JPH09328483A - Herbicidal isoxazoline derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound, a specific isoxazoline derivative, having extremely excellent herbicidal activity on persistent weeds in the fields, while having no chemical injury to useful crops such as corn, beet, soybean and paddy rice, thus useful as a herbicide. SOLUTION: This compound is a new isoxazoline derivative of formula I [R is a (substituted) pyridyl, (substituted) furyl, (substituted) thienyl, (substituted) isoxazolyl, (substituted) thiazolyl, (substituted) benzothiazolyl, etc.; the substituent is a halogen, lower alkyl or lower alkoxy; (n) is 0, 1 or 2; Me is methyl], having excellent herbicidal activity and being useful as an agrochemical. This compound of formula I is obtained by reaction of methallyl chloride of formula II with 2-hydroxyiminoacetic acid and N-chlorosuccinimide to form a 3-chloro-5-chloromethyl-5-methyl-2-isoxazoline which is then reacted with a mercaptan compound followed by, according as necessary, oxidation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel isoxazoline derivative having excellent herbicidal activity.

[0002]

2. Description of the Related Art Up to now, a compound having a 2-isoxazoline skeleton having herbicidal activity has been disclosed in EP334120A.
1 and EP 514987A1.

However, the compound described in EP334120A1 is a compound in which the substituent at the 3-position of the 2-isoxazoline ring is alkyl, cycloalkyl, substituted phenyl, a 5-membered and a 6-membered heterocycle, and the 2-isoxazoline ring Three
The structure is completely different from the compound of the present invention in which the substituent at the position is sulfide, sulfoxide, or sulfone. Also, EP51
The compound described in 4987A1 is only a compound in which the substituent at the 3-position of the 2-isoxazoline ring is a substituted phenyl group, and the structure is completely different from the compound of the present application.

Further, compounds having a 2-isoxazoline ring are described in JP-A-5-105672, but all of these compounds are compounds in which the substituent at the 5-position of the isoxazoline ring is a cyano group, This point is completely different in structure from the compound of the present invention. Furthermore, the Japanese Patent Laid-Open No. 5-10
Japanese Patent No. 5672 does not describe any herbicidal activity.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of years of intensive research on the synthesis of a derivative having a 2-isoxazoline ring and its biological activity, the present inventors have found that the structure differs from that of a known compound. The present inventors have found that the novel 2-isoxazoline derivative has excellent herbicidal activity, and completed the present invention.

[0006]

Configuration of the Invention

[0007]

The present invention provides a compound represented by the following general formula (I):

[0008]

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[Wherein R represents a pyridyl group, a furyl group, a thienyl group, an isoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group or a benzofuryl group (the pyridyl group, a furyl group, a thienyl group, an isoxazolyl group, a thiazolyl group, The thiadiazolyl group, the benzothiazolyl group and the benzofuryl group may be substituted by the same or different 1 or 2 substituents selected from the following substituent group a), and n is 0, 1 or 2.

(Substituent group a) a halogen atom, a lower alkyl group, a lower alkoxy group].

In the present application, the "halogen atom" is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In the substituent group a, a fluorine atom and a chlorine atom are preferable, and a chlorine atom is more preferable.

In the present application, the "lower alkyl group" means
For example, methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, s-butyl, t-butyl, n
-Pentyl, isopentyl, 2-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl,
2,2-dimethylbutyl, 1,1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl,
It is a linear or branched alkyl group having 1 to 6 carbon atoms such as 2,3-dimethylbutyl and 2-ethylbutyl. In the substituent group a, a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.

In the present application, the "lower alkoxy group" is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentyloxy, isopentyloxy, 2 -Methylbutoxy, neopentyloxy, 1
-Ethylpropoxy, n-hexyloxy, 4-methylpentyloxy, 3-methylpentyloxy, 2-methylpentyloxy, 1-methylpentyloxy, 3,3
-Dimethylbutoxy, 2,2-dimethylbutoxy, 1,
1-dimethylbutoxy, 1,2-dimethylbutoxy,
1,3-dimethylbutoxy, 2, -dimethylbutoxy,
It is a linear or branched alkoxy group having 1 to 6 carbon atoms such as 2-ethylbutoxy. In the substituent group a, a linear or branched alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group is most preferable.

The compound (I) of the present invention has an asymmetric carbon atom. The present invention includes each optically active substance itself and a mixture thereof in any ratio.

The compound (I) of the present invention can be converted into salts, and those salts are also included in the present invention.

The salt is not particularly limited as long as it can be used as a pesticide or as an intermediate for medicines and pesticides, but it is preferably sodium salt or potassium salt. Alkali metal salts; metal salts such as alkaline earth metal salts such as calcium salts and magnesium salts; organic base salts such as guanidine salts, triethylamine salts, dicyclohexylamine salts; hydrofluoride salts, hydrochloride salts, bromide salts Hydrohalides such as hydrous salts and hydroiodides; inorganic salts such as nitrates, perchlorates, sulfates and phosphates; methanesulfonates, trifluoromethanesulfonates, ethanesulfones Lower alkane sulfonates such as acid salts; benzene sulfonates, aryl sulfonates such as p-toluene sulfonate; fumarate, succinate It can be exemplified, and glutamate, an amino acid salt such as aspartate salts; salts, citrates, tartrates, oxalates, organic acid salts such as maleate.

Hydrates of the compounds of the present invention are also included in the present invention.

In the general formula (I), R is preferably
A furyl group, a thienyl group, an isoxazolyl group, a thiazolyl group, a thiadiazolyl group, a benzothiazolyl group or a benzofuryl group, and more preferably a furyl group, a thienyl group or an isoxazolyl group.

In R, the pyridyl group is preferably 2
-Pyridyl group or 3-pyridyl group.

In R, the furyl group is preferably 2-
It is a frill group.

In R, the thienyl group is preferably 2
A thienyl group.

In R, the isoxazolyl group is preferably a 4-isoxazolyl group.

In R, the thiazolyl group is preferably
It is a 5-thiazolyl group.

In R, the benzothiazolyl group is preferably a 2-benzothiazolyl group.

In R, the benzofuryl group is preferably a 2-benzofuryl group.

In the general formula (I), n is preferably
2.

Substituent group a is preferably a chlorine atom, a methyl group or a methoxy group.

Representative compounds of the present invention are shown in Tables 1 to 9 below, but the present invention is not limited to these compounds.

In the table, Me represents a methyl group, Xp represents a substituent on R, and a number indicates a substitution position on R.

In Tables 1 to 9, "-" in the column of Xp means no substitution.

[0031]

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[0032]

[Table 1] ─────────────────────────────── Substitution position of the compound number R Xpn ──────── ──────────────────────── 1.1 2-0 1.2 2-2 1.3 3-0 1.4 3-2 1.5 4-0 1.6 4-2 ── ─────────────────────────────

[0033]

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[0034]

[Table 2] ─────────────────────────────── Substitution position of the compound number R Xpn ──────── ──────────────────────── 2.1 2-2 2.2 3-2 2.3 4-2 ────────────── ─────────────────

[0035]

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[0036]

[Table 3] ─────────────────────────────── Substitution position of the compound number R Xpn ──────── ──────────────────────── 3.1 2-0 3.2 2 3-Me 0 3.3 2 4-Me 0 3.4 2 5-Me 0 3.5 2 3- OMe 0 3.6 2 4-OMe 0 3.7 2 5-OMe 0 3.8 2-2 3.9 2 3-Me 2 3.10 2 4-Me 2 3.11 2 5-Me 2 3.12 2 3-OMe 2 3.13 2 4-OMe 2 3.14 2 5-OMe 2 3.15 3-0 3.16 3 2-Me 0 3.17 3 4-Me 0 3.18 3 5-Me 0 3.19 3 2-OMe 0 3.20 3 4-OMe 0 3.21 3 5-OMe 0 3.22 3-2 3.23 3 2-Me 2 3.24 3 4-Me 2 3.25 3 5-Me 2 3.26 3 2-OMe 2 3.27 3 4-OMe 2 3.28 3 5-OMe 2 ───────────────── ───────────────

[0037]

[Chemical 6]

[0038]

[Table 4] ─────────────────────────────── Substitution position of compound number R Xpn ──────── ──────────────────────── 4.1 2-0 4.2 2 3-Me 0 4.3 2 4-Me 0 4.4 2 5-Me 0 4.5 2 3- OMe 0 4.6 2 4-OMe 0 4.7 2 5-OMe 0 4.8 2-2 4.9 2 3-Me 2 4.10 2 4-Me 2 4.11 2 5-Me 2 4.12 2 3-OMe 2 4.13 2 4-OMe 2 4.14 2 5-OMe 2 4.15 3-0 4.16 3 2-Me 0 4.17 3 4-Me 0 4.18 3 5-Me 0 4.19 3 2-OMe 0 4.20 3 4-OMe 0 4.21 3 5-OMe 0 4.22 3-2 4.23 3 2-Me 2 4.24 3 4-Me 2 4.25 3 5-Me 2 4.26 3 2-OMe 2 4.27 3 4-OMe 2 4.28 3 5-OMe 2 ───────────────── ───────────────

[0039]

[Chemical 7]

[0040]

[Table 5] ─────────────────────────────── Substitution position of compound number R Xpn ──────── ──────────────────────── 5.1 3-0 5.2 3 4-Me 0 5.3 3 5-Me 0 5.4 3 4-OMe 0 5.5 3 5- OMe 0 5.6 3 4-Cl 0 5.7 3 5-Cl 0 5.8 3-2 5.9 3 4-Me 2 5.10 3 5-Me 2 5.11 3 4-OMe 2 5.12 3 5-OMe 2 5.13 3 4-Cl 2 5.14 3 5-Cl 2 5.15 4-0 5.16 4 3-Me 0 5.17 4 5-Me 0 5.18 4 3,5-Me ₂ 0 5.19 4 3-OMe 0 5.20 4 5-OMe 0 5.21 4 3-Me, 5-OMe 0 5.22 4 3-OMe, 5-Me 0 5.23 4 3-Cl 0 5.24 4 5-Cl 0 5.25 4 3,5-Cl ₂ 0 5.26 4-2 5.27 4 3-Me 2 5.28 4 5-Me 2 5.29 4 3,5-Me ₂ 2 5.30 4 3-OMe 2 5.31 4 5-OMe 2 5.32 4 3-Me, 5-OMe 2 5.33 4 3-OMe, 5-Me 2 5.34 4 3-Cl 2 5.35 4 5-Cl 2 5.36 4 3,5-Cl ₂ 2 5.37 5-0 5.38 5 3-Me 0 5.39 5 4-Me 0 5.40 5 3-OMe 0 5.41 5 4-OMe 0 5.42 5 3-Cl 0 5.43 5 4-Cl 0 5.44 5-2 5.45 5 3-Me 2 5.46 5 4-Me 2 5.47 5 3-OMe 2 5.48 5 4-OMe 2 5.49 5 3-Cl 2 5.50 5 4-Cl 2 ────────── ─────────────────────

[0041]

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[0042]

[Table 6] ─────────────────────────────── Substitution position of compound number R Xpn ──────── ──────────────────────── 6.1 2-0 6.2 2 4-Me 0 6.3 2 5-Me 0 6.4 2 4,5-Me ₂ 0 6.5 2 4-OMe 0 6.6 2 5-OMe 0 6.7 2-2 6.8 2 4-Me 2 6.9 2 5-Me 2 6.10 2 4,5-Me ₂ 2 6.11 2 4-OMe 2 6.12 2 5-OMe 2 6.13 4 -0 6.14 4 2-Me 0 6.15 4 5-Me 0 6.16 4 2,5-Me ₂ 0 6.17 4 2-OMe 0 6.18 4 5-OMe 0 6.19 4-2 6.20 4 2-Me 2 6.21 4 5-Me 2 6.22 4 2,5-Me ₂ 2 6.23 4 2-OMe 2 6.24 4 5-OMe 2 6.25 5-0 6.26 5 2-Me 0 6.27 5 4-Me 0 6.28 5 2,4-Me ₂ 0 6.29 5 2 -OMe 0 6.30 5 4-OMe 0 6.31 5-2 6.32 5 2-Me 2 6.33 5 4-Me 2 6.34 5 2,4-Me ₂ 2 6.35 5 2-OMe 2 6.36 5 4-OMe 2 ──── ────────────────────────────

[0043]

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[0044]

[Table 7] ─────────────────────────────── Substitution position of the compound number R X n ──────── ──────────────────────── 7.1 4-0 7.2 4 5-Me 0 7.3 4 5-OMe 0 7.4 4 5-Cl 0 7.5 4-2 7.6 4 5-Me 2 7.7 4 5-OMe 2 7.8 4 5-Cl 2 7.9 5-0 7.10 5 4-Me 0 7.11 5 4-OMe 0 7.12 5 4-Cl 0 7.13 5-2 7.14 5 4-Me 2 7.15 5 4-OMe 2 7.16 5 4-Cl 2 ───────────────────────────────

[0045]

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[0046]

[Table 8] ─────────────────────────────── Substitution position of compound number R Xpn ──────── ──────────────────────── 8.1 2-0 8.2 2 4-Me 0 8.3 2 5-Me 0 8.4 2 6-Me 0 8.5 2 7- Me 0 8.6 2 4-OMe 0 8.7 2 5-OMe 0 8.8 2 6-OMe 0 8.9 2 7-OMe 0 8.10 2 4-Cl 0 8.11 2 5-Cl 0 8.12 2 6-Cl 0 8.13 2 7-Cl 0 8.14 2-2 8.15 2 4-Me 2 8.16 2 5-Me 2 8.17 2 6-Me 2 8.18 2 7-Me 2 8.19 2 4-OMe 2 8.20 2 5-OMe 2 8.21 2 6-OMe 2 8.22 2 7- OMe 2 8.23 2 4-Cl 2 8.24 2 5-Cl 2 8.25 2 6-Cl 2 8.26 2 7-Cl 2 ───────────────────────── ───────

[0047]

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[0048]

[Table 9] ─────────────────────────────── Substitution position of compound number R Xpn ──────── ──────────────────────── 9.1 2-0 9.2 2 3-Me 0 9.3 2 4-Me 0 9.4 2 5-Me 0 9.5 2 6- Me 0 9.6 2 7-Me 0 9.7 2 3-OMe 0 9.8 2 4-OMe 0 9.9 2 5-OMe 0 9.10 2 6-OMe 0 9.11 2 7-OMe 0 9.12 2 3-Cl 0 9.13 2 4-Cl 0 9.14 2 5-Cl 0 9.15 2 6-Cl 0 9.16 2 7-Cl 0 9.17 2-2 9.18 2 3-Me 2 9.19 2 4-Me 2 9.20 2 5-Me 2 9.21 2 6-Me 2 9.22 2 7- Me 2 9.23 2 3-OMe 2 9.24 2 4-OMe 2 9.25 2 5-OMe 2 9.26 2 6-OMe 2 9.27 2 7-OMe 2 9.28 2 3-Cl 2 9.29 2 4-Cl 2 9.30 2 5-Cl 2 9.31 2 6-Cl 2 9.32 2 7-Cl 2 ─────────────────────────────── Preferred among the above exemplified compounds Among them are 1.2, 1.4,
3.8, 3.22, 3.23, 4.8, 5.29, 5.33, 6.20, 6.31, 7.1
The compounds of 3, 9.17 can be mentioned.

More preferred are 3.8, 4.8 and 5.2.
The compounds of 9, 5.33 can be mentioned.

[0050]

BEST MODE FOR CARRYING OUT THE INVENTION The isoxazoline derivative having the general formula (I) of the present invention can be produced by the method described below.

Process A

[0052]

[Chemical 12]

In the above steps, R has the same meaning as described above, and X
¹ represents a halogen atom. X ¹ is preferably a chlorine atom.

Step A is a method for producing a compound (Ia) in which n is 0 in the general formula (I).

Step A-1 is a step for producing a compound having the general formula (II) in which a halogen atom is substituted at the 3-position of the isoxazoline ring, and the compound having the general formula (III) is treated with a base in an inert solvent. This is achieved by reacting with a compound having general formula (IV) in the presence.

The compound (IV) can be obtained, for example, from Liebig Annalen Chemie, page 985, 198.
It is a compound described in 9 years (Liebigs Annalen der Chemie 985 (1989)), and a commercially available compound is used, or it is produced according to the method described in the literature.

The base used in the step A-1 is not particularly limited as long as it is a base capable of generating nitrile oxide from the compound (IV), but sodium hydrogen carbonate and potassium hydrogen carbonate are preferred. Such as alkali metal hydrogen carbonates; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; such as sodium carbonate and potassium carbonate Alkali metal carbonates; Alkali metal acetates such as sodium acetate and potassium acetate; Alkali metal fluorinated salts such as sodium fluoride and potassium fluoride; Tertiary lower alkyl amines such as triethylamine, ethyldiisopropylamine and tributylamine 1,8-diazabicyclo [5.4.0] undecane-7-ene DBU), 1,4-diazabicyclo [2.2.2] tertiary alicyclic amines such as octane (DABCO) can be exemplified.

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 preferably, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethyl ether, Ethers such as dioxane, tetrahydrofuran; methylene chloride, chloroform, carbon tetrachloride,
Halogenated hydrocarbons such as dichloroethane; aromatic hydrocarbons such as benzene and toluene; ethyl acetate,
Examples thereof include acetic acid esters such as butyl acetate; nitriles such as acetonitrile; a mixed solvent of the above organic solvent and water; water.

The reaction temperature and reaction time are as follows:
The reaction temperature is usually 0 ° C. to 150 ° C., preferably 15 ° C. to 80 ° C., and the reaction time is generally 15 minutes to 24 hours, preferably 3 although it depends on the kind of the solvent and the base.
0 minutes to 8 hours.

Step A-2 is a step for producing a compound having the general formula (Ia), using a base in an inert solvent,
It is achieved by reacting the mercaptan compound having the general formula (V) with the compound having the general formula (II) prepared by the step A-1.

The base used is not particularly limited as long as it is a base having a strength that preferentially desorbs the protons of thiols, but is preferably sodium hydride, potassium hydride or lithium hydride. Alkali metal hydrides such as;
Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide;
Alkali metal amides such as sodium amide, lithium isopropylamide; tertiary lower alkylamines such as triethylamine, ethyldiisopropylamine, tributylamine; 1,8-diazabicyclo [5.4.
0] Undecane-7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO) and other tertiary alicyclic amines can be mentioned.

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 preferably ethers such as dioxane and tetrahydrofuran; methylene chloride, chloroform, Halogenated hydrocarbons such as carbon tetrachloride and dichloroethane; Aromatic hydrocarbons such as benzene and toluene;
Amides such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidinone; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol; acetone, Mention may be made of ketones such as 2-butanone; nitriles such as acetonitrile; sulfoxides such as dimethyl sulfoxide; and mixed solvents thereof.

The reaction temperature and reaction time are as follows:
The reaction temperature is usually 0 ° C. to 150 ° C., preferably 0 ° C. to 80 ° C., depending on the type of solvent and base,
The reaction time is usually 15 minutes to 24 hours, preferably 30 minutes to 8 hours.

Step C

[0065]

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In the above steps, R and m have the same meanings as described above.

In step C, n is 1 in the general formula (I).
Is a compound (Ic2) and a compound (Ic3) in which n is 2 in the general formula (I).

The steps C-1 and C-2 are of the general formula (I
In the step of producing the compound having the formula (c2) and the compound having the formula (Ic3), a compound (Ic in which n is 0 in the formula (I) is used in an inert solvent using an oxidizing agent.
It is achieved by carrying out the oxidation reaction of 1).

The compound (Ic1) is produced by the above step A.

The oxidizing agent used is not particularly limited as long as it is an oxidizing agent having a strength capable of oxidizing sulfides and sulfoxides, and preferably m-chloroperbenzoic acid,
Examples thereof include organic peroxides such as formic acid and peracetic acid; inorganic peroxides such as hydrogen peroxide, potassium permanganate, and sodium periodate.

The oxidizing agent is used in 1.0 to 1.1 equivalents relative to the substrate in both C-1 and C-2 steps, but the sulfones (Ic3) are directly isolated without isolation of the sulfoxides (Ic2). To obtain the compound (Ic1), 2.
It is achieved by using 0 to 3.0 equivalents.

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 preferably halogen such as methylene chloride, chloroform, carbon tetrachloride or dichloroethane. Hydrocarbons; ethers such as tetrahydrofuran, dioxane, diethyl ether; ketones such as acetone, 2-butanone; alcohols such as methanol, ethanol, t-butanol; N, N-dimethylacetamide, N, Examples thereof include amides such as N-dimethylformamide and N-methyl-2-pyrrolidinone; nitriles such as acetonitrile; acetic acid; water; and a mixed solvent of water and the above organic solvent.

The reaction temperature and reaction time are as follows:
When the target compound is the compound (Ic2), the reaction temperature is usually −2, although it varies depending on the kind of the solvent, the oxidizing agent and the target compound.
0 ° C to 50 ° C, preferably -5 ° C to 10 ° C. When the target compound is compound (Ic3), the reaction temperature is usually 0 ° C.
To 100 ° C., preferably 10 ° C. to 60 ° C., and the reaction time is usually 15 minutes to 2 days, preferably 30 minutes to 1
Days.

When R of the compound (Ic2) or (Ic3) has a heterocyclic structure containing a nitrogen atom or a sulfur atom, at the same time as the oxidation of the sulfides or sulfoxides in the step C, the heterocyclic structure is formed. The nitrogen atom or sulfur atom in the ring may also be oxidized.

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 impurities by filtration, if any, and then 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 is mixed with a carrier and, if necessary, other auxiliary agents, and has a formulation form usually used as a herbicide, such as powder, coarse powder, granule, granule, wettable powder,
It is used after being adjusted to a water solvent, emulsion, liquid agent, etc. 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, transport or handling of the active ingredient. means.

Examples of suitable solid carriers include clays represented by kaolinite group, montmorillonite group, attapulgite group, talc, mica, pyrophyllite, pumice, vermiculite, gypsum, dolomite, diatomaceous earth, magnesium. Lime, phosphorus lime, zeolite, silicic acid 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;

Examples of suitable liquid carriers include 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, and chlorotoluene; ethers such as dioxane and tetrahydrofuran; acetone; methyl ethyl ketone;
Ketones such as diisobutyl ketone, cyclohexanone, acetophenone, and isophorone, ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, esters such as diethyl succinate, methanol, n-hexanol, ethylene glycol, diethylene glycol , Cyclohexanol, 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 purposes of emulsification, dispersion, wetting, spreading, binding, control of disintegration, stabilization of active ingredient, improvement of fluidity, rust prevention, promotion of absorption into plants, etc. It may be nonionic.

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. Ethylene oxide polymer adducts, butylnaphthol, octylnaphthol, and other alkylnaphthol ethylene oxide polymer adducts, palmitic acid, stearic acid, oleic acid, and other higher fatty acid ethylene polymer adducts, stearyl phosphate, dilauryl phosphate, and other mono- or dialkyls. Ethylene oxide polymerization adducts of phosphoric acid, ethylene oxide polymerization adducts of higher aliphatic amines such as dodecylamine and stearic acid amide, higher fatty acid esters of polyhydric alcohols such as sorbitan, and ethylene oxide thereof. Copolymers of emissions polymerization adducts and ethylene oxide and propylene oxide can be cited.

Suitable anionic surfactants include, for example, alkyl sulphate salts such as sodium lauryl sulphate, oleyl alcohol sulphate amine salt, etc., fatty acid salts such as sodium sulfosuccinate dioctyl ester, sodium oleate, sodium stearate. ,
Alkyl aryl sulfonates such as sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate and sodium dodecylbenzenesulfonate can be mentioned.

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

Further, in the herbicide of the present invention, other ingredients such as gelatin, gum arabic, casein, albumin, glue, sodium alginate, polyvinyl alcohol, and the like are used for the purpose of improving the properties of the preparation and enhancing the biological effect. Carboxymethyl cellulose, methyl cellulose,
It may contain a high molecular compound such as hydroxymethylcellulose, a thixotropic agent such as sodium polyphosphate, bentonite, and other auxiliary agents.

The above-mentioned carrier and various auxiliary agents are appropriately used alone or in combination depending on the purpose in consideration of the application situation of the dosage form of the preparation.

Dusts usually contain 2 to 10 parts by weight of the active ingredient compound, the rest being a solid carrier.

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

Granules usually contain 0.1 to 1 of the active ingredient compound.
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,
The diameter of the grains is about 0.2 to 1.5 mm.

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

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

Further, when the weeds are treated in the field before the germination of the soil or after the germination of the foliage, 1 to 1000 g, preferably 10 to 3 g, of the active ingredient is added per 10a.
By treating 00g, weeds can be effectively controlled.

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

Examples and formulation examples of the herbicide of the present invention are shown below and specifically described, but the present invention is not limited thereto.

[0093]

【Example】

[0094]

Example 1 5-chloromethyl-5-methyl-3- (2-pyridylmethyl) thio-2-isoxazoline (Compound No. 1.
1) (Step A) (1) 3-chloro-5-chloromethyl-5-methyl-
2-Isoxazoline (Step A-1) 43.2 g of 2-hydroxyiminoacetic acid and 129.6 g of N-chlorosuccinimide were added to 400 ml of dimethoxyethane.
And was heated to 80 ° C. in an oil bath and stirred. After 3 minutes, the oil bath was removed and the mixture was allowed to cool to room temperature. 48 ml of methallyl chloride, 194.4 g of potassium hydrogen carbonate,
8 ml of water was sequentially added, and the mixture was stirred at room temperature for 8 hours. After adding hexane to the reaction solution, suction filtration was performed using Celite. After evaporating the organic solvent of the filtrate, the residue was purified by silica gel column chromatography (hexane: ethyl acetate) to obtain 51.6 g (64%) of the title compound as an oil.

¹ H-NMR (CDCl ₃ ) δ: 3.57 (2H, Abq, J = 11.
4, Δν = 16.0Hz), 3.14 (2H, Abq, J = 17.5, Δν = 7
6.4Hz), 1.59 (3H, s) ppm (2) 5-chloromethyl-5-methyl-3- (2-pyridylmethyl) thio-2-isoxazoline (step A-2) 2-pyridylmethylmercaptan 400. 0 mg was dissolved in tetrahydrofuran 5 ml, 60% sodium hydride 128.0 mg was added little by little at room temperature, and N, N- was added.
3 ml of dimethylformamide was added. Then (1)
A mixed solution of 179.8 mg of 3-chloro-5-chloromethyl-5-methyl-2-isoxazoline obtained in 3 and 2 ml of tetrahydrofuran was added at room temperature. After stirring at room temperature for 1 hour and 40 minutes, water was added to the reaction solution and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After filtering and evaporating the solvent, the residue was purified by silica gel column chromatography (hexane: ethyl acetate) to obtain 190.0 mg (69.2%) of the desired product as an oil.
I got

¹ H-NMR (CDCl ₃ ) δ: 8.57 (1H, dd, J = 5.1,
0.9Hz), 7.66 (1H, td, J = 7.7, 0.8Hz), 7.42 (1H, d, J
= 7.8Hz), 7.23-7.16 (1H, m), 4.38 (2H, s), 3.51 (2H,
d, J = 2.4Hz), 36.04 (2H, ABq, J = 16.1, Δν = 76.3H
z), 1.53 (3H, s) ppm The compound produced according to the method of Example 1 is shown below.

In the following, the numbers in parentheses after the compound name indicate the compound numbers in Tables 1 to 9 above, followed by the melting point (° C.) as “mp” or the oil as “oil”. And finally the yield (%) is shown.

5-Chloromethyl-5-methyl-3- (3-pyridylmethyl) thio-2-isoxazoline (1.3, oil, 49.2) ¹ H-NMR (CDCl ₃ ) δ: 8.63 (1H, d, J = 1.9Hz), 8.53 (1H,
dd, J = 3.2, 1.7Hz), 7.74 (1H, dt, J = 7.0, 1.7Hz), 7.2
6 (1H, d, J = 12.6Hz), 4.24 (2H, s), 3.52 (2H, d, J = 2.1H
z), 2.99 (2H, ABq, J = 16.7, Δν = 75.6Hz), 1.54 (3H,
s) ppm 5-chloromethyl-3-furfurylthio-5-methyl-2-isoxazoline (3.1, oil, 65.
1) ¹ H-NMR (CDCl ₃ ) δ: 7.36 (1H, s), 7.26 (2H, s), 4.29
(2H, s), 3.53 (2H, d, J = 2.4Hz), 3.01 (2H, ABq, J = 17.
2, Δν = 76.1Hz), 1.54 (3H, s) ppm 5-chloromethyl-3- (3-furylmethyl) thio-5-methyl-2-isoxazoline (3.15, oi
l, 19.9) 5-chloromethyl-3-((2-methyl-3-furyl) methyl) thio-5-methyl-2-isoxazoline
(3.16, oil, 15.9) 5-chloromethyl-5-methyl-3- (2-tenyl) thio-2-isoxazoline (4.1, oil, 7
3.8) ¹ H-NMR (CDCl ₃ ) δ: 7.24-7.21 (1H, m), 7.06-7.03 (1H,
m), 6.96-6.91 (1H, m), 4.49 (2H, s), 3.53 (2H, ABq, J
= 11.2, Δν = 7.7Hz), 3.01 (2H, ABq, J = 16.6, Δν = 75.
6Hz), 1.55 (3H, s) ppm 5-chloromethyl-3-((3,5-dimethyl-4-isoxazolyl) methyl) thio-5-methyl-2-
Isoxazoline (5.18, oil, 40.9) ¹ H-NMR (CDCl ₃ ) δ: 4.00 (2H, s), 3.53 (2H, ABq, J = 1
1.3, Δν = 8.3Hz), 2.99 (2H, ABq, J = 16.8, Δν = 75.
8Hz), 2.39 (3H, s), 2.29 (3H, s), 1.55 (3H, s) ppm 5-chloromethyl-3-((3-methoxy-5-methyl-4-isoxazoaryl) methyl) thio-5 -Methyl
-2-isoxazoline (5.22, mp69-73, 29.0) ¹ H-NMR (CDCl ₃ ) δ: 3.99 (3H, s), 3.93 (2H, s), 3.52
(2H, ABq, J = 11.2, Δν = 7.8Hz), 2.99 (2H, ABq, J = 1
6.7, Δν = 75.2Hz), 2.35 (3H, s), 1.54 (3H, s) ppm 5-chloromethyl-5-methyl-3-((2-methyl-4-thiazolyl) methyl) thio-2-iso Oxazoline (6.14, oil, 19.5) ¹ H-NMR (CDCl ₃ ) δ: 7.09 (1H, s), 4.32 (2H, s), 3.51
(2H, ABq, J = 11.2, Δν = 7.8Hz), 3.01 (2H, ABq, J = 1
6.7, Δν = 75.5Hz), 2.69 (3H, s), 1.52 (3H, s) ppm 5-chloromethyl-5-methyl-3- (5-thiazolylmethyl) thio-2-isoxazoline (6.25,
mp120-121, 7.7) ¹ H-NMR (CDCl ₃ ) δ: 8.73 (1H, s), 7.83 (1H, s), 4.51
(2H, s), 3.54 (2H, ABq, J = 11.5, Δν = 7.4Hz), 3.01 (2
H, ABq, J = 16.8, Δν = 76.1Hz), 1.56 (3H, s) ppm 5-chloromethyl-5-methyl-3-((4-methyl-5- (1,2,3-thiadiazolyl)) Methyl) thio-2-isoxazoline (7.10, oil, 22.4) ¹ H-NMR (CDCl ₃ ) δ: 4.45 (2H, d, J = 1.4Hz), 3.53 (2H, A
Bq, J = 11.4, Δν = 6.8Hz), 3.00 (2H, ABq, J = 16.8, Δ
ν = 77.7Hz), 2.70 (3H, s), 1.54 (3H, s) ppm 3- (2-Benzothiazolylmethyl) thio-5-chloromethyl-5-methyl-2-isoxazoline
(8.1, oil, 19.3) ¹ H-NMR (CDCl ₃ ) δ: 8.0 (1H, d, J = 7.6Hz), 7.87 (1H,
d, J = 7.6Hz), 7.52-7.39 (2H, m), 4.68 (2H, s), 3.54 (2
H, ABq, J = 11.2, Δν = 9.8Hz), 3.08 (2H, ABq, J = 16.9,
Δν = 78.9Hz), 1.56 (3H, s) ppm 3- (2-Benzofuranylmethyl) thio-5-chloromethyl-5-methyl-2-isoxazoline (9.
1, oil, 52.5) ¹ H-NMR (CDCl ₃ ) δ: 7.55-7.43 (2H, m), 7.31-7.21 (2H,
m), 6.71 (1H, s), 4.41 (2H, d, J = 1.0Hz), 3.53 (2H,
d, J = 2.8Hz), 3.03 (2H, ABq, J = 16.8, Δν = 77.2Hz),
1.55 (3H, s) ppm

[0099]

Example 2 5-Chloromethyl-5-methyl-3- (2-pyridylmethyl) sulfonyl-2-isoxazoline (Compound No. 1.2) (Steps C-1 and C-2) The method of Example 1. 5-chloromethyl-5-methyl-3- (2-pyridylmethyl) thio-2-isoxazoline (Compound No. 1.1) 145.9 mg prepared in 1,2-
It was dissolved in 5 ml of dichloroethane, and 309.1 mg of m-chloroperbenzoic acid was added at room temperature while stirring. After stirring at room temperature for 2 hours, saturated aqueous sodium sulfite solution was added to the reaction solution, extracted with methylene chloride, and the organic layer was washed with aqueous sodium hydrogen carbonate solution. After drying over anhydrous sodium sulfate, the mixture was filtered, the solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate) to give 29.6 mg of the desired product having a melting point of 116-117 ° C.
(18.0%) was obtained. At the same time, 2- (3-
(5-chloromethyl-5-methyl-2-isooxazolinyl)) sulfonylmethylpyridine N-oxide (Compound No. 2.1) 85.7 mg (49.5%) had a melting point of 1.
Obtained as crystals with a temperature of 47-149 ° C.

5-chloromethyl-5-methyl-3- (2-polymethyl) sulfonyl-2-
Isoxazoline (Compound No. 1.2) ¹ H-NMR (CDCl ₃ ) δ: 8.62 (1H, d, J = 4.9Hz), 7.84-7.73
(1H, m), 7.51 (1H, d, J = 7.8Hz), 7.34 (1H, q, J = 7.7H
z), 4.73 (2H, s), 3.61 (2H, ABq, J = 11.4, Δν = 20.0H
z), 3.20 (2H, ABq, J = 17.6, Δν = 77.0Hz), 1.60 (3H,
s) ppm 2- (3- (5-chloromethyl-5-methyl-2-isooxazolinyl)) sulfonylmethyl pyridine
N-Oxide (Compound No. 2.1) ¹ H-NMR (CDCl ₃ ) δ: 8.25-8.21 (1H, m), 7.62-7.57 (1H,
m), 7.36-7.31 (2H, m), 4.92 (2H, s), 3.71 (2H, ABq, J
= 11.3, Δν = 40.9Hz), 3.43 (2H, ABq, J = 17.4, Δν = 67.
0 Hz), 1.66 (3H, s) ppm The compound produced according to the method of Example 2 is shown below.

5-chloromethyl-5-methyl-3- (3-polymethylmethyl) sulfonyl-2-
Isoxazoline (1.4, mp105-107, 10.6) ¹ H-NMR (CDCl ₃ ) δ: 8.66 (2H, br), 7.83-7.79 (1H, m),
7.39-7.26 (1H, m), 4.63 (2H, s), 3.55 (2H, ABq, J = 1
1.7, Δν = 10.1Hz), 3.16 (2H, ABq, J = 17.8, Δν = 81.8
Hz), 1.55 (3H, s) ppm 5-chloromethyl-3-furfurylsulfonyl-5-methyl-2-isoxazoline (3.8, oil,
53.3) ¹ H-NMR (CDCl ₃ ) δ: 7.52-7.49 (1H, m), 6.60-6.55 (1H,
m), 6.46-6.44 (1H, m), 4.69 (2H, s), 3.57 (2H, d, J =
3.5Hz), 3.12 (2H, ABq, J = 17.6, Δν = 82.9Hz), 1.58 (3
H, s) ppm 5-chloromethyl-3- (3-furylmethyl) sulfonyl-5-methyl-2-isoxazoline (3.22,
mp77-78, 71.8) ¹ H-NMR (CDCl ₃ ) δ: 7.55 (1H, s), 7.47 (1H, d, J = 1.6H
z), 6.54 (1H, d, J = 1.4Hz), 4.48 (2H, s), 3.55 (2H, AB
q, J = 11.6, Δν = 8.5Hz), 3.17 (2H, ABq, J = 17.7, Δ
ν = 81.0Hz), 1.56 (3H, s) ppm 5-chloromethyl-3-((2-methyl-3-furyl) methyl) sulfonyl-5-methyl-2-isoxazoline (3.23, mp100-103, 45.2 ) ¹ H-NMR (CDCl ₃ ) δ: 7.32 (1H, d, J = 1.8Hz), 6.43 (1H,
d, J = 2.1Hz), 4.39 (2H, s), 3.55 (2H, ABq, J = 11.7, Δ
ν = 7.9Hz), 3.11 (2H, ABq, J = 17.9, Δν = 84.4Hz),
2.32 (3H, s), 1.56 (3H, s) ppm 5-Chloromethyl-5-methyl-3- (2-thenyl) sulfonyl-2-isoxazoline (4.8, mp7
6-78, 88.2) ¹ H-NMR (CDCl ₃ ) δ: 7.41 (1H, d, J = 5.1Hz), 7.15 (1H,
d, J = 3.7Hz), 7.09-7.05 (1H, m), 4.82 (2H, s), 3.52 (2
H, t, J = 12.3Hz), 3.07 (2H, ABq, J = 17.9, Δν = 84.2
Hz), 1.54 (3H, s) ppm 5-chloromethyl-3-((3,5-dimethyl-4-isoxazolyl) methyl) sulfonyl-5-methyl
-2-isoxazoline (5.29, mp142-144, 87.7) ¹ H-NMR (CDCl ₃ ) δ: 4.38 (2H, s), 3.61 (2H, ABq, J = 1
1.8, Δν = 14.1Hz), 3.27 (2H, ABq, J = 17.8, Δν = 85.7
Hz), 2.45 (3H, s), 2.33 (3H, s), 1.60 (3H, s) ppm 5-chloromethyl-3-((3-methoxy-5-methyl-4-isoxazolyl) methyl) sulfonyl-5- Methyl-2
-Isoxazoline (5.33, mp114-115, 79.9) ¹ H-NMR (CDCl ₃ ) δ: 4.30 (2H, s), 4.01 (3H, s), 3.59
(2H, d, J = 3.5Hz), 3.26 (2H, ABq, J = 17.7, Δν = 85.
9Hz), 2.43 (3H, s), 1.60 (3H, s) ppm 5-chloromethyl-5-methyl-3-((2-methyl-4-thiazolyl) methyl) sulfonyl-2-isoxazoline (6.20, mp108 -111,34.6) ¹ H-NMR (CDCl ₃ ) δ: 7.33 (1H, s), 4.72 (2H, s), 3.61
(2H, ABq, J = 11.4, Δν = 16.0Hz), 3.22 (2H, ABq, J =
17.6, Δν = 74.5Hz), 2.71 (3H, s), 1.61 (3H, s) ppm 5-chloromethyl-5-methyl-3- (5-thiazolylmethyl) sulfonyl-2-isoxazoline (6.
31, oil, 48.1) ¹ H-NMR (CDCl ₃ ) δ: 8.89 (1H, s), 7.94 (1H, s), 4.89
(2H, s), 3.56 (2H, ABq, J = 11.9, Δν = 10.8Hz), 3.19 (2
H, ABq, J = 17.8, Δν = 82.5Hz), 1.56 (3H, s) ppm 5-chloromethyl-5-methyl-3-((4-methyl-5- (1,2,3-thiadiazolyl)) methyl ) Sulfonyl-2
-Isoxazoline (7.13, mp93-95, 83.1) ¹ H-NMR (CDCl ₃ ) δ: 4.94 (2H, s), 3.59 (2H, ABq, J = 1
1.9, Δν = 14.3Hz), 3.24 (2H, ABq, J = 17.8, Δν = 83.1
Hz), 2.78 (3H, s), 1.58 (3H, s) ppm 3- (2-Benzothiazolylmethyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline (8.14, mp136-139, 23.9) ¹ H-NMR (CDCl ₃ ) δ: 8.07 (1H, d, J = 7.6Hz), 7.93 (1H,
dd, J = 6.8, 1.6Hz), 7.58-7.46 (2H, m), 5.07 (2H, s),
3.61 (2H, ABq, J = 11.7, Δν = 19.4Hz), 3.24 (2H, ABq, J
= 17.9, Δν = 84.4Hz), 1.61 (3H, s) ppm 3- (2-Benzofuranylmethyl) sulfonyl-5-chloromethyl-5-methyl-2-isoxazoline
(9.17, mp108-110, 48.8) ¹ H-NMR (CDCl ₃ ) δ: 7.62-7.48 (2H, m), 7.35-7.26 (2H,
m), 6.95 (1H, s), 4.83 (2H, s), 3.57 (2H, ABq, J = 11.
6, Δν = 11.6Hz), 3.17 (2H, ABq, J = 17.8, Δν = 8
6.0Hz), 1.57 (3H, s) ppm

[0102]

[Formulation example]

[0103]

[Formulation Example 1] (Wettable powder) 25% of compound No. 5.33, dodecylbenzene sulfonic acid sodium salt 2.5%, lignin sulfonic acid calcium salt 2.5% and diatomaceous earth 70% are well pulverized and mixed. To obtain a wettable powder.

[0104]

[Formulation Example 2] (Emulsion) 30% of compound No. 3.8, calcium dodecylbenzene sulfonate 2.68%, polyoxyethylene alkyl ether 4.92%, polyoxyethylene nonylphenyl ether calcium phosphate 0.
An emulsion was obtained by thoroughly mixing 4% and xylene 62%.

[0105]

[Formulation Example 3] (Granule) Compound No. 5.29, compound 5%, white carbon 1%, ligninsulfonic acid calcium salt 5%,
Bentonite 20% and clay 69% were well pulverized and mixed, water was added and well kneaded, and then granulated and dried to obtain granules.

[0106]

[Formulation Example 4] (Hydrated granules) Compound No. 1.4, compound 80%, special polycarboxylic acid polymer sodium salt 1.25%, water 3.
75%, dodecylbenzene sulfonic acid sodium salt 3
%, Dextrin 7% and titanium oxide 5% were mixed, then ground in an air mill, added to a rotary mixer or fluidized bed mixer, and sprayed with water to granulate. When most of the granules became 1.0-0.15 mm, the granules were taken out, dried and sieved. Crush oversized material,
Granules of 1.0-0.15 mm were obtained.

[0107]

Formulation Example 5 (Aqueous Suspension) 25 parts of the compound No. 1.2, 0.7 parts of sodium dioctyl sulfosuccinate, 0.15 parts of propylene glycol, 10 parts of lignin sulfonic acid calcium salt, water 44. 15 parts and 10 parts of propylene glycol were milled together in a ball mill, sand mill or roller mill until the solid particles were reduced to a diameter of 5 microns or less. To 90 parts of this pulverized slurry, 0.0
10 parts of a 5% (W / W) xanthan gum aqueous solution was added and mixed to obtain an aqueous suspension.

[0108]

INDUSTRIAL APPLICABILITY The compound of the present invention shows excellent herbicidal activity in paddy fields, especially against Tainubie, which is a highly damaging weed in paddy fields, and has very little phytotoxicity against paddy rice, and It also has a strong herbicidal action against broad-leaved weeds such as Azena, Abunome, and Oyster grass, and Cyperaceae weeds such as Firefly, Spodoptera litura.

Further, even in the field, it exhibits excellent herbicidal activity at low doses against grass weeds such as crabgrass, barnyardgrass, green foxtail and the like, and has very little phytotoxicity to corn, beet, soybean, and cotton. It also has a strong herbicidal action against broad-leaved weeds such as Inubiyu, Akaza, mustard and Aogate.

The compound (I) of the present invention has a herbicidal action and can be used as a herbicide. Its action is generally stronger on monocots than on dicots. For example, in the paddy field, by treating the waterlogged soil before or after the germination of the weeds, the grass weeds, such as the paddy field strong weeds Tainubie, Himetainubiae, and Keiubie, are particularly strongly exterminated, and conventional herbicides are also used. It is possible to exterminate difficult-to-control matsubai, firefly, kurogwai, cyperaceae perennial weeds such as Cyperus japonicus, and perennial weeds such as Urikawa and Omodaka, and further, weeds such as Azena, scutellaria japonicus, swordgrass, etc. It is also possible to effectively exterminate broad-leaf weeds of the genus Weederaceae, weeds of the family Liliaceae, pearl millet, and weeds.

On the other hand, the selectivity for paddy rice is high,
Transplanted paddy rice has the advantage that it does not suffer chemical damage and has a wide range of treatment applications.

In the field, by treating the soil before the germination of the weeds or by treating the foliage after germination, the strong weeds of the field, such as red weeds such as red pistol, white pomegranate, and core pear, weeds such as mustard mustard. It is possible to effectively exterminate weeds of the family Amaranthaceae, Amaranthus japonicus, Amaranthus japonicus, etc., and weeds of the Solanaceae family, such as Aedes japonicum. Weeds and Cyperaceae weeds such as yellow sedge can be controlled extremely strongly, while crops such as corn, beet, cotton and soybean are not affected by phytotoxicity.

Next, the effects will be concretely shown by giving examples of biological tests.

[0114]

[Test example]

[0115]

[Test Example 1] Pretreatment for germination of paddy field weeds 100 cm ² pots were filled with paddy field soil, and seeds of Tainubie and firefly, which were awakened, were mixed into the surface layer of 1 cm.
Further, 2-leaf stage paddy rice seedlings were transplanted into a submerged state and grown in a greenhouse. Three days later, the soil was treated with a prescribed amount of a flooded soil using a wettable powder prepared according to Formulation Example 1, and 21 days later, an investigation was performed according to the following criteria. Table 10 shows the results.

(Judgment Criteria) 0: Growth inhibition rate 0-10% 1: Growth inhibition rate 11-30% 2: Growth inhibition rate 31-50% 3: Growth inhibition rate 51-70% 4: Growth inhibition rate 71- 90% 5: Growth inhibition rate 91-100%

[0117]

[Test Example 2] 1.5 leaf stage treatment of Tainubie In the same manner as in Test Example 1, a prescribed dose was submerged in the 1.5 leaf stage of Tainubie using a wettable powder prepared according to Formulation Example 1. The soil was treated and surveyed 21 days later. The results are shown in Table 10 (determination criteria are the same as in Test Example 1).

In Table 2, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, Comparative Example 5, and Comparative Example 6 are Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, Comparative Compound 4, and Comparative Compound, respectively. 5 and Comparative Compound 6.

Comparative compound 1 is (5-chloromethyl-3
-Phenylsulfonyl-2-isoxazoline), and Heterocycles, Vol. 22, No. 10, 218.
It is the compound described on page 7 (1984).

Comparative compound 2 is (3-benzylthio-5
-Cyano-5-methyl-2-isoxazoline), which is a compound described in JP-A-5-105672.

Comparative compound 3 is (5-cyano-5-methyl-3- (3-trifluoromethylbenzyl) sulfonyl-2-isoxazoline) and is disclosed in JP-A-5-105.
It is a compound described in Japanese Patent No. 672.

Comparative compound 4 is (3- (3-pyridyl))
Thio-5-cyano-2-isoxazoline), which is a compound described in JP-A-5-105672.

Comparative compound 5 is (3- (2-pyridyl))
Thio-5-cyano-2-isoxazoline), which is a compound described in JP-A-5-105672.

Comparative compound 6 is (3- (2-pyridyl))
Sulfonyl-5-cyano-2-isoxazoline), which is a compound described in JP-A-5-105672.

The fact that these comparative compounds have herbicidal activity is not described in the above literature.

[0126]

[Table 10] ──────────────────────────────── Compound Dosage Paddy Weed Pre-emergence Treatment Tainubie 1.5 Leaf Stage Treatment Number (g / a) Taine-hota Paddy rice Taine-hota Paddy rice Vier Louis Vier Louis ─────────────────────────────── 1.2 5 5 5 1 5 5 0 1.4 5 5 5 0 5 4-2.1 5 5 5 0 5 5 0 3.8 5 5 4 3 5 5 0 3.22 5 5 5 4 5 5 0 3.23 5 5 5 1 4 5 0 4.8 5 5 5 4 5 5 0 5.29 5 5 5 4 5 5 3 5.33 5 5 5 4 5 5 4 6.20 5 5 5 2 5 5 0 6.31 5 5 4 0 5 4 0 7.13 5 5 3 0 5 5 0 8.1 5 5 3 0 3 3 0 9.17 5 5 3 0 4 4 0 Comparison 1 5 2 0 0 0 0 0 Comparison 2 5 2 0 0 1 0 0 Comparison 3 5 0 0 0---Comparison 4 5 0 0 0---Comparison 5 5 0 0 0---Comparison 6 5 0 0 0---──────────────────────────────── In the table above, "- "Indicates untested.

[0127]

[Test Example 3] Pretreatment for germination of upland weeds A square pot with 60 cm3 and a depth of 4 cm was filled with Kureha horticultural soil, and seeds of various test weeds and crops were sown and covered with about 1 cm of soil. Emulsions prepared according to Formulation Example 2 were used in these pots, and a predetermined amount was uniformly sprayed. After the treatment, plants were grown in these pots in a greenhouse. Twenty-one days after the treatment, the herbicidal effect on each weed and the phytotoxicity to the crops were investigated according to the following criteria. The results are shown in Table 11.

In the table below, BG is barnacle (bar).
CR is for crabg
ras) and FO are foxtails (foxtail),
JO is seiban sorghum (johnsongras
s), PA indicates a giant millet (panicum), LA indicates a lambsquarters, and PI indicates a pigweed.

(Judgment Criteria) 0: Growth inhibition rate 0-9% 1: Growth inhibition rate 10-19% 2: Growth inhibition rate 20-29% 3: Growth inhibition rate 30-39% 4: Growth inhibition rate 40- 49% 5: Growth inhibition rate 50-59% 6: Growth inhibition rate 60-69% 7: Growth inhibition rate 70-79% 8: Growth inhibition rate 80-89% 9: Growth inhibition rate 90-99% 10: Growth Suppression rate 100%

[0130]

[Table 11] ──────────────────────────────────── Compound dose BG CR FO JO PALA PI Tomoro Cotton Soybean number (kg / ha) ) Koshi ──────────────────────────── 1.2 2.0 8 9-7 10 9 10 0 0 0 1.4 2.0 10 10 10 10 10 5 9 2 0 2 3.8 2.0 10 10 10 10 10 2 9 3 0 0 3.23 2.0 10 10-9 10 0 7 0 0 0 4.8 2.0 8 7 9 9 10 10 10 0 0 0 5.29 2.0 10 10-10 10 10 10 0 0 0 5.33 2.0 7 7-7 10 10 10 0 0 0 6.20 2.0 10 10-10 10 9 10 0 0 0 6.31 2.0 10 9 10 9 10 10 10 0 0 0 9.17 2.0 10 10 10 10 10 9 9 0 0 0 ──────────────────────────── In the above table, “−” indicates untested.

[0131]

[Test Example 4] Field foliage treatment A square pot of 60 cm ³ and a depth of 4 cm was filled with Kureha horticultural cultivating soil, and seeds of various test weeds and crops were sown to cover about 1 cm of soil. Plants were grown in these pots in a greenhouse. When each plant reached the 2-3 leaf stage (10 days after seeding), the pots were uniformly sprayed with a predetermined dose using an emulsion prepared according to Formulation Example 2 in these pots. On the 14th day after the treatment, the herbicidal effect on each weed and the phytotoxicity to the crops were investigated. Table 1 shows the results.
2 (the criteria and abbreviations are the same as in Test Example 3).

[0132]

[Table 12] ──────────────────────────────────── COMPOUND FOJO PAPI TOMORO COTTON SOYBEAN NUMBER (kg / ha) Koshi ─ ─────────────────────────── 3.8 2.0 10 9 7 10 0 2 1 ────────────── ──────────────

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A01N 43/78 101 A01N 43/78 101 43/80 101 43/80 101 43/828 C07D 417/12 261 C07D 417/12 261 261/08 // C07D 261/08 261/10 261/10 261/12 261/12 A01N 43/82 102 (72) Inventor Toyokuni Honma 1041 Yasu Town, Yasu Town, Shiga Prefecture Sankyo Stock Association In-house (72) Inventor Tadashi Amasa 1041 Yasu, Yasu-cho, Yasu-gun, Shiga Sankyo Stock Company In-house

Claims (4)

[Claims] 1. A compound represented by the following general formula (I): [In the formula, R represents a pyridyl group, a furyl group, a thienyl group, an isoxazolyl group, a thiazolyl group, a thiadiazolyl group,
A benzothiazolyl group or a benzofuryl group (the pyridyl group, furyl group, thienyl group, isoxazolyl group, thiazolyl group, thiadiazolyl group, benzothiazolyl group and benzofuryl group are the same or different 1 or 2 substituents selected from the following substituent group a; (May be substituted by a group), and n represents 0, 1 or 2. (Substituent group a) halogen atom, lower alkyl group, lower alkoxy group]. 2. The compound according to claim 1, wherein n is 2. 3. The compound according to claim 1, wherein the substituent group a is a chlorine atom, a methyl group or a methoxy group. 4. The compound according to claim 1, wherein R is a furyl group, a thienyl group or an isoxazolyl group.