyl-1H-tetrazole)
-5-yl) phenoxymethyl] benzothiazole (Compound No. 3.8) The title compound was synthesized according to the method of Example 36. Melting point: 139-142 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.06 (1
H, d, J = 8.2 Hz), 7.41 (4H, ABq, J = 8.9 Hz), 7.9
2 (1H, d, J = 7.7 Hz), 7.55-7.43 (1H, quintet, J =
6.8 Hz), 1.68 (6H, d, J = 6.8 Hz).

[0234]

Example 39 2- [4- (2-Ethyl-2H-tetrazol-5-yl) phenoxymethyl] benzothiazole (Compound No. 4.4) The title compound was synthesized according to the method of Example 36. Melting point: 152-154 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, dd, J = 8.7, 0.7 Hz), 7.91 (1H, dd, J = 6.8, 0.
9 Hz), 7.63 (4H, ABq, J = 8.9 Hz), 7.56-7.38 (2H,
m), 5.56 (2H, s), 4.68 (2H, q, J = 7.4 Hz), 1.67
(3H, t, J = 7.4 Hz).

[0235]

Example 40 2- [4- (2-isopropyl-2H-tetrazole)
-5-yl) phenoxymethyl] benzothiazole (Compound No. 4.5) The title compound was synthesized according to the method of Example 36. Melting point: 124-127 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 7.6 Hz), 7.91 (1H, d, J = 6.9 Hz), 7.60
(4H, ABq, J = 9.0 Hz), 7.59-7.37 (2H, m), 5.55 (2
H, s), 5.08 (1H, septet, J = 6.7 Hz), 1.69 (6H, d,
J = 6.7 Hz).

[0236]

Example 41 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] -4-methyl-1,4-dihydrotetrazole-5-
ON (Compound No. 6.3) (1) 1- (4-methoxyphenyl) -1,4-dihydrotetrazol-5-one (Step B-1) 4-methoxyphenyl isocyanate (10.64 g, 71.3 mmo)
l) and trimethylsilyl azide (18.9 mL)
The mixture was stirred for 3 days while heating to 10 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature, hexane was added, the precipitated crystals were filtered, and the obtained crystals were washed with a mixed solvent of hexane-methylene chloride to give the title compound 1- (4-methoxyphenyl)
12.8 g of -1,4-dihydrotetrazol-5-one was obtained. Melting point: 185-188 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.79 (2
H, d, J = 9.1 Hz), 7.04 (2H, d, J = 9.1 Hz), 3.87
(3H, s). (2) 1- (4-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one (Step B-1) 1- ( 4-methoxyphenyl)-
1,4-dihydrotetrazol-5-one (0.87 g, 4.53 mmol)
Was dissolved in dimethylformamide (17 mL) .Sodium hydride (60% in oil, 0.22 g) was added to this solution at 0 ° C., and the mixture was stirred at the same temperature for 10 minutes.
mL) and stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to give the title compound 1- (4-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one 0.76 g
I got ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.79 (2
H, d, J = 9.1 Hz), 7.00 (2H, d, J = 9.1 Hz), 3.85
(3H, s), 3.70 (3H, s). (3) 1- [4- (benzothiazol-2-ylmethoxy) phenyl] -4-methyl-1,4-dihydrotetrazol-5-one (B-
2 step) 1- (4-methoxyphenyl) -4 obtained by the method of the above (2)
-Methyl-1,4-dihydrotetrazol-5-one (0.55 g, 2.
66 mmol) was dissolved in methylene chloride (10 mL), and aluminum chloride (1.06 g) and propanethiol (1.20 g) were added to this solution.
mL) at 0 ° C. and stirred at room temperature for 90 minutes. After completion of the reaction, the reaction solution was poured into water and extracted with methylene chloride. The extract was washed with water and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and 1- (4-hydroxyphenyl) -4-
0.43 g of methyl-1,4-dihydrotetrazol-5-one was obtained.

The obtained 1- (4-hydroxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one (0.25 g, 1.28 g)
mmol) in dimethylformamide (5 mL), the solution was cooled to 0 ° C., and sodium hydride (60% in oil, 61 m
g) and 2-iodomethylbenzothiazole (0.42 g) were added, and the mixture was stirred at room temperature for 90 minutes. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, and the extract was washed with brine,
Dry over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to obtain 0.39 g of the title compound. Melting point: 185-190 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 7.3 Hz), 7.91 (1H, dd, J = 7.3, 1.4 Hz),
7.85 (2H, d, J = 9.2 Hz), 7.52-7.41 (2H, m), 7.16
(2H, d, J = 9.2 Hz), 5.53 (2H, s), 3.69 (3H, s).

[0238]

Example 42 1- [4- (benzoxazol-2-ylmethoxy) phenyl] -4-methyl-1,4-dihydrotetrazole-5
-On (Compound No. 6.4) The title compound was synthesized according to the method of Example 41. Melting point: 136-138 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.85 (2
H, d, J = 9.1 Hz), 7.79-7.75 (1H, m), 7.59-7.55 (2
H, m), 7.40-7.36 (2H, m), 7.18 (2H, d, J = 9.1 H
z), 5.37 (2H, s), 3.69 (3H, s).

[0239]

Example 43 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] -4-ethyl-1,4-dihydrotetrazole-5-
On (Compound No. 6.5) The title compound was synthesized according to the method of Example 41. Melting point: 165-169 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 8.1 Hz), 7.91 (1H, dd, J = 7.0, 1.5 Hz),
7.86 (2H, d, J = 8.9 Hz), 7.55-7.37 (2H, m), 7.16
(2H, d, J = 8.9 Hz), 5.53 (2H, s), 4.07 (2H, q, J
= 7.3 Hz), 1.49 (3H, t, J = 7.3 Hz).

[0240]

Example 44 1- [4- (Benoxaxazol-2-ylmethoxy) phenyl] -4-ethyl-1,4-dihydrotetrazole-5
-On (Compound No. 6.6) The title compound was synthesized according to the method of Example 41. Melting point: 108-110 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.86 (2
H, d, J = 9.2 Hz), 7.79-7.74 (1H, m), 7.59-7.54 (1
H, m), 7.40-7.35 (2H, m), 7.18 (2H, d, J = 9.2 H
z), 5.37 (2H, s), 4.08 (2H, q, J = 7.3 Hz), 1.49
(3H, t, J = 7.3 Hz).

[0241]

Example 45 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] -4-isopropyl-1,4-dihydrotetrazol-5-one (Compound No. 6.9) According to the method of Example 41 The title compound was synthesized. Melting point: 158-160 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 7.3 Hz), 7.90 (1H, d, J = 7.3 Hz), 7.86
(2H, d, J = 9.3 Hz), 7.56-7.41 (2H, m), 7.15 (2H,
d, J = 9.3 Hz), 5.53 (2H, s), 4.57 (1H, septet, J
= 6.6 Hz), 1.54 (6H, d, J = 6.6 Hz).

[0242]

Example 46 1- [4- (Benoxaxazol-2-ylmethoxy) phenyl] -4-isopropyl-1,4-dihydrotetrazol-5-one (Compound No. 6.10) According to the method of Example 41 The title compound was synthesized. Melting point: 86-90 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.87 (2
H, d, J = 9.2 Hz), 7.79-7.75 (1H, m), 7.57-7.54 (1
H, m), 7.40-7.35 (2H, m), 7.18 (2H, d, J = 9.2 H
z), 6.37 (2H, s), 4.56 (1H, septet, J = 6.8 Hz),
1.54 (6H, d, J = 6.8 Hz).

[0243]

Example 47 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] -4-propyl-1,4-dihydrotetrazole-5
-On (Compound No. 6.7) The title compound was synthesized according to the method of Example 41. Melting point: 154-157 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 7.4 Hz), 7.90 (1H, d, J = 7.4 Hz), 7.87
(2H, d, J = 9.2 Hz), 7.56-7.37 (2H, m), 7.16 (2H,
d, J = 9.3 Hz), 5.53 (2H, s), 3.98 (2H, t, J = 7.0
Hz), 1.92 (2H, sextet, J = 7.0 Hz), 1.02 (3H, t, J
= 7.0 Hz).

[0244]

Example 48 1- [4- (Benzoxazol-2-ylmethoxy) -phenyl] -4-propyl-1,4-dihydrotetrazol-5-one (Compound No. 6.8) According to the method of Example 41. To synthesize the title compound. Melting point: 118-121 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.87 (2
H, d, J = 9.4 Hz), 7.79-7.74 (1H, m), 7.59-7.55 (1
H, m), 7.42-7.36 (2H, m), 7.18 (2H, d, J = 9.4 H
z), 5.37 (2H, s), 3.98 (2H, t, J = 7.0 Hz), 1.91
(2H, sextet, J = 7.0 Hz), 1.02 (3H, t, J = 7.0 H
z).

[0245]

Example 49 2- [4- (5-Methoxytetrazol-1-yl)
[Phenoxymethyl] benzothiazole (Compound No. 7.
7) (1) 1- (4-benzyloxyphenyl) -1,4-dihydrotetrazol-5-one (Step B-1) 4-benzyloxybenzoic acid (6.1 g, 26.7 mmol) and thionyl chloride (3.9 mL) ) Was added to toluene (30 mL), heated to 90 ° C and stirred for 2 hours. The reaction mixture was concentrated, the resulting residue was diluted with toluene (40 mL), and trimethylsilyl azide (17.7 mL) was added to the solution.
Stir for 7 hours. After completion of the reaction, the reaction solution was concentrated, the residue was washed with a mixed solvent of hexane-ethyl acetate, and the obtained crystals were dried to give the title compound 1- (4-benzyloxyphenyl)
4.33 g of -1,4-dihydrotetrazol-5-one was obtained. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 9.81 (1
H, s), 7.79 (2H, d, J = 9.0 Hz), 7.53-7.37 (5H, m),
7.10 (2H, d, J = 9.0 Hz), 5.12 (2H, s). (2) 2- [4- (5-methoxytetrazol-1-yl) phenoxymethyl] benzothiazole (Step B-1) 1- (4-benzyloxyphenyl) -1,4-dihydrotetrazol-5-one obtained by the method of 1) (0.50 g, 1.86
mmol) was dissolved in 1,2-dichloroethane (10 mL), and silver (I) oxide (0.86 g) and methyl iodide (1.16 m
L), heated to 50 ° C., and stirred for 80 minutes. After completion of the reaction, the reaction solution was filtered using Celite, the solvent of the filtrate was distilled off, and the obtained residue was purified by silica gel chromatography to give 5-methoxy-1- (4-benzyloxyphenyl)-
0.10 g of 1H-tetrazole was obtained.

The obtained 5-methoxy-1- (4-benzyloxyphenyl) -1H-tetrazole (0.10 g, 0.36 mmol) was mixed with 1,2-
Dissolve in dichloroethane (6 mL) and add 5% Pd / C (3
0 mg), and the mixture was stirred at room temperature for 100 minutes under a hydrogen atmosphere.
The reaction solution was filtered using celite, the solvent of the filtrate was distilled off, and the obtained residue was diluted with dimethylformamide (5 mL) .The solution was cooled to 0 ° C., and sodium hydride ( 60% in oil, 17 mg) and 2-iodomethylbenzothiazole (0.12 g) were added, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to obtain the title compound (76 mg). Melting point: 170-173 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 7.6 Hz), 7.91 (1H, d, J = 7.6 Hz), 7.63
(2H, d, J = 9.0 Hz), 7.59-7.42 (2H, m), 7.18 (2H,
d, J = 9.0 Hz), 5.55 (2H, s), 4.30 (3H, s).

[0247]

Example 50 2- [4- (5-methoxytetrazol-1-yl)
[Phenoxymethyl] benzoxazole (Compound No. 7.8) The title compound was synthesized according to the method of Example 49. Melting point: 111-114 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.80-7.
75 (1H, m), 7.63 (2H, d, J = 9.1 Hz), 7.62-7.58 (1
H, m), 7.41-7.37 (2H, m), 7.21 (2H, d, J = 9.1 H
z), 5.39 (2H, s), 4.31 (3H, s).

[0248]

Example 51 2- [4- (Tetrazol-1-yl) phenoxymethyl] benzoxazole (Compound No. 7.3) (B
-1 step) Ethyl orthoformate (13.5 mL) and sodium azide (5.3 mL) were added to an acetic acid solution (30 mL) of p-anisidine (2.0 g, 16.2 mmol).
g) was added, and the mixture was heated to 80 ° C. and stirred for 100 minutes. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water and an aqueous solution of sodium hydrogen carbonate, and dried over anhydrous sodium sulfate. After filtering the desiccant, the solvent was distilled off and 1-
2.76 g of (4-methoxyphenyl) -1H-tetrazole was obtained.

The obtained 1- (4-methoxyphenyl) -1H-tetrazole (0.66 g, 3.75 mmol) was dissolved in methylene chloride (15 mL), and aluminum chloride (1.50 g) and ethanethiol (1.39 g) were added to this solution. mL) at 0 ° C. and stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, washed with water of the extract, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off to obtain 0.56 g of 1- (4-hydroxyphenyl) -1H-tetrazole.

The obtained 1- (4-hydroxyphenyl) -1H-tetrazole (0.20 g, 1.23 mmol) was dissolved in dimethylformamide (10 mL), and the solution was cooled to 0 ° C., and sodium hydride (60% in oil, 0.156 mg) and iodomethylbenzoxazole (0.38 g) were added and stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained crystals were washed with isopropyl ether to give the title compound (0.31 g).
I got Melting point: 175-178 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.90 (1
H, s), 7.81-7.75 (1H, m), 7.64 (2H, d, J = 9.1 Hz),
7.60-7.56 (1H, m), 7.42-7.37 (2H, m), 7.26 (2H, d,
J = 9.1 Hz), 5.42 (2H, s).

[0251]

Example 52 2- [4- (Tetrazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 7.2) The title compound was synthesized according to the method of Example 51. Melting point: 200-203 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.89 (1
H, s), 8.06 (1H, d, J = 7.2 Hz), 7.92 (1H, dd, J =
6.9, 0.9 Hz), 7.63 (2H, d, J = 9.1 Hz), 7.57-7.43
(2H, m), 7.23 (2H, d, J = 9.1 Hz), 5.57 (2H, s).

[0252]

Example 53 2- [2,6-Dichloro-4- (tetrazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 7.5) The title compound was synthesized according to the method of Example 51. Melting point: 142-145 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.99 (1
H, s), 8.06 (1H, d, J = 8.3 Hz), 7.97 (1H, dd, J =
6.6, 0.9 Hz), 7.79 (2H, s), 7.57-7.45 (2H, m), 5.54
(2H, s).

[0253]

Example 54 N '-[4- (Benzothiazol-2-ylmethoxy) benzylidene] -N-methylhydrazine (Compound No. 2)
8.1) (Step A-2) Methylhydrazine (0.09 mL) was added to a solution of 4- (benzothiazol-2-ylmethoxy) benzaldehyde (0.15 g, 0.55 mmol) in ethanol (6 mL), and the mixture was added at room temperature for 30 minutes. 8 at 50 ° C
Stirred for 0 minutes. After completion of the reaction, water was poured into the reaction solution, and the precipitated crystals were filtered. The obtained crystals were washed with isopropyl ether and dried under reduced pressure to obtain 0.10 g of the title compound. Melting point: 114-118 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 8.8 Hz), 7.96 (1H, d, J = 7.9 Hz), 7.51
(1H, s), 7.50 (2H, d, J = 8.8 Hz), 7.49-7.36 (2H,
m), 7.01 (2H, d, J = 8.8 Hz), 5.49 (2H, s), 5.56-
5.40 (1H, br), 2.96 (3H, s).

[0254]

Example 55 N '-[4- (benzoxazol-2-ylmethoxy) benzylidene] -N-methylhydrazine (Compound No. 28.2) The title compound was synthesized according to the method of Example 54. Melting point: 94-96 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.79-7.
74 (1H, m), 7.59-7.48 (1H, m), 7.52 (2H, d, J = 8.8
Hz), 7.51 (1H, s), 7.49-7.32 (2H, m), 7.04 (2H, d,
J = 8.8 Hz), 5.39-5.34 (1H, br), 5.34 (2H, s), 2.
96 (3H, s).

[0255]

Example 56 N '-[4- (benzothiazol-2-ylmethoxy) benzylidene] -N-ethylhydrazine (Compound No. 2)
8.3) The title compound was synthesized according to the method of Example 54. Melting point: 124-127 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.03 (1
H, d, J = 7.2 Hz), 7.90 (1H, d, J = 7.2 Hz), 7.57
(1H, s), 7.56-7.52 (2H, m), 7.51 (2H, d, J = 8.8 H
z), 7.01 (2H, d, J = 8.8 Hz), 5.49 (2H, s), 5.30-
5.10 (1H, br), 3.26 (2H, q, J = 7.1 Hz), 1.22 (3H,
t, J = 7.1 Hz).

[0256]

Example 57 N '-[4- (Benzoxazol-2-ylmethoxy) benzylidene] -N-ethylhydrazine (Compound No. 28.4) The title compound was synthesized according to the method of Example 54. Melting point: 103-106 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.78-7.
74 (1H, m), 7.58-7.49 (1H, m), 7.56 (1H, s), 7.51
(2H, d, J = 8.9 Hz), 7.41-7.34 (2H, m), 7.03 (2H,
d, J = 8.9 Hz), 5.40-5.30 (1H, br), 5.33 (2H, s),
3.26 (2H, q, J = 7.2 Hz), 1.22 (3H, t, J = 7.2 Hz).

[0257]

Example 58 N '-[4- (Benzothiazol-2-ylmethoxy) benzylidene] -N, N-dimethylhydrazine (Compound No. 28.5) The title compound was synthesized according to the method of Example 54. Melting point: 123-124 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, dd, J = 7.3, 0.8 Hz), 7.90 (1H, dd, J = 7.5,
1.3 Hz), 7.53 (2H, d, J = 8.8 Hz), 7.53-7.39 (2H,
m), 7.23 (1H, s), 7.01 (2H, d, J = 8.8 Hz), 5.49
(2H, s), 2.93 (6H, s).

[0258]

Example 59 N ′-[4- (benzoxazol-2-ylmethoxy) benzylidene] -N, N-dimethylhydrazine (Compound No. 28.6) The title compound was synthesized according to the method of Example 54. Melting point: 105-108 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.78-7.
73 (1H, m), 7.58-7.51 (1H, m), 7.53 (2H, d, J = 8.9
Hz), 7.39-7.34 (2H, m), 7.23 (1H, s), 7.03 (2H, d,
J = 8.9 Hz), 5.33 (2H, s), 2.93 (6H, s).

[0259]

Example 60 N ′-[4- (Benzothiazol-2-ylmethoxy) benzylidene] -N-phenylhydrazine (Compound No. 28.7) The title compound was synthesized according to the method of Example 54. Melting point: 178-179 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.7 Hz), 7.91 (1H, d, J = 8.8 Hz), 7.65
(1H, s), 7.62 (2H, d, J = 8.9 Hz), 7.57-7.37 (5H,
m), 7.11 (1H, s), 7.05 (2H, d, J = 8.9 Hz), 6.90-
6.82 (1H, m), 5.30 (2H, s).

[0260]

Example 61 [4- (Benzothiazol-2-ylmethoxy) benzylidene] hydrazide acetate (Compound No. 28.8) The title compound was synthesized according to the method of Example 54. Melting point: 214-217 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.96 (1
H, brs), 8.05 (1H, d, J = 7.0 Hz), 7.90 (1H, d, J =
7.0 Hz), 7.69 (1H, s), 7.62 (2H, d, J = 8.8 Hz),
7.56-7.34 (2H, m), 7.07 (2H, d, J = 8.8 Hz), 5.53
(2H, s), 2.36 (3H, s).

[0261]

Example 62 [4- (Benoxaxazol-2-ylmethoxy) benzylidene] hydrazide (Compound No. 28.
9) The title compound was synthesized according to the method of Example 54. Melting point: 185-187 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.85 (1
H, s), 7.79-7.74 (1H, m), 7.68 (1H, s), 7.62 (2H,
d, J = 8.8 Hz), 7.59-7.55 (1H, m), 7.40-7.35 (2H,
m), 7.10 (2H, d, J = 8.8 Hz), 5.36 (2H, s), 2.36
(3H, s).

[0262]

Example 63 N '-[4- (Benzothiazol-2-ylmethoxy) benzylidene] hydrazinecarboxylic acid methyl ester (Compound No. 28.10) The title compound was synthesized according to the method of Example 54. Melting point: 167-169 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.2 Hz), 7.90 (1H, dd, J = 7.6, 2.0 Hz),
7.87 (1H, brs), 7.80 (1H, brs), 7.65 (2H, d, J =
8.8 Hz), 7.52-7.41 (2H, m), 7.05 (2H, d, J = 8.8 H
z), 5.52 (2H, s), 3.85 (3H, s).

[0263]

Example 64 N ′-[4- (Benoxazol-2-ylmethoxy) benzylidene] hydrazinecarboxylic acid methyl ester (Compound No. 28.11) The title compound was synthesized according to the method of Example 54. Melting point: 132-135 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.01 (1
H, brs), 7.79 (1H, brs), 7.78-7.74 (1H, m), 7.65
(2H, d, J = 8.8 Hz), 7.61-7.53 (1H, m), 7.43-7.35
(2H, m), 7.07 (2H, d, J = 8.8 Hz), 5.36 (2H, s),
3.85 (3H, s).

[0264]

Example 65 2- [4- (5-Chloro-1-methyl-1H-imidazol-2-yl) phenoxymethyl] benzothiazole (Compound No. 20.2) (1) 5-Chloro-2- (4 -Methoxyphenyl) -1-methyl-1H-
Imidazole (Step B-1) N- (4-methoxybenzyl) -N'-methyloxalic acid amide (5.3
To a suspension of 5 g (24.1 mmol) of phosphorus oxychloride (35 mL) was added phosphorus pentachloride (15 g), and the mixture was stirred at 80 ° C for 4 hours. After completion of the reaction, excess phosphorus oxychloride was removed under reduced pressure, and the obtained residue was treated with water, extracted with ethyl acetate, and the extract was washed with brine and dried over anhydrous sodium sulfate. After filtration of the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to give the title compound 5-chloro-2- (4-
3.63 g of (methoxyphenyl) -1-methyl-1H-imidazole was obtained. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.52 (2
H, d, J = 8.6 Hz), 7.03 (1H, s), 6.98 (2H, d, J =
(8.6 Hz), 3.86 (3H, s), 3.63 (3H, s). (2) 2- [4- (5-chloro-1-methyl-1H-imidazol-2-yl) phenoxymethyl] benzothiazole (B -2 step) 5-chloro-2- (4-methoxyphenyl) -1-methyl-1H-imidazole obtained by the method of the above (1) (0.88 g, 3.95 mmol)
l) in methylene chloride (20 mL), and add aluminum chloride (1.05 g) and ethanethiol (1.46 mL) to this solution.
The mixture was added at 0 ° C. and stirred at room temperature for 7 hours. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, washed with water of the extract, and dried over anhydrous sodium sulfate. After filtering the desiccant,
The solvent was distilled off to obtain 0.58 g of 5-chloro-2- (4-hydroxyphenyl) -1-methyl-1H-imidazole.

The obtained 5-chloro-2- (4-hydroxyphenyl) -1-methyl-1H-imidazole (0.29 g, 1.4 mmol) was dissolved in dimethylformamide (8 mL), and the solution was added at 0 ° C.
Then, potassium tert-butoxide (0.156 mg) and iodomethylbenzothiazole (0.38 g) were added, and the mixture was added at room temperature.
Stirred for 20 hours. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. After the drying agent was filtered, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to obtain 0.25 g of the title compound. Melting point: 127-128 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.07-8.
03 (1H, m), 7.93-7.89 (1H, m), 7.55 (2H, d, J = 8.9
Hz), 7.53-7.33 (2H, m), 7.13 (2H, d, J = 8.9 Hz),
7.03 (1H, s), 5.54 (2H, s), 3.63 (3H, s).

[0266]

Example 66 2- [4- (5-Chloro-1-methyl-1H-imidazol-2-yl) phenoxymethyl] benzoxazole (Compound No. 20.3) The title compound was prepared according to the method of Example 65. Synthesized. Melting point: 139-142 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.80-7.
75 (1H, m), 7.60-7.53 (3H, m), 7.43-7.32 (2H, m),
7.15 (2H, d, J = 8.9 Hz), 7.30 (1H, s), 5.38 (2H,
s), 3.63 (3H, s).

[0267]

Example 67 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] ethanone oxime (Compound No. 28.2)
0) (Step A-2) 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] methyl ketone (0.30 g, 1.1 mmol) in methanol (15 mL)-
Hydroxylamine hydrochloride (0.44 g) and triethylamine (0.84 mL) were added to a water (15 mL) solution, and the mixture was stirred at 80 ° C for 30 minutes. The precipitated crystals were filtered, and the obtained crystals were washed with water and methanol and dried to obtain the title compound (0.32 g). Melting point: 224-225 ° C. ¹ H-NMR (200 MHz, CDCl ₃ + DMSO-d ₆ ) spectrum, δ (ppm):
10.55-10.31 (1H, br), 8.03 (1H, d, J = 7.1 Hz), 7.
92 (1H, d, J = 6.8 Hz), 7.32 (4H, ABq, J = 8.8 Hz),
7.58-7.39 (2H, m), 5.51 (2H, m), 2.63 (3H, s).

[0268]

Example 68 4- (Benzothiazol-2-ylmethoxy)
Benzaldehyde O-methyl oxime (Compound No. 2
8.12) The title compound was synthesized according to the method of Example 67. Melting point: 112-114 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.06-7.
88 (3H, m), 7.57-7.41 (4H, m), 7.06-7.02 (2H, m),
5.51 (2H, s), 3.59 (3H, s).

[0269]

Example 69 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] ethanone O-methyloxime (Compound No. 28.14) The title compound was synthesized according to the method of Example 67. Melting point: 104-105 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 8.1 Hz), 7.90 (1H, d, J = 7.8 Hz), 7.32
(4H, ABq, J = 9.2 Hz), 7.50-7.40 (2H, m), 5.51 (2
H, s), 3.97 (3H, s), 2.19 (3H, s).

[0270]

Example 70 1- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] ethanone O-methyloxime (Compound No. 28.20) The title compound was synthesized according to the method of Example 67. Melting point: 118-119 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 8.3 Hz), 7.90 (1H, d, J = 7.6 Hz), 7.54-
7.36 (2H, m), 7.17 (1H, d, J = 8.1 Hz), 6.88-6.83
(2H, m), 5.48 (2H, s), 3.95 (3H, s), 2.34 (3H, s),
2.14 (3H, s).

[0271]

Example 71 1- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] ethanone O-methyloxime (Compound No. 28.18) The title compound was synthesized according to the method of Example 67. Melting point: 68-69 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 8.0 Hz), 7.90 (1H, dd, J = 6.9 Hz), 7.54
-7.41 (2H, m), 7.00 (1H, d, J = 7.8 Hz), 6.91-6.87
(2H, m), 5.74 (2H, s), 3.80 (3H, s), 2.22 (3H,
s), 2.10 (3H, s).

[0272]

Example 72 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] ethanone O-ethyloxime (Compound No. 28.22) The title compound was synthesized according to the method of Example 67. Melting point: 105-108 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.8 Hz), 7.90 (1H, dd, J = 7.8, 2.2 Hz),
7.54-7.37 (2H, m), 7.32 (4H, ABq, J = 9.0 Hz), 5.
51 (2H, s), 4.22 (2H, q, J = 7.0 Hz), 2.20 (3H,
s), 1.32 (3H, t, J = 7.0 Hz).

[0273]

Example 73 1- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] ethanone O-ethyloxime (Compound No. 28.23) The title compound was synthesized according to the method of Example 67. Melting point: 105-107 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.03 (1
H, d, J = 7.5 Hz), 7.90 (1H, dd, J = 6.8, 0.9 Hz),
7.54-7.36 (2H, m), 7.17 (1H, d, J = 8.1 Hz), 6.88
-6.83 (2H, m), 5.48 (2H, s), 4.20 (2H, q, J = 7.0
Hz), 2.35 (3H, s), 2.14 (3H, s), 1.31 (3H, t, J =
7.0 Hz).

[0274]

Example 74 1- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] ethanone O-ethyloxime (Compound No. 28.23) The stereoisomer of Example 73 according to the method of Example 67. The title compound was synthesized. Melting point: 53-54 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.3 Hz), 7.91 (1H, d, J = 7.7 Hz), 7.53-
7.40 (2H, m), 7.00 (1H, d, J = 7.8 Hz), 6.91-6.85
(2H, m), 5.47 (2H, s), 4.06 (2H, q, J = 6.9 Hz),
2.22 (3H, s), 2.10 (3H, s), 1.20 (3H, t, J = 6.9 H
z).

[0275]

Example 75 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] ethanone O-isopropyloxime (Compound No. 28.26) The title compound was synthesized according to the method of Example 67. Melting point: 105-107 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 8.0 Hz), 7.90 (1H, dd, J = 7.7, 1.5 Hz),
7.58-7.36 (2H, m), 7.33 (4H, ABq, J = 8.5 Hz), 5.
51 (2H, s), 4.43 (1H, quintet, J = 6.3 Hz), 2.16
(3H, s), 1.29 (6H, d, J = 6.3 Hz).

[0276]

Example 76 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] ethanone O-allyl oxime (Compound No. 28.21) The title compound was synthesized according to the method of Example 67. Melting point: 83-85 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, dd, J = 8.8, 1.6 Hz), 7.90 (1H, dd, J = 8.3, 1.
6 Hz), 7.57-7.36 (2H, m), 7.32 (4H, ABq, J = 9.0 H
z), 6.13-5.96 (1H, m), 5.51 (2H, s), 5.37-5.19 (2
H, m), 4.68 (2H, d, J = 5.7 Hz), 2.26 (3H, s).

[0277]

Example 77 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] ethanone O-tert-butyloxime (Compound No. 28.25) The title compound was synthesized according to the method of Example 67. Melting point: 122-124 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 8.5 Hz), 7.90 (1H, d, J = 6.8 Hz), 7.51-
7.40 (2H, m), 7.34 (4H, ABq, J = 9.0 Hz), 5.51 (2
H, s), 2.17 (3H, s), 1.34 (9H, s).

[0278]

Example 78 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] ethanone O-benzyloxime (Compound No. 28.27) Melting point: 98-100 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum δ (ppm): 8.04 (1
H, dd, J = 7.3, 0.9 Hz), 7.90 (1H, dd, J = 7.5, 0.
9 Hz), 7.51-7.32 (7H, m), 7.32 (4H, ABq, J = 9.1 H
z), 5.51 (2H, s), 5.21 (2H, s), 2.24 (3H, s).

[0279]

Example 79 2- [4- (1H-pyrazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 1.5) (A
-2 step) 1- [4- (benzothiazol-2-ylmethoxy) phenyl] -3-
Hydrazine monohydrate (0.05 mL) was added to a solution of dimethylaminopropenone (0.30 g, 0.89 mmol) in ethanol (5 mL), and the mixture was heated under reflux for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, ethyl acetate was added, the solution was washed with water and brine, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was washed with isopropyl ether to obtain 0.22 g of the title compound. Melting point: 192-194 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.5 Hz), 7.91 (1H, d, J = 6.8 Hz), 7.71
(2H, d, J = 8.7 Hz), 7.60 (1H, d, J = 2.3 Hz), 7.5
5-7.40 (2H, m), 7.10 (2H, d, J = 8.7 Hz), 6.55 (1
H, d, J = 2.3 Hz), 5.53 (2H, s).

[0280]

Working Example 80 2- [3-Methyl-4- (2-pyrazol-3-yl)
[Phenoxymethyl] benzothiazole (Compound No. 1.
13) The title compound was synthesized according to the method of Example 79. Melting point: 137-138 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, br.d, J = 8.2 Hz), 7.90 (1H, dd, J = 6.8, 1.2 H
z), 7.62 (1H, d, J = 2.1 Hz), 7.54-7.32 (4H, m), 6.
98-6.88 (2H, m), 6.39 (1H, d, J = 2.0 Hz), 5.51 (2
H, s), 2.41 (3H, s).

[0281]

Example 81 a) 2- [4- (2-Methyl-2H-pyrazole-3-
Yl) phenoxymethyl] benzothiazole (Compound No. 1.7) and b) 2- [4- (1-methyl-1H-pyrazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 2.1) (A- 2 steps) To a solution of 1- [4- (benzothiazol-2-ylmethoxy) phenyl] -3-dimethylaminopropenone (0.30 g, 0.89 mmol) in ethanol (5 mL) obtained according to the method of Example 118. Methylhydrazine (0.06 mL) was added, and the mixture was heated under reflux for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, ethyl acetate was added, the solution was washed with water and brine, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography.
Title compound a) 2- [4- (2-methyl-2H-pyrazol-3-yl)
0.14 g of phenoxymethyl] benzothiazole and 90 mg of the title compound b) 2- [4- (1-methyl-1H-pyrazol-3-yl) phenoxymethyl] benzothiazole were obtained. a) Melting point: 125-131 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 8.0 Hz), 7.92 (1H, d, J = 6.8 Hz), 7.56-
7.40 (2H, m), 7.50 (1H, d, J = 2.0 Hz), 7.25 (4H, A
Bq, J = 8.8 Hz), 6.26 (1H, d, J = 2.0 Hz), 5.54 (2
B) Melting point: 150-153 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1H, s), 3.86 (3H, s).
H, d, J = 7.8 Hz), 7.90 (1H, dd, J = 6.9, 1.3 Hz),
7.54-7.37 (2H, m), 7.40 (4H, ABq, J = 8.9 Hz), 7.
35 (1H, d, J = 2.5 Hz), 6.46 (1H, d, J = 2.5 Hz),
5.51 (2H, s), 3.93 (3H, s).

[0282]

Example 82 2- [4- (2-Ethyl-2H-pyrazol-3-yl)
[Phenoxymethyl] benzothiazole (Compound No. 1.
12) The title compound was synthesized according to the method of Example 81. Melting point: 89-92 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.06 (1
H, dd, J = 7.8, 1.1 Hz), 7.92 (1H, d, J = 7.3 Hz),
7.53 (1H, d, J = 1.8 Hz), 7.51-7.38 (2H, m), 7.24
(4H, ABq, J = 8.7 Hz), 6.23 (1H, d, J = 1.8 Hz),
5.55 (2H, s), 4.15 (2H, q, J = 7.0 Hz), 1.41 (3H,
t, J = 7.0 Hz).

[0283]

Example 83 2- [4- (1-Ethyl-1H-pyrazol-3-yl)
[Phenoxymethyl] benzothiazole (Compound No. 2.
2) The title compound was synthesized according to the method of Example 81. Melting point: 103-104 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 8.1 Hz), 7.90 (1H, d, J = 7.7 Hz), 7.54-
7.36 (2H, m), 7.41 (4H, ABq, J = 8.9 Hz), 7.40 (1
H, d, J = 2.1 Hz), 6.46 (1H, d, J = 2.1 Hz), 5.52
(2H, s), 4.21 (2H, q, J = 7.3 Hz), 1.52 (3H, t, J
= 7.3 Hz).

[0284]

Example 84 2- [3-Methyl-4- (1-methyl-1H-pyrazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 2.3) The title compound was prepared according to the method of Example 81. Synthesized. Melting point: 125-127 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.03 (1
H, br.d, J = 8.0 Hz), 7.90 (1H, dd, J = 7.3, 1.5 H
z), 7.54-7.40 (3H, m), 7.37 (1H, d, J = 2.2 Hz),
6.94-6.87 (2H, m), 6.33 (1H, d, J = 2.4 Hz), 5.51
(2H, s), 3.94 (3H, s), 2.45 (3H, s).

[0285]

Working Example 85 2- [4- (1-Ethyl-1H-pyrazol-3-yl)
3-Methylphenoxymethyl] benzothiazole (Compound No. 2.25) The title compound was synthesized according to the method of Example 81. Physical properties: Oil ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.03 (1
H, dd, J = 8.1, 1.5 Hz), 7.90 (1H, dd, J = 8.2, 1.
2 Hz), 7.55-7.35 (3H, m), 7.40 (1H, d, J = 2.2 H
z), 6.95-6.84 (2H, m), 6.32 (1H, d, J = 2.3 Hz),
5.50 (2H, s), 4.20 (2H, q, J = 7.3 Hz), 2.45 (3H,
s), 1.52 (3H, t, J = 7.3 Hz).

[0286]

Working Example 86 2- [4- (1-Ethyl-1H-pyrazol-3-yl)
[-3-methylphenoxymethyl] benzoxazole (Compound No. 2.26) The title compound was synthesized according to the method of Example 81. Physical properties: Oil ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.79-7.
73 (1H, m), 7.60-7.53 (1H, m), 7.50 (1H, d, J = 8.7
Hz), 7.41 (1H, d, J = 2.3 Hz), 7.40-7.32 (2H, m),
6.95-6.88 (2H, br.m), 6.32 (1H, d, J = 2.2 Hz),
5.34 (2H, s), 4.21 (2H, q, J = 7.3 Hz), 2.45 (3H,
s), 1.52 (3H, t, J = 7.3 Hz).

[0287]

Example 87 2- [3-Methyl-4- (2-methyl-2H-pyrazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 1.17) The title compound was prepared according to the method of Example 81. Synthesized. Melting point: 89-90 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, br.d, J = 7.4 Hz), 7.92 (1H, br.d, J = 7.2 Hz),
7.57-7.37 (2H, m), 7.52 (1H, d, J = 1.7 Hz), 7.15
(1H, d, J = 8.4 Hz), 6.99-6.88 (2H, m), 6.16 (1H,
d, J = 1.8 Hz), 5.52 (2H, s), 3.64 (3H, s), 2.15 (3
H, s).

[0288]

Example 88 2- [3-Methyl-4- (2-methyl-2H-pyrazol-3-yl) phenoxymethyl] benzoxazole (Compound No. 1.29) The title compound was prepared according to the method of Example 81. Synthesized. Melting point: 57-58 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.81-7.7
5 (1H, m), 7.60-7.55 (1H, m), 7.52 (1H, d, J = 1.9
Hz), 7.41-7.35 (2H, m), 7.15 (1H, d, J = 8.1 Hz),
7.02-6.92 (2H, m), 6.16 (1H, d, J = 1.9 Hz), 5.37
(2H, s), 3.64 (3H, s), 2.14 (3H, s).

[0289]

Working Example 89 2- [4- (2-ethyl-2H-pyrazol-3-yl)
[-3-methylphenoxymethyl] benzothiazole (Compound No. 1.31) The title compound was synthesized according to the method of Example 81. Physical properties: Oil ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, br.d, J = 7.2 Hz), 7.91 (1H, dd, J = 7.6, 1.5 H
z), 7.55 (1H, d, J = 1.8 Hz), 7.56-7.36 (2H, m), 7.
14 (1H, d, J = 8.3 Hz), 7.05-6.88 (2H, m), 6.14 (1
H, d, J = 1.8 Hz), 5.52 (2H, s), 3.91 (2H, q, J =
7.2 Hz), 2.13 (3H, s), 1.30 (3H, t, J = 7.2 Hz).

[0290]

Working Example 90 2- [4- (2-Ethyl-2H-pyrazol-3-yl)
[-3-methylphenoxymethyl] benzoxazole (Compound No. 1.32) The title compound was synthesized according to the method of Example 81. Melting point: 43-45 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.82-7.
74 (1H, m), 7.62-7.50 (1H, m), 7.55 (1H, d, J = 1.8
Hz), 7.45-7.32 (2H, m), 7.15 (1H, d, J = 8.3 Hz),
7.04-6.92 (2H, m), 6.14 (1H, d, J = 1.8 Hz), 5.37
(2H, s), 3.91 (2H, q, J = 7.2 Hz), 2.13 (3H, s),
1.30 (3H, t, J = 7.2 Hz).

[0291]

Example 91 2- [4- (2-tert-butyl-2H-pyrazole-3-
Yl) -3-methylphenoxymethyl] benzothiazole (Compound No. 1.33) The title compound was synthesized according to the method of Example 81. Melting point: 107-108 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, br.d, J = 7.7 Hz), 7.92 (1H, dd, J = 7.7, 1.1 H
z), 7.56-7.37 (2H, m), 7.50 (1H, d, J = 1.6 Hz),
7.17 (1H, d, J = 8.1 Hz), 6.95-6.84 (2H, m), 6.05
(1H, d, J = 1.8 Hz), 5.51 (2H, s), 2.10 (3H, s),
1.43 (9H, s).

[0292]

Example 92 3- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] pyrazole-1-carboxylic acid dimethylamide (Compound No. 2.30) The title compound was prepared according to the method of Example 81. Synthesized. Melting point: 83-84 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.17 (1
H, d, J = 2.7 Hz), 8.04 (1H, dd, J = 8.0, 0.8 Hz),
7.90 (1H, dd, J = 7.9, 1.9 Hz), 7.55-7.36 (3H,
m), 6.96-6.87 (2H, m), 6.49 (1H, d, J = 2.6 Hz),
5.52 (2H, s), 3.28 (6H, br.s), 2.50 (3H, s).

[0293]

Example 93 3- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] pyrazole-1-carboxylic acid diethylamide (Compound No. 2.31) The title compound was synthesized according to the method of Example 81. did. Melting point: 126-128 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.20 (1
H, d, J = 2.8 Hz), 8.04 (1H, dd, J = 8.6, 0.9 Hz),
7.90 (1H, dd, J = 7.3, 1.2 Hz), 7.55-7.36 (3H, m)
6.98-6.89 (2H, m), 6.49 (1H, d, J = 2.7 Hz), 5.52
(2H, s), 3.68 (2H, br.q, J = 7.0 Hz), 2.50 (3H,
s), 1.30 (3H, t, J = 7.0 Hz).

[0294]

Example 94 3- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] pyrazole-1-sulfonic acid dimethylamide (Compound No. 2.34) The title compound was prepared according to the method of Example 81. Synthesized. Melting point: 130-131 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, br.d, J = 8.0 Hz), 7.99 (1H, d, J = 2.7 Hz), 7.9
0 (1H, dd, J = 7.7, 1.4 Hz), 7.55-7.35 (3H, m), 6.9
7-6.88 (2H, m), 6.52 (1H, d, J = 2.7 Hz), 5.52 (2
H, s), 2.99 (6H, s), 2.50 (3H, s).

[0295]

Example 95 a) 2- [4- (Benzothiazol-2-ylmethoxy) phenyl] -5-methyl-2,4-dihydropyrazole-3
-One (Compound No. 13.1) and b) 2- [4- (5-ethoxy-3-methylpyrazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 14.6) (Step A-2) J . O. C. , 30, 3946 (1965), obtained according to the method described in 4- (benzothiazol-2-ylmethoxy).
Phenylhydrazine hydrochloride (1.33 g, 4.3 mmol) was dissolved in ethanol (13 mL), and sodium acetate (0.
44 g) and ethyl 3-oxobutyrate (0.55 mL) were added, and the mixture was heated to 80 C and stirred for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, and the extract was washed with brine and dried over anhydrous sodium sulfate. After filtration of the drying agent, the solvent is distilled off and the residue obtained is purified by silica gel chromatography to give the title compound a)
2- [4- (benzothiazol-2-ylmethoxy) phenyl] -5-
80 mg of methyl-2,4-dihydropyrazol-3-one and 0.21 g of the title compound b) 2- [4- (5-ethoxy-3-methylpyrazol-1-yl) phenoxymethyl] benzothiazole were obtained. a) Melting point: 181-186 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.03 (1
H, d, J = 7.5Hz), 7.89 (1H, dd, J = 7.9, 0.9Hz), 7.
77 (2H, d, J = 9.1Hz), 7.50 (1H, td, J = 7.6, 1.1H
z), 7.40 (1H, td, J = 7.4, 1.2Hz), 7.06 (2H, d, J
= 9.2 Hz), 5.49 (2H, s), 3.40 (2H, s), 2.18 (3H, s). B) Melting point: 150-153 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm) : 8.03 (1
H, d, J = 8.0 Hz), 7.90 (1H, dd, J = 8.4, 0.7 Hz),
7.62 (2H, d, J = 9.1 Hz), 7.50 (1H, td, J = 8.2,
1.1 Hz), 7.40 (1H, td, J = 7.5, 1.4 Hz), 7.06 (2H,
d, J = 9.1 Hz), 5.50 (2H, s), 5.45 (1H, s), 4.11
(2H, q, J = 7.0 Hz), 2.25 (3H, s), 1.41 (3H, t, J
= 7.1 Hz).

[0296]

Example 96 2- (4-Pyrazol-1-ylphenoxymethyl) benzothiazole (Compound No. 14.2) The title compound was synthesized according to the method of Example 95. Melting point: 167-170 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1H,
d, J = 8.1Hz), 7.91 (1H, dd, J = 8.4, 2.2Hz), 7.83 (1H,
d, J = 2.2Hz), 7.69 (1H, br.s), 7.63 (2H, d, J = 9.1Hz),
7.59-7.38 (2H, m), 7.13 (2H, d, J = 9.1Hz), 6.45-6.42
(1H, m), 5.53 (2H, s).

[0297]

Example 97 2- (4-Pyrazol-1-ylphenoxymethyl) benzoxazole (Compound No. 14.1) The title compound was synthesized according to the method of Example 95. Melting point: 85-86 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.83 (1H,
d, J = 2.2Hz), 7.79-7.74 (1H, m), 7.69 (1H, d, J = 1.7H
z), 7.62 (2H, d, J = 9.2Hz), 7.63-7.54 (1H, m), 7.40-7.
36 (2H, m), 7.15 (2H, d, J = 9.2Hz), 6.45-6.42 (1H, m),
5.36 (2H, s).

[0298]

Example 98 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] pyrrolidin-2-one (Compound No. 5.2) (1) N- [4- (Benzothiazol-2-ylmethoxy) phenyl] -4-Bromobutyramide 4-Bromobutyric acid (0.50 g) and thionyl chloride (0.44 mL) were added to toluene (10 mL), and the reaction solution was added.
The mixture was refluxed for 2 hours. After the reaction solution was cooled to room temperature, it was concentrated under reduced pressure, the obtained residue was diluted with methylene chloride (10 mL), the solution was cooled to 0 ° C., and 4- (benzothiazol-2-ylmethoxy) was added to the reaction solution. Aniline (0.76 g, 0.30 mmol) and triethylamine (0.46 mL) were added, and the mixture was stirred for 2 hours.
After completion of the reaction, the reaction solution was poured into an aqueous ammonium chloride solution,
The mixture was extracted with methylene chloride, and the extract was washed with water and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent is distilled off,
The obtained crude crystals were recrystallized using a mixed solvent of hexane-methylene chloride to give the title compound N- [4- (benzothiazole
-2-ylmethoxy) phenyl] -4-bromobutyramide 0.17 g
I got Melting point: 163-165 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05-8.
01 (1H, m), 7.93-7.88 (1H, m), 7.51-7.40 (4H, m),
7.11 (1H, br.), 7.01 (2H, d, J = 8.9 Hz), 5.47 (2
H, s), 3.54 (2H, t, 6.4 Hz), 2.55 (2H, t, J = 6.4
Hz), 2.24 (2H, t, J = 6.4 Hz). (2) 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] pyrrolidin-2-one (Step A-2) The method of (1) above. N- [4- (benzothiazole-2) obtained by
-Ylmethoxy) phenyl] -4-bromobutyramide (0.10
g, 0.25 mmol) in dimethylformamide (3 mL) .Sodium hydride (10 mg) was added to this solution at 0 ° C, and the mixture was stirred at 0 ° C for 30 minutes, at room temperature for 4 hours, and at 50 ° C for 4 hours. did. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, and the extract was washed with water and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to give the title compound (26 m).
g. Melting point: 193-197 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.03 (1
H, dd, J = 8.1, 0.7 Hz), 7.90 (1H, dd, J = 6.8, 1.
2 Hz), 7.56-7.36 (4H, m), 7.08-7.02 (2H, m), 5.48
(2H, s), 3.82 (2H, t, J = 7.0Hz), 2.59 (2H, t, J =
8.2 Hz), 2.14 (2H, quintet, J = 7.6 Hz).

[0299]

Example 99 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] piperidin-2-one (Compound No. 5.9) The title compound was synthesized according to the method of Example 98. Melting point: 169-173 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.03 (1
H, d, J = 8.1 Hz), 7.90 (1H, dd, J = 7.2, 1.2 Hz),
7.55-7.36 (2H, m), 7.20-7.15 (2H, m), 7.09-7.03
(2H, m), 5.30 (2H, s), 3.62-3.56 (2H, m), 2.56-2.5
1 (2H, m), 1.96-1.89 (4H, m).

[0300]

Example 100 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] azepan-2-one (Compound No. 5.1)
3) The title compound was synthesized according to the method of Example 98. Melting point: 153-155 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.03 (1
H, br.d, J = 7.3 Hz), 7.90 (1H, dd, J = 5.8, 2.1 H
z), 7.55-7.35 (2H, m), 7.15 (2H, br.d, J = 9.0Hz),
7.03 (2H, br.d, J = 9.0Hz), 5.48 (2H, s), 3.78-3.
63 (2H, m), 2.78-2.58 (2H, m), 1.98-1.70 (6H, m).

[0301]

Working Example 101 2- [4- (4,5-dihydrooxazole-2-
Yl) phenoxymethyl] benzothiazole (compound number 16.2) (1) O-ethyl, O-4- (4,5-dihydrooxazol-2-yl) phenyl carbonate (Step B-1) 4-ethoxycarbonyloxy Benzoaldehyde (3.06 g,
Concentrated sulfuric acid (2.7 mL) in benzene (25 mL) solution of 15.8 mmol)
Was gradually added dropwise, and 2-azidoethanol (1.42 g) was added little by little, followed by stirring at room temperature for 15 minutes. After completion of the reaction, water was added to the reaction solution, and the pH was adjusted to 8 by further adding potassium carbonate, extracted with ethyl acetate, and the extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the desiccant, the solvent was distilled off to obtain 3.08 g of the title compound O-ethyl, O-4- (4,5-dihydrooxazol-2-yl) phenyl carbonate. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.98 (2
H, d, J = 9.0 Hz), 7.24 (2H, d, J = 9.0 Hz), 4.50-
4.28 (4H, m), 4.07 (2H, q, J = 7.1 Hz), 1.40

(3H, t, J = 7.1 Hz). (2) 4- (4,5-dihydrooxazol-2-yl) phenol (Step B-2) O-ethyl obtained by the method of the above (1) , O-4- (4,5-dihydrooxazol-2-yl) phenyl carbonate (1.06
g, 4.49 mmol) in tetrahydrofuran (6 mL),
Aqueous ammonia (28%, 1 mL) was added to this solution, and
Stirred for hours. After completion of the reaction, the reaction solution was acidified, extracted with ethyl acetate, and the extract was washed with brine and dried and concentrated to obtain 0.45 g of the title compound 4- (4,5-dihydrooxazol-2-yl) phenol. . ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 10.05
(1H, s), 7.71 (2H, d,

J = 8.7 Hz), 6.82 (2H, d, J = 8.7 Hz),
4.34 (2H, t, J = 9.1 Hz), 3.90 (2H, t, J = 9.1 H
z). (3) 2- [4- (4,5-dihydrooxazol-2-yl) phenoxymethyl] benzothiazole (Step A-1) 4- (4,5- Dihydrooxazol-2-yl) phenol (0.17 g, 1.0 mmol) was dissolved in dimethylformamide (3 mL), and 2-bromomethylbenzothiazole (0.24 g) and cesium carbonate were added to the solution at 0 ° C.
(0.35 g), and the mixture was stirred at room temperature for 4 hours. After the reaction,
The precipitated crystals were collected by filtration, and the obtained crystals were washed with a mixed solvent of water and ethanol to obtain 0.23 g of the title compound. Melting point: 189-191 ° C ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 8.17-
8.03 (2H, m), 7.85 (2H, d, J = 8.8Hz), 7.57-7.48
(2H, m), 7.20 (2H, d, J = 8.8Hz), 5.69 (2H, s), 4.
39 (2H, t, J = 9.0Hz), 3.93 (2H, t, J = 9.4Hz).

[0304]

Working Example 102 2- [4- (2-Methyloxazol-5-yl)
Phenoxymethyl] benzothiazole (Compound No. 1
7.2) Melting point: 167-169 ° C (1) 4-Acetylaminoacetylphenyl benzoate 4-aminoacetylphenyl benzoate hydrochloride (1.87 g, 6.
(4 mmol) in chloroform (20 mL) at 0 ° C was added to triethylamine (1.8 mL) and acetyl chloride (0.49 mL).
Were sequentially added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, and the extract was dried and concentrated to obtain 1.70 g of 4-acetylaminoacetylphenyl benzoate as the title compound. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.23-8.
19 (2H, m), 8.11-8.07 (2H, m), 7.72-7.64 (1H, m),
7.56-7.50 (2H, m), 7.39 (3H, d, J = 8.8 Hz), 6.58-
6.52 (1H, m), 4.79 (2H, d, J = 4.3 Hz), 2.12 (3H,
s). (2) 4- (2-Methyloxazol-5-yl) phenyl benzoate (Step B-1) 4-Acetylaminoacetylphenyl benzoate obtained by the method of the above (1) (0.30 g, 1.0 mmol) ) Was added to phosphorus oxychloride (4 mL), and the mixture was heated to reflux for 2 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, the mixture was poured into water, extracted with ethyl acetate, and the extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the desiccant,
The solvent was distilled off to obtain 0.14 g of the title compound, 4- (2-methyloxazol-5-yl) phenyl benzoate. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.24-8.
19 (2H, m), 7.70-7.62 (3H, m), 7.57-7.49 (2H, m),
7.30-7.22 (3H, m), 2.55 (3H, s). (3) 4- (2-methyloxazol-5-yl) phenol (Step B-2) Benzoic acid 4 obtained by the method of (2) above. -(2-methyloxazol-5-yl) acetylaminoacetylphenyl (0.1
4 g, 0.50 mmol) was dissolved in ethanol (5 mL), and to this solution was added a 2.5N aqueous sodium hydroxide solution (0.6 mL) to give 50
The mixture was stirred at ℃ for 10 minutes. After completion of the reaction, the reaction solution was adjusted to pH 4 by adding 1N hydrochloric acid, and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was recrystallized from a mixed solvent of methylene chloride-hexane to give the title compound 4- (2-methyloxazol-5-yl) phenol 59 mg
I got ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.50 (2
H, d, J = 8.8 Hz), 7.08 (1H, s), 6.88 (2H, d, J =
(8.8 Hz), 2.51 (3H, s). (4) 2- [4- (2-methyloxazol-5-yl) phenoxymethyl] benzothiazole (Step A-1) 4 obtained by the method of (3) above. -(2-Methyloxazole-
(5-yl) phenol (59 mg, 0.29 mmol) was dissolved in dimethylformamide (3 mL), 2-bromomethylbenzthiazole (74 mg) and sodium hydride (15 mg) were added to this solution, and the mixture was stirred at room temperature for 2 hours. did. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the desiccant,
The solvent was distilled off, and the obtained residue was recrystallized using a mixed solvent of methylene chloride-hexane to obtain the title compound (59 mg). Melting point: 167-169 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.07-7.
89 (2H, m), 7.58-7.34 (4H, m), 7.12-7.06 (3H, m),
5.53 (2H, s), 2.52 (3H, s).

[0305]

Example 103 2- [4- (5-Chloromethyl-5-methyl-4,5-
Dihydroisoxazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 18.3) (1) 5-chloromethyl-3- (4-methoxyphenyl) -5-methyl-4,5-dihydroisoxazole (Step B-1) 4-methoxybenzaldehyde oxime (4.52 g, 30.0 mm
ol) in dimethylformamide (40 mL) solution.
4-Dioxane solution, 9 mL) and OXONE (trademark)
(9.5 g) was added and the mixture was stirred at room temperature for 1 day. After the reaction,
The reaction solution was poured into water and extracted with ether. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off to obtain 6.74 g of a solid.

0.98 g of the obtained solid was dissolved in methylene chloride, and 3-chloro-2-methyl-2-propene (0.99 g) was added to this solution.
g), potassium carbonate (0.70 g), benzyltriethylammonium chloride (30 mg) and water (1 mL).
Stirred for hours. After completion of the reaction, the reaction solution was poured into water and extracted with methylene chloride. The extract was washed with water and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to give the title compound 5-chloromethyl-3- (4-methoxyphenyl) -5-methyl-4,5-dihydroiso. 0.91 g of xazole was obtained. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.60 (2
H, d, J = 9.0 Hz), 6.92 (2H, d, J = 9.0 Hz), 3.85
(3H, s), 3.60 (2H, s), 3.29 (2H, ABq, J = 17.0 H
z), 1.61 (3H, s). (2) 5-chloromethyl-3- (4-hydroxyphenyl) -5-methyl-4,5-dihydroisoxazole (Step B-2) 5-chloromethyl-3- (4-methoxyphenyl) -5-methyl-4,5-dihydroisoxazole obtained by the method
(0.21 g, 0.90 mmol) was dissolved in methylene chloride (3 mL).
After cooling to ℃, boron tribromide (1M methylene chloride solution, 1.8 mL) was added to the reaction mixture, and the mixture was stirred at 0 ℃ for 1 hour and at room temperature for 1 hour. After completion of the reaction, the reaction solution was added to water, extracted with methylene chloride, and the extract was dried over anhydrous sodium sulfate.
After filtering the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to give the title compound 5-chloromethyl-3- (4-hydroxyphenyl) -5-methyl-4,5-dihydroiso. 0.17 g of xazole was obtained. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.54 (2
H, d, J = 8.8 Hz), 6.87 (2H, d, J = 8.8 Hz), 3.60
(2H, s), 3.30 (2H, ABq, J = 17.0 Hz), 1.61 (3H,
s). (3) 2- [4- (5-chloromethyl-5-methyl-4,5-dihydroisoxazol-3-yl) phenoxymethyl] benzothiazole (Step A-1) 5-Chloromethyl-3- (4-hydroxyphenyl) -5-methyl-4,5-dihydroisoxazole (0.10 g, 0.47 mmol) obtained by the method was dissolved in acetone (4 mL), and to this solution, At room temperature 2-bromomethylbenzothiazole (0.2
1 g) and cesium carbonate (0.17 g) were added, and the mixture was stirred at room temperature for 2 hours. After the completion of the reaction, the resulting crystals were filtered, and the obtained crude crystals were recrystallized from a mixed solvent of hexane-ethyl acetate to give the title compound (0.18 g). Melting point: 120-122 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.07-7.
88 (2H, m), 7.64-7.41 (4H, m), 7.09-7.04 (2H, m),
5.53 (2H, s), 3.59 (2H, s), 3.28 (2H, ABq, J = 17 H
z), 1.60 (3H, s).

[0307]

Example 104 2- [4- (5-Methyl- [1,2,4] oxadiazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 12.1) (Step A-2) (Benzothiazol-2-ylmethoxy) -N-hydroxybenzamidine (0.30 g, 1.0 mmol) was diluted in toluene (10 mL), acetic anhydride (0.28 mL) was added to the reaction solution, and the mixture was heated under reflux for 19 hours. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, an aqueous solution of sodium hydrogen carbonate and brine, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the residue was purified by silica gel chromatography to obtain 0.17 g of the title compound. Melting point: 180-182 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.07-8.
00 (1H, m), 7.91 (1H, dd, J = 7.1, 1.0 Hz), 7.59 (4
H, ABq, J = 9.1 Hz), 7.55-7.42 (2H, m), 5.56 (2H,
s), 2.61 (3H, s).

[0308]

Example 105 2- [4- (5-trifluoromethyl- [1,2,4]
[Oxadiazol-3-yl) phenoxymethyl] benzothiazole (Compound No. 12.2) The title compound was synthesized according to the method of Example 104. Melting point: 150-153 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.09 (1
H, d, J = 6.1 Hz), 7.91 (1H, dd, J = 9.5, 1.8 Hz),
7.63 (4H, ABq, J = 9.2 Hz), 7.53-7.38 (2H, m), 5.5
8 (2H, s).

[0309]

Working Example 106 2- [4- (5-Methyl- [1,3,4] oxadiazol-2-yl) phenoxymethyl] benzothiazole (Compound No. 19.3) (Step A-2) 4- (Benzothiazol-2-ylmethoxy) benzoic acid hydrazide (0.15 g, 0.49 mmol) was dissolved in pyridine (5 mL),
Ethyl acetimidate hydrochloride (71 mg) was added, and the mixture was heated under reflux for 3 hours. After completion of the reaction, the reaction solution was poured into water, and the precipitated crystals were collected by filtration. The obtained crude crystals were recrystallized from a mixed solvent of methylene chloride-hexane to give the title compound (0.11 g). Melting point: 168-171 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.07-7.
89 (4H, m), 7.53-7.42 (2H, m), 7.18-7.13 (2H, m),
5.56 (2H, s), 2.60 (3H, s).

[0310]

Example 107 4- (Benzothiazol-2-ylmethoxy) phenyl-1,3-oxazolidin-2-one (Compound No. 22.3) The title compound was synthesized according to the method of Example 106. Melting point: 206-209 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.03 (1
H, d, J = 7.3Hz), 7.90 (1H, dd, J = 7.1, 1.0Hz), 7.55-
7.37 (4H, m), 7.06 (2H, d, J = 9.1Hz), 5.49 (2H, s),
4.51-4.43 (2H, m), 4.06-3.98 (2H, m).

[0311]

Example 108 4- (Benzothiazol-2-ylmethoxy) phenyl-5-tert-butyl-4-oxazolin-2-one (Compound No. 21.2) The title compound was synthesized according to the method of Example 106. . Melting point: 171-174 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
(H, d, J = 7.4Hz), 7.91 (1H, d, J = 7.6Hz), 7.55-7.38
(4H, m), 7.09 (2H, d, J = 9.0Hz), 6.41 (1H, s), 5.50
(2H, s), 1.25 (9H, s).

[0312]

Working Example 109 4- (Benzothiazol-2-ylmethoxy) phenyl-5-tert-butyl-4-chloro-4-oxazoline-
2-one (Compound No. 21.3) The title compound was synthesized according to the method of Example 106. Melting point: 139-142 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 7.5Hz), 7.91 (1H, dd, J = 7.5, 2.0Hz), 7.56-
7.38 (2H, m), 7.30 (2H, d, J = 9.1Hz), 7.13 (2H, d,
J = 9.1Hz), 5.52 (2H, s), 1.35 (9H, s).

[0313]

Example 110 2-[(4-benzothiazol-2-yl) -3-
Methylphenoxymethyl) benzothiazole (Compound No. 26.7) The title compound was synthesized according to the method of Example 106. Melting point: 145-148 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.06 (2
H, dd, J = 8.0, 1.9 Hz), 7.91 (2H, dd, J = 7.3, 1.
4 Hz), 7.75 (1H, d, J = 8.4 Hz), 7.60-7.33 (4H,
m), 7.04-6.93 (2H, m), 5.55 (2H, s), 2.67 (3H, s).

[0314]

Example 111 4- (Benzothiazol-2-ylmethoxy) -N-hydroxybenzamidine (Compound No. 28.2)
8) (Step A-2) 4- (benzothiazol-2-ylmethoxy) benznitrile (1.50 g, 5.6) prepared according to the method of Example 112 below.
mmol) was added to a mixed solvent of ethanol (50 mL) -water (10 mL), and hydroxylamine hydrochloride (2.34 g)
And sodium acetate (3.0 g) were added, and the mixture was heated under reflux for 18 hours. After completion of the reaction, the reaction solution was cooled, extracted with ethyl acetate, and the organic layer was washed and dried over anhydrous sodium sulfate.
After filtration of the drying agent, the solvent was distilled off.
The residue was washed with a mixed solvent of -ethyl acetate to obtain 1.12 g of the title compound 4- (benzothiazol-2-ylmethoxy) -N-hydroxybenzamidine. Melting point: 174-177 ° C. ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 9.64
(1H, br.), 8.14 (1H, d, J = 7.5 Hz), 8.10 (1H, d,
J = 8.0 Hz), 7.39 (4H, ABq, J = 8.4 Hz), 7.90-7.44
(2H, m), 6.03 (2H, br.), 5.66 (2H, s).

[0315]

Example 112 4- (Benzothiazol-2-ylmethoxy) benzaldehyde (Compound No. 51.48) (A-
3 steps) A solution of 4-hydroxybenzaldehyde (2.01 g, 16.4 mmol) in dimethylformamide (30 mL) was cooled to 0 ° C, and potassium tert-butoxy (1.84 g) and 2-iodomethylbenzothiazole (4.53 g) were added to the reaction mixture. g) was added and the mixture was stirred at 0 ° C for 50 minutes and at room temperature for 20 hours. After completion of the reaction, water was poured into the reaction solution, and the precipitated crystals were filtered.The obtained crystals were washed with a mixed solvent of isopropyl ether-methylene chloride, dried, and dried to give the title compound 4- (benzothiazol-2-ylmethoxy). ) 2.33 g of benzaldehyde were obtained. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 9.90 (1
H, s), 8.09-8.01 (1H, m), 7.92-7.80 (1H, m), 7.86
(2H, d, J = 8.8 Hz), 7.56-7.38 (2H, m), 7.16 (2H,
d, J = 8.8 Hz), 5.57 (2H, s).

[0316]

Example 113 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] ethanone (Compound No. 31.36) (A
-3 step) 1- (4-hydroxyphenyl) ethanone (1.0 g, 7.34 mmol)
Sodium hydride (0.32 g) was added to a solution of dimethylformamide (20 mL) at 0 ° C., and the mixture was stirred for 5 minutes, and then 2-bromomethylbenzothiazole (1.84 g) was added to the reaction solution.
Stirred for hours. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water, an aqueous solution of sodium hydroxide and brine, and dried over anhydrous sodium sulfate. After filtration of the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to give 1- [4- (benzothiazole-2).
1.65 g of [-ylmethoxy) phenyl] ethanone were obtained. Melting point: 128-130 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 7.5 Hz), 7.96 (2H, d, J = 9.0 Hz), 7.90
(1H, d, J = 8.4 Hz), 7.56-7.42 (2H, m), 7.09 (2H,
d, J = 9.0 Hz), 5.56 (2H, s), 2.56 (3H, s).

[0317]

Example 114 1- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] ethanone (Compound No. 31.
39) The title compound was synthesized according to the method of Example 113. Melting point: 83-85 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 8.1 Hz), 7.90 (1H, d, J = 8.7 Hz), 7.76
(1H, d, J = 9.3 Hz), 7.56-7.38 (2H, m), 6.91-6.87
(2H, m), 5.53 (2H, s), 2.56 (3H, s), 2.54 (3H, s).

[0318]

Example 115 2- (4-Fluorophenoxymethyl) benzothiazole (Compound No. 31.58) The title compound was synthesized according to the method of Example 113. Melting point: 88-90 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.6 Hz), 7.91 (1H, dd, J = 6.9, 1.0 Hz),
7.55-7.37 (2H, m), 7.01 (2H, s), 6.98 (2H, s), 5.4
6 (2H, s).

[0319]

Example 116 2- (4-Chlorophenoxymethyl) benzothiazole (Compound No. 31.60) The title compound was synthesized according to the method of Example 113. Melting point 105-110 C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.3 Hz), 7.91 (1H, d, J = 6.8 Hz), 7.55-
7.37 (2H, m), 7.12 (4H, ABq, J = 9.1 Hz), 5.46 (2
H, s).

[0320]

Example 117 2- (4-Bromo-3-methylphenoxymethyl) benzothiazole (Compound No. 31.66) The title compound was synthesized according to the method of Example 113. Melting point: 94-95 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1H,
dd, J = 8.5, 1.1Hz), 7.92 (1H, dd, J = 8.8, 0.9Hz), 7.
65-7.32 (2H, m), 7.42 (1H, d, J = 8.4Hz), 6.94 (1H, d,
J = 2.9Hz), 6.78-6.70 (1H, m), 5.45 (2H, s), 2.37 (3H,
s).

[0321]

Example 118 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] -3-dimethylaminopropenone (Compound No. 31.8) (Step F) 1- [4- (Benzothiazol-2-ylmethoxy) ) Phenyl] ethanone (1.50 g, 5.3 mmol) was stirred in N, N-dimethylformamide dimethyl acetal (45 mL) for 2 days while heating to 150 ° C. After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration.The obtained crystals were washed with hexane and dried under reduced pressure to give the title compound 1- [4- (benzothiazol-2-ylmethoxy). [Phenyl] -3-dimethylaminopropenone 1.34 g was obtained. Melting point: 187-188 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, d, J = 7.2 Hz), 7.93-7.88 (1H, m), 7.91 (2H, d,
J = 9.0 Hz), 7.79 (1H, d, J = 12.3 Hz), 7.52-7.40
(2H, m), 7.06 (2H, d, J = 9.0 Hz), 5.69 (1H, d, J
= 12.3 Hz), 5.54 (2H, s), 3.10-2.95 (6H, br.).

[0322]

Example 119 1- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -3-dimethylaminopropenone (Compound No. 31.17) The title compound was synthesized according to the method of Example 118. did. Physical properties: Yellow-white crystal ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.04 (1
H, dd, J = 7.7, 0.7 Hz), 7.91 (1H, dd, J = 7.6, 1.
6 Hz), 7.58-7.30 (2H, m), 6.92-6.79 (2H, m), 5.50
(2H, s), 5.34 (1H, d, J = 12.6 Hz), 3.05 (3H, br.
s), 2.89 (3H, br.s), 2.42 (3H, s).

[0323]

Example 120 1- [4- (Benzoxazol-2-ylmethoxy) -2-methylphenyl] -3-dimethylaminopropenone (Compound No. 31.18) The title compound was synthesized according to the method of Example 118. did. Properties: yellow white crystals ^{1 H-NMR (200MHz, CDCl} 3) spectrum, δ (ppm): 7.80-7.
71 (1H, m), 7.62-7.50 (1H, m), 7.50-7.25 (4H, m),
6.95-6.80 (2H, m), 5.34 (1H, d, J = 12.7 Hz), 5.34
(2H, s), 3.03 (3H, br.), 2.88 (3H, br.), 2.42 (3
H, s).

[0324]

Example 121 4- (Benzothiazol-2-ylmethoxy) benzoic acid (Compound No. 31.33) The title compound was synthesized according to the method of Example 118. Melting point: 235-250 ° C

[0325]

Example 122 4- (Benzothiazol-2-ylmethoxy) -2-methylbenzoic acid (Compound No. 31.34) The title compound was synthesized according to the method of Example 118. Physical properties: Solid-state ¹ H-NMR (200 MHz, CDCl ₃ + CD ₃ OD) spectrum, δ (ppm):
8.06-7.90 (3H, m), 7.60-7.40 (2H, m), 6.95-6.87 (2
H, m), 5.54 (2H, s), 2.62 (3H, s).

[0326]

Example 123 Ethyl 4- (benzothiazol-2-ylmethoxy) benzoate (Compound No. 31.29) The title compound was synthesized according to the method of Example 118. Melting point: 126-127 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.08-7.
97 (1H, m), 8.03 (2H, d, J = 9.0Hz), 7.90 (1H, dd, J = 7.9,
0.9Hz), 7.56-7.37 (2H, m), 7.07 (2H, d, J = 9.0Hz),
5.55 (2H, s), 4.35 (2H, q, J = 7.1Hz), 1.38 (3H, t, J =
7.1Hz).

[0327]

Working Example 124 4- (Benzothiazol-2-ylmethoxy) benznitrile (Compound No. 31.51) (A-3)
Step) To a solution of 4-hydroxybenzonitrile (1.0 g, 8.4 mmol) in dimethylformamide (30 mL) was added sodium hydride (60% in oil, 0.37 g) at 0 ° C, and after stirring for 5 minutes, the reaction mixture was further added. To the mixture was added 2-bromomethylbenzothiazole (2.10 g), and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, and the extract was washed with water and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was purified by silica gel chromatography to obtain 2.24 g of the title compound 4- (benzothiazol-2-ylmethoxy) benzonitrile. Melting point: 140-142 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, d, J = 7.8 Hz), 7.91 (1H, dd, J = 7.8, 1.0 Hz),
7.58-7.39 (2H, m), 7.37 (4H, ABq, J = 9.1 Hz), 5.
55 (2H, s).

[0328]

Example 125 4- (Benzothiazol-2-ylmethoxy) -2-methylbenznitrile (Compound No. 31.52) The title compound was synthesized according to the method of Example 124. Physical properties: Yellow crystal ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1H,
dd, J = 8.6, 0.9Hz), 7.91 (1H, dd, J = 7.7, 1.6Hz), 7.5
9-7.39 (2H, m), 7.55 (1H, d, J = 7.6Hz), 6.98-6.88 (2H,
m), 5.52 (2H, s), 2.52 (3H, s).

[0329]

Working Example 126 4- (Benzothiazol-2-ylmethoxy) benzamide (Compound No. 31.41) 4- (Benzothiazol-2-ylmethoxy) benznitrile
(0.53 g, 2.0 mmol) in 1,4-dioxane (5 mL) solution was added aqueous ammonia (30%, 4 mL) and aqueous hydrogen peroxide (35%, 1.5 m
L), stirred at room temperature for 3 hours, and further added 5% Pd / C
(0.2 g) was added and stirred vigorously for 10 minutes. After the reaction,
The reaction solution was filtered using celite, the filtrate was extracted with ethyl acetate, the extract was washed, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was recrystallized from a mixed solvent of hexane-ethyl acetate to give the title compound 4- (benzothiazol-2-ylmethoxy) benzamide 4
0 mg was obtained. Melting point: 230-231 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.95 (1
H, d, J = 7.4 Hz), 7.82 (1H, d, J = 9.0 Hz), 7.38
(4H, ABq, J = 8.9 Hz), 7.46-7.29 (2H, m), 5.80-5.7
0 (2H, br.), 5.45 (2H, s).

[0330]

Working Example 127 4- (Benzothiazol-2-ylmethoxy) -2-methylbenzamide (Compound No. 31.42)
(Step F) To a solution of 4- (benzothiazol-2-ylmethoxy) benzoic acid (0.21 g, 0.71 mmol) in tetrahydrofuran (5 mL) prepared according to the method of Example 118 at 0 ° C was added ethyl chloroformate (0.070 g). mL) and triethylamine (0.10 mL) were added, and the mixture was stirred for 30 minutes. Then, ammonia gas was introduced into the reaction solution for 10 minutes, followed by stirring at 0 ° C. for 1 hour and room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the obtained residue was washed with ether to obtain 52 mg of the title compound 4- (benzothiazol-2-ylmethoxy) -2-methylbenzamide. Melting point: 190-192 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.26 (1
H, dd, J = 8.4, 1.0 Hz), 7.90 (1H, dd, J = 7.4, 1.
5 Hz), 7.56-7.37 (3H, m), 6.92-6.85 (2H, m), 5.62
(2H, br.), 5.51 (2H, s), 2.51 (3H, s).

[0331]

Example 128 4- (Benzothiazol-2-ylmethoxy) benzoic acid hydrazide (Compound No. 31.56) 4- (Benzothiazol-2-ylmethoxy) benzoic acid (0.28
g, 0.99 mmol) in toluene (5 mL).
(0.090 mL) and 0.010 mL of dimethylacetamide were added, and the reaction solution was stirred for 1 hour while heating to 130 ° C.
Thereafter, the reaction solution was concentrated under reduced pressure, the residue was diluted with tetrahydrofuran (8 mL), and hydrazine (0.12
mL) in tetrahydrofuran (8 mL) was added, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent of the reaction solution was distilled off, water was added to the obtained residue, the precipitated solid was filtered, and the obtained solid was washed with a mixed solvent of hexane-ethyl acetate to give the title.
0.17 g of-(benzothiazol-2-ylmethoxy) benzoic acid hydrazide was obtained. Physical properties: Solid-state ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 9.66
(1H, s), 8.17-8.12 (1H, m), 8.06-8.03 (1H, m), 7.8
4 (2H, d, J = 8.9 Hz), 7.60-7.47 (2H, m), 7.17 (2
H, d, J = 8.9 Hz), 5.68 (2H, s), 4.46-4.44 (2H, b
r.).

[0332]

Example 129 4- (Benzothiazol-2-ylmethoxy) -N-ethoxybenzamide (Compound No. 31.44) 4- (Benzothiazol-2-ylmethoxy) benzoic acid (1.50
g, 5.26 mmol) in benzene (40 mL).
(0.77 mL), heated for 1 hour, cooled the reaction solution to room temperature, concentrated under reduced pressure, added methylene chloride (6 mL) to the residue, cooled to 0 ° C, and added O-ethyl to the reaction solution. Hydroxylamine hydrochloride (0.77 g) and triethylamine (2.2 mL) were added, and the mixture was stirred at 0 ° C for 2 hours. After the completion of the reaction, the reaction solution was poured into water and extracted with methylene chloride. The extract was washed with brine and dried over anhydrous sodium sulfate. After filtering the desiccant,
The solvent was distilled off, and the obtained residue was recrystallized from a mixed solvent of hexane-methylene chloride to give the title compound 4-
0.63 g of (benzothiazol-2-ylmethoxy) -N-ethoxybenzamide was obtained. Melting point: 160-162 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.52 (1
H, s), 8.07-8.02 (1H, m), 7.93-7.88 (1H, m), 7.73
(2H, dd, J = 6.8, 2.1 Hz), 7.56-7.38 (2H, m), 7.08
(2H, dd, J = 6.8, 2.1 Hz), 5.53 (2H, s), 4.07 (2
H, q, J = 7.0 Hz), 1.33 (3H, t, J = 7.0 Hz).

[0333]

Example 130 4- (Benzothiazol-2-ylmethoxy) -N-methylbenzamide (Compound No. 31.45) The title compound was synthesized according to the method of Example 129. Melting point: 174-176 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1H,
d, J = 9.2Hz), 7.91 (1H, d, J = 9.7Hz), 7.74 (2H, d, J = 8.
9Hz), 7.56-7.37 (2H, m), 7.07 (2H, d, J = 8.9Hz), 6.02
(1H, br.s), 5.53 (2H, s), 3.00 (3H, d, J = 4.9Hz).

[0334]

Example 131 4- (Benzothiazol-2-ylmethoxy) -N-phenylbenzamide (Compound No. 31.57) The title compound was synthesized according to the method of Example 129. Melting point: 213-215 ° C. ¹ H-NMR (200 MHz, DMSO-d ₆ ) spectrum, δ (ppm): 10.14
(1H, s), 8.18-7.97 (4H, m), 7.66 (2H, d, J = 7.6Hz), 7.
58-7.48 (2H, m), 7.35 (2H, t, J = 7.4Hz), 7.25 (2H, q,
J = 9.0Hz), 7.13-7.09 (1H, m), 5.74 (2H, s).

[0335]

Example 132 4- (Benzothiazol-2-ylmethoxy) -N-methoxy-benzamide (Compound No. 31.4)
3) The title compound was synthesized according to the method of Example 129. Melting point: 183-184 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.53 (1H,
s), 8.05 (1H, d, J = 7.2Hz), 7.91 (1H, d, J = 6.9Hz),
7.72 (2H, d, J = 9.0Hz), 7.67-7.38 (2H, m), 7.08 (2H,
d, J = 9.0Hz), 5.54 (2H, s), 3.88 (3H, s).

[0336]

Example 133 Ethyl N- [4- (benzothiazol-2-ylmethoxy) -2-methylphenyl] -acetimidate (Compound No. 50.8) The title compound was synthesized according to the method of Example 129. Melting point: 99-100 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.03 (1H,
d, J = 8.1 Hz), 7.94-7.81 (1H, m), 7.54-7.36 (2H,
m), 6.89-6.78 (2H, m), 6.57 (1H, d, J = 8.4 Hz), 5.
45 (2H, s), 4.25 (2H, q, J = 7.0 Hz), 2.09 (3H, s),
1.75 (3H, s), 1.35 (3H, t, J = 7.0 Hz).

[0337]

Working Example 134 Ethyl N- [4- (benzothiazol-2-ylmethoxy) phenyl] -acetimidate (Compound No. 5)
0.9) The title compound was synthesized according to the method of Example 129. Melting point: 103-105 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.03 (1H,
d, J = 7.8 Hz), 7.90 (1H, dd, J = 7.0, 1.0 Hz), 7.54
-7.36 (2H, m), 6.97 (2H, d, J = 9.0 Hz), 6.70 (2H, m
d, J = 9.0 Hz), 5.45 (2H, s), 4.28 (2H, q, J = 7.1 H
z), 1.82 (3H, s), 1.35 (3H, t, J = 7.1 Hz).

[0338]

Example 135 3- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -1,1,2-trimethylisothiourea (Compound No. 50.5) Titled according to the method of Example 129. Compounds were synthesized. Melting point: 61-62 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.02 (1H,
d, J = 7.6 Hz), 7.90 (1H, dd, J = 7.2, 1.0 Hz), 7.53
-7.35 (2H, m), 6.87-6.68 (3H, m), 5.43 (2H, s), 3.0
9 (6H, s), 2.13 (3H, s), 2.02 (3H, s).

[0339]

EXAMPLE 136 3- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -1,1-dimethyl-2- (2-propynyl) isothiourea (Compound No. 50.6) The title compound was synthesized according to the method described in the above. Physical properties: Oil ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.00 (1H,
dd, J = 7.0, 1.0 H), 7.90 (1H, dd, J = 7.0, 1.0 H)
z), 7.53-7.35 (2H, m), 6.88-6.70 (3H, m), 5.43 (2H,
s), 3.17 (2H, d, J = 2.6 Hz), 3.11 (3H, s), 2.18
(1H, t, J = 2.6 Hz), 2.16 (3H, s).

[0340]

Working Example 137 O-Methyl-S- [4- (benzothiazol-2-ylmethoxy) -2-methylphenyl] thiocarbimidate
Ethoxycarbonyl methyl ester (Compound No. 50.
7) The title compound was synthesized according to the method of Example 129. Physical properties: Oil ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.03 (1H,
d, J = 7.5 Hz), 7.91 (1H, dd, J = 7.2, 1.0 Hz), 7.56
-7.38 (2H, m), 6.97-6.80 (3H, m), 6.36 (1H, s), 5.4
6 (2H, s), 2.84 (6H, s), 2.26 (3H, s).

[0341]

Example 138 [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] dithiocarbimidic acid dimethyl ester (Compound No. 50.1) The title compound was synthesized according to the method of Example 129. Melting point: 94-95 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05-8.01
(1H, m), 7.92-7.88 (1H, m), 7.54-7.35 (2H, m), 6.9
1-6.68 (3H, m), 5.45 (2H, s), 2.50 (6H, s), 2.11 (3
H, s).

[0342]

Example 139 [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] thiocarbimidic acid dimethyl ester (Compound No. 50.2) The title compound was synthesized according to the method of Example 129. Melting point: 95-96 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.01 (1H,
dd, J = 7.2, 1.0 Hz), 7.91 (1H, dd, J = 7.6, 1.6 H
z), 7.54-7.36 (2H, m), 6.90-6.70 (3H, m), 5.44 (2H,
s), 3.99 (3H, s), 2.33 (3H, s), 2.14 (3H, s).

[0343]

Example 140 O-methyl-S- [4- (benzothiazol-2-ylmethoxy) -2-methylphenyl] thiocarbimidate
Benzyl ester (Compound No. 50.3) The title compound was synthesized according to the method of Example 129. Melting point: 64-65 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.02 (1H,
dd, J = 8.5, 1.0 Hz), 7.91-7.87 (1H, m), 7.54-7.27
(7H, m), 6.87-6.67 (3H, m), 5.42 (2H, s), 4.12 (2
H, s), 3.98 (3H, s), 2.08 (3H, s).

[0344]

Example 141 [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] dithiocarbimidic acid S-ethyl-S-methyl ester (Compound No. 50.4) Titled according to the method of Example 129. Compounds were synthesized. Melting point: 84-85 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05-8.01
(1H, m), 7.92-7.88 (1H, m), 7.54-7.36 (2H, m), 6.9
1-6.68 (3H, m), 5.45 (2H, s), 3.14-32 (2H, m), 2.5
0 (3H, s), 2.12 (3H, s), 1.37-1.30 (3H, m).

[0345]

Example 142 N- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -N'-cyanoethaneimidoamide (Compound No. 49.8) The title compound was prepared according to the method of Example 129. Synthesized. Melting point: 180-183 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.03 (1H,
d, J = 7.9 Hz), 7.90 (1H, d, J = 6.7 Hz), 7.56-7.36
(2H, m), 6.95-6.74 (3H, m), 5.46 (2H, s), 2.24 (3
H, s), 2.18 (3H, s).

[0346]

Working Example 143 N- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -N′-cyano-N ″ -methylguanidine (Compound No. 49.6) According to the method of Working Example 129 To synthesize the title compound. Physical properties: amorphous ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 8.1 Hz), 7.92 (1H, dd, J = 7.3, 1.4 Hz), 7.57
-7.39 (2H, m), 7.13 (1H, d, J = 8.7 Hz), 7.01-6.90
(2H, m), 6.75-6.70 (1H, m), 5.49 (2H, s), 4.44-4.3
7 (1H, m), 2.82 (3H, d, J = 4.7 Hz), 2.25 (3H, s).

[0347]

Example 144 N- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -N′-cyano-N ″, N ″ -dimethylguanidine (Compound No. 49.7) Example 129 The title compound was synthesized according to the method described in the above. Physical properties: amorphous ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
dd, J = 8.4, 1.0 Hz), 7.91 (1H, dd, J = 7.2, 1.0 H
z), 7.56-7.38 (2H, m), 6.97-6.80 (3H, m), 3.63 (1H,
s), 5.46 (2H, s), 2.84 (6H, s), 2.26 (3H, s).

[0348]

Example 145 1- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -3-cyano-2-methylisothiourea (Compound No. 49.4) Titled according to the method of Example 129. Compounds were synthesized. Melting point: 182-184 ° C. ¹ H-NMR spectrum (200 Hz, DMSO-d ₆ ) δ (ppm): 10.12-9.
87 (1H, m), 8.14 (1H, dd, J = 7.6, 1.6 Hz), 8.06-8.0
2 (1H, m), 7.56-7.47 (2H, m), 7.19-6.95 (3H, m),
5.62 (2H, s), 2.56 (3H, s), 2.17 (3H, s).

[0349]

Example 146 1- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -3-cyano-2-methylisourea (Compound No. 49.5) Titled according to the method of Example 129. Compounds were synthesized. Melting point: 112-121 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.06-8.01
(1H, m), 7.93-7.87 (1H, m), 7.65-7.37 (3H, m), 6.9
2-6.86 (2H, m), 6.23-6.22 (1H, m), 5.47 (2H, s), 3.
77 (3H, s), 2.25 (3H, s).

[0350]

EXAMPLE 147 N- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -N- (1-methylthio-2-nitrovinyl) amine (Compound No. 49.1) The title compound was synthesized according to the procedure. Melting point: 190-193 ° C ¹ H-NMR spectrum (200 Hz, DMSO-d ₆ ) δ (ppm): 11.32-1
1.28 (1H, m), 8.17-8.13 (1H, m), 8.06-8.02 (1H, m),
7.61-7.44 (2H, m), 7.24-6.99 (3H, m), 6.73 (1H,
s), 5.65 (2H, s), 2.42 (3H, s), 2.20 (3H, s).

[0351]

Working Example 148 N- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -N ′, N′-dimethyl-2-nitro-1,
1-Ethylenediamine (Compound No. 49.3) The title compound was synthesized according to the method of Example 129. Melting point: 155-156 ° C. ¹ H-NMR spectrum (200 Hz, DMSO-d ₆ ) δ (ppm): 10.45-1
0.28 (1H, m), 8.16-8.02 (2H, m), 7.61-7.44 (2H, m),
7.14-6.94 (3H, m), 6.51 (1H, s), 5.60 (2H, s), 2.7
9 (6H, s), 2.22 (3H, s).

[0352]

Working Example 149 N- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -N'-methyl-2-nitro-1,1-ethylenediamine (Compound No. 49.2) The title compound was synthesized according to the method. Melting point: 234-235 ° C ¹ H-NMR spectrum (200 Hz, DMSO-d ₆ ) δ (ppm): 9.99-9.8
4 (1H, m), 8.76-8.71 (1H, m), 8.17-8.13 (1H, m),
8.07-8.03 (1H, m), 7.60-7.43 (2H, m), 7.20-6.96 (3
H, m), 5.77 (2H, s), 3.00-2.78 (3H, m), 2.18 (3H,
s).

[0353]

Example 150 2- [4- (thiophen-3-yl) phenoxymethyl] benzoxazole (Compound No. 35.1) The title compound was synthesized according to the method of Example 129. Melting point: 142-145 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.75
(1H, m), 7.59-7.53 (1H, m), 7.55 (2H, d, J = 8.8 H
z), 7.39-7.31 (5H, m), 7.10 (2H, d, J = 8.8 Hz), 5.
36 (2H, s).

[0354]

Example 151 2- [4- (thiophen-3-yl) phenoxymethyl] benzothiazole (Compound No. 35.2) The title compound was synthesized according to the method of Example 129. Melting point: 185-188 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.07-8.02
(1H, m), 7.93-7.88 (1H, m), 7.55 (2H, d, J = 9.0 H
z), 7.51-7.33 (5H, m), 7.08 (5.53 (2H, s).

[0355]

Example 152 2- [4- (Pyrazin-2-yl) phenoxymethyl] benzothiazole (Compound No. 43.2) The title compound was synthesized according to the method of Example 129. Melting point: 155-159 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 9.01-8.96
(1H, m), 8.59 (1H, s), 8.46-8.43 (1H, m), 8.07-7.89
(3H, m), 7.55-7.38 (2H, m), 7.18 (2H, d, J = 8.8 H
z), 7.00-6.95 (1H, m), 5.57 (2H, s).

[0356]

Example 153 2- [4- (thiophen-2-yl) phenoxymethyl] benzothiazole (Compound No. 36.2) The title compound was synthesized according to the method of Example 129. Melting point: 166-167 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 7.9 Hz), 7.90 (1H, dd, J = 6.8, 1.1 Hz), 7.57
-7.36 (4H, m), 7.24-7.19 (2H, m), 7.07-7.03 (3H,
m), 5.52 (2H, s).

[0357]

Example 154 2- [4- (Thiazol-2-yl) phenoxymethyl] benzothiazole (Compound No. 37.2) The title compound was synthesized according to the method of Example 129. Melting point: 165-166 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H,
dd, J = 7.7, 1.6 Hz), 7.95-7.88 (3H, m), 7.81 (1H,
d, J = 3.3 Hz), 7.55-7.37 (2H, m), 7.28 (1H, s), 7.1
4-7.07 (2H, m) 5.56 (2H, s).

[0358]

Example 155 2- [4- (Pyrazin-2-yl) phenoxymethyl] benzothiazole (Compound No. 43.2) The title compound was synthesized according to the method of Example 129. Melting point: 155-159 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 9.01-8.96
(1H, m), 8.59 (1H, s), 8.46-8.43 (1H, m), 8.07-7.89
(3H, m), 7.55-7.38 (2H, m), 7.18 (2H, d, J = 8.8 H
z), 7.00-6.95 (1H, m), 5.57 (2H, s).

[0359]

Example 156 4- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -6-methyl-3-thione-3,4-dihydro-2H- [1,2,4] triazine- 5-one (compound number 48.
2) The title compound was synthesized according to the method of Example 129. Melting point: 120-130 ° C ¹ H-NMR spectrum (200 Hz, DMSO-d ₆ ) δ (ppm): 8.18-8.0
4 (2H, m), 7.61-7.45 (2H, m), 7.17-6.99 (3H, m),
5.65 (2H, s), 2.18 (3H, s), 2.04 (3H, s).

[0360]

Example 157 2- [4- (4-Methyl-5-trifluoromethyl-4H- [1,2,4] triazol-3-yl) phenoxymethyl]
Benzothiazole (Compound No. 39.2) The title compound was synthesized according to the method of Example 129. Melting point: 182-185 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.08-8.04
(1H, m), 7.95-7.91 (1H, m), 7.61 (2H, d, J = 8.8 H
z), 7.60-7.28 (2H, m), 7.21 (2H, d, J = 8.8 Hz), 5.
58 (2H, s), 3.78 (3H, s).

[0361]

Working Example 158 2- [4- (4-Methyl-5-trifluoromethyl-4H- [1,2,4] triazol-3-yl) phenoxymethyl]
Benzoxazole (Compound No. 39.1) The title compound was synthesized according to the method of Example 129. Melting point: 144-148 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.80-7.76
(2H, m), 7.63-7.35 (2H, m), 7.61 (2H, d, J = 8.8 H
z), 7.24 (2H, d, J = 8.8 Hz), 5.42 (2H, s), 3.78 (3
H, s).

[0362]

Example 159 2- [4- (3,5-Dimethylpyrazol-1-yl) -3-methylphenoxymethyl] benzothiazole (Compound No. 14.20) The title compound was synthesized according to the method of Example 129. did. Melting point: 124-126 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 8.0Hz), 7.92 (1H, dd, J = 7.0, 0.9Hz), 7.54-7.
37 (2H, m), 7.17 (1H, d, J = 8.7Hz), 6.98-6.88 (2H,
m), 5.94 (1H, s), 5.51 (2H, s), 2.27 (3H, s), 2.03
(3H, s), 2.02 (3H, s).

[0363]

Working Example 160 2- [4- (3,5-dimethylpyrazol-1-yl) -3-methylphenoxymethyl] benzoxazole (Compound No. 14.21) The title compound was synthesized according to the method of Working Example 129. did. Physical properties: Oil ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.75
(1H, m), 7.60-7.55 (1H, m), 7.43-7.36 (2H, m), 7.1
7 (1H, d, J = 8.3Hz), 6.99-6.90 (2H, m), 5.94 (1H,
s), 5.35 (2H, s), 2.27 (3H, s), 2.03 (3H, s), 2.02
(3H, s).

[0364]

Working Example 161 2- [4- (3,4,5-trimethylpyrazole-1)
-Yl) phenoxymethyl] benzothiazole (Compound No. 14.24) The title compound was synthesized according to the method of Example 129. Melting point: 107-110 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 7.2Hz), 7.92 (1H, d, J = 6.8Hz), 7.56-7.37 (2H,
m), 7.33 (2H, d, J = 9.1Hz), 7.09 (2H, d, J = 9.1Hz),
5.52 (2H, s), 2.23 (3H, s), 2.17 (3H, s), 1.97 (3
H, s).

[0365]

Working Example 162 2- [4- (3,4,5-Trimethylpyrazole-1-
Yl) phenoxymethyl] benzoxazole (Compound No. 14.25) The title compound was synthesized according to the method of Example 129. Melting point: 118-119 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.74
(1H, m), 7.59-7.55 (1H, m), 7.40-7.32 (2H, m), 7.
33 (2H, d, J = 9.1Hz), 7.12 (2H, d, J = 9.1Hz), 5.36 (2
H, s), 2.23 (3H, s), 2.17 (3H, s), 1.97 (3H, s).

[0366]

Working Example 163 2- [4- (3,5-di-t-butylpyrazole-1-)
Yl) phenoxymethyl] benzoxazole (Compound No. 14.23) The title compound was synthesized according to the method of Example 129. Melting point: 152-153 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.75
(1H, m), 7.60-7.55 (1H, m), 7.41-7.36 (2H, m), 7.
32 (2H, d, J = 9.0Hz), 7.08 (2H, d, J = 9.0Hz), 5.97 (1
H, s), 5.36 (2H, s), 1.30 (9H, s), 1.15 (9H, s).

[0367]

Working Example 164 2- [4- (3,5-di-t-butylpyrazole-1-)
Yl) phenoxymethyl] benzothiazole (Compound No. 14.22) The title compound was synthesized according to the method of Example 129. Melting point: 185-186 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
(dd, J = 8.8, 1.4Hz), 7.93 (1H, dd, J = 6.9, 0.8Hz), 7.
55-7.42 (2H, m), 7.32 (2H, d, J = 9.0Hz), 7.06 (2H, m
d, J = 9.0Hz), 5.98 (1H, s), 5.52 (2H, s), 1.31 (9H,
s), 1.15 (9H, s).

[0368]

Example 165 2- [4- (3,5-Dimethyl- [1,2,4] triazol-1-yl) phenoxymethyl] benzoxazole (Compound No. 23.12) According to the method of Example 129 The title compound was synthesized. Melting point: 110-113 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.80-7.74
(1H, m), 7.59-7.55 (1H, m), 7.40-7.32 (2H, m), 7.36
(2H, d, J = 9.0Hz), 7.16 (2H, d, J = 9.0Hz), 5.38 (2
H, s), 2.43 (3H, s), 2.39 (3H, s).

[0369]

Example 166 2- [4- (3,5-Dimethyl- [1,2,4] triazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 23.11) According to the method of Example 129 The title compound was synthesized. Melting point: 156-159 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H,
d, J = 8.1Hz), 7.92 (1H, d, J = 7.9Hz), 7.56-7.34 (2H,
m), 7.36 (2H, d, J = 9.1Hz), 7.14 (2H, d, J = 9.1Hz),
5.54 (2H, s), 2.43 (3H, s), 2.39 (3H, s).

[0370]

Example 167 2- [4- (3,5-Diethyl- [1,2,4] triazol-1-yl) phenoxymethyl] benzoxazole (Compound No. 14.27) According to the method of Example 129 The title compound was synthesized. Physical properties: Oil ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.75
(1H, m), 7.59-7.54 (1H, m), 7.43-7.31 (2H, m), 7.3
5 (2H, d, J = 8.9Hz), 7.12 (2H, d, J = 8.9Hz), 6.02 (1
H, s), 5.36 (2H, s), 2.67 (2H, q, J = 7.7Hz), 2.59
(2H, q, J = 7.7Hz), 1.27 (3H, t, J = 7.7Hz), 1.23 (3H,
t, J = 7.7Hz).

[0371]

Example 168 2- [4- (3,5-Diethyl- [1,2,4] triazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 14.26) According to the method of Example 129 The title compound was synthesized. Melting point: 100-103 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 7.1Hz), 7.91 (1H, dd, J = 7.7, 1.8Hz), 7.55-7.38
(2H, m), 7.35 (2H, d, J = 9.0Hz), 7.10 (2H, d, J = 9.0
Hz), 6.03 (1H, s), 5.53 (2H, s), 2.67 (2H, q, J = 7.
7Hz), 2.59 (2H, q, J = 7.7Hz), 1.27 (3H, t, J = 7.7H
z), 1.19 (3H, t, J = 7.7Hz).

[0372]

Working Example 169 2- [4- (5-Methylpyrazol-1-yl) phenoxymethyl] benzoxazole (Compound No. 1)
4.29) The title compound was synthesized according to the method of Example 129. Melting point: 98-100 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.75
(1H, m), 7.60-7.54 (2H, m), 7.43-7.34 (2H, m), 7.3
8 (2H, d, J = 9.0Hz), 7.15 (2H, d, J = 9.0Hz), 6.17-6.
16 (1H, s), 5.38 (2H, s), 2.30 (3H, s).

[0373]

Working Example 170 2- [4- (5-Chloro-3-methylpyrazole-)
1-yl) phenoxymethyl] benzothiazole (Compound No. 14.30) The title compound was synthesized according to the method of Example 129. Melting point: 145-147 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H,
d, J = 7.7Hz), 7.92 (1H, dd, J = 6.7, 0.9Hz), 7.55-7.42
(2H, m), 7.47 (2H, d, J = 9.0Hz), 7.12 (2H, d, J = 9.0
Hz), 6.16 (1H, s), 5.54 (2H, s), 2.29 (3H, s).

[0374]

Working Example 171 2- [4- (Benzothiazol-2-ylmethoxy) phenyl] cyclohexane-1,3-dione (Compound No. 31.1) The title compound was synthesized according to the method of Working Example 129. Melting point: 162-164 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.03 (1H,
d, J = 7.6Hz), 7.92 (1H, d, J = 6.8Hz), 7.57-7.35 (2H,
m), 6.96 (3H, br.m), 5.48 (2H, s), 2.83 (4H, br.t, J
= 6.6Hz), 2.12 (2H, q, J = 6.7Hz), 2.06 (3H, s).

[0375]

Working Example 172 3- [4- (Benzothiazol-2-ylmethoxy) phenyl] furan-2,4-dione (Compound No. 32.
1) The title compound was synthesized according to the method of Example 129. Melting point: 193-194 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 8.2Hz), 7.91 (1H, d, J = 7.0Hz), 7.57-7.37 (2H,
m), 7.12 (1H, d, J = 8.4Hz), 7.05-6.9 (2H, m), 5.50 (2
H, s), 4.90 (2H, s), 2.20 (3H, s).

[0376]

Working Example 173 2- [4- (2-Chloropyrimidin-4-yl) phenoxymethyl] benzothiazole (Compound No. 44.
2) The title compound was synthesized according to the method of Example 129. Melting point: 210-213 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.58 (1H,
d, J = 5.5Hz), 8.09 (2H, d, J = 8.8Hz), 8.05 (1H, d, J =
8.4Hz), 7.91 (1H, dd, J = 7.4, 1.4Hz), 7.57 (1H, d,
J = 5.5Hz), 7.53-7.42 (2H, m), 7.17 (2H, d, J = 8.8H
z), 5.58 (2H, s).

[0377]

Working Example 174 2- [4- (4,6-dimethylpyrimidin-2-yl) phenoxymethyl] benzothiazole (Compound No. 4)
5.2) The title compound was synthesized according to the method of Example 129. Melting point: 150-153 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.41 (2H,
d, J = 9.0Hz), 8.04 (1H, d, J = 8.0Hz), 7.90 (1H, d, J =
8.8Hz), 7.54-7.40 (2H, m), 7.12 (2H, d, J = 9.0Hz),
6.88 (1H, s), 5.56 (2H, s), 2.51 (6H, s).

[0378]

Example 175 2- [4- (4,6-Dimethylpyrimidin-2-yl) phenoxymethyl] benzoxazole (Compound No. 45.1) The title compound was synthesized according to the method of Example 129. Melting point: 130-133 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.41 (2H,
d, J = 9.0Hz), 7.79-7.74 (1H, m), 7.58-7.54 (1H, m),
7.39-7.35 (2H, m), 7.14 (2H, d, J = 9.0Hz), 6.88 (1
H, s), 5.39 (2H, s), 2.51 (6H, s).

[0379]

Example 176 2- [4- (2-Methylsulfanylpyrimidin-4-yl) phenoxymethyl] benzothiazole (Compound No. 44.1) The title compound was synthesized according to the method of Example 129. Melting point: 139-141 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.50 (1H,
d, J = 5.3Hz), 8.10 (2H, d, J = 9.0Hz), 8.05 (1H, d, J =
8.1Hz), 7.91 (1H, d, J = 8.0Hz), 7.56-7.37 (2H, m),
7.30 (1H, d, J = 5.4Hz), 7.15 (2H, d, J = 9.0Hz), 5.57
(2H, s), 2.64 (3H, s).

[0380]

Working Example 177 2- [4- (6-Methylpyridin-2-yl) phenoxymethyl] benzoxazole (Compound No. 40.
1) The title compound was synthesized according to the method of Example 129. Melting point: 99-101 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.96 (2H,
d, J = 9.1Hz), 7.79-7.75 (1H, m), 7.64-7.55 (2H, m),
7.47-7.35 (3H, m), 7.15 (2H, d, J = 9.1Hz), 7.05 (1
(H, t, J = 7.7Hz), 5.39 (2H, s), 2.60 (3H, s).

[0381]

Working Example 178 2- [4- (6-Methylpyridin-2-yl) phenoxymethyl] benzothiazole (Compound No. 40.
2) The title compound was synthesized according to the method of Example 129. Melting point: 139-141 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 8.0Hz), 7.96 (2H, d, J = 9.1Hz), 7.90 (1H, d, J =
8.0Hz), 7.64-7.37 (4H, m), 7.13 (2H, d, J = 9.1Hz),
7.05 (1H, t, J = 8.0Hz), 5.55 (2H, s), 2.60 (3H, s).

[0382]

Example 179 2- [4- (2,6-Dimethylpyrimidin-4-yl) phenoxymethyl] benzoxazole (Compound No. 44.3) The title compound was synthesized according to the method of Example 129. Melting point: 137-139 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (2H,
d, J = 9.0Hz), 7.79-7.75 (1H, m), 7.59-7.54 (1H, m),
7.40-7.35 (2H, m), 7.31 (1H, s), 7.17 (2H, d, J = 9.
0Hz), 5.40 (2H, s), 2.53 (3H, s), 2.24 (3H, s).

[0383]

Working Example 180 2- [4- (2,6-Dimethylpyrimidin-4-yl) phenoxymethyl] benzothiazole (Compound No. 4)
4.3) The title compound was synthesized according to the method of Example 129. Melting point: 129-132 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (2H,
d, J = 9.0Hz), 8.07-8.02 (1H, m), 7.92-7.88 (1H, m),
7.55-7.37 (2H, m), 7.31 (1H, s), 7.14 (2H, d, J = 9.0
Hz), 5.56 (2H, s), 2.74 (3H, s), 2.53 (3H, s).

[0384]

Example 181 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] -1H-pyrazole-3-carbaldehyde (Compound No. 14.31) The title compound was synthesized according to the method of Example 129. Melting point: 149-152 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 9.85 (1H,
s), 8.05 (1H, d, J = 7.7Hz), 7.92 (1H, dd, J = 6.7, 0.
9Hz), 7.74 (1H, d, J = 2.1Hz), 7.57-7.39 (2H, m), 7.4
5 (2H, d, J = 9.0Hz), 7.18 (2H, d, J = 9.0Hz), 7.09 (1
(H, d, J = 2.1Hz), 5.56 (2H, s).

[0385]

Working Example 182 2- [4- (5-Methoxypyrazol-1-yl)
Phenoxymethyl] benzothiazole (Compound No. 1
4.33) The title compound was synthesized according to the method of Example 129. Melting point: 113-115 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
dd, J = 7.2, 1.0Hz), 7.93-7.89 (1H, m), 7.62 (2H, d,
J = 9.1Hz), 7.54-7.40 (2H, m), 7.47 (1H, d, J = 2.0H
z), 7.09 (2H, d, J = 9.1Hz), 5.65 (1H, d, J = 2.0Hz),
5.52 (2H, s), 3.93 (3H, s).

[0386]

Working Example 183 2- [4- (3,5-diphenylpyrazole-1-)
Yl) phenoxymethyl] benzothiazole (Compound No. 14.35) The title compound was synthesized according to the method of Example 129. Melting point: 157-158 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 7.7Hz), 7.94-7.89 (3H, m), 7.56-7.30 (12H, m),
7.02 (2H, d, J = 9.0Hz), 6.81 (1H, s), 5.50 (2H, s).

[0387]

Working Example 184 2- [4- (3,5-diphenylpyrazole-1-)
Yl) phenoxymethyl] benzoxazole (Compound No. 14.36) The title compound was synthesized according to the method of Example 129. Physical properties: Amorphous ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.93-7.88
(2H, m), 7.80-7.74 (1H, m), 7.60-7.55 (1H, m), 7.4
7-7.30 (12H, m), 7.04 (2H, d, J = 9.0Hz), 6.81 (1H,
s), 5.34 (2H, s).

[0388]

Working Example 185 2- [3-Methyl-4- (2-methylthiazole-)
4-yl) phenoxymethyl] benzothiazole (Compound No. 38.2) The title compound was synthesized according to the method of Example 129. Melting point: 77-80 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 8.1Hz), 7.91 (1H, d, J = 7.6Hz), 7.58-7.35 (2H,
m), 7.01 (1H, s), 6.98-6.85 (3H, m), 5.52 (2H, s), 2.
76 (3H, s), 2.42 (3H, s).

[0389]

Working Example 186 2- [4- (2-aminothiazol-4-yl) -3
[-Methylphenoxymethyl] benzothiazole (Compound No. 38.4) The title compound was synthesized according to the method of Example 129. Melting point: 179-185 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.03 (1H, d
d, J = 8.6, 1.0Hz), 7.90 (1H, dd, J = 7.3, 1.5Hz), 7.49
(1H, d, J = 7.9Hz), 7.55-7.38 (2H, m), 6.95-6.85 (2H,
m), 6.41 (1H, s), 5.50 (2H, s), 4.87 (2H, br.s), 2.43
(3H, s).

[0390]

Working Example 187 N- [4- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] thiazol-2-yl] acetamide (Compound No. 38.6) Titled according to the method of Working Example 129. Compounds were synthesized. Melting point: 196-198 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 10.37 (1H,
br.s), 8.04 (1H, d, J = 7.3Hz), 7.91 (1H, d, J = 8.4Hz),
7.65-7.35 (3H, m), 6.97-6.85 (2H, m), 6.84 (1H, s),
5.52 (2H, s), 2.40 (3H, s), 1.89 (3H, s).

[0391]

Working Example 188 Methyl N- [4- [4- (benzothiazole-
2-ylmethoxy) -2-methylphenyl] thiazol-2-yl] carbamate (Compound No. 38.8) The title compound was synthesized according to the method of Example 129. Melting point: 181-182 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.65 (1H,
s), 8.04 (1H, d, J = 7.6Hz), 7.90 (1H, dd, J = 7.3, 1.2H
z), 7.58-7.36 (3H, m), 6.97-6.85 (2H, m), 5.51 (2H,
s), 3.77 (3H, s), 2.41 (3H, s).

[0392]

Working Example 189 N- [4- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] thiazol-2-yl] formamide (Compound No. 38.10) Titled according to the method of Example 129. Compounds were synthesized. Melting point: 204-210 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 12.19 (1H,
br.s), 8.05 (1H, dd, J = 8.3, 1.0Hz), 7.94 (1H, dd, J =
8.4, 1.5), 7.72 (1H, s), 7.56-7.35 (3H, m), 7.02-6.8
9 (2H, m), 6.83 (1H, s), 5.54 (2H, s), 2.34 (3H, s).

[0393]

Working Example 190 2- [4- (5-Methylpyridin-2-yl) phenoxymethyl] benzoxazole (Compound No. 40.
3) The title compound was synthesized according to the method of Example 129. Melting point: 153-156 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.48 (1H,
s), 7.94 (2H, d, J = 9.0Hz), 7.79-7.74 (1H, m), 7.59
-7.53 (3H, m), 7.42-7.35 (2H, m), 7.15 (2H, d, J = 9.
0Hz), 5.39 (2H, s), 2.36 (3H, s).

[0394]

Working Example 191 2- [4- (5-Methylpyridin-2-yl) phenoxymethyl] benzothiazole (Compound No. 40.
4) The title compound was synthesized according to the method of Example 129. Melting point: 177-180 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.47 (1H,
s), 8.05 (1H, d, J = 8.1Hz), 7.94 (2H, d, J = 8.8Hz),
7.91 (1H, dd, J = 8.4, 1.5Hz), 7.56-7.37 (4H, m), 7.1
3 (2H, d, J = 8.8Hz), 5.55 (2H, s), 2.36 (3H, s).

[0395]

Working Example 192 2- [4- (6-Methylpyridazin-2-yl) phenoxymethyl] benzothiazole (Compound No. 47.
2) The title compound was synthesized according to the method of Example 129. Melting point: 207-210 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (2H,
d, J = 8.8Hz), 7.91 (1H, dd, J = 9.2, 2.2Hz), 7.70 (1H,
d, J = 8.8Hz), 7.55-7.41 (2H, m), 8.70-8.03 (1H, m),
7.35 (1H, d, J = 8.8Hz), 7.18 (2H, d, J = 8.8Hz), 5.5
7 (2H, s), 2.74 (3H, s).

[0396]

Example 193 2- [4- (Pyridin-2-yl) phenoxymethyl] benzothiazole (Compound No. 40.6) The title compound was synthesized according to the method of Example 129. Melting point: 143-145 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.68-8.64
(1H, m), 7.97 (2H, d, J = 9.0Hz), 8.07-7.88 (2H, m),
7.73-7.68 (2H, m), 7.56-7.41 (2H, m), 7.22-7.13 (1
H, m), 7.14 (2H, d, J = 9.0Hz), 5.56 (2H, s).

[0397]

Example 194 2- [4- (Pyridin-2-yl) phenoxymethyl] benzoxazole (Compound No. 40.5) The title compound was synthesized according to the method of Example 129. Melting point: 97-101 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.67-8.64
(1H, m), 7.97 (2H, d, J = 9.0Hz), 7.79-7.62 (3H, m),
7.59-7.55 (1H, m), 7.42-7.35 (2H, m), 7.22-7.13 (1
H, m), 7.17 (2H, d, J = 9.0Hz), 5.39 (2H, s).

[0398]

Example 195 2- [4- (Pyridin-3-yl) phenoxymethyl] benzothiazole (Compound No. 41.2) The title compound was synthesized according to the method of Example 129. Melting point: 140-143 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.81 (1H,
br.s), 8.57-8.54 (1H, m), 8.05 (1H, d, J = 7.4Hz), 7.
92 (1H, d, J = 6.8Hz), 7.82 (1H, td, J = 7.7, 2.2Hz),
7.54 (2H, d, J = 8.8Hz), 7.55-7.31 (3H, m), 7.16 (2
(H, d, J = 8.8Hz), 5.55 (2H, s).

[0399]

Working Example 196 2- [4- (Pyridin-3-yl) phenoxymethyl] benzoxazole (Compound No. 41.1) The title compound was synthesized according to the method of Working Example 129. Melting point: 128-131 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.81 (1H,
br.s), 8.57-8.54 (1H, m), 7.85-7.75 (2H, m), 7.60-
7.50 (1H, m), 7.54 (2H, d, J = 8.9Hz), 7.43-7.31 (3
H, m), 7.18 (2H, d, J = 8.9Hz), 5.39 (2H, s).

[0400]

Example 197 2- [4- (4,6-Dimethoxy- [1,3,5] triazin-2-yl) phenoxymethyl] benzothiazole (Compound No. 46.2) According to the method of Example 129 The title compound was synthesized. Melting point: 157-159 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 8.2Hz), 7.92 (1H, d, J = 7.9Hz), 7.52-7.41 (2H,
m), 7.13 (2H, d, J = 8.9Hz), 7.06 (2H, d, J = 8.9Hz),
5.49 (2H, s), 3.99 (6H, s).

[0401]

Example 198 2- [4- (thiophen-3-yl) phenoxymethyl] benzoxazole (Compound No. 35.1) The title compound was synthesized according to the method of Example 129. Melting point: 142-145 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.75
(1H, m), 7.59-7.53 (1H, m), 7.55 (2H, d, J = 8.8 H
z), 7.39-7.31 (5H, m), 7.10 (2H, d, J = 8.8 Hz), 5.
36 (2H, s).

[0402]

Working Example 199 2- [4- (thiophen-3-yl) phenoxymethyl] benzothiazole (Compound No. 35.2) The title compound was synthesized according to the method of Working Example 129. Melting point: 185-188 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.07-8.02
(1H, m), 7.93-7.88 (1H, m), 7.55 (2H, d, J = 9.0 H
z), 7.51-7.33 (5H, m), 7.08 (2H, d, J = 9.0 Hz), 5.
53 (2H, s).

[0403]

Example 200 2- [4- (2-Methylthiazol-4-yl) phenoxymethyl] benzothiazole (Compound No. 38.
1) The title compound was synthesized according to the method of Example 129. Melting point: 172-174 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 7.9Hz), 7.90 (1H, dd, J = 7.4, 1.3Hz), 7.83 (2H,
d, J = 9.0Hz), 7.55-7.35 (2H, m), 7.19 (1H, s), 7.08 (2H
H, d, J = 9.0Hz), 5.53 (2H, s), 2.78 (3H, s).

[0404]

Example 201 4- [4- (Benzothiazol-2-ylmethoxy) phenyl] thiazol-2-ylamine (Compound No. 38.1) The title compound was synthesized according to the method of Example 129. Melting point: 168-170 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 7.3Hz), 7.91 (1H, d, J = 7.4Hz), 7.54-7.36 (2H,
m), 7.28 (1H, d, J = 8.0Hz), 6.98-6.85 (2H, m), 5.50 (2H
H, s), 4.94 (2H, br.s), 2.30 (3H, s).

[0405]

Working Example 202 1- [4- (Benzothiazol-2-ylmethoxy) phenyl] -1H-pyridin-2-one (Compound No. 4)
2.2) The title compound was synthesized according to the method of Example 129. Melting point: 187-189 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H,
d, J = 8.0Hz), 7.92 (1H, d, J = 8.0Hz), 7.56-7.28 (6H,
m), 7.14 (2H, d, J = 7.9Hz), 6.64 (1H, d, J = 9.4Hz),
6.21 (1H, t, J = 6.7Hz), 5.53 (2H, s).

[0406]

Working Example 203 2- [4- (2-ethyl-5-methylthiazole-)
4-yl) phenoxymethyl] benzothiazole (Compound No. 38.12) The title compound was synthesized according to the method of Example 129. Melting point: 114-115 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H, d
d, J = 8.2, 1.0Hz), 7.91 (1H, dd, J = 7.0, 1.0Hz), 7.56
-7.30 (2H, m), 7.58 (2H, d, H = 8.9Hz), 7.08 (2H, d, J =
8.9Hz), 5.53 (2H, s), 3.00 (2H, q, J = 7.6Hz), 2.43 (3H
H, s), 1.39 (3H, t, J = 7.6Hz).

[0407]

Working Example 204 2- [4- (2-Ethylthiazol-4-yl) phenoxymethyl] benzothiazole (Compound No. 38.
13) The title compound was synthesized according to the method of Example 129. Melting point: 110-112 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 8.0Hz), 7.90 (1H, d, J = 8.8Hz), 7.84 (2H, d, J =
8.9Hz), 7.55-7.36 (2H, m), 7.21 (1H, s), 7.08 (2H, d, J
= 9.0Hz), 5.53 (2H, s), 3.08 (2H, q, J = 7.6Hz), 1.42 (3
(H, t, J = 7.6Hz).

[0408]

Working Example 205 2- [4- (2-Chlorothiazol-4-yl) phenoxymethyl] benzothiazole (Compound No. 38.
14) The title compound was synthesized according to the method of Example 129. Melting point: 123-124 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H,
d, J = 7.1Hz), 7.91 (1H, d, J = 7.1Hz), 7.89 (2H, d, J =
9.0Hz), 7.56-7.35 (2H, m), 7.26 (1H, s), 7.11 (2H, d,
J = 9.0Hz), 5.54 (2H, s)

[0409]

Example 206 2- [4- (Thiazol-4-yl) phenoxymethyl] benzothiazole (Compound No. 38.15) The title compound was synthesized according to the method of Example 129. Melting point: 159-161 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.86 (1H,
d, J = 2.0Hz), 8.04 (1H, d, J = 7.7Hz), 7.95-7.85 (1H,
m), 7.89-7.85 (1H, m), 7.89 (2H, d, J = 9.0Hz), 7.55-
7.37 (2H, m), 7.43 (1H, d, J = 1.9Hz), 7.11 (2H, d, J =
8.9Hz), 5.54 (2H, s).

[0410]

Example 207 Methyl N- [4- (benzothiazol-2-ylmethoxy) phenyl] -2-nitrilothioacetamidinate (Compound No. 50.10) The title compound was synthesized according to the method of Example 129. Melting point: 175-177 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 7.7Hz), 7.91 (1H, dd, J = 7.9, 1.9Hz), 7.56-7.38
(2H, m), 7.00-6.83 (3H, m), 5.48 (2H, s), 2.71 (1H,
s), and2.61 (2H, s), 2.24 (2H, s), and2.20 (1H, s).

[0411]

Example 208 S, S-Dimethyl-N- [4- (benzothiazol-2-ylmethoxy) phenyl] sulfimide (Compound No. 50.11) The title compound was synthesized according to the method of Example 129. Melting point: 160-170 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.03 (1H,
d, J = 7.5Hz), 7.91 (1H, d, J = 7.5Hz), 7.67-7.38 (2H,
m), 7.24 (2H, d, J = 9.0Hz), 7.02 (2H, d, J = 9.0Hz), 5.
46 (2H, s), 3.45 (6H, s).

[0412]

Example 209 1- [4- (Benzothiazol-2-ylmethoxy) -2-methylphenyl] -4-methyl-1,4-dihydro-tetrazol-5-one (Compound No. 6.12) Example 129 The title compound was synthesized according to the method described in the above. Melting point: 185-187 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H,
d, J = 7.5Hz), 7.92 (1H, dd, J = 7.1, 1.0Hz), 7.51-7.41
(2H, m), 7.28-7.24 (1H, m), 7.01-6.95 (2H, m), 5.52
(2H, s), 3.71 (3H, s), 2.25 (3H, s).

[0413]

Example 210 1- [4- (Benoxaxazol-2-ylmethoxy) -2-methylphenyl] -4-methyl-1,4-dihydro-
Tetrazol-5-one (Compound No. 6.13) The title compound was synthesized according to the method of Example 129. Melting point: 154-155 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.80-7.75
(1H, m), 7.58-7.55 (1H, m), 7.41-7.36 (2H, m), 7.29-
7.25 (1H, m), 7,05-6.95 (2H, m), 5.37 (2H, s), 3.71 (3
H, s), 2.25 (3H, s).

[0414]

Example 211 2- [4- (4-Chloropyrazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 14.
10) The title compound was synthesized according to the method of Example 129. Melting point: 174-176 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H,
d, J = 8.0Hz), 7.91 (1H, dd, J = 7.1, 0.7Hz), 7.81 (1H,
s), 7.60 (1H, s), 7.56 (2H, d, J = 9.1Hz), 7.55-7.37 (2
H, m), 7.12 (2H, d, J = 9.1Hz), 5.52 (2H, s).

[0415]

Example 212 2- [4- (4-Chloropyrazol-1-yl) phenoxymethyl] benzoxazole (Compound No. 1)
4.11) The title compound was synthesized according to the method of Example 129. Melting point: 114-116 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.80 (1H,
s), 7.79-7.74 (1H, m), 7.69 (1H, s), 7.56 (2H, d, J =
9.1 Hz), 7.59-7.51 (1H, m), 7.43-7.35 (2H, m), 7.14 (2
(H, d, J = 9.1Hz), 5.36 (2H, s).

[0416]

Working Example 213 2- [3-Methyl-4- (pyrazol-1-yl)
Phenoxymethyl] benzoxazole (Compound No. 1
4.12) The title compound was synthesized according to the method of Example 129. Physical properties: Oil ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.75
(1H, m), 7.69 (1H, d, J = 1.4Hz), 7.60-7.55 (1H, m),
7.53 (1H, d, J = 2.2Hz), 7.43-7.36 (2H, m), 7.26 (1H,
d, J = 8.5Hz), 7.00-6.93 (2H, m), 6.41 (1H, t, J = 2.2H
z), 5.36 (2H, s), 2.18 (3H, s).

[0417]

Example 214 2- (3-Methyl-4-pyrazol-1-ylphenoxymethyl) benzothiazole (Compound No. 14.
13) The title compound was synthesized according to the method of Example 129. Melting point: 81-83 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H,
d, J = 7.4Hz), 7.92 (1H, dd, J = 6.9, 1.0Hz), 7.69 (1H,
d, J = 1.8Hz), 7.56-7.38 (3H, m), 7.26 (1H, d, J = 8.5H
z), 6.99-6.89 (2H, m), 6.41 (1H, t, J = 2.1Hz), 5.52 (2H
H, s), 2.18 (3H, s).

[0418]

Example 215 2- [4- (3-Methylpyrazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 14.
14) The title compound was synthesized according to the method of Example 129. Melting point: 137-140 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 8.1Hz), 7.91 (1H, dd, J = 7.9, 1.0Hz), 7.71 (1H,
d, J = 2.4Hz), 7.58 (2H, d, J = 9.1Hz), 7.56-7.41 (2H,
m), 7.10 (2H, d, J = 9.1Hz), 6.22 (1H, d, J = 2.4Hz), 5.
52 (2H, s), 2.36 (3H, s).

[0419]

Working Example 216 2- [4- (3-Methylpyrazol-1-yl) phenoxymethyl] benzoxazole (Compound No. 1)
4.15) The title compound was synthesized according to the method of Example 129. Physical properties: Oil ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.74
(1H, m), 7.71 (1H, d, J = 2.0Hz), 7.57 (2H, d, J = 8.8H
z), 7.59-7.55 (1H, m), 7.40-7.36 (2H, m), 7.12 (2H,
d, J = 8.8Hz), 6.22 (1H, d, J = 2.0Hz), 5.36 (2H, s), 2.
36 (3H, s).

[0420]

Working Example 217 2- [4- (3,5-dimethylpyrazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 1)
4.16) The title compound was synthesized according to the method of Example 129. Melting point: 79-82 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 7.7Hz), 7.92 (1H, d, J = 7.7Hz), 7.55-7.34 (2H,
m), 7.36 (2H, d, J = 9.0Hz), 7.10 (2H, d, J = 9.0Hz), 5.
96 (1H, s), 5.52 (2H, s), 2.28 (3H, s), 2.25 (3H, s).

[0421]

Example 218 2- [4- (3,5-Dimethylpyrazol-1-yl) phenoxymethyl] benzoxazole (Compound No. 14.17) The title compound was synthesized according to the method of Example 129. Melting point: 75-77 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.74
(1H, m), 7.60-7.55 (1H, m), 7.40-7.31 (2H, m), 7.36 (2
H, d, J = 9.1Hz), 7.13 (2H, d, J = 9.1Hz), 5.96 (1H, s),
5.36 (2H, s), 2.28 (3H, s), 2.25 (3H, s).

[0422]

Working Example 219 2- [4- (4-Methylpyrazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 14.
18) The title compound was synthesized according to the method of Example 129. Melting point: 143-145 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 7.6Hz), 7.91 (1H, d, J = 7.7Hz), 7.61 (1H, s), 7.
56 (2H, d, J = 9.1Hz), 7.51-7.38 (2H, m), 7.49 (1H, s),
7.10 (2H, d, J = 9.1Hz), 5.52 (2H, s), 2,14 (3H, s).

[0423]

Working Example 220 2- [4- (4-Methylpyrazol-1-yl) phenoxymethyl] benzoxazole (Compound No. 1)
4.19) The title compound was synthesized according to the method of Example 129. Melting point: 83-85 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.74
(1H, m), 7.61 (1H, s), 7.58 (2H, d, J = 9.2Hz), 7.59-
7.56 (1H, m), 7.49 (1H, s), 7.42-7.35 (2H, m), 7.13 (2
(H, d, J = 9.1Hz), 5.36 (2H, s), 2,14 (3H, s).

[0424]

Working Example 221 2- [4- (2,5-dichloroimidazole-1-)
Yl) phenoxymethyl] benzothiazole (Compound No. 24.15) The title compound was synthesized according to the method of Example 129. Melting point: 162-165 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H,
d, J = 8.1Hz), 7.92 (1H, dd, J = 6.8, 1.0Hz), 7.59-7.42
(2H, m), 7.31 (2H, d, J = 9.0Hz), 7.14 (2H, d, J = 9.0H
z), 7.04 (1H, s), 5.54 (2H, s).

[0425]

Working Example 222 2- [4- (2,5-Dichloroimidazole-1-)
Yl) phenoxymethyl] benzoxazole (Compound No. 24.16) The title compound was synthesized according to the method of Example 129. Melting point: 141-143 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.81-7.76 (1
H, m), 7.60-7.56 (1H, m), 7.41-7.37 (2H, m), 7.32 (2
H, d, J = 9.0Hz), 7.17 (2H, d, J = 9.0Hz), 7.05 (1H, s),
5.39 (2H, s).

[0426]

Working Example 223: 5- [4- (Benzothiazol-2-ylmethoxy) phenyl] -1,3,5-trimethylimidazolidine-2,4-
Dione (Compound No. 25.7) The title compound was synthesized according to the method of Example 129. Melting point: 161-164 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H,
d, J = 7.2Hz), 7.90 (1H, d, J = 6.8Hz), 7.55-7.37 (2H,
m), 7.22 (2H, d, J = 9.0Hz), 7.05 (2H, d, J = 9.0Hz), 5.
47 (2H, s), 3.05 (3H, s), 2.82 (3H, s), 1.78 (3H, s).

[0427]

Working Example 224 2- [4- (5-Methoxy-4-methyl-4H- [1,2,
4] Triazol-3-yl) phenoxymethyl] benzoxazole (Compound No. 27.1) The title compound was synthesized according to the method of Example 129. Melting point: 125-127 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.79-7.74
(1H, m), 7.59 (2H, d, J = 9.0Hz), 7.59-7.55 (1H, m),
7.40-7.36 (2H, m), 7.17 (2H, d, J = 9.0Hz), 5.36 (2H, m
s), 4.19 (3H, s), 3.43 (3H, s).

[0428]

Working Example 225: 2- [4- [4-Methyl-5- (2,2,2-trifluoroethoxy) -4H- [1,2,4] triazol-3-yl] phenoxymethyl] benzoxazole (Compound No. 27.9) The title compound was synthesized according to the method of Example 129. Melting point: 192-193 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.80-7.76 (1
H, m), 7.63-7.56 (1H, m), 7.60 (2H, d, J = 8.7Hz), 7.4
1-7.37 (2H, m), 7.19 (2H, d, J = 8.7Hz), 5.40 (2H, s),
4.90 (2H, q, J = 8.1Hz), 3.51 (3H, s).

[0429]

Working Example 226 2- [4- [4-Methyl-5- (2,2,2-trifluoroethoxy) -4H- [1,2,4] triazol-3-yl] phenoxymethyl] benzothiazole (Compound No. 27.8) The title compound was synthesized according to the method of Example 129. Melting point: 204-206 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.06 (1H,
d, J = 8.1Hz), 7.92 (1H, d, J = 8.1Hz), 7.60 (1H, d, J =
9.0Hz), 7.56-7.43 (2H, m), 7.17 (2H, d, J = 9.0Hz), 5.
56 (2H, s), 4.90 (2H, q, J = 8.3Hz), 3.51 (3H, s).

[0430]

Working Example 227 2- [4- (Imidazol-1-yl) phenoxymethyl] benzoxazole (Compound No. 24.4) The title compound was synthesized according to the method of Working Example 129. Melting point: 120-123 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.80-7.60
(2H, m), 7.60-7.56 (1H, m), 7.44-7.32 (2H, m), 7.34 (2
H, d, J = 9.1Hz), 7.17 (2H, d, J = 9.1Hz), 7.20-7.16 (2
H, m), 5.38 (2H, s).

[0431]

Working Example 228 2- [4- (2,5-Dimethylpyrrolo-1-yl) phenoxymethyl] benzoxazole (Compound No. 3)
3.1) The title compound was synthesized according to the method of Example 129. Melting point: 90-92 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.81-7.76
(1H, m), 7.61-7.56 (1H, m), 7.41-7.37 (2H, m), 7.14 (4
H, s), 5.88 (2H, s), 5.37 (2H, s), 2.00 (6H, s).

[0432]

Working Example 229 2- [4- (2,5-Dimethylpyrrolo-1-yl) phenoxymethyl] benzothiazole (Compound No. 33.
2) The title compound was synthesized according to the method of Example 129. Melting point: 133-136 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.06 (1H, d
d, J = 8.1, 0.9Hz), 7.93 (1H, dd, J = 7.1, 1.3Hz), 7.56
-7.43 (2H, m), 7.19-7.08 (4H, m), 5.88 (2H, s), 5.53 (2
H, s), 2.01 (6H, s).

[0433]

Example 230 2- [4- (Pyrrolo-1-yl) phenoxymethyl] benzoxazole (Compound No. 34.3) The title compound was synthesized according to the method of Example 129. Melting point: 120-123 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.80-7.75
(1H, m), 7.60-7.56 (1H, m), 7.43-7.37 (2H, m), 7.34 (2
H, d, J = 9.1Hz), 7.12 (2H, d, J = 9.1Hz), 7.00 (2H, t,
J = 2.2Hz), 6.33 (2H, t, J = 2.2Hz), 5.36 (2H, s).

[0434]

Working Example 231 2- [4- (Pyrrolo-1-yl) phenoxymethyl] benzothiazole (Compound No. 34.4) The title compound was synthesized according to the method of Working Example 129. Melting point: 168-170 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H,
d, J = 8.3Hz), 7.92 (1H, dd, J = 7.0, 0.9Hz), 7.52-7.34
(2H, m), 7.34 (2H, d, J = 9.1Hz), 7.09 (2H, d, J = 9.1H
z), 7.01 (2H, t, J = 2.2Hz), 6.33 (2H, t, J = 2.2Hz), 5.
52 (2H, s).

[0435]

Working Example 232 2- [4- (2-Chloropyrrol-1-yl) phenoxymethyl] benzoxazole (Compound No. 33.
5) The title compound was synthesized according to the method of Example 129. Melting point: 75-77 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 7.80-7.76
(1H, m), 7.61-7.56 (1H, m), 7.44-7.36 (2H, m), 7.32 (2
H, d, J = 9.1Hz), 6.96 (2H, d, J = 9.1Hz), 6.76-6.74 (1
H, m), 6.24-6.17 (2H, m), 5.38 (2H, s).

[0436]

Example 233 2- [4- (2-Chloropyrrolo-1-yl) phenoxymethyl] benzothiazole (Compound No. 33.6) The title compound was synthesized according to the method of Example 129. Melting point: 90-91 ° C. ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.06 (1H,
d, J = 8.1Hz), 7.92 (1H, d, J = 8.1Hz), 7.56-7.38 (2H,
m), 7.32 (2H, d, J = 8.9Hz), 7.11 (2H, d, J = 8.9Hz), 6.
76-7.74 (1H, m), 6.24-6.17 (2H, m), 5.54 (2H, s).

[0437]

Example 234 3- [4- (Benzothiazol-2-ylmethoxy) phenyl] -1-methylimidazolidin-2,4-dione (Compound No. 34.1) The title compound was prepared according to the method of Example 129. Synthesized. Melting point: 109-111 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.04 (1H, d
d, J = 8.1, 1.3Hz), 7.91 (1H, dd, J = 7.6, 0.7Hz), 7.51
-7.41 (2H, m), 7.36 (2H, d, J = 9.2Hz), 7.12 (2H, d, J =
9.2Hz), 5.51 (2H, s), 4.03 (2H, s), 3.08 (3H, s).

[0438]

Working Example 235 2- [4- (5-Methylpyrazol-1-yl) phenoxymethyl] benzothiazole (Compound No. 14.
28) The title compound was synthesized according to the method of Example 129. Melting point: 85-87 ° C ¹ H-NMR spectrum (200 Hz, CDCl ₃ ) δ (ppm): 8.05 (1H, d,
J = 8.1Hz), 7.92 (1H, dd, J = 7.0, 1.5Hz), 7.56-7.41 (3
H, m), 7.39 (2H, d, J = 9.1Hz), 7.12 (2H, d, J = 9.1Hz),
6.17 (1H, s), 5.54 (2H, s), 2.31 (3H, s).

[0439]

Reference Example 1 2-bromomethyl-4-phenylthiazo-
(Step C-4) Dissolve 818.9 mg of 2-methyl-4-phenylthiazole in 16 ml of carbon tetrachloride, and add 831.7 mg of N-bromosuccinimide (NBS) and 22.6 mg of benzoyl peroxide. The mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and insoluble materials were removed by filtration.
The solvent of the filtrate was distilled off, and the obtained residue was purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate = 20/1) to obtain 649.8 mg (yield 55%) of the title compound. Physical properties: Oil ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.91-7.8
5 (2H, m), 7.51 (1H, s), 7.48-7.30 (3H, m), 4.80 (2H, s).

[0440]

Reference Example 2 2-bromomethyl-4-chloro-5-difluoromethylthiazole (1) 4-chloro-5-difluoromethyl-2-methylthiothiazole (Step C-1) 2,4-dichloro-5-difluoromethyl Dissolve 2.95 g of thiazole in 5.9 ml of methanol,
At room temperature, 7.08 ml of a 15% aqueous solution of sodium methyl mercaptan was added, and the mixture was stirred for 15 minutes. Thereafter, 1N-hydrochloric acid was added until the reaction solution became acidic, and the mixture was extracted with ethyl acetate. The extract was washed successively with water and saturated saline, and dried over anhydrous sodium sulfate. After filtration of the drying agent, the solvent was distilled off to obtain 3.33 g of a crude product of the title compound. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 6.85 (1H,
(t, J = 54.1Hz), 2.71 (3H, s). (2) 4-chloro-5-difluoromethyl-2-methanesulfonylthiazole (Step C-2) 4-chloro produced by the method of the above (1) 3.33 g of -5-difluoromethyl-2-methylthiothiazole was added to 1,
The mixture was dissolved in 67 ml of 2-dichloroethane, and 6.72 g of meta-chloroperbenzoic acid was added to the reaction solution at room temperature.
For 1 hour. After the completion of the reaction, the reaction solution was allowed to cool to room temperature, water was added, and the mixture was extracted with methylene chloride. After filtering the desiccant,
The solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate = 2/1) to obtain 3.75 g (yield 98%) of the title compound. Physical properties: solid (3) 4-chloro-5-difluoromethyl-2-methylthiazole 2.01 g of 4-chloro-5-difluoromethyl-2-methanesulfonylthiazole produced by the method of the above (2).
Was dissolved in 40 ml of tetrahydrofuran (THF), and 2.7 ml of 3.0 M methylmagnesium bromide was gently added dropwise to the reaction solution under a nitrogen atmosphere under ice-cooling and stirred for 30 minutes. After the completion of the reaction, a saturated aqueous solution of ammonium chloride was added to the reaction solution, and the mixture was extracted with ethyl acetate.
Dry over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate = 8/1) to obtain 936.6 mg (yield: 63%) of the title compound. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 6.88 (1H,
(4) 2-bromomethyl-4-chloro-5-difluoromethylthiazole 4-chloro-5-difluoromethyl-2 produced by the method of (3) above. (t, J = 54.2Hz), 2.76 (3H, s). 936.6 mg of methylthiazole was dissolved in 19 ml of carbon tetrachloride, and 1.997 g of N-bromosuccinimide (NBS) and benzoyl peroxide
2.7 mg was added, and the mixture was stirred for 63.5 hours while heating under reflux.
After completion of the reaction, the reaction solution was allowed to cool to room temperature, insoluble materials were removed by filtration, the solvent of the filtrate was distilled off, and methanol 20m was added to the residue.
1 was added to the reaction solution in an ice water bath until the dibromo compound disappeared (the reaction was followed by thin layer chromatography).
Sodium borohydride was added in small portions. Further, water was added to the reaction solution, extracted with ethyl acetate, the extract was washed with water,
Dry over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate = 30/1) to obtain 964.1 mg (yield: 72%) of the title compound. Physical properties: Oil ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 6.90 (1
(H, t, J = 54.0Hz), 4.67 (2H, s).

[0441]

Reference Example 3 2-Methanesulfonyloxymethyl-4-
Trifluoromethylthiazole (1) 2-benzoyloxymethyl-4-trifluoromethylthiazole 1.00 g of benzoyloxythioacetamide in 20 m
of 3-bromo-1,1,1,
0.54 ml of 1-trifluoropropan-2-one was added, and the mixture was refluxed for 4 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, dichloromethane and water were added, the organic layer was separated, washed with water and saturated saline, and dried over anhydrous sodium sulfate. After filtering the desiccant, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (elution solvent: hexane / hexane).
(Ethyl acetate = 10/3) to give the title compound (1.07).
g (73% yield). Physical properties: Oil ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.15-8.
05 (2H, m), 7.82 (1H, s), 7.68-7.41 (3H, m), 5.66 (2H, s). (2) 2-Hydroxymethyl-4-trifluoromethylthiazole (Step D-3) 1.07 g of 2-benzoyloxymethyl-4-trifluoromethylthiazole produced by the method of the above (1) was added to 5
The mixture was dissolved in methanol (1 ml), 1 ml of a 10% aqueous sodium hydroxide solution was further added, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was extracted with ethyl acetate, and the extract was washed with water and dried over anhydrous sodium sulfate. After filtering the desiccant,
The solvent was distilled off, thereby obtaining 964.4 mg of crude crystals of the title compound. (3) 2-Methanesulfonyloxymethyl-4-trifluoromethylthiazole 964.4 mg of the crude 2-hydroxymethyl-4-trifluoromethylthiazole produced by the above method (2) is dissolved in 10 ml of dichloromethane, and the reaction solution is dissolved. In an ice-water bath, 0.88 ml of triethylamine and 0.49 ml of methanesulfonyl chloride were added, and the mixture was stirred at 0 ° C. for 1 hour. After the reaction was completed, an aqueous ammonium chloride solution was added to the reaction solution, and the mixture was extracted with dichloromethane. The extract was washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate = 5/1) to obtain 454.2 mg (yield: 33%) of the title compound. Physical properties: yellow oil

[0442]

Reference Example 4 2-Methanesulfonyloxymethyl-6
-Fluorobenzothiazole (1) 2-methoxycarbonyl-6-fluorobenzothiazole (Step D-1) 2-cyano-6-fluorobenzothiazole 137.2
Hydrogen chloride gas was introduced into a suspension of 2.7 ml of methanol in 2.7 ml of an ice water bath for 3 minutes, and the mixture was further stirred for 2 minutes. After completion of the reaction, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed sequentially with water and an aqueous sodium chloride solution, and dried over anhydrous sodium sulfate. After filtering the desiccant, the solvent was distilled off and the residue was subjected to silica gel column chromatography (elution solvent:
Hexane / ethyl acetate = 5/1) to give 106.8 mg (yield 68%) of the title compound. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.21 (1
H, dd, J = 9.1,4.9Hz), 7.66 (1H, dd, J = 8.1,2.5Hz), 7.34 (1
(H, td, J = 8.9, 2.6 Hz), 4.09 (3H, s). (2) 2-hydroxymethyl-6-fluorobenzothiazole (Step D-2) 2-methoxy obtained by the method of the above (1) Carbonyl-
106.1 mg of 6-fluorobenzothiazole was dissolved in 2.1 ml of methanol, 16.5 mg of lithium borohydride was added in an ice water bath, and the mixture was stirred for 10 minutes.
10 mg of lithium borohydride was added and stirred for 10 minutes. After completion of the reaction, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed with water and an aqueous sodium chloride solution, and dried over anhydrous sodium sulfate. After filtering the desiccant,
The solvent was distilled off, and 93.1 mg (yield 100) of the title compound was obtained.
%). ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.92 (1H,
dd, J = 9.0,4.8Hz), 7.57 (1H, dd, J = 8.2,2.6Hz), 7.26-7.1
6 (1H, m), 5.06 (2H, s), 3.30-3.00 (1H, br.s). (3) 2-Methanesulfonyloxymethyl-6-fluorobenzothiazole (Step D-7) (2) 2-hydroxymethyl-6 obtained by the method of
-Dissolve 93.1 mg of fluorobenzothiazole in 1.8 ml of methylene chloride, add 0.08 ml of triethylamine and 0.05 ml of methanesulfonyl chloride in an ice water bath, raise the temperature of the reaction solution to room temperature, and allow it to stand at room temperature for 1 hour. Stirred. After completion of the reaction, water was added to the reaction solution, and extracted with methylene chloride. The extract was washed with water and an aqueous solution of sodium chloride, and dried over anhydrous sodium sulfate. After filtering the desiccant,
After evaporating the solvent, the residue was purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate = 1/1) to obtain the title compound (125.3 mg, yield 94%). ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.01 (1H,
dd, J = 8.9,4.8Hz), 7.61 (1H, dd, J = 8.1,2.5Hz), 7.23 (1H,
td, J = 8.9,2.5Hz), 5.58 (2H, s), 3.15 (3H, s).

[0443]

Reference Example 5 2- (1-Methanesulfonyloxyethyl) benzothiazole (1) 2-Formylbenzothiazole (Step D-4) 2.26 g of 2-hydroxymethylbenzothiazole was dissolved in 20 ml of acetone, and the solution was added to the reaction solution. At room temperature, 5.47 g of manganese dioxide was added, and the mixture was stirred under reflux for 5 hours, allowed to cool to room temperature, left standing for 14 hours, further added with 3.06 g of manganese dioxide, and stirred under reflux for 6 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, insolubles were removed by filtration, the solvent of the filtrate was distilled off, petroleum ether was added to the obtained crude crystals, and insolubles were removed by filtration. The filtrate was concentrated to about half the volume, and the precipitated crystals were collected by filtration to obtain 432.6 mg (yield: 19.3%) of the title compound. Melting point: 69-70 ° C ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 10.18
(1H, s), 8.28-8.23 (1H, m), 8.05-8.00 (1H, m), 7.68
-7.54 (2H, m). (2) 2- (1-hydroxyethyl) benzothiazole (Step D-5) 0.61 g of 2-formylbenzothiazole produced by the above method (1) was added to tetrahydrofuran (THF). 12
and 5.0 ml of methylmagnesium bromide was added dropwise to this solution in an acetone-dry ice bath.
The reaction vessel was transferred into an ice-water bath and stirred for 3.5 hours. After the completion of the reaction, a saturated aqueous solution of ammonium chloride was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed with an aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate = 4/1) to obtain 0.44 g (yield 66%) of the title compound. Melting point: 59-60 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.97 (1
H, d, J = 8.3Hz), 7.87 (1H, dd, J = 8.2, 1.3Hz), 7.47
(1H, td, J = 7.7, 1.5Hz), 7.37 (1H, td, Jt = 7.5Hz, Jd
= 1.4Hz), 5.26 (1H, qd, J = 14.1, 4.8Hz), 3.7-3.5 (1
H, br.s), 1.71 (1H, d, J = 6.6 Hz). (3) 2- (1-methanesulfonyloxyethyl) benzothiazole (Step D-7) produced by the method of (2) above. Dissolve 384.4 mg of 2- (1-hydroxyethyl) benzothiazole in 4 ml of methylene chloride, add 0.33 ml of triethylamine in an ice water bath, further add 0.18 ml of methanesulfonyl chloride, and warm to room temperature. And stirred for 2 hours. After completion of the reaction, saline was added to the reaction solution, and the mixture was extracted with methylene chloride. The extract was washed with water and dried over anhydrous sodium sulfate.
After filtering the drying agent, the solvent was distilled off to give the title compound 519.4.
mg (94.3% yield). Physical properties: Oil ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 8.05 (1
H, dd, J = 7.5, 1.3Hz), 7.92 (1H, dd, J = 7.7, 2.0Hz),
7.51 (1H, td, J = 7.2, 1.4Hz), 7.44 (1H, td, J = 7.7,
1.5Hz), 6.10 (1H, q, J = 6.6Hz), 3.07 (3H, s), 1.93
(3H, d, J = 6.6Hz).

[0444]

Reference Example 6 2- (1-Methyl-1-hydroxyethyl) benzothiazole (Step D-6) 304.4 mg of ethyl (benzothiazol-2-yl) carboxylate was dissolved in 6.1 ml of diethyl ether, and acetone was added. -In a dry ice bath, 5.0 ml of a 3M-methylmagnesium bromide / THF solution was added dropwise, and the mixture was stirred at the same temperature for 30 minutes, heated to room temperature, and stirred for 2 hours. After completion of the reaction, 1N-hydrochloric acid was added to the reaction solution,
The mixture was extracted with diethyl ether, and the extract was washed with water and an aqueous solution of sodium chloride, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off, and the residue was purified by silica gel column chromatography (elution solvent: hexane / ethyl acetate = 6/1) to obtain 197.1 mg (yield: 70%) of the title compound. Physical properties: White crystalline ¹ H-NMR (200 MHz, CDCl ₃ ) spectrum, δ (ppm): 7.99 (1
H, br.d, J = 8.8Hz), 7.89 (1H, br.d, J = 7.7Hz), 7.52-
7.30 (2H, m), 3.06 (1H, s), 1.76 (6H, s).

[0445]

Test Example 1 Herbicidal Effect and Chemical Damage (Pre-emergence treatment of paddy weeds) A 100 cm ² pot was filled with paddy field soil, and the seeds of a sleepy awakened Aedes millet were mixed with 1 cm of the surface layer. In addition, seedlings of paddy rice at the 2 leaf stage were transplanted into a flooded state and grown in a greenhouse. Three days later, a prescribed dose was applied to flooded soil using a wettable powder prepared according to Formulation Example 1, and 21 days later, the herbicidal effect on rice millet and the phytotoxicity on rice were investigated. Table 4 shows the results. The herbicidal effect and the phytotoxicity are represented by indices, each of which indicates the growth inhibition rate described in Table 3 below, and the test compounds are indicated by the example numbers (exemplary compound numbers).

[0446]

[Table 3] 指数 Index of herbicidal effect and phytotoxicity Growth inhibition rate (% ) ─────────────────────────────────── 00 to 10 11 11 to 30 2 31 to 50 351 70 4 71 to 90 5 91 to 100 ───────────────────────────────────

[0447]

Table 4 ─────────────────────────────────── Test compound Pre-emergence treatment (g / A) Thai rice millet paddy rice (index of herbicidal effect) (index of phytotoxicity) ──────────────────────────────────化合物 Compound 20 50 described in Example 81 a) (Exemplary Compound No. 1.7) Compound 205 0 described in Example 81 b) (Exemplary Compound No. 2.1) Compound 205 described in Example 83 0 (Exemplary Compound No. 2.2) Compound 20 50 described in Example 84 (Exemplified Compound No. 2.3) Compound 20 50 described in Example 36a) (Exemplary Compound No. 3.5) Compound 20 50 described in Example 98 (Exemplary Compound No. 5.2) Compound 20 50 described in Example 99 (Exemplified Compound No. 5.9) Compound 20 50 described in Example 41 (Exemplary Compound No. 6.3) Compound 20 50 described in Example 42 (Exemplary Compound No. 6.4) described in Example 209 Compound 2050 (Exemplary Compound No. 6.12) Compound 2050 (Exemplary Compound No. 6.13) described in Example 210 Compound 2050 (Exemplary Compound No. 9.2) described in Example 2 ) Compound 205 0 described in Example 4 (Exemplary Compound No. 11.2) Compound 205 0 described in Example 96 (Exemplary Compound No. 14.2) Compound 205 0 described in Example 213 Exemplified Compound No. 14.12) Compound 20 50 described in Example 214 (Exemplary Compound No. 14.13) Compound 20 50 described in Example 215 (Exemplified Compound No. 14.14) Example 21 Compound 2050 (Exemplary Compound No. 14.16) described in Example 218 Compound 20500 (Exemplary Compound No. 14.17) described in Example 218 Compound 20500 (Exemplary Compound No. 14) described in Example 235 .28) Compound 2050 described in Example 169 (Exemplary Compound No. 14.29) Compound 2040 described in Example 170 (Exemplary Compound No. 14.30) Compound 20 described in Example 181 50 (Exemplary Compound No. 14.31) Compound 20 50 described in Example 182 (Exemplary Compound No. 14.33) Compound 20 50 described in Example 101 (Exemplary Compound No. 16.2) Compound 20 50 described in Example 108 (Exemplary Compound No. 21.2) Compound 20 50 described in Example 109 (Exemplary Compound No. 21.3) Example 10 Compound 2050 (Exemplified Compound No. 22.3) described in Example 20 Compound 20500 (Exemplified Compound No. 23.3) described in Example 31 Compound 2050 (Exemplified Compound No. 23) described in Example 30 No. 4. 4) Compound 20 50 described in Example 25 (Exemplary Compound No. 24.3) Compound 20 50 described in Example 221 (Exemplary Compound No. 24.15) Compound 20 described in Example 69 50 (Exemplary Compound No. 28.14) Compound 20 50 described in Example 72 (Exemplary Compound No. 28.22) Compound 20 50 described in Example 7 (Exemplary Compound No. 29.4) Compound 20 40 described in Example 8 (Exemplary Compound No. 29.7) Compound 20 40 described in Example 10 (Exemplified Compound No. 30.3) Compound 20 40 described in Example 11 (No. Compound No. 30.4) Compound 20 40 described in Example 228 (Exemplary Compound No. 33.1) Compound 20 50 described in Example 229 (Exemplary Compound No. 33.2) Example 230 Compound 2050 described (Exemplary Compound No. 33.3) Compound 2050 described in Example 231 (Exemplary Compound No. 33.4) Compound 20500 described in Example 233 (Exemplary Compound No. 33. No. 6) Compound 20 50 described in Example 234 (Exemplary Compound No. 34.1) Compound 20 50 described in Example 154 (Exemplary Compound No. 37.2) Compound 20 5 described in Example 200 0 (Exemplary Compound No. 38.1) Compound 20 50 described in Example 185 (Exemplary Compound No. 38.2) Compound 20 50 described in Example 206 (Exemplary Compound No. 8.15) Compound 2050 described in Example 178 (Exemplary Compound No. 40.2) Compound 2040 described in Example 202 (Exemplary Compound No. 42.2) Compound described in Example 173 20 50 (Exemplary Compound No. 44.2) Compound 20 50 described in Example 146 (Exemplary Compound No. 49.5) Compound 20 50 described in Example 142 (Exemplary Compound No. 49.8) Compound 20 50 described in Example 139 (Exemplary Compound No. 50.2) Compound 20 50 described in Example 140 (Exemplified Compound No. 50.3) Compound 20 40 described in Example 136 (Exemplary) Compound No. 50.6) Compound 20 50 described in Example 137 (Exemplary Compound No. 50.7) Compound 20 50 described in Example 133 (Exemplary Compound No. 50.8) Compound 2050 described in Example 134 (Exemplary Compound No. 50.9) Compound 2050 described in Example 208 (Exemplary Compound No. 50.11) ──────────── ───────────────────────

[0448]

The compound of the present invention has a herbicidal action and can be used as a herbicide for paddy fields, uplands, orchards, pastures, turf, forests or non-agricultural lands.

The compounds of the present invention exhibit herbicidal activity against various weeds which are problematic in foliage treatment and soil treatment of upland crops.

The compound of the present invention can be used for various weeds that are problematic in paddy fields, for example, grass weeds such as porpoise; broadleaf weeds such as oak, azaena, staghorn beetle, mizohacobe; It shows herbicidal activity against Cyperaceae weeds such as Cyperus serrata and does not show any problematic phytotoxicity against rice.

In particular, by treating the paddy field with flooded soil before or after germination of the weeds, it is possible to strongly control rice grass weeds such as the rice weeds, such as the rice weeds, such as the rice breeder, the sandweed, the beetle and the canine. On the other hand, there is an advantage in that the selectivity to rice is high, and transplanted rice is not harmed by transplantation.

Further, it can be used not only in fields and paddy fields, but also in orchards, mulberry fields, and non-agricultural lands.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 43/56 A01N 43/56 43/58 43/58 A 43/60 43/60 43/653 43/653 43/707 43 / 707 43/713 43/713 43/76 43/76 101 101 43/78 43/78 101 101 43/82 43/82 C07D 263/32 C07D 263/32 263/44 263/44 277/24 277/24 277 / 26 277/26 277/32 277/32 277/42 277/42 277/64 277/64 413/12 249 413/12 249 417/12 249 417/12 249 (72) Inventor Noriaki Kudo Yasu, Shiga Prefecture 1041, Yasu, Yasu-cho, Gunma, In-house (72) Inventor Sotsugu Morimoto, 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga Prefecture In-house (72) Inventor Junji Kadoya 1041, Yasu-cho, Yasu-gun, Yasu, Shiga Prefecture In-house

Claims (15)

[Claims] 1. A compound represented by the following general formula (I):[Wherein, Z¹Is at least one oxygen, sulfur or
Containing 3 to 7 ring atoms including a nitrogen atom and
A heterocyclic group which may be condensed with a ring (the heterocyclic group is
1 to 3 identical or selected from the group consisting of
It may be substituted by different substituents. ), Formula-
C (R⁶) = NR⁷[Wherein, R⁶Is a hydrogen atom, C1-C
6 alkyl group or formula -NR⁸R⁹中 where R⁸And R⁹Is
Same or different, hydrogen atom, C1-C6 alkyl group
(The alkyl group may be one to four identical or different
A halogen atom or one C1-C6 alkoxy group
It may be exchanged. ), C2-C6 alkenyl groups, C2-
A C6 alkynyl group, a C2-C7 alkylcarbonyl group,
C2-C7 alkoxycarbonyl group or phenyl group (this
The phenyl group is selected from the following substituent groups b.
May be substituted with 5 identical or different substituents
No. ).基 represents a group represented by
⁷Is a C1-C6 alkyl group (the alkyl group is
Up to four identical or different halogen atoms or one ferrite
It may be substituted by a nyl group. ), C1-C6 alcohol
A xy group (the alkoxy group may be 1 to 4 identical or different
Substituted by one halogen atom or one phenyl group
C2 -C6 alkenyloxy group, C3-
C6 alkynyloxy group, hydroxyl group or formula -NR^8aR
^9a中 where R^8aAnd R^9aIs the aforementioned R⁸And R⁹Equivalent to
Is shown. Represents a group represented by｝. A group represented by the formula:
NH-C (R^Ten) = G ｛where R^TenIs C1-C6 al
Kill group, C1-C6 alkoxy group, C1-C6 alkyl
A thio group or an amino group (the amino group is one or two identical
Or even if substituted by a different C1-C3 alkyl group
Good. G is the formula = CHNO_TwoThe base represented by
Represents a group represented by the formula = N-CN. The base represented by｝
Is the formula -N = J where J is the formula = S (CH_Three)_TwoRepresented by
Group or formula = C (R¹¹) Q ^a-R¹²中 where R¹¹Is C
1-C6 alkyl group, C1-C6 alkoxy group, C1-
C6 alkylthio group, amino group (the amino group is 1 or
Two identical or different C1-C3 alkyl groups
It may be exchanged. ) Or a cyano group; ¹²Is C1
-C6 alkyl group (where the alkyl group is a C2-C7 alkyl group)
Even if substituted by a oxycarbonyl group or a phenyl group
Good. ) Or a C2-C6 alkynyl group;^aIs
Indicates an oxygen atom or a sulfur atom. Indicates a group represented by｝
You. And R¹Is a C1-C6 alkyl group (the a
The alkyl group is one to four identical or different halogen atoms.
, Or one C1-C6 alkoxy group, C1-C6
Alkylthio group, C2-C7 alkylcarbonyl group, C
2-C7 alkoxycarbonyl group, hydroxyl group, mercapto
Group, formyl group or carboxyl group
Good. ), C1-C6 alkoxy groups (the said alkoxy groups
Represents 1 to 4 identical or different halogen atoms or 1
Of C1-C6 alkoxy groups.
No. ), C1-C6 alkylthio group, C2-C7 alkyl
Carbonyl group, C2-C7 alkoxycarbonyl group,
Halogen atom, nitro group, formyl group or carboxyl
And n represents 0, 1, 2, 3 or 4;^TwoPassing
And R^ThreeAre the same or different and represent a hydrogen atom or C1-C6
X represents an alkyl group;Ｐwherein p represents 0, 1 or 2;^FourAre C1 to C
6 alkyl groups (the alkyl groups may be 1 to 4 identical or
Are different halogen atoms or one C1-C6 alkoxy
It may be substituted by a silyl group. ), C2-C6 alkenyl
Group, C2-C6 alkynyl group, C1-C6 alkoxy
Group (the alkoxy group is 1 to 4 identical or different
May be substituted by a halogen atom. ), C1-C
6 alkylthio group, C2-C7 alkylcarbonyl group,
C2-C7 alkoxycarbonyl group, phenyl group (the
The phenyl group is 1 to 5 selected from the following substituent group b.
May be substituted by the same or different substituents
No. ), A phenyloxy group (the phenyloxy group is
1 to 5 identical or different groups selected from the following substituent group b
May be substituted by the substituted substituent. ), Phenylti
Group (the phenylthio group is selected from the following substituent group b)
Substituted by 1 to 5 identical or different substituents
May be done. ), Halogen atom, hydroxyl group, nitro group,
Represents a cyano group, a formyl group or a carboxyl group;
Means that when p is 2, two R^FourBut together C3
~ C4 alkylene group may be formed, and q is 0, 1,
2, 3, or 4;^FiveIs a C1-C6 alkyl group
(The alkyl group may be one to four identical or different
A halogen atom or one C1-C6 alkoxy group
It may be exchanged. ), C2-C6 alkenyl groups, C2-
C6 alkynyl group, C1-C6 alkoxy group (the
Coxy groups are one to four identical or different halogen radicals.
May be replaced by a child. ), C1-C6 alkylthio
O group, C2-C7 alkylcarbonyl group, C2-C7
Alkoxycarbonyl group, phenyl group (the phenyl group
Represents 1 to 5 identical or selected from the following substituent group b:
May be substituted by different substituents. ), Pheni
Ruoxy group (the phenyloxy group is a group of the following substituents)
b to 1 to 5 identical or different substituents
It may be more substituted. ), Phenylthio group (
The nilthio group is 1 to 5 selected from the following substituent group b.
May be substituted by the same or different substituents
No. ), Halogen atom, hydroxyl group, nitro group, cyano group,
Q represents a formyl group or a carboxyl group;
Indicates a yellow atom. Represents a group represented by｝, and A represents oxygen or
Represents a sulfur atom, and the substituent group a is a C1-C6 alkyl group
(The alkyl group may be one to four identical or different
A halogen atom or one C1-C6 alkoxy group
It may be exchanged. ), C2-C6 alkenyl groups, C2-
C6 alkynyl group, C1-C6 alkoxy group (the
Coxy groups are one to four identical or different halogen radicals.
May be replaced by a child. ), Phenyl group (
The n-yl group includes 1 to 5 substituents selected from the following substituent group b.
It may be substituted by the same or different substituents. ),
A phenyloxy group (the phenyloxy group is
1 to 5 identical or different substituents selected from substitution group b
It may be substituted by a substituent. ), Phenylthio group (this
The phenylthio group is a 1 selected from the following substituent group b.
From 5 to 5 identical or different substituents
Good. ), A phenylsulfonyl group (the phenylsulfo
The n-yl group includes 1 to 5 substituents selected from the following substituent group b.
It may be substituted by the same or different substituents. ),
Formyl group, carboxyl group, C2-C7 alkyl carb
Bonyl group, C2-C7 alkoxycarbonyl group, C1-
C6 alkylthio group, C1-C6 alkylsulfinyl
Group, C1-C6 alkylsulfonyl group, halogen atom,
Hydroxyl group, nitro group, amino group (the amino group is
C6 alkyl group, C2-C7 alkylcarbonyl group, C
By a 2-C7 alkoxycarbonyl group or a formyl group
It may be replaced. ), Cyano group, di (C1-C6 al
Kill) carbamoyl group and di (C1-C6 alkyl) s
A group consisting of a rufamoyl group;
Gen atom, nitro group, cyano group, C1-C6 alkyl group
(The alkyl group may be one to four identical or different
It may be substituted by a halogen atom. ) And C1-C6
A group consisting of an alkoxy group is shown. Azole represented by
Derivatives or salts thereof. 2. Z¹Has at least one oxygen, sulfur or
Or 5 to 7 ring atoms containing a nitrogen atom and
A heterocyclic group which may be condensed with a zen ring (the heterocyclic group is
1 to 3 identical or different ones selected from the substituent group a1
May be substituted by such substituents. ), Formula -C
(R⁶) = NR⁷[Wherein, R⁶Is a hydrogen atom, C1-C6
Alkyl group or formula -NR⁸R⁹(Where R⁸And R⁹Is the same
One or different, a hydrogen atom, a C1-C6 alkyl group,
2-C7 alkylcarbonyl group, C2-C7 alkoxy
It represents a carbonyl group or a phenyl group. )
And R⁷Is a C1-C6 alkoxy group, a C2-C6
Lucenyloxy group, hydroxyl group or formula -NR^8aR^9a(Where
R^8aAnd R^9aIs the aforementioned R⁸And R⁹Is equivalent to )
Represents a group represented by A group represented by the formula: -NH-C
(R^Ten) = G ｛where R^TenIs a C1-C6 alkyl group,
A C1-C6 alkoxy group, a C1-C6 alkylthio group or
Is an amino group (the amino group is one or two identical or different
Or a C1-C3 alkyl group. )
G is the formula = CHNO_TwoOr a group represented by the formula: N
And a group represented by -CN. A group represented by｝ or a formula -N
= J [where J is the formula = S (CH_Three)_TwoA group represented by or
Formula = C (R¹¹) Q ^a-R¹²中 where R¹¹Are C1 to C6
Alkyl group, C1-C6 alkoxy group, C1-C6 alkyl
A quinthio group or an amino group (the amino group is one or two
Substituted by one or different C1-C3 alkyl groups
Is also good. ) Or a cyano group; ¹²Are C1-C6
Alkyl group (the alkyl group is a C2-C7 alkoxy group)
It may be substituted by a rubonyl group or a phenyl group. )
Or a C2-C6 alkynyl group;^aIs oxygen
Represents an atom or a sulfur atom. Represents a group represented by
Group a1 includes a C1 to C6 alkyl group (the alkyl group
Is represented by one to four identical or different halogen atoms
It may be replaced. ), C1-C6 alkoxy groups (such
An alkoxy group can be one to four identical or different halogen atoms.
And may be substituted by a substituent atom. ), Phenyl group, phor
A mill group, an amino group (the amino group is a C1-C6 alkyl
Group, C2-C7 alkylcarbonyl group C2-C7 alkyl
Even if substituted by a carbonyl group or a formyl group
Good. ), C1-C6 alkylthio group, C1-C6 alkyl
Killsulfonyl group, halogen atom, di (C1-C6
Kill) carbamoyl group and di (C1-C6 alkyl) s
2. The method according to claim 1, which represents a group consisting of a rufamoyl group.
A sol derivative or a salt thereof. 3. Z¹But furyl, thienyl, pyrrolyl,
Xazolyl, isoxazolyl, thiazolyl, isothia
Zolyl, oxazolidinyl, imidazolyl, pyrazoly
, Pyranyl, pyridyl, oxopyridinyl, dioxo
Piperidinyl, dioxooxazolidinyl, pyridazini
, Pyrimidinyl, pyrazinyl, pyrrolinyl, pyrrolidi
Nil, pyrrolidinonyl, pyrrolidonyl, piperidonyl,
Imidazolyl, imidazolidinyl, pyrazolidinyl,
Peridinyl, piperazinyl, azepanonyl, morpholini
, Oxadiazolyl, triazolyl, triazinyl,
Tetrazolyl, oxazolinonyl, thiazolinonyl,
Lazolinonyl, imidazolinonyl, triazolinonyl,
Triazolidinonyl, tetrazolinonyl, tetrazolidi
Nonyl, indolyl, benzofuranyl, benzothiophene
Nil, quinolyl, indazolyl, isoxazolinyl,
Oxazolidinonyl, benzoxazolyl, benzothia
Selected from the group consisting of zolyl and dioxoimidazolidinyl
Heterocyclic group (the heterocyclic group is a substituent group a1 shown below)
By one to three identical or different substituents selected from
It may be replaced. ), Formula -C (R⁶) = NR⁷(In the formula,
R⁶Represents a hydrogen atom or a C1-C6 alkyl group;⁷
Is a C1-C6 alkoxy group, a C2-C6 alkenylo
Xy group or formula -NR⁸R⁹(Where R⁸And R⁹Are the same or
Is different from a C1-C6 alkyl group, a C1-C6 alkyl
Carbonyl group or C1-C6 alkoxycarbonyl group
Is shown. ). A group represented by the formula:
NH-C (R^Ten) = G ｛where R^TenAre C1-C3 al
Kill group, C1-C3 alkoxy group, C1-C3 alkyl
A thio group or an amino group (the amino group is one or two identical
Or even if substituted by a different C1-C3 alkyl group
Good. G is the formula = CHNO_TwoThe base represented by
Represents a group represented by the formula = N-CN. The base represented by｝
Is the formula -N = J where J is the formula = S (CH_Three)_TwoRepresented by
Group or formula = C (R¹¹) Q ^a-R¹²中 where R¹¹Is C
1-C3 alkyl group, C1-C3 alkoxy group, C1-
A C3 alkylthio group, a dimethylamino group or a cyano group
And R¹²Is a C1-C3 alkyl group (the alkyl
The group is a C2-C4 alkoxycarbonyl group or a phenyl group
May be substituted by ) Or C2-C4 alkynyl
Represents a group, Q ^aRepresents an oxygen atom or a sulfur atom. }so
Shows the group represented. And a substituent group a1
Is a C1-C6 alkyl group (the alkyl group is 1 to
Substituted by four identical or different halogen atoms
Is also good. ), C1-C6 alkoxy groups (the alkoxy
The group is formed by one to four identical or different halogen atoms.
May be replaced. ), Phenyl group, formyl group,
Amino group (the amino group is a C1-C6 alkyl group, C2
-C7 alkylcarbonyl group C2-C7 alkoxycar
It may be substituted by a bonyl group or a formyl group. ),
C1-C6 alkylthio group, C1-C6 alkyl sulfo
Nyl group, halogen atom, di (C1-C6 alkyl) cal
Bamoyl group and di (C1-C6 alkyl) sulfamoi
An azole derivative according to claim 1, wherein the azole derivative represents a group consisting of
The body or its salts. 4. Z ¹ is a compound of the formula [In the formula, m represents 1, 2 or 3, and D and D ′ are the same or different and are each a hydrogen atom, a C1-C6 alkyl group, a di (C1-C6 alkyl) carbamoyl group or a di (C1-
C6 alkyl) sulfamoyl group, E, E ′ and E ″ are the same or different and are each a hydrogen atom, a C1-C6 alkyl group (the alkyl group is substituted by 1 to 4 same or different halogen atoms, And C1 to C1.
C6 alkoxy (the alkoxy group may be substituted by 1 to 4 same or different halogen atoms), phenyl group, formyl group, amino group (the amino group is a C1-C6 alkyl group, a C2- A C7 alkylcarbonyl group, which may be substituted by a C2 to C7 alkoxycarbonyl group or a formyl group), a C1 to C6 alkylthio group, a C1 to C6 alkylsulfonyl group, or a halogen atom. Groups represented by] the formula -C (R ⁶⁾ = NR ⁷
[Wherein, R ⁶ represents a hydrogen atom or a C1-C6 alkyl group, and R ⁷ represents a C1-C6 alkoxy group, a C2-C6 alkenyloxy group or a formula —NR ⁸ R ⁹ (wherein, R ⁸ and R ⁹
Are the same or different and are C1-C6 alkyl groups, C2-
It represents a C7 alkylcarbonyl group or a C2-C7 alkoxycarbonyl group. ). ], Formula -N
^{H-C (R 10) =} G { wherein, R ¹⁰ is, C1 to C3 alkyl group, C1 to C3 alkoxy group, C1 to C3 alkylthio group or an amino group (said amino group one or two identical or different may be substituted by C1~C3 alkyl group.) indicates, G represents a group represented by the group or the formula = N-CN formula = CHNO _2. Or a group represented by the formula -N = J [wherein J is a group represented by the formula = S (CH ₃ ) ₂ or a formula = C (R ¹¹ ) Q ^a -R ¹² } ¹¹ is C1
-C3 alkyl group, C1-C3 alkoxy group, C1-C
3 represents an alkylthio group, a dimethylamino group or a cyano group, and R ¹² represents a C1 to C3 alkyl group (the alkyl group may be substituted by a C2 to C4 alkoxycarbonyl group or a phenyl group) or a C2 to C4 alkynyl. And Q ^a represents an oxygen atom or a sulfur atom. Represents a group represented by｝. The azole derivative or a salt thereof according to claim 1, which is a group represented by the formula: 5. Z¹Has the formula[In the formula, m represents 1 or 2, D represents a hydrogen atom or C
1-C3 alkyl group, wherein E, E 'and E "are the same or
Is different from a hydrogen atom, a C1-C4 alkyl group
Alkyl groups are substituted by one to three identical halogen atoms.
It may be exchanged. ), C1-C3 alkoxy group, holmi
A halogen group or a halogen atom. A group represented by the formula -C
(R⁶) = NR⁷(Where R⁶Is a C1-C3 alkyl group
And R⁷Represents a C1-C3 alkoxy group. )so
A group represented by the formula -NH-C (R^Ten) = G (where R
^TenIs a C1-C3 alkyl group, a C1-C3 alkoxy group
And G represents the formula = N-CN. )
Is the formula -N = J where J is the formula = S (CH_Three)_TwoRepresented by
Group or formula = C (R¹¹) Q ^a-R¹²中 where R¹¹Is C
Represents a 1-C3 alkyl group or a C1-C3 alkoxy group
Then R¹²Is a C1-C3 alkyl group (the alkyl group
Represents a C2-C4 alkoxycarbonyl group or a phenyl group
It may be more substituted. ) And Q^aIs an oxygen atom or
Represents a sulfur atom. Represents a group represented by｝. ]
The azole derivative according to claim 1 or a group thereof.
salt. 6. The azole derivative according to claim 1, wherein R ¹ is a C1 to C6 alkyl group or a halogen atom, or a salt thereof. 7. The azole derivative or a salt thereof according to claim 1, wherein R ¹ is a C1-C3 alkyl group. 8. An azole derivative or a salt thereof according to claim 1, wherein n is 0 or 1. 9. The azole derivative or a salt thereof according to claim 1, wherein R ² and R ³ are both hydrogen atoms. 10. X is a 2-benzothiazolyl group or 2-
The azole derivative or a salt thereof according to any one of claims 1 to 9, which is a benzoxazolyl group. (11) X is a 2-benzothiazolyl group,
An azole derivative or a salt thereof according to any one of claims 1 to 9. 12. The azole derivative or a salt thereof according to claim 1, wherein X is a 2-benzoxazolyl group. 13. The method according to claim 1, wherein A is an oxygen atom.
3. The azole derivative or a salt thereof according to any one of 2. 14. A paddy herbicide comprising the azole derivative according to any one of claims 1 to 13 or a salt thereof as an active ingredient. 15. The following general formula (II): Wherein Z ² is a halogen atom, a cyano group, a formula —COR
¹³ wherein R ¹³ is a hydrogen atom, a C1-C6 alkyl group {the alkyl group is one to four identical or different halogen atoms or one amino group (the amino group is one or two The same or different, a C1-C6 alkyl group, C
It may be substituted by a 1-C6 alkoxy group or a phenyl group, or may form a quaternary ammonium salt. ). {C1-C6 alkenyl group} The alkenyl group has 1 to 4 identical or different halogen atoms or 1
Amino groups (the amino groups may be substituted with one or two identical or different C1-C6 alkyl groups, C1-C6 alkoxy groups or phenyl groups, and form a quaternary ammonium salt May be shown). ｝, Hydroxyl group,
C 1 -C ⁶ alkoxy group, formula —NR ⁸ R ⁹ } wherein R ⁸ and R ⁹ are the same or different and are a hydrogen atom, a C 1 -C 6 alkyl group (the alkyl group is 1 to 4 same or different May be substituted by a halogen atom or one C1-C6 alkoxy group), a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C2-C7 alkylcarbonyl group, a C2-C7 alkoxycarbonyl group or a phenyl group ( The phenyl group may be substituted with 1 to 5 identical or different substituents selected from the following substituent group b). A group represented by｝,
Formula —NH—NR ⁸ R ⁹ } wherein R ⁸ and R ⁹ are as defined above. Represents a group represented by｝, a fluorine atom, a chlorine atom or a bromine atom. Or a thiocarbamoyl group;
¹ is a C1 to C6 alkyl group (the alkyl group is 1 to 4 identical or different halogen atoms, or 1 C1 to C6 alkoxy group, C1 to C6 alkylthio group,
It may be substituted by a C2-C7 alkylcarbonyl group, a C2-C7 alkoxycarbonyl group, a hydroxyl group, a mercapto group, a formyl group or a carboxyl group. ), C1
C6 alkoxy group (the alkoxy group may be substituted by 1 to 4 identical or different halogen atoms or 1 C1 to C6 alkoxy group), C1 to C6 alkylthio (the alkylthio group is 1 to 4 May be substituted by four identical or different halogen atoms.), A C2-C7 alkylcarbonyl group, a C2-C7
Represents an alkoxycarbonyl group, a halogen atom, a nitro group, a formyl group or a carboxyl group, and n is 0, 1,
2, 3 or 4; R ² and R ³ are the same or different and each represent a hydrogen atom or a C1-C6 alkyl group;
Formula In the formula, p represents 0, 1 or 2, and R ⁴ represents C 1 to C
6 alkyl groups (the alkyl groups may be substituted by 1 to 4 identical or different halogen atoms or 1 C1 to C6 alkoxy group), C2 to C6 alkenyl groups, C2 to C6 alkynyl groups, C1-C6 alkoxy groups (the alkoxy groups may be substituted by 1 to 4 identical or different halogen atoms), C1 to C6
6 alkylthio group, C2-C7 alkylcarbonyl group,
C2 to C7 alkoxycarbonyl group, phenyl group (the phenyl group is 1 to 5 selected from the following substituent group b)
May be substituted by the same or different substituents. ), A phenyloxy group (the phenyloxy group is
It may be substituted by 1 to 5 identical or different substituents selected from the following substituent group b. ), A phenylthio group (the phenylthio group may be substituted by 1 to 5 identical or different substituents selected from the following substituent group b), a halogen atom, a hydroxyl group, a nitro group,
A cyano group, a formyl group or a carboxyl group; or when p is 2, two R ⁴ 's together form C3
~ C4 alkylene group may be formed, and q is 0, 1,
Represents 2, 3 or 4, wherein R ⁵ is a C1 to C6 alkyl group (the alkyl group may be substituted by 1 to 4 identical or different halogen atoms or one C1 to C6 alkoxy group). ), C2-C6 alkenyl groups, C2-
C6 alkynyl group, C1-C6 alkoxy group (the alkoxy group may be substituted by 1 to 4 same or different halogen atoms), C1-C6 alkylthio group, C2-C7 alkylcarbonyl group, C2- A C7 alkoxycarbonyl group, a phenyl group (the phenyl group may be substituted with 1 to 5 identical or different substituents selected from the following substituent group b), a phenyloxy group (the phenyloxy group) May be substituted with 1 to 5 identical or different substituents selected from the following substituent group b), phenylthio group (the phenylthio group is 1 to 5 selected from the following substituent group b) 5
May be substituted by the same or different substituents. ), Halogen atom, hydroxyl group, nitro group, cyano group,
It represents a formyl group or a carboxyl group, and Q represents an oxygen or sulfur atom. A represents an oxygen or sulfur atom; Substituent group b represents a halogen atom, a nitro group, a cyano group, a C1 to C6 alkyl group (the alkyl group has 1 to 4 And the same or different halogen atoms may be substituted) and C1-C6 alkoxy groups. ] Or a salt thereof.