JP2605651B2 - Guanidine derivatives, their production and insecticides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a guanidine derivative or a salt thereof useful as an insecticide, a process for producing the same, and an insecticide containing the same.

[0002]

2. Description of the Related Art Conventionally, a large number of synthetic compounds having a pest control effect have been used as insecticides, but most of them are organophosphates, carbamates, organic chlorine-containing compounds or pyrethroid compounds. Belongs to It is well known that the frequent use of such a limited range of compounds causes adverse effects such as an increase in insecticide resistance of insect pests, and is currently a problem in various places. In addition, among the above insecticides, some have high insecticidal activity, but are highly toxic to humans and animals, and sometimes exhibit toxicity to natural enemies of insects, and their persistence in soil is too strong. At present, satisfactory effects have not always been obtained in practice.

On the other hand, with respect to guanidine derivatives or salts thereof, for example, 3-nitro-1- (3-pyridylmethyl) guanidine is chemically and pharmacologically britten (Chem. Pharm. Bul).
l. ), 23 , 2744 (1975), and compounds having an anti-ulcer effect represented by cimetidine are known.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a guanidine derivative or a salt thereof which is low in human and animal toxicity, fish toxicity and natural enemy, and which is safe and has an excellent controlling effect on insect pests. It is intended to be provided as an insecticide.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies for many years in order to find an insecticide having a completely different structure from the conventionally used insecticides. As a result, the expression

Embedded image [In the formula, R ¹ a substituted optionally good Ifuku heterocyclic group, n represents 0 or 1, the R ² is hydrogen or optionally substituted hydrocarbon group, R ³ is the first, X represents a secondary or tertiary amino group, and X represents an electron withdrawing group. (I) X is a nitro group
R ² is a substituted C _1-4 alkyl, or
_{Or a} C _5-15 alkyl which may have a substituent ,
_3-10 cycloalkyl, C _2-10 alkenyl C
_2-10 alkynyl, C _3-10 cycloalkenyl, C
_{Represents a 6-10} aryl or C _7-10 aralkyl group.
And (ii) when X is a nitro group, R ² is a hydrogen atom
_Or C _1-4 alkyl, wherein R ³ is of the formula

Embedded image (Wherein, one of R ⁴ and R ⁵ is a hydrogen atom or
Represents a hydrocarbon group which may have a substituent,
C _1-4 alkyl having a substituent or having a substituent
Represents an optionally substituted hydrocarbon group, or R ⁴ and R ⁵ are
Together with adjacent nitrogen, aziridino, azetidino, pi
Selected from loridino morpholino and thiomorpholino
To form a cyclic amino group. Represents an amino group represented by)
And (i ii ) when X is a cyano group, R ¹ is
Heterocyclic group optionally having a substituent (excluding pyridyl group)
Is shown. The present inventors have found that the guanidine derivative represented by the formula [1] and salts thereof have an unexpectedly strong insecticidal action, and that they have low toxicity. Based on these findings, they have completed the present invention.

That is, the present invention relates to (1) a compound represented by the general formula [I]:

Embedded image [In the formula, ^{R 1} is oxygen radicals, indicates the 5-8 membered heterocyclic group containing 1-5 hetero atoms selected from oxygen, sulfur and nitrogen atoms, said heterocyclic _{group, C 1-15} alkyl, C _3-10
Cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl, C _7-10 aralkyl, nitro, hydroxyl group, mercapto, oxo, thioxo, cyano, carbamoyl, carboxyl, C _1-4 alkoxy-carbonyl, sulfo, halogen, C _1-4 alkoxy, C _6-10 aryloxy, C _1-4 alkylthio, C _6-10 arylthio, C _1-4 alkylsulfinyl, C _6-10 arylsulfinyl , C _1-4 alkylsulfonyl, C
_6-10 arylsulfonyl, amino, C _2-6 acylamino, mono- or di-C _1-4 alkylamino, C
_{3-6 cycloalkylamino, C 6-10 arylamino, C 2-4 acyl, C 6-10} aryl - carbonyl, and oxygen, 5-6 membered heterocyclic containing 1 to 4 hetero atoms selected from oxygen, sulfur and nitrogen 1 to 5 selected from ring groups
Substituents (A), and the substituents (A)
Is C _6-10 aryl, C _7-10 aralkyl, C
_3-10 cycloalkyl, _C3-10 cycloalkenyl, _C6-10 aryloxy, _C6-10 arylthio, _C6-10 arylsulfinyl, _C6-10 arylsulfonyl, _C6-10 arylamino or heterocyclic group Is 1 to 5 halogens, hydroxyl groups,
It may be substituted with a C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _6-10 aryl, C _1-4 alkoxy, phenoxy, C _1-4 alkylthio or phenylthio group. When the substituent (A) is C
_{1- 15 alkyl, C 2-10 alkenyl, C 2-10}
Alkynyl, C _1-4 alkoxy, C _1-4 alkylthio, C _1-4 alkylsulfinyl, C _1-4 alkylsulfonyl, amino, mono- or di-C _1-4 alkylamino, C _3-6 cycloalkylamino or C
_When it is a _6-10 arylamino group, 1 to 5 halogen, hydroxyl, C _1-4 alkoxy or C
_It may be substituted with a _1-4 alkylthio group.

R ² is a hydrogen atom or C _1-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C A hydrocarbon group selected from _7-10 aralkyl groups;
^It may have 1 to 5 substituents similar to 1.

[0008] R ³ is a formula

Embedded image (Wherein R ⁴ and R ⁵ are the same or different and represent hydrogen or a hydrocarbon group which may have a substituent, or R ⁴ and R ⁵ together form a cyclic amino group together with an adjacent nitrogen. rather it may also form a group, the hydrocarbon group, C
_1-15 alkyl, C _3-10 cycloalkyl, C
_2-10 alkenyl, C _2-10 alkynyl, C
Selected from _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the hydrocarbon group is
It may have the same substituent as the substituent in the heterocyclic group for R ¹ . The cyclic amino group is selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. ) Represents an amino group. X is cyano, nitro, C _1-4 alkoxy-carbonyl, hydroxycarbonyl, C _6-10 aryl-oxycarbonyl, heterocyclic oxycarbonyl, C _1-4 alkylsulfonyl optionally substituted with halogen, sulfamoyl, di- C _1-4 alkoxyphosphoryl, C _1-4 acyl optionally substituted with halogen, C _6-10 aryl-carbonyl, carbamoyl or C _1-4 alkylsulfonylthiocarbamoyl are shown.

However, (i) when X is a nitro group, R ¹
Represents an agreed definition as above SL, n represents 0 or 1, ^{R 2} is _{C 1-4} alkyl or optionally _{C 5-15} alkyl optionally having substituent has a _{substituent, C 3-10 cycloalkyl, C 2-10 alkenyl, C 2-10} show _{alkynyl, C 3-10 cycloalkenyl,} a _{C 6-10} aryl or _{C 7-10} aralkyl group, the substituents and substituents of the above ^{R 2} shows the like, R ³ is top Symbol
And indicates agreement definition, when (ii) X is a nitro group, ^{R 1} is shows <br/> consent defined as above SL, n represents 0 or 1, ^{R 2} is a hydrogen atom or a C
R _1-4 represents _1-4 alkyl, and R ³ is a group represented by the formula:

Embedded image (In the formula, one of R ⁴ and R ⁵ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and the hydrocarbon group is a C _1-15 alkyl, a C _3-10 cycloalkyl. , C _2-10 alkenyl, C _2-10 alkynyl, C
Selected from _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituents of the hydrocarbon group are the same as the above-mentioned substituents in the heterocyclic group of R ¹ , and the other is A C _1-4 alkyl having a substituent or a hydrocarbon group which may have a substituent, wherein the hydrocarbon group is C _5-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl,
Selected from C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituent of the C _1-4 alkyl hydrocarbon group and the substituent of the hydrocarbon group are the aforementioned heterocyclic ring of R ¹ R ⁴ and R ⁵ together with the substituents on the group, or together with the adjacent nitrogen, form a cyclic amino group selected from aziridino, azetidino, virolidino, morpholino and thiomorpholino groups. And (iii) when X is a cyano group, R ¹ represents a pyridyl group;
Excluding a heterocyclic group, wherein the heterocyclic group has a substituent.
Indicates what may be done. An insecticide composition comprising a guanidine derivative or a salt thereof represented by the formula:

(2) The general formula [I ^a ]

Embedded image [Wherein, R ^1a represents a 5- to 8-membered heterocyclic group containing 1 to 5 heteroatoms selected from an oxygen atom, a sulfur atom and a nitrogen atom, and the heterocyclic group is a C _1-15 alkyl,
_3-10 cycloalkyl, C _2-10 alkenyl, C
_2-10 alkynyl, C _3-10 cycloalkenyl, C
_6-10 aryl, C _7-10 aralkyl, nitro, hydroxyl group, mercapto, oxo, thioxo, cyano, carbamoyl, carboxyl, C _1-4 alkoxycarbonyl, sulfo, halogen, C _1-4 alkoxy, C
_6-10 aryloxy, C _1-4 alkylthio, C
_{6-10 arylthio, C 1-4 alkylsulfinyl, C 6-10 arylsulfinyl, C 1-4 alkylsulfonyl, C 6-10} arylsulfonyl, _{amino, C 2-6} acylamino, mono- - or di -C _{1 -4}
Alkylamino, C _3-6 cycloalkylamino, C
_6-10 arylamino, C _2-4 acyl, C _6-10
It may have 1 to 5 substituents (A) selected from arylcarbonyl and a 5- to 6-membered heterocyclic group containing 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, wherein The substituent (A) is C _6-10 aryl, C _7-10 aralkyl, C _3-10 cycloalkyl, C _3-10 cycloalkenyl, C _6-10 aryloxy, C _6-10 arylthio, C _{6 10} arylsulfinyl, C _6-10 arylsulfonyl, C
_{When it is a 6-10} arylamino or heterocyclic group, 1 to 5 halogen, hydroxyl, C _1-4 alkyl,
_C2-4 alkenyl, _C2-4 alkynyl, _C6-10
Aryl, C _1-4 alkoxy, phenoxy, C _1-4
It may be substituted with an alkylthio or phenylthio group, and the substituent (A) is a C _1-15 alkyl,
_2-10 alkenyl, C _2-10 alkynyl, C _1-4
Alkoxy, C _1-4 alkylthio, C _1-4 alkylsulfinyl, C _1-4 alkylsulfonyl, amino, mono- or di-C _1-4 alkylamino, C
_{When it is a 3-6} cycloalkylamino or C _6-10 arylamino group, it may be further substituted with 1 to 5 halogens, hydroxyl groups, C _1-4 alkoxy or C _1-4 alkylthio groups.

R ^2a is a hydrogen atom or C _1-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _{7 -10} represents a hydrocarbon group selected from aralkyl groups, and these hydrocarbon groups are represented by R
^It may have 1 to 5 substituents similar to ^1a .

R ^3a is a formula

Embedded image (Wherein R ⁴ and R ⁵ are the same or different and represent hydrogen or a hydrocarbon group which may have a substituent, or R ⁴ and R ⁵ together form a cyclic amino group together with an adjacent nitrogen. rather it may also be form a group, the hydrocarbon group, C
_1-15 alkyl, C _3-10 cycloalkyl, C
_2-10 alkenyl, C _2-10 alkynyl, C
Selected from _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the hydrocarbon group is
^It may have the same substituent as the substituent in the heterocyclic group of ^1a . The cyclic amino group is selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. ) Represents an amino group. X ^a is two <br/> DOO Roma other represents a trifluoroacetyl group.

[0013] However, when (i) ^{X a} is nitro radical, R
^1a shows the agreed definition as ^{above, R 2a} is C having a substituent
_1-4 alkyl or an optionally substituted C
_5-15 alkyl, C _3-10 cycloalkyl, C
_2-10 alkenyl, C _2-10 alkynyl, C
_{3-10 cycloalkenyl,} a _{C 6-10} aryl or _{C 7-10} aralkyl ^group, the substituents ^{R 2a} represents those similar to the substituents of the above ^{R 2a, R 3a} and upper SL <br / (Ii) when X ^a is a nitro group, R ^1a is the same as defined above ;
Where R ^2a is hydrogen or C _1-4 alkyl, and R ^3a is of the formula

Embedded image (In the formula, one of R ⁴ and R ⁵ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and the hydrocarbon group is a C _1-15 alkyl, a C _3-10 cycloalkyl. , C _2-10 alkenyl, C _2-10 alkynyl, C
Selected from _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituents on the hydrocarbon group are the same as those described above for the heterocyclic group of R ^1a , _Represents a C _1-4 alkyl having a substituent or a hydrocarbon group optionally having a substituent, wherein the hydrocarbon group is a C _5-15 alkyl, a C _3-10 cycloalkyl, a C _2-10 alkenyl. , C _2-10 alkynyl, C
_3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituent of the C _1-4 alkyl and the substituent of the hydrocarbon group are the above-mentioned R ^1a
Or R ⁴ and R ⁵ together with an adjacent nitrogen form a cyclic amino group selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. Good. ) An amino group represented by. A guanidine derivative or a salt thereof,

(3), equation

Embedded image [Wherein, R ^1a , R ^2a and X ^a have the same meaning as described above;
Represents a leaving group. A compound represented by the formula

Embedded image (The symbols in the formula have the same meanings as described above.) Or a salt thereof, characterized by reacting the guanidine derivative [I ^a ] or a salt thereof,

(4), equation

Embedded image [The symbols in the formula are as defined above. A compound represented by the formula

Embedded image [The symbols in the formula are as defined above. A guanidine derivative [I ^a ] or a salt thereof,

(5), Equation

Embedded image [The symbols in the formula are as defined above. A compound represented by the formula

Embedded image [The symbols in the formula are as defined above. A method for producing ^a guanidine derivative [ ^Ia ] or a salt thereof,

(6), Equation

Embedded image [Wherein, R ^1a and X ^a are as defined above, R ^2b is hydrogen or an optionally substituted hydrocarbon group, and R ^3b is a group represented by the formula

Embedded image (The symbols in the formula have the same meanings as described above.) Represents a primary, secondary or tertiary amino group, and when R ^3b is a tertiary amino group, R ^2b is hydrogen. A compound represented by the formula

Embedded image [Wherein, R has the same meaning as the aforementioned optionally substituted hydrocarbon group for R ^2a or the optionally substituted hydrocarbon group for R ⁴ and R ⁵ , and Y represents a leaving group. A method for producing ^a guanidine derivative [ ^Ia ] or a salt thereof,

(7), equation

Embedded image [The symbols in the formula are as defined above. A compound represented by the formula

Embedded image [The symbols in the formula are as defined above. And a method for producing ^a guanidine derivative [I ^a ] or a salt thereof.

[0019] In the above formulas, R ¹ is showing a good Ifuku <br/> heterocyclic group which may be substituted. Provided that when X is cyano group, R ¹ is an optionally substituted good Ifuku heterocyclic group except pyridyl group, preferably a halogenopyridyl or halogeno carbonothioyl azolyl group, more preferably halogen carbonothioyl azolyl group Is shown . R
^1a represents an ^optionally substituted heterocyclic group, and the above R ¹
The above-mentioned is used . As the heterocyclic group represented by R ¹ or R ^1a , for example, a 5- to 8-membered ring containing 1 to 5 hetero atoms such as an oxygen atom, a sulfur atom, a nitrogen atom or a condensed ring thereof is used. Include, for example, 2- or 3-thienyl, 2- or 3-furyl, 2- or 3-pyrrolyl, 2-, 3- or 4-pyridyl, 2-, 4- or 5-oxazolyl, 2-, 4
-Or 5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-imidazolyl, 3-, 4-
Or 5-isoxazolyl, 3-, 4- or 5-isothiazolyl, 3- or 5- (1,2,4-oxadiazolyl), 1,3,4-oxadiazolyl, 3- or 5- (1,2,4- Thiadiazolyl), 1,3,4-
Thiadiazolyl, 4- or 5- (1,2,3-thiadiazolyl), 1,2,5-thiadiazolyl, 1,2,3
-Triazolyl, 1,2,4-triazolyl, 1H- or 2H-tetrazolyl, N-oxide-2-, 3- or 4-pyridyl, 2-, 4- or 5-pyrimidinyl, N-oxide-2-, 4 -Or 5-pyrimidinyl, 3- or 4-pyridazinyl, pyrazinyl, N-oxide-3- or 4-pyridazinyl, benzofuryl,
Benzothiazolyl, benzoxazolyl, triazinyl, oxotriazinyl, tetrazolo [1,5-b] pyridazinyl, triazolo [4,5-b] pyridazinyl,
Oxoimidazinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1,4
-Oxazinyl, morpholinyl, 1,4-thiazinyl,
1,3-thiazinyl, piperazinyl, benzimidazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolizinyl, quinolizinyl, 1,8-naphthyridinyl, purinyl, pteridinyl, dibenzofuranyl, carbazolyl,
Acridinyl, phenanthridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like are used.
Preferred heterocyclic groups are, for example, 5-, 3- or 4-viridyl, 2-, 4- or 5-thiazolyl.
— Or a 6-membered nitrogen-containing heterocyclic group. Represented by these R ¹ <br/> Re that multiple heterocyclic group, the heterocyclic group represented by R ^1a is one to five identical or different substituents which may be the (preferably 1) has, Such substituents include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Alkyl groups having 1 to 15 carbon atoms such as s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and the like, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like C3-10 cycloalkyl groups such as vinyl, allyl, 2-methylallyl, 2-butenyl, 3-butenyl,
An alkenyl group having 2 to 10 carbon atoms such as 3-octenyl, for example, an alkynyl group having 2 to 10 carbon atoms such as ethynyl, 2-propynyl, and 3-hexynyl; 10 cycloalkenyl groups, for example, aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl, aralkyl groups having 7 to 10 carbon atoms such as benzyl and phenylethyl, nitro, hydroxyl, mercapto, oxo, thioxo,
Cyano, carbamoyl, carboxyl, C _1-4 alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl, etc., sulfo, halogen such as fluorine, chlorine, bromine, iodine, etc., for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s- butoxy, _{C 6-10} aryloxy of _{C 1-4} alkoxy, such as phenoxy such as t- butoxy, such as methylthio, ethylthio, n- propylthio, isopropylthio, n- butylthio, etc. t- butylthio _{C 1- 4} alkylthio, e.g. _{C 6-10} arylthio such as phenylthio, for example methylsulfinyl, _{C 1-4} alkylsulfinyl such as ethylsulfinyl, eg _{C 6-10} aryl sulfide such as phenylsulfinyl Alkylsulfonyl, for example methylsulfonyl, C _1-4 alkylsulfonyl such as ethylsulfonyl, for example C _6-10 arylsulfonyl such as phenylsulfonyl, amino, for example acetylamino, propionylamino C _2-6 acylamino amino or the like, for example methylamino, ethyl amino, n- pro building amino, isopropylamino, n- butylamino, dimethylamino, mono-diethylamino or the like - or di _{-C 1-4} alkylamino, for example _{C 3-6} cycloalkylamino, such as cyclohexylamino, for example anilino _C6-10 arylamino, for example _C2-4 acyl such as acetyl, for example _C6-10 aryl-carbonyl such as benzoyl, for example 2- or 3-thienyl, 2- or 3-furyl, 3-, 4- Or 5-pyra Ryl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5- Imidazolyl, 1,2,3- or 1,2,4-triazolyl, 1H or 2H-tetrazolyl, 2-, 3- or 4-pyridyl, 2-, 4- or 5-pyrimidinyl, 3
-Or 4-pyridanidyl, quinolyl, isoquinolyl,
1-5 selected from a 5- to 6-membered heterocyclic group containing 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen such as indolyl
Are used. These substituents are, for example, C
_6-10 aryl, C _7-10 aralkyl, C
_3-10 cycloalkyl, C _3-10 cycloalkenyl, C _6-10 aryloxy, C _6-10 arylthio, C _6-10 arylsulfinyl, C _6-10 arylsulfonyl, C _6-10 arylamino, heterocyclic group And the like, a halogen, a hydroxyl group as described above, for example, a _C1-4 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, etc., for example, vinyl, allyl, 2- _C2-4 alkenyl such as methylallyl, for example ethynyl,
1 to 5 C _2-4 alkynyl such as 2-propynyl, C _6-10 aryl, C _1-4 alkoxy, phenoxy, C _1-4 alkylthio, phenylthio and the like may be substituted. _1-15 alkyl, C _2-10
Alkenyl, C _2-10 alkynyl, C _1-4 alkoxy, C _1-4 alkylthio, C _1-4 alkylsulfinyl, C _1-4 alkylsulfonyl, amino, mono- or di-C _1-4 alkylamino, C _{3 When it is -6} cycloalkylamino, C _6-10 arylamino, etc., it may be further substituted with 1 to 5 halogens, hydroxyl groups, C _1-4 alkoxy, C _1-4 alkylthio and the like. . Preferred examples of R ¹ are, for example, 1
And a 5- or 6-membered nitrogen-containing heterocyclic ring such as pyridyl or thiazolyl which may be substituted by 2 or more.

N represents 0 or 1, but is preferably 1.

Examples of the hydrocarbon group of the "optionally substituted hydrocarbon group" represented by R ² , R ^2a , R ^2b and R include the alkyl group having 1 to 15 carbon atoms described above for R ¹ , A cycloalkyl group having 3 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; an alkynyl group having 2 to 10 carbon atoms;
A cycloalkenyl group having 10 to 10, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms and the like are used.
Examples of the substituent of the "optionally substituted hydrocarbon group", such as those mentioned above as substituents of the double heterocyclic group Ru represented by R ¹ are used. Preferred examples of R ^{2, R 2a} and ^{R 2b} are, for example hydrogen, for example methyl, ethyl, _{C 1-4} alkyl groups propyl, preferred examples of R in the _{C 1-4} alkyl group as described above is there. In addition,
In the above reaction [Invention (6)], the group R ^2b and the group R ^2a
And the case where is different.

R ³ , R ^3a and R ^3b represent primary, secondary or tertiary amino groups, for example, of the formula

Embedded image [In the formula, R ⁴ and R ⁵ are the same or different and each represents hydrogen or a hydrocarbon group which may be substituted, or R ⁴ and R ⁵ together represent a cyclic amino group together with adjacent nitrogen. And the like represented by the formula (wherein
The primary amino group is, for example, R ⁴ and R ^{5 in the} above formula.
Is a hydrogen, an unsubstituted amino group is defined as R ⁴
Or one is mono-substituted amino group is a hydrogen R ^5, and tertiary amino groups means a di-substituted amino group not hydrogen either R ⁴ and R ^5). As the “optionally substituted hydrocarbon group” represented by R ⁴ and R ⁵ , for example, those described above for R ² , R ^2a , R ^2b and R can be used. Examples of the cyclic amino group represented by R ⁴ and R ⁵ together with the adjacent nitrogen include an aziridino, azetidino, pyrrolidino, morpholino, and thiomorpholino group. Preferred examples of R ³ , R ^3a and R ^3b include, for example, unsubstituted amino groups such as mono-C
_1-4 alkylamino groups, for example di-C _1-4 alkylamino groups such as dimethylamino, ethylmethylamino,
Examples thereof include a _C1-4 acylamino group such as formamide, N-methylformamide, and acetamido. In addition,
In the above reaction [Invention (6)], the group R ^3b and the group R ^3a
And the case where is different.

Examples of the electron-withdrawing group represented by X include cyano, nitro, alkoxycarbonyl (for example, _C1-4 alkoxy-carbonyl such as methoxycarbonyl and ethoxycarbonyl), hydroxycarbonyl, C
_6-10 aryl-oxycarbonyl (for example, phenoxycarbonyl and the like), heterocyclic oxycarbonyl (for the heterocyclic group, those described above and the like are used, for example, pyridyloxycarbonyl, thienyloxycarbonyl and the like), for example, halogen (Cl, Br and the like) ) Etc., optionally substituted with C _1-4 alkylsulfonyl (eg, methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl, etc.), sulfamoyl, di- _C1-4 alkoxyphosphoryl (eg, diethoxyphosphoryl, etc.), for example, ( Cl, Br, F, etc.)
_1-4 acyl (for example, acetyl, trichloroacetyl, trifluoroacetyl, etc.), C _6-10 aryl-
Carbonyl (such as benzoyl), carbamoyl,
C _1-4 alkylsulfonylthiocarbamoyl (eg, methylsulfonylthiocarbamoyl) and the like are used. Preferred electron withdrawing groups are, for example, nitro and the like. X
^a represents a nitro or trifluoroacetyl group.

The leaving group represented by Y includes, for example, halogens such as chlorine, bromine, iodine and fluorine, such as halogens such as methanesulfonyloxy, ethanesulfonyloxy, butanesulfonyloxy and trifluoromethanesulfonyloxy (Cl, Br, F or the like; C _1-4 alkylsulfonyloxy optionally substituted with 1 to 3 halogen atoms such as benzenesulfonyloxy, p-toluenesulfonyloxy, p-bromobenzenesulfonyloxy, mesitylenesulfonyloxy and the like (Cl, Br ,
F 6) optionally substituted C _6-10 arylsulfonyloxy, for example, acetyloxy, propionyloxy, trifluoroacetyloxy and the like halogen (Cl, Br, F etc.) 1 to 3 substituted optionally be a _{C 1-6} acyloxy, for example _{C 6-10} aryl benzoyloxy - carbonyloxy, hydroxyl, for example methoxy, _{C 1-4} alkoxy ethoxy, for example methylthio, _{C 1-4} ethylthio, etc. Alkylthio groups such as C _1-4 such as methylsulfinyl;
Alkylsulfinyl, for example C _1-4 alkylsulfonyl such as methylsulfonyl, for example phenoxy, p
C _6-10 aryloxy _optionally substituted with 1 to 3 halogens such as -chlorophenoxy, p-nitrophenoxy and the like (Cl, Br, F and the like), nitro and the like, for example, 2-
One or two carbon atoms which may be substituted with one or two heterocyclic oxy groups such as pyridyloxy and 2-benzoxazolyloxy, for example, nitro groups such as phenylthio and p-nitrophenylthio.
_6-10 arylthio, for example benzylthio, p- nitrobenzyl thiosulfate etc. nitro, etc. with one to two optionally substituted _{C 7-12} also be aralkylthio, such as 2-pyridylthio, and 2-benzothiazolylthio heterocyclic Thio,
Amino, e.g. methylamino, ethylamino, mono dimethylamino etc. - or di _{-C 1-4} alkylamino,
For example, nitrogen-containing 5-membered heterocyclic groups such as 1-imidazolyl and 1,2,4-triazol-1-yl are used.

As a preferred example of Y, in the compounds [II] and [III], C _1-4 alkylthio such as methylthio and ethylthio, C _7-12 aralkylthio such as benzylthio, and C ₁ such as methoxy and ethoxy are preferable. _-4 alkoxy, amino, for example, mono- or di-C _1-4 alkylamino such as methylamino, dimethylamino and the like are used, and compounds [VI], [VII] are used.
In I] and [X], _C1-4 alkylsulfonyloxy optionally substituted with 1 to 3 halogens such as chloro and bromo, for example, halogens such as methanesulfonyloxy and trifluoromethanesulfonyloxy, for example, benzene C _6-10 arylsulfonyloxy such as sulfonyloxy and p-toluenesulfonyloxy; C _1-4 acyloxy which may be substituted with 1 to 3 hydroxyl groups such as halogens such as acetyloxy and trifluoroacetyloxy; Used.

Preferred examples of the guanidine derivative [I] or a salt thereof include, for example,

Embedded image [Wherein, R ^1b represents a pyridyl group, a halogenopyridyl group or a halogenothiazolyl group, and R ^2c , R ^4a , R
^5a is the same or different and represents hydrogen, methyl group, ethyl group, formyl group or acetyl group. However, R ^2c
Is hydrogen, a methyl group or an ethyl group, R ^4a and
Among the fine ^{R 5a,} one is hydrogen, methyl, ethyl, Ho
Lumyl group or acetyl group, and the other is formyl group
Or an acetyl group. Or a salt thereof. In the formula [I ^b ], R ^1b represents, for example, a 3-pyridyl group, for example, a halogenopyridyl group such as 6-chloro-3-pyridyl, 6-bromo-3-pyridyl, 5-bromo-3-pyridyl, or 2 -Chloro-5
And halogenothiazolyl groups such as -thiazolyl and 2-bromo-5-thiazolyl.

The guanidine derivative [I] or a salt thereof is represented by X
Cis and trans isomers are generated with respect to the position of, and when R ² is hydrogen and R ³ is a primary or secondary amino group, a tautomer is theoretically produced,
All of these isomers are included in the compound [I] of the present invention or a salt thereof.

Embedded image [The symbols in the formula are as defined above. The salts of the guanidine derivatives [I], [ ^Ia ] and [ ^Ib ] include, for example, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid,
Even when salts with inorganic acids such as perchloric acid and organic acids such as formic acid, acetic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, benzoic acid, picric acid and p-toluenesulfonic acid are used. Good.

When the guanidine derivative [I] or a salt thereof is used as an insecticide, one or more of the compounds of the general formula [I] or a salt thereof may be used according to the intended use. It is dissolved or dispersed in a liquid carrier, or mixed or adsorbed with a suitable solid carrier, and used as a dosage form such as emulsions, oils, wettable powders, powders, granules, tablets, sprays, and ointments. If necessary, these preparations may contain, for example, an emulsifier, a suspending agent, a spreading agent, a penetrant, a wetting agent, a mucilage, a stabilizer and the like, and can be prepared by a method known per se.

The content ratio of the active ingredient in the insecticide varies depending on the purpose of use, but about 10 to 90% by weight is suitable for emulsions, wettable powders and the like, and 0.1 to 90% for oils and powders.
About 10% by weight is appropriate, and about 1 to 20% by weight is appropriate as a granule, but these concentrations may be appropriately changed depending on the purpose of use. Emulsions, wettable powders and the like may be diluted appropriately with water or the like before use (for example, 100 to 1).
(000,000 times).

Examples of the liquid carrier (solvent) used include water, alcohols (eg, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, etc.) and ketones (eg, acetone, methyl ethyl ketone, etc.). , Ethers (eg, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), aliphatic hydrocarbons (eg, kerosene, kerosene, fuel oil, machine oil, etc.), aromatic hydrocarbons (Eg, benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, etc.) Solvents such as acid amides (eg, dimethylformamide, dimethylacetamide, etc.), esters (eg, ethyl acetate, butyl acetate, fatty acid glycerin ester, etc.) and nitriles (eg, acetonitrile, propionitrile, etc.) are suitable. These can be used singly or as a mixture of two or more at an appropriate ratio.

Examples of the solid carrier (diluting / extending agent) include vegetable powders (eg, soybean powder, tobacco powder, flour, wood flour, etc.), mineral powders (eg, kaolin, bentonite, clay such as acid clay, etc.) Talc powder, talc powder, talc powder, silica powder such as diatomaceous earth, mica powder, etc.), alumina, sulfur powder, activated carbon, and the like are used. can do.

Examples of ointment bases include polyethylene glycol, pectin, polyhydric alcohol esters of higher fatty acids such as glyceryl monostearate, for example, cellulose derivatives such as methylcellulose, sodium alginate, bentonite, and higher alcohols. One or more of polyhydric alcohols such as glycerin, petrolatum, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hydrogenated oil, resins, and the like, or various surfactants shown below And the like are appropriately used.

Surfactants used as emulsifiers, spreading agents, penetrants, dispersants and the like include soaps and polyoxyethylene alkyl aryl ethers [eg Neugen (TM: trade name; Same as above.)
A142 (TM); manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Nonal (TM); manufactured by Toho Chemical Co., Ltd.], alkyl sulfates [eg, Emal 10 (TM), Emar 40 (TM)] Kao Corporation], alkyl sulfonates [eg, Neogen (TM), Neogen T (TM); Daiichi Kogyo Seiyaku Co., Ltd., Neoperex (TM); Kao Corporation], polyethylene glycol Ethers [eg,
Nonipol 85 (TM), Nonipol 100 (TM),
Nonipol 160 (TM); manufactured by Sanyo Chemical Industries, Ltd.], polyhydric alcohol esters [eg, Tween 20 (TM),
Nonionic and anionic surfactants such as Tween 80 (TM); Kao Corporation] are used as appropriate.

Further, the guanidine derivative [I] or a salt thereof and, for example, other kinds of insecticides (pyrethroid insecticides, organophosphorus insecticides, carbamate insecticides, natural insecticides, etc.), acaricides, nematicides Herbicides, phytohormones,
Contains plant growth regulators, fungicides (eg, copper fungicides, organochlorine fungicides, organosulfur fungicides, phenolic fungicides, etc.), synergists, attractants, repellents, pigments, fertilizers, etc. However, it is also possible to mix and use as appropriate.

The guanidine derivative [I] and its salt are effective for controlling sanitary insect pests and animal and plant parasites, and exhibit a strong insecticidal action when brought into direct contact with insects, such as by direct application to animals and plants infested with the insect pests. However, the more distinctive property is that once the drug is once absorbed into the plant from the roots, leaves, stems, etc., the plant shows strong insecticidal action even when the pest sucks, chews, or contacts it. is there. Such a property is advantageous for controlling sucking and biting biworms. In addition, compound [I] and salts thereof have both safe and advantageous properties as insect-controlling agents for sanitary use, horticultural use, particularly agricultural use, such as low phytotoxicity to plants and low toxicity to fish.

The preparation containing the guanidine derivative [I] or a salt thereof is specifically described in, for example, Nagame ( Eury).
dema rugosum ), rice stink bug ( Sc
otinophara lurida , Riptortus clavatus , Negumbai ( Stephanitis nashi ), and Japanese ground beetle ( Laodelphax striatel )
rus ), brown planthopper ( Nilaparvata )
lugens ), leafhopper ( Nephotet )
ix cincticeps ), Unabis yanon is erysim
i ), radish aphids ( Brevicoryne )
brassicae ) and cotton aphid ( A phis)
gossypii) Hemiptera such as, for example, common cutworm (Spodoptera litura), diamondback moth (Plutella xylostella), cabbage butterfly (Pieris rapae cruciv
ora), rice stem borer (Chilo suppress
alis ), Tamanaginubawaba ( Autographa )
nigrisigna ), tobacco moth ( Helikov )
erpa assulta ), armyworm ( Pseud )
altea separata ), armyworm ( Mam )
estra brassicae ), apple cocoon monamaki ( Adoxophys orana fasc)
iata ), Watanomeiga ( Notarcha der )
ogata ), Kobunomeiga ( Cnaphalocro )
cis medicinalis ), potato moth ( Phth )
Lepidopteran pests such as Orimaea percu llella , for example, Epilil
achna vigintioctounctat
a ), beetle beetle ( Aulacophora femo )
ralis), Kisujinomihamushi (Phyllotre
ta striolata ), rice beetle ( Ou
lema oryzae ), rice weevil ( Echin )
beetle pests such as Ocnemus squameus )
For example, the house fly ( Musca domestic)
a ), Culex pipiens pa
llens ), Tabanus trigon
us ), onion fly ( Delia antiqu )
a), seedcorn maggot (Delia platura) Diptera, such as, for example locust (Locusta
migratoria , Kera ( Gryll otalp)
a africana ) and other pests such as German cockroaches ( Blattellagermanic)
a), black cockroach (Periplaneta ful
ignosa, etc., for example, spider mites ( T
etranychus urticae ), Mandarin spider mite ( Panonychus citri ), Kanzawa spider mite ( Tetranychus kanzawa ),
The spider mite, Tetranychus cina
barinus ), Apple spider mite ( Panonychu )
s ulmi), mandarin orange rust mite (Aculops p
elekassi) spider mites such as, for example, rice Shin Galle nematode (Aphelenchoides bes
It is particularly effective for controlling nematodes such as seiii ).

The insecticide of the present invention thus obtained is a safe and excellent pesticide with extremely low toxicity. And the insecticide of this invention can be used by the same method as the conventional insecticide, As a result, the effect excellent compared with the conventional product can be exhibited. For example, the insecticide of the present invention can be used for a target pest by, for example, treatment of a nursery box, foliage application of crops, application of insects, application to paddy water in water, or soil treatment. The amount of application can be varied over a wide range according to the time of application, the place of application, the method of application, etc. In general, the amount of the active ingredient (guanidine derivative [I] or its salt) per hectare is from 0.3 g to 3,
It is desirable that the application be performed so as to be 000 g, preferably 50 g to 1,000 g. When the insecticide of the present invention is a wettable powder, the final concentration of the active ingredient is 0.1 to 1,
000 ppm, preferably 10-500 ppm.

The guanidine derivative [I ^a ] or a salt thereof can be produced by the following methods (A) to (F). When the compound [I ^a ] is obtained as a free compound by the following production method, it can be converted into a salt as described above, or when the compound [I ^a ] is obtained in the form of a salt, into a free compound according to a conventional method. Further, when a compound contained in the compound [I ^a] is used as a raw material for producing other types of compound [I ^a] can be used as a free left or salts. When other raw materials can be salts as described above, they can be used not only free but also as salts. As for the starting compounds and products used in the following production methods, their salts (for example, the compound [I]
Etc.), and the like).
(A) In the present invention, a guanidine derivative [I ^a ] or a salt thereof can be produced by reacting a compound [II] or a salt thereof with ammonia, a primary amine or a secondary amine or a salt thereof. .

The ammonia, primary or secondary amine or a salt thereof used in the present invention has the formula

Embedded image Wherein R ^3a has the same meaning as described above. And the salts thereof. In this reaction, Y of the compound [II] is particularly preferably C _1-4 alkylthio, amino or the like such as methylthio. In contrast to compound [II] or a salt thereof, compound [XI] or a salt thereof is approximately 0.1%.
It is preferable to use 8 to 2.0 equivalents, but if there is no problem in the reaction, about 2.0 to 20 equivalents may be used.

The reaction may be carried out without a solvent, but is usually carried out in a suitable solvent. Examples of such a solvent include water, for example, alcohols such as methanol, ethanol, n-propanol, and isopropanol; aromatic hydrocarbons, such as benzene, toluene, and xylene;
For example, halogenated hydrocarbons such as dichloromethane and chloroform, and saturated hydrocarbons such as hexane, heptane and cyclohexane, for example, diethyl ether,
Ethers such as tetrahydrofuran (hereinafter abbreviated as THF), ethers such as dioxane, ketones such as acetone, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), and N, N Acid amides such as dimethylformamide (hereinafter abbreviated as DMF), for example, esters such as ethyl acetate, and carboxylic acids such as acetic acid and propionic acid; These solvents can be used alone or, if necessary, two or more of them in an appropriate ratio such as 1: 1 to 1
They may be mixed and used at a ratio of 1:10. When the reaction mixture is not a homogeneous phase, for example, triethylbenzylammonium chloride, tri-n-octylmethylammonium chloride, trimethyldecylammonium chloride,
The reaction may be performed in the presence of a quaternary ammonium salt such as tetramethylammonium bromide or a phase transfer catalyst such as crown ethers.

In this reaction, a base or a metal salt is used in an amount of 0.01 to 1
It may be promoted by adding 0 equivalent, preferably 0.1 to 3 equivalent. Such bases include, for example, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, phenyllithium, butyllithium, sodium hydride, potassium hydride, sodium methoxide , Sodium ethoxide, metallic sodium, metallic potassium and the like, for example, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, lutidine, collidine, 4- (dimethylamino) pyridine, D
An organic base such as BU (1,8-diazabicyclo [5,4,0] undecene-7) can be used. The organic base can itself be used as a solvent. Further, as the metal salt, for example, a copper salt such as copper chloride, copper bromide, copper acetate, and copper sulfate, and a mercury salt such as mercury chloride, mercury nitrate, and mercury acetate can be used.

The reaction temperature of this reaction is usually from -20.degree.
C. and the reaction time are usually from 10 minutes to 50 hours, preferably from 0 ° C. to 100 ° C. and from 1 hour to 20 hours, respectively. (B) The compound [ ^Ia ] or a salt thereof can be produced by reacting the starting compound [III] or a salt thereof with the compound [IV] or a salt thereof. Preferred examples of Y and reaction conditions in this reaction are the same as those described in Method (A). (C) The guanidine derivative [ ^Ia ] or a salt thereof can also be produced by reacting the compound [V] or a salt thereof with the compound [VI].

[0043] As the leaving group represented by Y of the compound (VI), for example chloro, halogen bromo and the like, for example, C _1-4 alkylsulfonyloxy, for example p- toluenesulfonyloxy such as methanesulfonyloxy C _{6 -10} arylsulfonyloxy, e.g. acetyloxy, optionally C _1-4 acyloxy such be 1-3 substituted with a halogen such as trifluoroacetyloxy is particularly preferred.

The compound [VI] is preferably used in an amount of about 0.8 to 1.5 equivalents relative to the compound [V]. This reaction may be carried out in the presence of a base to promote the reaction. As such a base, for example, those described in the method (A) can be used. The base can be used in an amount of 0.5 equivalent to a large excess, preferably about 0.8 to 1.5 equivalent, relative to compound [V]. When an organic base is used as the base, the base itself can be used as the solvent.

This reaction is generally preferably carried out in a solvent as described in method (A). If the reaction system is not a homogeneous phase, a phase transfer catalyst as described in method (A) may be used. Good. The reaction temperature is usually -20 to 150C, preferably 0 to 80C. The reaction time is usually 10 minutes to 50 hours,
Preferably, it is in the range of 2 hours to 20 hours. (D) The compound [ ^Ia ] or a salt thereof can be produced by reacting the raw material compound [VII] or a salt thereof with the compound [VIII].

Preferred examples of Y and reaction conditions in this reaction are the same as those described in the above method (C). (E) Compound [ ^Ia ] or a salt thereof can be produced by reacting starting compound [IX] or a salt thereof with compound [X]. In this reaction, Y is a C _1-4 acyloxy optionally substituted by 1 to 3 halogens such as bromo, chloro and the like, for example, acetyloxy, trifluoroacetyloxy and the like, for example, trifluoromethanesulfonyloxy and the like. 1 with halogen etc.
Particularly preferred is C _1-4 alkylsulfonyloxy which may be substituted with up to 3 carbon atoms. This reaction can be carried out under the same conditions as described in Method [C].

A compound in which Xa of the compound [I ^a ] is ^a nitro group, that is, a compound of the formula

Embedded image [Wherein, R ^1a , R ^2a and R ^3a have the same meaning as described above. Can be produced by the methods (A) to (E) described above, but can also be produced by the following method. (F) Compound [ ^Ia ] or a salt thereof can be produced by nitrating compound [IX] or a salt thereof.

As nitrating agents, 60 to 100% nitric acid is frequently used. For example, alkali metal nitrates such as sodium nitrate and potassium nitrate, for example, alkyl nitrates such as ethyl nitrate and amyl nitrate, and nitronium tetrafluoroborate ( NO ₂ BF ₄ ), nitronium trifluoromethanesulfonate (NO ₂ CF ₃ SO ₃ ), or the like may be used. The nitrating agent can be used in an amount of about 1.0 to 20 equivalents to the compound [IX] or a salt thereof, and preferably 2.0 to 10 equivalents when nitric acid is used.

This reaction may be carried out without solvent, but is usually carried out using sulfuric acid, acetic acid, acetic anhydride, trifluoroacetic anhydride, trifluoromethanesulfonic acid or the like as a solvent.
In some cases, a solvent as described in the method (A) or a mixture thereof may be used. The reaction temperature of this reaction is-
The reaction time is 50 ° C to 100 ° C and the reaction time is 10 minutes to 10 hours, preferably -20 ° C to 60 ° C and 30 minutes to 2 hours, respectively.
Time.

The compound [I ^a ] thus obtained or a salt thereof can be obtained by known means, for example, concentration, concentration under reduced pressure, distillation, fractionation, solvent extraction, liquid conversion, phase transfer, chromatography, crystallization, It can be isolated and purified by recrystallization or the like.

The compounds [II] and [III] or their salts used as raw materials in the above-mentioned method of the present invention are partially known compounds, for example, Journal of Medicinal Chemistry (J. Med. Chem.),
20 , 901 (1977) and Chemical and Pharmaceutical Bulletin (Chem. Pharm. B
ull. ), 23 , 2744 (1975), Japanese Patent Application Laid-Open No. 63-233903, or a method similar thereto.

The primary or secondary amine [XI] and the compound [IV] or a salt thereof used in the above method (A) are described, for example, in "Shin Jikken Kagaku Koza" (Maruzen), 14-III.
, Pages 1332 to 1399, or a method similar thereto.

Compounds [V] and [IX] or a salt thereof can be used, for example, in Rods' Chemistry (Rod's Chemistry).
of Carbon Compounds), 1 Volume Part C, 341~353 page and Chemical Reviews (Chem.Reviews), 5 1,301 (195
It can be produced by the method described in 2) or the like or a method similar thereto. Since the compound [VII] or a salt thereof is included in the compound [ ^Ia ] or a salt thereof, it can be produced, for example, by the methods (A), (B), (C), (E), (F) and the like described above. it can.

Compounds [VI], [VIII] and [X] are described, for example, in "New Experimental Chemistry Course" (Maruzen), Vol.
Pages 07-450 and 14-II, 1104-11
It can be produced by the method described on page 33 or the like or a method similar thereto.

[0055] Operation for guanidine derivative [I] and salts thereof have an excellent insecticidal activity and this is obvious from the following test examples.

Test Example 1 Brown Planthopper ( Nilapa)
Effect on rvata lugens ): 5 mg of a test compound (indicated by No. of the compound obtained in the following Examples) contains 5 mg of Tween 20 (TM) in the foliage of rice seedlings grown at the two-leaf stage grown in a nursery box. .5ml
And a predetermined concentration (500 pp) with 3000 times diluted dyne (spreading agent, manufactured by Takeda Pharmaceutical Co., Ltd.) water.
As m), a chemical solution of 10 ml / paper pot was sprayed with a spray gun. After putting water in the bottom of the test tube and putting the treated rice seedlings in it, 10 larvae of the third generation brown planthopper were released,
Aluminum stoppered. The test tube was housed in a constant temperature room at 25 ° C., and the dead insects were counted 7 days after the release. The mortality was calculated by the following formula ([Equation 1]), and the results are shown in [Table 1] and [Table 2].

(Equation 1)

[Table 1]

[Table 2] Tables 1 and 2 show that the guanidine derivative [I] or a salt thereof has an excellent insecticidal action against brown planthopper.

Test Example 2 Spodoptera litura ( Spodop)
effects on tera litura): soybean seedlings (monoplane spreading stage), shown by No. of test compound (the compound obtained in the following Examples) was dissolved in acetone 0.5ml containing Tween 20 (TM) and 1mg ,
Prescribed concentration (500ppm) with 3000 times dilution of Dyne water
Was sprayed with a spray gun at 20 ml / pot. After the drug solution dries, cut two soybean single leaves, put them in an ice cream cup, release 10 third-instar larvae of Lotus armyworm, put the cup indoors (25 ° C.)
Two days later, dead insects were counted. The mortality was calculated from the formula shown in Test Example 1, and the results are shown in [Table 3].

[Table 3] This [Table 3] proves that the guanidine derivative [I] or a salt thereof has an excellent insecticidal action against Spodoptera litura.

Test Example 3 Cotton Aphid ( Aphis)
Effects on gossypii ): Each test compound (indicated by the compound No. obtained in the following Examples) is applied to the stalks and leaves of the cucumber at the first leaf development stage, in which 10 adult female aphids were released 1 day before spraying. 0.5 mg containing 5 mg of Tween 20 (TM)
After dissolving with acetone, the concentration was adjusted to a predetermined concentration (100 ppm) with 3000-fold diluted dyne water, and 10 ml / pot of the drug solution was sprayed with a spray gun. 27 test plants
The cells were housed in a glass thermostat at ℃ and the number of surviving female adults was counted 2 days after the treatment. The mortality was calculated by the following formula ([Equation 2]), and the results are shown in [Table 4] and [Table 5].

(Equation 2)

[Table 4]

[Table 5] Tables 4 and 5 show that the guanidine derivative [I] or a salt thereof has an excellent insecticidal activity against cotton aphids.

[0059]

Next, the present invention will be described in more detail with reference to Examples and Reference Examples, but the present invention should not be construed as being limited to these Examples.

The column chromatography of Examples and Reference Examples was eluted by TLC (Thin Layer C).
Chromatography (thin layer chromatography). In the TLC observation, Kieselgel 60F ₂₅₄ (70 to 230 mesh) manufactured by Merck was used as a TLC plate.
, A solvent used as an elution solvent in column chromatography was used as a developing solvent, and a UV detector was used as a detection method. As the silica gel for the column, Kieselgel 60 (70-230 mesh) also manufactured by Merck was used.
The NMR spectrum shows proton NMR, using VARIAN EM using tetramethylsilane as an internal standard.
Measured with a 390 (90 MHz) type spectrum meter,
All δ values are given in ppm. When a mixed solvent is used as a developing solvent, the numerical values shown in parentheses indicate the volume mixing ratio of each solvent.

The abbreviations used in the following Examples, Reference Examples and Table 6 have the following significance.

Me: methyl group, Et: ethyl group, Ph:
Phenyl group, s: singlet, br: broad (wide), d: doublet, t: triplet, q: quartet, m: multiplet, dd: doublet doublet, J: coupling constant, Hz: hertz, CDCl
₃ : heavy chloroform, DMSO-d ₆ : heavy DMSO,
%: Weight%, mp: melting point and room temperature are about 15 to 2
Means 5 ° C.

Reference Example 1 87.4 g of thionyl chloride, 1,2-dichloroethane 10
0 ml of the mixture in a water bath at 5-20 ° C. with 2-chloro-
70.3 g of 5- (hydroxymethyl) pyridine and 1,2
-A mixture of 50 ml of dichloroethane was added dropwise over 30 minutes, then 1 hour and 30 minutes at room temperature and 4 hours under heating and reflux.
I stirred for 0 minutes. After concentration, chloroform 20 was added to the residue.
0 ml and 60 ml of water were added, and 20 g of sodium hydrogen carbonate was added little by little with stirring. Separate the organic layer,
After the treatment with activated carbon, the mixture was concentrated to give 75.9 g of 2-chloro-5-
(Chloromethyl) pyridine was obtained as a tan solid. ¹
1 H NMR (CDCl ₃ ): 4.57 (2H, s),
7.34 (1H, d, J = 8.5 Hz), 7.72 (1
H, dd, J = 8.5, 2.5 Hz), 8.40 (1
(H, d, J = 2.5 Hz) Similarly, 5- (chloromethyl) thiazole, 5- (chloromethyl) -2-methylthiazole and 5- (chloromethyl) -2-phenylthiazole were obtained.

Reference Example 2 2-chloro-5- (chloromethyl) pyridine 14.99
g, 25% ammonia water 63.01 g, and acetonitrile 60 ml in a stainless steel pressure-resistant reaction vessel,
Stirred in an 80 ° C. oil bath for 2 hours. 3 in the reaction mixture
12.3 g of a 0% aqueous sodium hydroxide solution was added and concentrated. Ethanol (200 ml) was added to the residue, and the mixture was dried over anhydrous magnesium sulfate. After the filtrate was concentrated, it was purified by column chromatography (developing solvent; dichloromethane-methanol (4: 1)) to obtain 7.66 g of 5- (aminomethyl) -2-chloropyridine as a yellow solid. ¹ H NMR (CDCl ₃ ): 1.60
(2H, s), 3.90 (2H, s), 7.28 (1
H, d, J = 8.5 Hz), 7.67 (1H, dd, J)
= 8.5, 2.5 Hz), 8.33 (1H, d, J =
2.5 Hz) Similarly, 5- (aminomethyl) -2-bromopyridine, 5- (aminomethyl) -2-chlorothiazole, 3-cyanobenzylamine, 5- (aminomethyl) thiazole, 5- (aminomethyl) ) 2-Methylthiazole, 5- (aminomethyl) -2-phenylthiazole and 5- (aminomethyl) -2- (trifluoromethyl) thiazole were obtained.

Reference Example 3 36 g of a 40% aqueous solution of methylamine and acetonitrile 20
In a 0 ml mixed solution, 15.05 g of 2-chloro-5- (chloromethyl) pyridine and 50 m of acetonitrile were added at room temperature.
of the mixed solution was added dropwise over 1 hour, and the mixture was further stirred for 1 hour and 30 minutes. The reaction mixture was concentrated and the residue
After neutralizing with sodium chloride, saturating with sodium chloride and extracting with dichloromethane (200 ml × 2), the organic layer was dried over anhydrous magnesium sulfate and concentrated, and the residue was subjected to column chromatography (developing solvent: dichloromethane- Methanol (4: 1)) and 8.77 g of 2-chloro-
5- (Methylaminomethyl) pyridine was obtained as a tan liquid. ¹ H NMR (CDCl ₃ ): 1.30 (1
H. br. s), 2.44 (3H, s), 3.75 (2
H, s), 7.30 (1H, d, J = 8.4 Hz),
7.68 (1H, dd, J = 8.4, 2.4 Hz),
8.35 (1H, d, J = 2.4Hz)

Reference Example 4 S, S'-dimethyl dithioiminocarbonate hydrochloride 3.15
g and pyridine (30 ml) were added dropwise in a water bath at 20 ° C. with 6.30 g of trifluoroacetic anhydride over 30 minutes, and then stirred for 5 hours. The reaction mixture was concentrated, 20 ml of water was added to the residue, and the mixture was extracted with dichloromethane (30 ml). The organic layer is dried over anhydrous magnesium sulfate and concentrated,
The residue was purified by column chromatography (developing solvent: dichloromethane) to obtain 2.33 g of S, S'-dimethyl N-trifluoroacetyldithioiminocarbonate as a yellow liquid. _{^{1 H NMR (CDCl 3):}} 2.66
(S)

Reference Example 5 N-cyanodithioiminocarbonate S, S'-dimethyl1.0
g and 15 ml of isopropyl alcohol, a solution of 0.89 g of 5- (aminomethyl) -2-chloropyridine in 5 ml of isopropyl alcohol was added under reflux with heating.
And the mixture was refluxed for 1 hour and 30 minutes. The reaction mixture was ice-cooled, and the resulting white solid was collected by filtration to obtain 1.35.
g of 1- (6-chloro-3-pyridylmethyl) -3-cyano-2-methylisothiourea were obtained. ¹ H NMR
(CDCl ₃ ): 2.63 (3H, s), 4.51 (2
H, d, J = 6 Hz), 7.51 (1H, d, J = 8H)
z), 7.83 (1H, dd, J = 8, 3 Hz), 8.
38 (1H, d, J = 3 Hz), 8.95 (1H, b
r. s) Similarly, 1- (6-chloro-3-pyridylmethyl) -2-methyl-3-trifluoroacetylisothiourea, 1- (6-chloro-3-pyridylmethyl)-
1,2-dimethyl-3-trifluoroacetylisothiourea and 1- (2-chloro-5-thiazolylmethyl)-
3-Cyano-2-methylisothiourea was obtained.

Reference Example 6 After washing 0.80 g of 60% sodium hydride (oil-based) with petroleum ether, 20 ml of DMF was added. To this suspension was added 3-cyano-1,2-dimethylisothiourea at room temperature.
A solution of 58 g of DMF in 10 ml was added dropwise over 10 minutes. 1
After stirring for an hour, 3.24 g of 2-chloro-5- (chloromethyl) pyridine was added over 5 minutes, and the mixture was further stirred at room temperature for 15 hours. DMF was distilled off under reduced pressure, 100 ml of dichloromethane was added to the residue, washed with water, and the organic layer was dried over anhydrous magnesium sulfate. After concentration, column chromatography (developing solvent; chloroform-ethanol (20:
1)), 3.55 g of 1- (6-chloro-3-)
Pyridylmethyl) -3-cyano-1,2-dimethylisothiourea was obtained as a yellow liquid. ¹ H NMR (CDC
l ₃ ): 2.84 (3H, s), 3.20 (3H,
s), 4.82 (2H, s), 7.35 (1H, d, J
= 8 Hz), 7.63 (1H, dd, J = 8.2H)
z), 8.31 (1H, d, J = 2 Hz)
-(6-chloro-3-pyridylmethyl) -3-cyano-
1-ethyl-2-methylisothiourea, 1- (6-chloro-3-pyridylmethyl) -1,2-dimethyl-3-nitroisothiourea, 1- (6-chloro-3-pyridylmethyl) -1-ethyl- 2-methyl-3-nitroisothiourea, 1- (2-chloro-5-thiazolylmethyl) -1
-Ethyl-2-methyl-3-nitroisothiourea and 1
-(2-Chloro-5-thiazolylmethyl) -1,2-dimethyl-3-nitroisothiourea was obtained.

Reference Example 7 A mixture of 4.07 g of 2-chloro-5-aminopyridine, 2.55 g of methyl isothiocyanate and 30 ml of acetonitrile was heated under reflux for 13.5 hours, and 0.70 g of methyl isothiocyanate was added. The mixture was heated under reflux for 3.5 hours. The reaction mixture was concentrated, and the residue was purified by column chromatography (developing solvent; dichloromethane-ethyl acetate (1: 1)) to obtain 4.51 g of 1- (6-chloro-3-pyridyl) -3-methylthiourea. I got mp.
From 164 to 164.5 ° C. (recrystallized from ^{acetonitrile) 1}
1 H NMR (CDCl ₃ ): 3.12 (3H, d, J =
4.8 Hz), 6.86 (1H, br.q, J = 4.8)
Hz), 7.33 (1H, d, J = 8.5 Hz), 7.
86 (1H, dd, J = 8.5, 2.8 Hz), 8.3
1 (1H, d, J = 2.8 Hz), 8.63 (1H, b
r. s)

Reference Example 8 A mixture of 4.45 g of 2-bromo-5-methylthiazole, 4.89 g of N-bromosuccinimide, 0.2 g of benzoyl peroxide and 50 ml of carbon tetrachloride was heated and refluxed for 50 minutes, and then cooled to room temperature. Allowed to cool to room temperature. After filtering off the insoluble matter, the filtrate was concentrated. The residue was subjected to column chromatography (developing solvent; hexane-dichloromethane (2: 3)).
To give 4.53 g of 2-bromo-5- (bromomethyl) thiazole as a yellow solid. ¹ H NMR
(CDCl ₃ ): 4.64 (2H, s), 7.54 (1
H, s) In a similar manner, 5- (bromomethyl) -3- (difluoromethyl) -2-thiazolone was obtained.

Reference Example 9 1.85 g of potassium phthalimide, 20 ml of dry DMF
2.57 g of 2-bromo-5- (bromomethyl) thiazole were added in portions over 20 minutes to the mixture at room temperature.
After that I stirred for one hour. The insolubles were removed by filtration, the filtrate was concentrated, 30 ml of ethanol was added, and 0.60 g of hydrazine hydrate was added dropwise in an oil bath at 20 ° C for 2 minutes. The reaction mixture was heated under reflux for 1 hour, concentrated, added with 20 ml of water and 10 ml of concentrated hydrobromic acid, and further heated under reflux for 30 minutes. After cooling, the mixture was neutralized with a 20% aqueous sodium hydroxide solution, concentrated, and 50 ml of acetonitrile was added to the residue.
Insolubles were removed by filtration. After concentrating the filtrate, column chromatography (developing solvent; dichloromethane-methanol (5:
1)), and 0.76 g of 5- (aminomethyl)-
2-Bromothiazole was obtained as a brown oil. ¹ H
_{NMR (CDCl 3): 1.59 (} 2H, s), 4.0
6 (2H, d, J = 1.2 Hz), 7.40 (1H,
t, J = 1.2 Hz)

Reference Example 10 0.88 g of diethylamine was added to a mixture of 1.35 g of S-methyl-N-nitroisothiourea and 5 ml of acetonitrile.
And stirred in a 60 ° C. oil bath for 6 hours. After concentration of the reaction mixture, the residue was purified by column chromatography (developing solvent; dichloromethane-methanol (20: 1)) to obtain 0.85 g of N, N-diethyl-N′-nitroguanidine as a white solid. . mp. 96-97 ° C ¹ H NMR (CDCl ₃ ): 1.23 (6H, t, J
= 7.2 Hz), 3.47 (4H, q, J = 7.2H)
z), 7.93 (2H, br.s)

Reference Example 11 A mixture of 1.0 g of S-methyl-N-nitroisothiourea and 15 ml of acetonitrile was added with 0.6 mol of pyrrolidine at room temperature.
1 g was added dropwise over 2 minutes, followed by stirring for 30 minutes.
Concentrate the reaction mixture, wash the remaining solid with ether,
1.09 g of 1- (N-nitroamidino) pyrrolidine was obtained as white crystals. mp. 188-191 ° C Similarly, N-ethyl-N-methyl-N'-nitroguanidine (mp. 124-125 ° C) was obtained.

Reference Example 12 To a mixture of 5.0 g of S-methyl-N-nitroisothiourea and 25 ml of pyridine, 11.3 g of acetic anhydride was added at room temperature.
It was dropped in 0 minutes. After dropping, stir at room temperature for 5 hours,
The reaction mixture was concentrated. The residue was poured into 50 ml of 2N hydrochloric acid, and the resulting solid was collected by filtration and dried to obtain 5.1 g of N-acetyl-S-methyl-N'-nitroisothiourea as white crystals. mp. 109-110 ° C

Reference Example 13 2-hydroxy-5-methylthiazole (5-methyl-
2-thiazolone) 11.5 g, dioxane 100 ml,
To a mixture of 100 g of a 40% aqueous sodium hydroxide solution, 8
Chlorodifluoromethane (gaseous) in an oil bath at 0 ° C
For one hour. 500 m of reaction mixture
1 liter of water and extracted twice with ether. The ether layer was dried over anhydrous magnesium sulfate, concentrated, and the residue was separated by column chromatography (eluent: dichloromethane-hexane (1: 1)) to give 2.0 g of 2- (difluoromethoxy) -5. -Methylthiazole (
¹ H NMR (CDCl ₃ ): 2.35 (3H, d, J =
1.5 Hz), 6.88 (1H, br.q, J = 1.5
Hz), 7.18 (1H, t, J = 72.0 Hz)) and 4.0 g of 3- (difluoromethyl) -5-methyl-
2- thiazolone _{^{(1 H NMR (CDCl 3)}} : 2.1
6 (3H, d, J = 1.5 Hz), 6.51 (1H, b
r. q, J = 1.5 Hz), 7.07 (1H, t, J =
60.0 Hz)). Both are pale yellow liquids.

Reference Example 14 2,22,2-trifluorothioacetamide 11.22
g, ethyl 2-chloro-2-formylacetate 10.14 g
The mixture was stirred in an oil bath at 70 ° C. for 30 minutes and in an oil bath at 100 ° C. for 1 hour and 30 minutes.
00 ml was added to remove insolubles. After concentration, the residue was purified by column chromatography (developing solvent; hexane-ethyl acetate (10: 1)) to obtain 3.74 g of ethyl 2- (trifluoromethyl) -5-thiazolecarboxylate as a yellow liquid. ¹ H NMR (CDCl ₃ ): 1.4
1 (3H, t, J = 7.2 Hz), 4.43 (2H,
q, J = 7.2 Hz), 8.50 (1H, s). Lithium aluminum hydride 0.50g, dry THF80m
l of the above ethyl thiazolecarboxylate (2.51 g) in THF (10 ml) was added dropwise to the mixture at room temperature over 45 minutes.
Stirred for another 30 minutes. 0.5 ml of water, 0.5 ml of a 10% aqueous sodium hydroxide solution, and 1.5 ml of water were added dropwise to the reaction mixture cooled with a cryogen in this order. After further stirring in an ice bath for 10 minutes and at room temperature for 30 minutes,
Insolubles were filtered off on celite. After concentrating the filtrate, 100 ml of chloroform was added, dried over anhydrous magnesium sulfate, and concentrated to obtain 1.24 g of 5- (hydroxymethyl) -2- (trifluoromethyl) thiazole as a brown liquid. ¹ H NMR (CDCl ₃ ):
3.45 (1H, br.s), 4.93 (2H, s),
7.77 (1H, s) 0.4 ml of thionyl chloride and 1,2
A mixture of 1 ml of dichloroethane in a 40 ° C. oil bath,
0.80 g of the above thiazole in 1,2-dichloroethane 2
The solution was added dropwise over 10 minutes and stirred at the same temperature for another hour. 2 ml of dichloromethane and 2 ml of water were added to the reaction mixture.
After adding ml, add weight while stirring,
The pH of the aqueous layer was set to 7. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The organic layers were combined, the insolubles were filtered off, washed with saturated saline, and dried over anhydrous magnesium sulfate. After concentration, 0.74 g of 5- (chloromethyl)
-2- (Trifluoromethyl) thiazole was obtained as a reddish brown liquid. _{^{1 H NMR (CDCl 3):}} 4.84
(2H, s), 7.90 (1H, s)

Production Example 1 A mixture of 0.42 g of 1- (6-chloro-3-pyridylmethyl) -3-cyano-1-ethyl-2-methylisothiourea and 5 ml of acetonitrile was heated under reflux to a 40% aqueous methylamine solution. 0.5 g 6 times per hour (total 3.0 g)
g) The reaction mixture was stirred for 6 hours while adding. The reaction mixture was concentrated and 0.32 g of 1- (6-chloro-3-
(Pyridylmethyl) -2-cyano-1-ethyl-3-methylguanidine (Compound No. 3) was obtained. mp 122
１２３123 ° C. ¹ H NMR (DMSO-d ₆ ): 1.07
(3H, t, J = 7 Hz), 3.00 (3H, d, J =
5 Hz), 3.35 (2H, q, J = 7 Hz), 4.6
2 (2H, s), 7.23 (1H, br.s), 7.5
0 (1H, d, J = 8 Hz), 7.78 (1H, dd,
J = 8.3 Hz, 8.33 (1 H, d, J = 3 Hz)

Production Example 2 60% sodium hydride (oil-based) 0.44 g, dry DM
F, N, N-dimethyl-N'-
1.32 g of nitroguanidine were added in 20 minutes. 10
After stirring for 1 minute, 1.62 g of 2-chloro-5- (chloromethyl) pyridine was added over 5 minutes, followed by stirring for 2 hours at room temperature and 4 hours in a 60 ° C. oil bath. The insolubles were removed by filtration, the filtrate was concentrated, and the residue was subjected to column chromatography (developing solvent; dichloromethane-ethyl acetate 5: 1 to 1
3: 1) and 0.82 g of 1- (6-chloro-3).
-Pyridylmethyl) -3,3-dimethyl-2-nitroguanidine (Compound No. 6) was obtained. mp from 160.5 to 162.5 ° C. Elemental analysis _{(C 9 H 12 N 5 O} 2 Cl) ¹ H NMR (CDCl ₃ ): 3.10 (6H, s),
4.49 (2H, br.s), 7.27 (1H, d, J
= 8.5 Hz), 7.70 (1H, dd, J = 8.5,
2.5 Hz), 8.2 to 8.5 (2H, m)

Production Example 3 1,2-Dimethyl-3-nitroisothiourea 0.45
g, 5- (aminomethyl) -2-chloropyridine 0.4
3g) A mixture of 25 ml of ethanol was heated under reflux for 6 hours and then concentrated. The residue was purified by column chromatography (developing solvent; chloroform-ethanol (5: 1)), and 0.25 g of 1- (6-chloro-3-pyridylmethyl) -3-methyl-2-nitroguanidine (compound N
o. 5) was obtained. mp 150 to 152 ° C. Elemental analysis _{(C 8 H 10 N 5 O} 2 Cl) ^{_{1 H NMR (CDCl 3 -DMSO-}} d 6): 2.9
4 (3H, d, J = 5 Hz), 4.51 (2H, d, J
= 5 Hz), 7.32 (1H, d, J = 8 Hz), 7.
75 (1H, dd, J = 8, 2 Hz), 7.82 (1
H, br. s), 8.37 (1H, d, J = 2 Hz),
8.90 (1H, br.s)

Production Example 4 0.676 g of S-methyl-N-nitroisothiourea, 2
-Chloro-5- (methylaminomethyl) pyridine 0.7
After heating a mixture of 83 g and 6 ml of acetonitrile under reflux for 17 hours, the reaction mixture was concentrated. The residue was recrystallized from ethanol to give 0.38 g of 1- (6-
Chloro-3-pyridylmethyl) -1-methyl-2-nitroguanidine (Compound No. 7) was obtained. mp 167
-170 ° C. Elemental analysis _{(C 8 H 10 N 5 O} 2 Cl) _{^{1 H NMR (DMSO-d 6}} ): 3.01 (3H,
s), 4.70 (2H, s), 7.48 (1H, d, J
= 8.4 Hz), 7.78 (1H, dd, J = 8.4,
2.2Hz), 8.37 (1H, d, J = 2.2H)
z), 8.56 (2H, br.s)

Production Example 5 0.82 g of 1- (6-chloro-3-pyridylmethyl) -1,2-dimethyl-3-nitroisothiourea, 0.464 g of a 40% aqueous solution of methylamine, 10 m of acetonitrile
The mixture was stirred at 70 ° C. for 2 hours. After the reaction mixture was concentrated, it was purified by column chromatography (developing solvent; dichloromethane-methanol (10: 1)).
56 g of 1- (6-chloro-3-pyridylmethyl)-
1,3-dimethyl-2-nitroguanidine (compound N
o. 8) was obtained. mp 136-137 ° C Elemental analysis value (C ₉ H ₁₂ N ₅ O ₂ Cl) _{^{1 H NMR (CDCl 3):}} 2.96 (3H, d, J
= 4.8 Hz), 3.05 (3H, s), 4.67 (2
H, s), 7.33 (1H, d, J = 8.3 Hz),
7.68 (1H, dd, J = 8.3, 2.4 Hz),
7.96 (1H, br.q, J = 4.8 Hz), 8.3
0 (1H, d, J = 2.4 Hz)

Production Example 6 A mixture of 0.53 g of nitroguanidine, 0.61 g of 3- (aminomethyl) pyridine and 10 ml of water was heated at 70 to 80 ° C.
For 1.5 hours. After standing at room temperature overnight, the deposited precipitate was collected by filtration and washed with ethanol to obtain 0.48 g of N-nitro-N '-(3-pyridylmethyl) guanidine (Compound No. 12). mp. 185-190 ° C ¹ H NMR (DMSO-d ₆ ): 4.47 (2H,
d, J = 5 Hz), 7.40 (1H, dd, J = 6, 4)
Hz), 7.67 to 7.85 (1H, m), 7.85 to
8.30 (2H, br.s), 8.47 to 8.67 (2
H, m)

Production Example 7 1- (6-Chloro-3-pyridylmethyl) -3,3-dimethyl-2-nitroguanidine (Compound No. 6)
To a mixture of 24 g and 6 ml of dry THF was added 0.045 g of 60% sodium hydride (oil-based) at room temperature.
Stirred for minutes. After adding a solution of 0.16 g of iodomethane in 1 ml of THF to the reaction mixture and reacting for 3 days, 0.1 ml of acetic acid was added, insolubles were filtered off, and the filtrate was concentrated.
The residue was purified by column chromatography (developing solvent; dichloromethane-methanol (20: 1)).
7 g of 1- (6-chloro-3-pyridylmethyl) -1,
3,3-trimethyl-2-nitroguanidine (compound N
o. 14) was obtained as a white solid. Elemental analysis value (C ₁₀ H ₁₄ N ₅ O ₂ Cl) mp. 99-101 ° C. ¹ H NMR (CDCl ₃ ): 2.90 (3H, s),
3.02 (6H, s), 4.03 (2H, s), 7.3
8 (1H, d, J = 8.5 Hz), 7.79 (1H, d
d, J = 8.5, 2.7 Hz), 8.37 (1H, d,
J = 2.7Hz)

Production Example 8 A mixture of 1.03 g of 1- (6-chloro-3-pyridyl) -3-methylthiourea, 0.32 g of cyanamide, 1.58 g of dicyclohexylcarbodiimide, 3 drops of ethyldiisopropylamine and 10 ml of acetonitrile was added for 34 hours. After stirring at room temperature, insolubles were collected by filtration. This insoluble material was first recrystallized from a mixed solvent of acetonitrile: methanol, and then further recrystallized from acetonitrile to give 0.3
1 g of 1- (6-chloro-3-pyridyl) -2-cyano-3-methylguanidine (Compound No. 24) was obtained.
mp. Two hundred twenty-seven to two hundred twenty-eight ° C. Elemental analysis _{(C 8 H 8 N 5 Cl} ) _{^{1 H NMR (DMSO-d 6}} ): 2.85 (3H,
d, 4.8 Hz), 7.2 to 7.65 (2H, m),
7.83 (1H, dd, J = 8.5, 3.0 Hz),
8.36 (1H, d, J = 3.0 Hz), 9.06 (1
H, br. s)

Production Example 9 5- (aminomethyl) -2-bromothiazole 0.39
g, 1,2-dimethyl-3-nitroisothiourea 0.3
0 g, cuprous bromide 0.58 g, anhydrous potassium carbonate 0.5
After stirring a mixture of 5 g and 4 ml of dry acetonitrile in an oil bath at 60 ° C. for 45 minutes, the reaction mixture was purified by column chromatography (developing solvent: dichloromethane-methanol (10: 1)), and 0.27 g of 1- (2
-Bromo-5-thiazolylmethyl) -3-methyl-2-
Nitroguanidine (Compound No. 39) was obtained as a white solid. mp 170 ° C. Elemental analysis value (C ₆ H ₈ N ₅ O ₂ SBr) _{^{1 H NMR (DMSO-d 6}} ): 2.81 (3H,
d, J = 5.0 Hz), 4.51 (2H, s), 7.6
0 (1H, s), 8.08 (1H, br.s), 8.9
3 (1H, br.s) Production examples 1 to 9 and the production method of the present invention
The compounds shown in the following [Table 6] to [Table 15] were prepared according to the manufacturing method.
Obtained. [Table 6]-[Table 6]
15].

[0086]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

Example 1 1- (6-Chloro-3-pyridylmethyl) -3,3-dimethyl-2-nitroguanidine (Compound No. 6)
To a mixture of 26 g and 3 ml of dry THF was added 0.08 g of 60% sodium hydride (oil-based) in a water bath at 20 ° C.
Stir for 30 minutes. Formic acid acetic anhydride 0.2 in the reaction mixture
6 g of a 0.5 ml solution of THF was added over 1 minute, the bath was removed and the mixture was stirred for another 12 hours. Acetic acid 0.5m to the reaction mixture
After adding l, the mixture was concentrated, and the residue was subjected to column chromatography (developing solvent; dichloromethane-methanol (30:
1)), and 0.10 g of 1- (6-chloro-3-
Pyridylmethyl) -1-formyl-3,3-dimethyl-
2-Nitroguanidine (Compound No. 22) was obtained as a syrupy liquid. ¹ H NMR (CDCl ₃ ): 3.
03 (6H, s), 4.70 (2H, s), 7.36
(1H, d, J = 8.7 Hz), 7.74 (1H, d
d, J = 8.7, 2.7 Hz), 8.40 (1H, d,
J = 2.7 Hz), 8.44 (1H, s)

Example 2 1- (6-Chloro-3-pyridylmethyl) -3,3-dimethyl-2-nitroguanidine (Compound No. 6)
A mixture of 20 g, 0.095 g of acetic anhydride and 1 ml of dry pyridine was stirred at 60 ° C. for 2 hours and at 100 ° C. for 5 hours, and then concentrated. The residue was purified by column chromatography (developing solvent; dichloromethane-methanol (40: 1)), and 0.12 g of 1-acetyl-1- (6-chloro-
3-Pyridylmethyl) -3,3-dimethyl-2-nitroguanidine (Compound No. 23) was obtained as a syrupy liquid (mixture of cis and trans forms). ¹ H NMR
(CDCl ₃ ): 2.10 + 2.16 (3H, S +
S), 2.6-3.3 (6H, m), 4.1-5.2.
(2H, m), 7.23 to 7.45 (1H, m), 7.
67 to 7.90 (1H, m), 8.30 to 8.50 (1
H, m)

Example 3 A mixture of 0.5 g of N-acetyl-S-methyl-N'-nitroisothiourea and 5 ml of acetonitrile was added under ice-cooling.
0.44 g of 5- (aminomethyl) -2-chloropyridine
Of acetonitrile was added dropwise, and the mixture was stirred for 30 minutes under ice-cooling. After concentrating the reaction mixture, the residue was recrystallized from ethanol to give 0.59 g of N-acetyl-
N ′-(6-Chloro-3-pyridylmethyl) -N ″ -nitroguanidine (compound No. 42) was obtained as white crystals, mp 125-126 ° C. Elemental analysis (C ₉ H ₁₀ N ₅ O ₃₎ Cl) ¹ H NMR (CDCl ₃ ): 2.33 (3H, s),
4.60 (2H, d, J According to Examples 1 to 3 and the production method of the present invention, the following [Table 1]
6] was obtained ~ Example compounds shown in Table 17]. The compounds obtained in the above Examples are shown in [Table 16 ] to [Table 17 ].

[0090]

[Table 16]

[Table 17]

Formulation Example 1 Compound no. 1 (20% by weight), xylene (75% by weight), and polyoxyethylene glycol ether (Noniball 85 (TM)) (5% by weight) were mixed well to prepare an emulsion.

Formulation Example 2 Compound no. 6 (30% by weight), sodium lignin sulfonate (5% by weight), polyoxyethylene glycol ether (Nonipol 85 (TM)) (5% by weight), white carbon (30% by weight), clay (30% by weight)
Was mixed well to produce a wettable powder.

Formulation Example 3 Compound No. 7 (3% by weight), white carbon (3% by weight) and clay (94% by weight) were mixed well to prepare a powder.

Formulation Example 4 Compound no. 8 (10% by weight), sodium ligninsulfonate (5% by weight), and clay (85% by weight) were thoroughly pulverized and mixed, and water was added and kneaded well.

[0095]

The present invention contributes to agriculture by providing an excellent insecticide.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location C07D 213/64 C07D 213/64 241/12 241/12 277/28 277/28 277/32 277 / 32 277/34 277/34 277/42 277/42 521/00 521/00 (72) Inventor Tetsuo Okauchi 10-11, Tsutsumicho, Hirakata-shi, Osaka (56) References JP-A-2-209868 (JP, A) JP-A-64-70467 (JP, A) JP-A-3-218354 (JP, A) JP-A-53-108970 (JP, A) JP-A-59-118767 (JP, A) AGR. FOOD. CHEM. 22 (3) (1974) p. 374-376

Claims (12)

(57) [Claims] 1. A compound of the general formula [I] [In the formula, ^{R 1} is oxygen radicals, indicates the 5-8 membered heterocyclic group containing 1-5 hetero atoms selected from oxygen, sulfur and nitrogen atoms, said heterocyclic _{group, C 1-15} alkyl, C _3-10
Cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl, C _7-10 aralkyl, nitro, hydroxyl group, mercapto, oxo, thioxo, cyano, carbamoyl, carboxyl, C _1-4 alkoxy-carbonyl, sulfo, halogen, C _1-4 alkoxy, C _6-10 aryloxy, C _1-4 alkylthio, C _6-10 arylthio, C _1-4 alkylsulfinyl, C _6-10 arylsulfinyl , C _1-4 alkylsulfonyl, C
_6-10 arylsulfonyl, amino, C _2-6 acylamino, mono- or di-C _1-4 alkylamino, C
_{3-6 cycloalkylamino, C 6-10 arylamino, C 2-4 acyl, C 6-10} aryl - carbonyl, and oxygen, 5-6 membered heterocyclic containing 1 to 4 hetero atoms selected from oxygen, sulfur and nitrogen 1 to 5 selected from ring groups
Substituents (A), and the substituents (A)
Is C _6-10 aryl, C _7-10 aralkyl, C
_3-10 cycloalkyl, _C3-10 cycloalkenyl, _C6-10 aryloxy, _C6-10 arylthio, _C6-10 arylsulfinyl, _C6-10 arylsulfonyl, _C6-10 arylamino or heterocyclic group Is 1 to 5 halogens, hydroxyl groups,
It may be substituted with a C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _6-10 aryl, C _1-4 alkoxy, phenoxy, C _1-4 alkylthio or phenylthio group. When the substituent (A) is C
_1-15 alkyl, C _2-10 alkenyl, C _2-10
Alkynyl, C _1-4 alkoxy, C _1-4 alkylthio, C _1-4 alkylsulfinyl, C _1-4 alkylsulfonyl, amino, mono- or di-C _1-4 alkylamino, C _3-6 cycloalkylamino or C
_When it is a _6-10 arylamino group, 1 to 5 halogen, hydroxyl, C _1-4 alkoxy or C
_It may be substituted with a _1-4 alkylthio group. R ² is a hydrogen atom or C _1-15 alkyl, C
_3-10 cycloalkyl, C _2-10 alkenyl, C
_2-10 alkynyl, C _3-10 cycloalkenyl, C
_6-10 a hydrocarbon group selected from aryl and _{C 7-10} aralkyl group, these hydrocarbon groups may have 1-5 the same substituents as ^{R 1.} R ³ has the formula (Wherein R ⁴ and R ⁵ are the same or different and represent hydrogen or a hydrocarbon group which may have a substituent, or R ⁴ and R ⁵ together form a cyclic amino group together with an adjacent nitrogen. rather it may also form a group, the hydrocarbon group, C
_1-15 alkyl, C _3-10 cycloalkyl, C
_2-10 alkenyl, C _2-10 alkynyl, C
Selected from _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the hydrocarbon group is
It may have the same substituent as the substituent in the heterocyclic group for R ¹ . The cyclic amino group is selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. ) Represents an amino group. X is cyano, nitro, C _1-4 alkoxy-carbonyl, hydroxycarbonyl, C _6-10 aryl-oxycarbonyl, heterocyclic oxycarbonyl, C _1-4 alkylsulfonyl optionally substituted with halogen, sulfamoyl, -C _1-4 alkoxyphosphoryl, C _1-4 acyl optionally substituted with halogen, C
_6-10 aryl-carbonyl, carbamoyl or C
_{1-4 represents} alkylsulfonylthiocarbamoyl. However, (i) when X is a nitro group, ^{R 1} is synonymous with top Symbol
Shows the definition, n represents 0 or 1, ^{R 2} is _{C 1-4} alkyl or optionally _{C 5-15} alkyl optionally having substituent has a _{substituent, C 3-10} cycloalkyl alkyl, C
_2-10 alkenyl, C _2-10 alkynyl, C
_{3-10 cycloalkenyl,} shows a _{C 6-10} aryl or _{C 7-10} aralkyl group, these substituents represents those similar to the substituents of the above ^{R 2, R 3} agree upper Symbol
Shows the definition, (ii) when X is a nitro group, ^{R 1} is shows <br/> consent defined as above SL, n represents 0 or 1, ^{R 2} is a hydrogen atom or a C
_And R ³ represents a compound represented by the formula: (In the formula, one of R ⁴ and R ⁵ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and the hydrocarbon group is a C _1-15 alkyl, a C _3-10 cycloalkyl. , C _2-10 alkenyl, C _2-10 alkynyl, C
Selected from _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituents of the hydrocarbon group are the same as the above-mentioned substituents in the heterocyclic group of R ¹ , and the other is A C _1-4 alkyl having a substituent or a hydrocarbon group which may have a substituent, wherein the hydrocarbon group is C _5-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl,
Selected from C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituent of the C _1-4 alkyl hydrocarbon group and the substituent of the hydrocarbon group are the aforementioned heterocyclic ring of R ¹ Similar to the substituents on the group, or R ⁴ and R ⁵ together with the adjacent nitrogen form a cyclic amino group selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. And (iii) when X is a cyano group, R ¹ represents a pyridyl group;
Excluding a heterocyclic group, wherein the heterocyclic group has a substituent.
Indicates what may be done. ] The insecticide composition containing the guanidine derivative represented by these, or its salt. 2. The insecticide composition according to claim 1, wherein X in Formula [I] is a nitro group. 3. The insecticide composition according to claim 1, wherein in the general formula [I], X is a cyano group. 4. A compound of the general formula [I ^a ] [Wherein, R ^1a represents a 5- to 8-membered heterocyclic group containing 1 to 5 heteroatoms selected from an oxygen atom, a sulfur atom and a nitrogen atom, and the heterocyclic group is a C _1-15 alkyl,
_3-10 cycloalkyl, C _2-10 alkenyl, C
_2-10 alkynyl, C _3-10 cycloalkenyl, C
_6-10 aryl, C _7-10 aralkyl, nitro, hydroxyl group, mercapto, oxo, thioxo, cyano, carbamoyl, carboxyl, C _1-4 alkoxycarbonyl, sulfo, halogen, C _1-4 alkoxy, C
_6-10 aryloxy, C _1-4 alkylthio, C
_6-10 arylthio, C _1-4 alkylsulfinyl, C _6-10 arylsulfinyl, C _1-4 alkylsulfonyl, C _6-10 arylsulfonyl, amino, C _2-6 acylamino, mono- or di-C _1-4
Alkylamino, C _3-6 cycloalkylamino, C
_6-10 arylamino, C _2-4 acyl, C _6-10
It may have 1 to 5 substituents (A) selected from arylcarbonyl and a 5- to 6-membered heterocyclic group containing 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, wherein The substituent (A) is C _6-10 aryl, C _7-10 aralkyl, C _3-10 cycloalkyl, C _3-10 cycloalkenyl, C _6-10 aryloxy, C _6-10 arylthio, C _{6 10} arylsulfinyl, C _6-10 arylsulfonyl, C
_{When it is a 6-10} arylamino or heterocyclic group, 1 to 5 halogen, hydroxyl, C _1-4 alkyl,
_C2-4 alkenyl, _C2-4 alkynyl, _C6-10
Aryl, C _1-4 alkoxy, phenoxy, C _1-4
It may be substituted with an alkylthio or phenylthio group, and the substituent (A) is a C _1-15 alkyl,
_2-10 alkenyl, C _2-10 alkynyl, C _1-4
Alkoxy, C _1-4 alkylthio, C _1-4 alkylsulfinyl, C _1-4 alkylsulfonyl, amino, mono- or di-C _1-4 alkylamino, C
_{When it is a 3-6} cycloalkylamino or C _6-10 arylamino group, it may be further substituted with 1 to 5 halogens, hydroxyl groups, C _1-4 alkoxy or C _1-4 alkylthio groups. R ^2a is a hydrogen atom, or C _1-15 alkyl, C
_3-10 cycloalkyl, C _2-10 alkenyl, C
_2-10 alkynyl, C _3-10 cycloalkenyl, C
_6-10 a hydrocarbon group selected from aryl and _{C 7-10} aralkyl group, these hydrocarbon groups may have 1-5 the same substituent as ^{R 1a.} R ^3a has the formula (Wherein R ⁴ and R ⁵ are the same or different and represent hydrogen or a hydrocarbon group which may have a substituent, or R ⁴ and R ⁵ together form a cyclic amino group together with an adjacent nitrogen. rather it may also be form a group, the hydrocarbon group, C
_1-15 alkyl, C _3-10 cycloalkyl, C
_2-10 alkenyl, C _2-10 alkynyl, C
Selected from _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the hydrocarbon group is
^It may have the same substituent as the substituent in the heterocyclic group of ^1a . The cyclic amino group is selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. ) Represents an amino group. X ^a is nitro Roma other represents a trifluoroacetyl group. However, (i) when ^{X a} is a nitro ^{group, R 1a} represents a agree defined as ^{above, R 2a} _{C 1-4} alkyl or optionally substituted _{C 5-15} having the substituent Alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl or C _7-10 aralkyl, and the substituent of R ^2a is as defined above. shows what similar to the substituents for ^{R 2a of, R 3a} represents a top SL as defined above, when (ii) ^{X a} is a nitro ^{group, R 1a} is the same as above
In meaning , R ^2a represents hydrogen or C _1-4 alkyl, and R ^3a has the formula (In the formula, one of R ⁴ and R ⁵ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and the hydrocarbon group is a C _1-15 alkyl, a C _3-10 cycloalkyl. , C _2-10 alkenyl, C _2-10 alkynyl, C
Selected from _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituents on the hydrocarbon group are the same as those described above for the heterocyclic group of R ^1a , _Represents a C _1-4 alkyl having a substituent or a hydrocarbon group optionally having a substituent, wherein the hydrocarbon group is a C _5-15 alkyl, a C _3-10 cycloalkyl, a C _2-10 alkenyl. , C _2-10 alkynyl, C
_3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituent of the C _1-4 alkyl and the substituent of the hydrocarbon group are the above-mentioned R ^1a
Or R ⁴ and R ⁵ together with an adjacent nitrogen form a cyclic amino group selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. Good. ) An amino group represented by. Or a salt thereof. 5. The guanidine derivative or a salt thereof according to claim 4, wherein X ^{a in the} general formula [I ^a ] is ^a nitro group. 6. A compound of the general formula [I ^b ] Wherein R ^1b represents a pyridyl group, a halogenopyridyl group or
Represents a halogenothiazolyl group, R ^2C , R ^4a and
R ^5a is the same or different and is hydrogen, methyl, ethyl,
Group, formyl group or acetyl group. However, R ^2c
Is hydrogen, a methyl group or an ethyl group, R ^4a and
Among the fine ^{R 5a,} one is hydrogen, methyl, ethyl, Ho
Lumyl group or acetyl group, and the other is formyl group
Or an acetyl group. Or a compound represented by the formula
The guanidine derivative according to claim 4, which is a salt of
salt. 7. A 1-formyl-1- (6-chloro-3-pi
Lysylmethyl) -3,3-dimethyl-2-nitroguani
Gin or a salt thereof, or 1-acetyl-1- (6-
Chloro-3-pyridylmethyl) -3,3-dimethyl-2
5. Nitroguanidine or a salt thereof.
A guanidine derivative or a salt thereof. 8. The formula: ^Wherein, R ^1a, it is ^{R 2a} and ^{X a} the same meaning as those of claim 4, Y represents a leaving group. And a salt thereof and a compound represented by the formula: [The symbols in the formula are the same as those in claim 4. [ ^Ia ] wherein the compound represented by the formula [Ia] [The symbols in the formula are the same as those in claim 4. ] The method for producing a guanidine derivative or a salt thereof represented by the formula: 9. A compound of the formula [Wherein, R ^3a and X ^a have the same meanings as those described in claim 4, and Y represents a leaving group. And a salt thereof, and a compound represented by the formula: [The symbols in the formula are the same as those in claim 4. [I ^a ] characterized by reacting with a compound represented by the formula: or a salt thereof. [The symbols in the formula are the same as those in claim 4. ] The method for producing a guanidine derivative or a salt thereof represented by the formula: 10. The formula: [The symbols in the formula are the same as those in claim 4. And a salt thereof and a compound represented by the formula: [Wherein, R ^1a has the same meaning as in claim 4 and Y represents a leaving group. Wherein the compound represented by the formula [I ^a ] is reacted with a compound represented by the formula: [The symbols in the formula are the same as those in claim 4. ] The method for producing a guanidine derivative or a salt thereof represented by the formula: 11. A compound of the formula [Wherein, R ^1a and X ^a have the same meanings as those described in claim 4, R ^2b is hydrogen or an optionally substituted hydrocarbon group, and R ^3b is a group represented by the formula: [The symbols in the formula are the same as those in claim 4. And R ^2b is hydrogen when R ^3b is a tertiary amino group. And a salt thereof and a compound represented by the formula: [Wherein, R has the same meaning as the optionally substituted hydrocarbon group for R ^2a or the optionally substituted hydrocarbon group for R ⁴ and R ⁵ , and Y represents a leaving group. Show. Wherein the compound represented by the formula [I ^a ] is reacted with a compound represented by the formula: [The symbols in the formula are the same as those in claim 4. ] The method for producing a guanidine derivative or a salt thereof represented by the formula: 12. A compound of the formula [The symbols in the formula are the same as those in claim 4. And a salt thereof, and a compound represented by the formula: Wherein the same as defined in the X ^a fourth aspect, Y represents a leaving group. [ ^Ia ] wherein the compound represented by the formula [Ia] [The symbols in the formula are the same as those in claim 4. ] The method for producing a guanidine derivative or a salt thereof represented by the formula: