JPH09143171A - Isooxazoline derivative and herbicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new safe compound not having phytotoxicity to crops such as paddy rice, useful as a herbicide having strong herbicidal action on lowland weed such as barnyard millet or Scirpus juncoides and free from toxicity to human and livestock and fishes. SOLUTION: This compound is represented by formula I [R<1> is a lower alkyl, a lower alkylamino, etc.; R<2> is a lower alkyl; R<3> is an aryl which may be substituted; X is O or NOR<4> (R<4> is a lower alkyl)], e.g. 3-benzoyl-5- methyl-5-(fluorobenzyloxymethyl)isoxazoline. The compound is obtained by reacting, e.g. a haloketone of the formula, R<1> COCH2 Cl with HCl gas and butyl nitrite, reacting the resultant compound of formula II with a substituted propenyl alcohol such as 2-methyl-2-propene-1-ol, then, reacting the resultant compound of formula III with a compound of the formula, R<3> CH2 Y (Y is a halogen) in the presence of a deoxidizer such as potassium carbonate at 20-50 deg.C for 1-12hr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel isoxazoline derivative and a herbicide containing the same as an active ingredient.

[0002]

BACKGROUND OF THE INVENTION Several isoxazoline derivatives have been known so far. For example, European Patent No. 3
No. 34120 discloses a general formula

Embedded image [In the formula, R ¹ represents a C ₁ -C ₁₂ alkyl group, a C ₃ -C ₇ cycloalkyl group, an optionally substituted phenyl group, a saturated or unsaturated 5- or 6-membered heterocycle, and R ² , R ³ , R ⁴ ,
R ⁵ and R ⁶ represent hydrogen, a C _{1 to} C ₄ alkyl group or a benzyl group, and R ⁷ is an optionally substituted C _{2 to} C ₆ alkenyl group, C _{5 to} C ₇ cycloalkyl group, phenyl group, naphthyl. Represents a group or a thienyl group. ] It is described that the isoxazole derivative represented by the formula has herbicidal activity.

Japanese Patent Laid-Open No. 5-178844 discloses
General formula

Embedded image [In the formula, X represents a nitro group, Y represents hydrogen or halogen, and R represents a C _{1 to} C ₆ alkyl group. ] It is described that the isoxazoline derivative represented by the formula [4] is useful as a herbicide, especially for fly of paddy field weeds. However, the compounds described in these documents are not sufficiently satisfactory in terms of phytotoxicity against crops such as paddy rice and herbicidal effect against paddy field weeds.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a herbicide which has no phytotoxicity on crops such as rice and exerts an excellent herbicidal effect on various weeds such as paddy weeds.

[0005]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors synthesized isoxazoline derivatives represented by the general formula (I) and conducted intensive studies on their herbicidal activity. As a result, it was found that the compound of the present invention has no phytotoxicity against crops such as paddy rice and has a strong herbicidal activity against paddy weeds such as millet and firefly.

That is, the gist of the first aspect of the present invention lies in the general formula (I):

Embedded image [In the formula, R ¹ represents a lower alkyl group, a lower alkoxy group, a lower alkylamino group, a lower dialkylamino group or an aryl group which may be substituted, R ² represents a lower alkyl group, and R ³ is substituted. Represents an aryl group,
X represents an oxygen atom or a group = NOR ⁴ , and R ⁴ represents a lower alkyl group. ] The isoxazoline derivative represented by The gist of the second invention is a herbicide containing an isoxazoline derivative represented by the general formula (I) as an active ingredient.

Of the definitions of the compound of formula (I) of the present invention, R ¹
Is a lower alkyl group, a lower alkoxy group, a lower alkylamino group, R ² is a lower alkyl group, and R ⁴ is a lower alkyl group, it has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms,
It may be linear or branched. Examples of such lower alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group,
Secondary butyl group, tertiary butyl group, n-pentyl group, isopentyl group, neopentyl group, tertiary pentyl group or n-
Hexyl group and the like.

Examples of the lower alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a secondary butyloxy group, a tertiary butyloxy group and an n-pentyloxy group. , Isopentyloxy group, neopentyloxy group, tertiary pentyloxy group, n-hexyloxy group and the like.

Examples of the lower alkylamino group include a monomethylamino group, a monoethylamino group, a mono-n-propylamino group, a monoisopropylamino group, a mono-n-butylamino group, a monoisobutylamino group and a mono-secondary-butylamino group. , Mono-tert-butylamino group, mono-n-pentylamino group, mono-isopentylamino group, mono-neopentylamino group, mono-tertiary-pentylamino group, n-hexylamino group and the like.

When R ¹ is a lower dialkylamino group, it has 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and may be linear or branched. Examples of the lower dialkylamino group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group and a di-n-amino group.
-Butylamino group, diisobutylamino group, di-tert-butylamino group, di-n-pentylamino group, di-n-hexylamino group and the like.

Examples of the aryl group in which R ¹ and R ³ may be substituted include, for example, phenyl group, 2-chlorophenyl group and 3
-Chlorophenyl group, 4-chlorophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,6-dichlorophenyl group, 2,6-difluorophenyl group, 2-methylphenyl group, 3- Methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2- (trifluoromethyl) phenyl group, 3-
(Trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2-nitrophenyl group, 2-fluoro-6-chlorophenyl group or 2-fluoro-6
-Methylphenyl group and the like.

Specific examples of the compound represented by the general formula (I) according to the present invention are shown in Table 1. Compound N
o. Is also referred to in the following Examples and Test Examples.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

[0016]

[Table 4]

[0017]

[Table 5]

[0018]

[Table 6]

[0019]

[Table 7]

[0020]

[Table 8]

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the method for producing the compound of formula (I) of the present invention will be explained concretely. The manufacturing method of the present invention will be described separately for methods (A) to (D). Method (A) The compound (I ′) of the present invention in which R ^{1 of the} formula (I) is a lower alkyl group, an optionally substituted aryl group, and X is an oxygen atom is synthesized by the following synthetic route.

(Reaction formula 1)

Embedded image [In the formula, R ² and R ³ have the same meanings as described above, and Y represents halogen. As shown in the above reaction scheme 1, the compound of formula (I ′) has the formula (I
It can be obtained by reacting a compound V) with a compound of formula (VI) in a suitable solvent or in the absence of a solvent in the presence of a deoxidizing agent.

Examples of the solvent which can be used in this step include hydrocarbons such as benzene, toluene or xylene; ethers such as diethyl ether, tetrahydrofuran or dioxane; ketones such as acetone or methyl ethyl ketone; acetonitrile, N, N- Examples thereof include aprotic polar solvents such as dimethylformamide and N, N-dimethylacetamide.

As the deoxidizing agent, inorganic salts such as potassium carbonate or sodium carbonate; metal hydrides such as sodium hydride can be used. The amount used is not particularly limited, but it is preferably used within the range of 1 to 2 mol per mol of the compound of the formula (IV). The reaction temperature is between 0 and
It can be arbitrarily set in the range of 100 ° C, preferably 20 to 50 ° C. Further, the reaction time may be variously changed depending on the set conditions, but usually it can be completed in 1 to 12 hours. The obtained compound of formula (I ′) can be isolated from the reaction mixture by a conventional method, and if necessary, can be easily purified by column chromatography, recrystallization and the like.

The compound of the formula (IV) used as a starting material for the compound of the formula (I ') is prepared by a known method, for example, using a haloketone represented by the formula (II) as a starting material, for example, Organic Synthesis Collective, Volume 3, p. 191. (1955
The compound of formula (III) is prepared according to the method described in (1), and then it is easily obtained by reacting with a substituted propenyl alcohol.
Reference production examples of the compound of the formula (IV) are shown in Production Examples 1 and 4. Examples of production by the method (A) are shown in Examples 1 and 4.

Method (B) The compound of the formula (I ″) of the present invention in which R ^{1 of the} formula (I) is a lower alkoxy group and X is an oxygen atom is synthesized by the following synthetic route.

(Reaction formula 2)

[Chemical 6] [In the formula, R ² and R ³ have the same meanings as described above, and Y represents halogen. As shown in the above Reaction Scheme 2, the compound (I ″) of the present invention is obtained by reacting the compound of formula (IV ′) and the compound of formula (VI) in a suitable solvent or without solvent in the presence of a deoxidizing agent. Can be obtained.

Examples of the solvent which can be used in this step include hydrocarbons such as benzene, toluene or xylene; ethers such as diethyl ether, tetrahydrofuran or dioxane; ketones such as acetone or methyl ethyl ketone; acetonitrile, N, N- Examples thereof include aprotic polar solvents such as dimethylformamide and N, N-dimethylacetamide. As the deoxidizing agent, inorganic salts such as potassium carbonate or sodium carbonate; metal hydrides such as sodium hydride can be used. The amount used is not particularly limited, but it is preferably used within the range of 1 to 2 mol per mol of the compound of the formula (IV ′).

The reaction temperature is 0 to 100 ° C., preferably 2
It can be arbitrarily set in the range of 0 to 50 ° C. Further, the reaction time may be variously changed depending on the set conditions, but usually it can be completed in 1 to 12 hours. The compound of formula (I ″) thus obtained can be isolated from the reaction mixture by a conventional method and, if necessary, can be easily purified by column chromatography, recrystallization or the like. The compound of the formula (IV ′) used as a starting material for the compound is a known method using the glycine ester hydrochloride represented by the formula (VII) as a starting material, for example, Journal of Organic Chemistry, Vol. 48, p. 366 (1983). The compound of formula (VIII) is prepared according to the method described in (1) above and then easily reacted with a substituted propenyl alcohol.
A reference production example of the compound of the formula (IV) is shown in Production Example 2. An example of production by the method (B) is shown in Example 2.

Method (C) The compound of the formula (I ′ ″) of the present invention in which R ^{1 of the} formula (I) is a lower aminoalkyl group or a lower dialkylamino group and X is an oxygen atom is synthesized by the following synthetic route. It (Reaction formula 3)

Embedded image [In the formula, R ⁵ and R ⁶ represent a lower alkyl or a hydrogen atom, both are not hydrogen at the same time, R ² and R ³ have the same meanings as described above, and Y represents a halogen. ]

As shown in Reaction Scheme 3 above, the compound of formula (I """) of the present invention is prepared by removing the compound of formula (IV") and the compound of formula (VI) in a suitable solvent or without solvent. Solvents that can be used in this step include, for example, hydrocarbons such as benzene, toluene or xylene; ethers such as diethyl ether, tetrahydrofuran or dioxane; acetone or methyl ethyl ketone. And the like; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide or N, N-dimethylacetamide, and the like.

As the deoxidizing agent, inorganic salts such as potassium carbonate or sodium carbonate; metal hydrides such as sodium hydride can be used. The amount used is not particularly limited, but is 1 to 1 mol per 1 mol of the compound of the formula (IV).
It is preferably used within the range of 2 mol. The reaction temperature is
It can be arbitrarily set within a range of 0 to 100 ° C, preferably 20 to 50 ° C. Further, the reaction time may be variously changed depending on the set conditions, but usually it can be completed in 1 to 12 hours.
The resulting compound of formula (I ″ ″) can be isolated from the reaction mixture by a conventional method and, if necessary, can be easily purified by column chromatography, recrystallization and the like.

The compound of the general formula (XIII) used as a starting material for the compound of the present invention represented by the general formula (I '''') can be prepared by a known method using an amine represented by the general formula (IX) as a starting material. It can be easily obtained by preparing (XII) according to the method described in European Patent No. 638074 and then reacting it with a substituted propenyl alcohol.
A reference production example of the compound of the formula (XIII) is shown in Example 3.
An example of production by the method (C) is shown in Example 3.

Method (D) When (X) of the formula (I) is a group = NOR ⁴ , the (I ′ ″ ″) compound of the present invention is synthesized by the following synthetic route.

(Reaction formula 4)

Embedded image [In the formula, X represents an oxygen atom, and R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above. As shown in Reaction Scheme 4 above, the compound of the present invention (I ″ ″ ″) is obtained by reacting the compound of formula (I ″) with the alkoxyamine represented by formula (XIV) in a suitable solvent. be able to.

Examples of the solvent which can be used in this step include alcohols such as methanol, ethanol or propanol; ethers such as diethyl ether, tetrahydrofuran or dioxane. The reaction temperature can be arbitrarily set within the range of 0 to 100 ° C, preferably 20 to 50 ° C. Further, the reaction time may be variously changed depending on the set conditions, but usually it can be completed in 1 to 12 hours. The resulting compound of formula (I ″ ″ ″) can be isolated from the reaction mixture by a conventional method and, if necessary, can be easily purified by column chromatography, recrystallization and the like. An example of production by the method (D) is shown in Example 5.

[0037]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. Example 1 3-benzoyl-5-methyl-5- (2-fluorobenzyloxymethyl) isoxazoline (Compound No. 5
7) Production (Method (A)) Phenacyl chloride 15.5 g of diethyl ether 10
While introducing hydrogen chloride gas into the 0 ml solution while cooling with ice water, 10.3 g of butyl nitrite was added dropwise. After the dropping, the introduction of hydrogen chloride gas is stopped and the mixture is stirred at room temperature for 2 hours. Thereafter, ether and butyl alcohol produced as a by-product were distilled off under reduced pressure, and the precipitated crystals were recrystallized with 150 ml of carbon tetrachloride and 50 ml of benzene (yield 16.4 g, melting point 126-7 ° C).

6.4 g of this crystal and 25 ml of 2-methyl-2-propen-1-ol were dissolved in 250 ml of methylene chloride, 24.6 g of anhydrous sodium carbonate was added, and the mixture was stirred at room temperature for 6 hours. Then, the inorganic salt was filtered, and the organic layer was concentrated under reduced pressure. The obtained residue is purified by column chromatography,
6.1 g of 3-benzoyl-5-methyl-isoxazoline-5-methanol (compound of formula (IV)) were obtained. Obtained 3-benzoyl-5-methyl-isoxazoline-
5-methanol (4.5 g) was added to dimethylformamide (100 m).
Soluble in 500 ml of sodium hydride,
Stir for 30 minutes at room temperature. Then, 3.9 g of 2-fluorobenzyl bromide was added, and the mixture was further stirred at room temperature for 2 hours. 100 ml of toluene and 100 ml of water were added to the reaction mixture for extraction, the organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by column chromatography to give 5.8 g of the title compound as an oil (n _D ²³ = 1.5581, yield 86).
%)was gotten.

Example 2 3-Ethoxycarbonyl-5-methyl-5 (2-fluorobenzyloxymethyl) isoxazoline (Compound N
Preparation of o.35) (Method (B)) 20 g of glycine ethyl ester hydrochloride was dissolved in 27 ml of water and 13 ml of concentrated hydrochloric acid, cooled to -5 ° C, and 14 ml of an aqueous solution of 9.9 g of sodium nitrite was added dropwise. After dropping, concentrated hydrochloric acid 1
3 ml was added, and again 9.9 g of sodium nitrite was added to 14 m of water.
The solution was added dropwise at -5 ° C. After dropping, the mixture was stirred at 0 ° C for 30 minutes. The reaction mixture is triturated with 50 ml of ethyl ether.
Extracted twice, dried the ether layer over anhydrous sodium sulfate,
It was concentrated under reduced pressure. The obtained crystals were recrystallized from hexane (yield 12.6 g, melting point 80-81 ° C).

4 g of this crystal and 15 ml of 2-methyl-2-propen-1-ol were dissolved in 100 ml of methylene chloride,
Anhydrous sodium carbonate (16.8 g) was added, and the mixture was stirred at room temperature for 2 hours. Then, the inorganic salt was filtered, and the organic layer was concentrated under reduced pressure. The residue obtained is purified by column chromatography to give 3.6 g.
To give 3-ethoxycarbonyl-5-methyl-isoxazoline-5-methanol (compound of formula (IV)). 3.7 g of the obtained 3-ethoxycarbonyl-5-methyl-isoxazoline-5-methanol was dissolved in 80 ml of tetrahydrofuran, 500 mg of sodium hydride was added, and the mixture was stirred at room temperature for 10 minutes. Next, 3.8 g of 2-fluorobenzyl bromide was added, and the mixture was stirred at room temperature for 4 hours. 100 ml of toluene and 100 ml of water were added to the reaction mixture for extraction, the organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is purified by column chromatography the title compound as an oil ^{_{29g (n D 23 = 1.5058,}} 49% yield).

Example 3 3-tert-Butylaminocarbonyl-5-methyl-5-
(Production of (2,6-difluorobenzyloxymethyl) isoxazoline (Compound No. 49) (Method (C)) 18.3 g of tert-butylamine was added dropwise to 21 g of diketene at 25 ° C. or lower in 250 ml of water, and then room temperature after the addition) Left for 6 hours. To this aqueous solution, while adding 38 ml of concentrated hydrochloric acid under ice water, 19 g of sodium nitrite was added at the same time. After stirring at room temperature for 2 hours, 20.6 g of hydrochloric acid gas was introduced in 40 minutes. After the introduction, the mixture was cooled to -5 ° C, and the precipitated crystals were filtered. The crystals were dissolved in 300 ml of ethyl acetate, the water portion was decanted, and dried over anhydrous sodium sulfate. Ethyl acetate was concentrated to obtain 31 g of crude crystals.

8.9 g of this crystal and 3.6 g of 2-methyl-2-propen-1-ol were added to 150 ml of diethyl ether.
And was added dropwise at room temperature with 5.1 g of triethylamine. After dropping, the mixture was stirred for 6 hours, the precipitated triethylamine hydrochloride was filtered, the ether layer was concentrated, and the residue was purified by column chromatography to give 3-tert-butylaminocarbonyl-
6 g (yield 56%) of 5-methyl-isoxazoline-5-methanol (compound of formula (XIII)) was obtained. 2.1 g of the obtained 3-tert-butylaminocarbonyl-5-methyl-isoxazoline-5-methanol was dissolved in 80 ml of tetrahydrofuran, and sodium hydride 240
mg was added and the mixture was stirred at room temperature for 30 minutes. 2, in this solution
1.7 g of 6-difluorobenzyl bromide was added, and the mixture was stirred at room temperature for 2 hours. 100 ml of toluene and 100 ml of water were added to the reaction mixture for extraction, the organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by column chromatography to give 1.8 g of the title compound as an oil (n _D ²³ = 1.4).
990, yield 53%) was obtained.

Example 4 3-pivaloyl-5-methyl-5- (2-fluorobenzyloxymethyl) isoxazoline (Compound No. 2
9) Production (Method (A)) 1-Chloropinacholine 14.9 g of diethyl ether 1
To the 50 ml solution, 11.4 g of butyl nitrite was added dropwise while introducing hydrogen chloride gas under cooling with ice water. After the dropping, introduction of hydrogen chloride gas was stopped, and the mixture was stirred at room temperature for 2 hours. Thereafter, ether and butyl alcohol produced as a by-product were distilled off under reduced pressure, and the precipitated crystals were washed with diisopropyl ether to give crude crystals 1
6 g were obtained. 10 g of the crystals and 2.5 ml of 2-methyl-2-propen-1-ol were dissolved in 200 ml of methylene chloride, 32.4 g of anhydrous sodium carbonate was added, and the mixture was stirred at room temperature for 8 hours. Then, the inorganic salt was filtered, and the organic layer was concentrated under reduced pressure. The obtained residue is purified by column chromatography,
12 g of 3-pivaloyl-5-methyl-isoxazoline-5-methanol (compound of formula (IV)) were obtained.

8 g of the above 3-pivaloyl-5-methyl-isoxazoline-5-methanol was dissolved in 100 ml of dimethylformamide, and 640 mg of sodium hydride was added thereto.
Was added, and the mixture was stirred at room temperature for 10 minutes, 5 g of 2-fluorobenzyl bromide was added, and the mixture was further stirred at room temperature for 4 hours. To the reaction mixture was added 150 ml of toluene and 150 ml of water for extraction, and the organic layer was dried over anhydrous sodium sulfate.
It was concentrated under reduced pressure. The residue is purified by column chromatography, the title compound 6g of oil ^{_{(n D 23 = 1.4898, 67}} % yield).

Example 5 Preparation of 3- (2,2-dimethyl-1-ethoxyiminopropane) -5-methyl-5- (2-fluorobenzyloxymethyl) isoxazoline (Compound No. 30) (Method (D )) 1.8 g of compound No. 29 obtained in Example 4 was dissolved in 20 ml of methanol, 3.7 g of ethoxyamine hydrochloride and 3.0 g of sodium acetate were added, and the mixture was stirred at 55 ° C. for 5 hours. The insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, and 100 ml of toluene and 50 ml of water were added to the residue for extraction. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by column chromatography to give 2.0 g of the oily title compound (n _D
²³ = 1.4860, yield 95%) was obtained.

Example (Method for formulating herbicide) When the compound of the present invention is used as an active ingredient of a herbicide,
Usually, a solid carrier, liquid carrier, surfactant, or other formulation auxiliary agent is mixed, and emulsions, wettable powders, liquids, flowable (sols), granules, fine granules, tablets and the like are appropriately prepared by a conventional formulation. Can be prepared in the form of

The carrier used here may be either solid or liquid as long as it is commonly used for agricultural and horticultural preparations, and is not limited to a particular one. For example, these solids include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate,
Apatite, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc., vegetable powder (soybean flour, wheat flour, wood flour, tobacco powder, starch, crystalline cellulose, etc.), polymer compound (petroleum resin, polyvinyl chloride, Ketone resin, dammal gum, etc.), alumina, silicates, sugar polymers, highly dispersible silicic acid, waxes and the like. As the liquid carrier, water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, butanol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, Ethylbenzene, methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene, trichlorofluoromethane, dichlorofluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, etc.) Tetrahydrofuran etc.), Ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone etc.), Esters (ethyl acetate, butyl acetate, ethylene glycol Cetate, amyl acetate, etc., acid amides (dimethylformamide, dimethylacetamide, etc.), nitrites (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether, ethylene) Glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, solvent naphtha, etc.), petroleum fraction (paraffins, kerosene, light oil, etc.), etc. Is mentioned.

In the preparation of emulsions, wettable powders, flowable agents, etc., various surfactants (or emulsifiers) are used for the purpose of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading and the like. . Such surfactants include nonionic type (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, etc.), anionic type (alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polysulfate). Oxyethylene alkyl sulfate, aryl sulfonate, etc.), cationic type [alkyl amines (lauryl amine, stearyl trimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, etc.), polyoxyethylene alkyl amines], amphoteric type [carboxylic acid (betaine type ), Sulfate ester salts, etc.]
Of course, it is not limited to these examples.

In addition to these, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC),
Various adjuvants such as gum arabic, polyvinyl acetate, sodium alginate, gelatin, tragacanth gum and the like can be used. In the present invention, when the above-mentioned various preparations are produced, the compound of the present invention is added in an amount of 0.001%.
~ 95% (wt%; same hereafter), preferably 0.01%
It can be formulated to contain in the range of ~ 75%. For example, normally, in the case of granules, 0.01% to 10%
%, Wettable powders, emulsions, and liquid preparations can be contained in the range of 1% to 75%.

In the case of granules, for example, the thus-prepared preparation may be sprayed as it is on the soil surface, in the soil or in water in an amount of about 0.3 g to 300 g per 10 ares as an active ingredient amount. In the case of a wettable powder, an emulsion, a sol and the like, it may be diluted with water or a suitable solvent and diluted in the range of about 0.3 to 300 g per 10 are as an active ingredient. Further, when using the compound of the present invention as a herbicide, it is possible to expand the applicability by mixing it with a known herbicide, insecticide or plant regulator, and in some cases, a synergistic effect may be expected. it can.

Regarding the method for formulating the compound of the present invention represented by the general formula (I) as a herbicide, the following Examples 6 to 8 are given.
Explain. However, the present invention is not limited only to these examples, it can be mixed with various other additives in any proportion, and other herbicides and the like can be mixed in any proportion to prepare a formulation. You can also In addition, Compound No.
Are those shown in Table 1 above, and all parts in the examples are parts by weight.

Example 6 (Granule) 1 part of the compound of Compound No. 29, 1 part of lauryl sulfate, 1 part of calcium ligninsulfonate, 30 parts of bentonite and 67 parts of clay were mixed with 15 parts of water and kneaded with a kneader. Then, it is granulated with a granulator and dried with a fluid dryer to obtain a granule containing 1% of the active ingredient.

Example 7 (wettable powder) 15 parts of compound No. 30 compound, white carbon
15 parts, calcium lignin sulfonate 3 parts, polyoxyethylene nonylphenyl ether 2 parts, diatomaceous earth 5
Parts and 60 parts of clay are homogeneously mixed in a mill mixer to obtain a wettable powder containing 15% of active ingredient.

Example 8 (Emulsion) Compound No. 35, 20 parts, Solbol 700H
20 parts of Toho Chemical Industry Co., Ltd. and 60 parts of xylene are mixed to obtain an emulsion containing 20% of the active ingredient. Next, in order to demonstrate the herbicidal effect of the compound of the present invention, Test Example 1
~ 2.

Test Example 1. Herbicidal effect test on fly and phytotoxicity test on transplanted rice paddy soil (plant soil) is filled in a plastic pot with a size of 1/5000 are, and water is added to perform scavenging. Sow seeds, 2
Leaf-stage paddy rice was planted at a depth of 2 cm, 2 plants per plant, 3 plants per pot, and the water depth was kept at 3 cm.

The drug treatment was carried out in Example 2 in the 2 leaf stage of Tainubie.
Dilute the emulsion prepared in accordance with the procedure of 1.
ml (3.0 g per are in terms of the amount of active ingredient used)
(Equivalent) was added dropwise. This test is conducted in duplicate for each chemical concentration group, and the herbicidal rate (%) is calculated by the following formula 21 days after the chemical treatment.
The herbicidal effect and the phytotoxicity of paddy rice were investigated based on the following evaluation indexes. Table 2 shows the results.

[0057]

(Equation 1)

[0058]

[0059]

[0060]

[Table 9]

Comparative drug A

Embedded image

Comparative drug B

Embedded image

Test Example 2. Herbicidal effect test on paddy field weeds and phytotoxicity test on transplanted paddy rice Paddy soil (plant soil) was filled in a plastic pot with a size of 1 / 5,000 are, and Tainubie, broad-leaved weeds (Azena, Kikusigusa) were filled. , Mizochabe) and firefly seeds were sown at a depth of 1 to 2 cm, 30 seeds each. One day after sowing, the water was flooded to keep the water depth at 2 cm. Three days after sowing, paddy rice at the 2.5 leaf stage was transplanted and grown in a greenhouse. One day after transplanting the paddy rice, the emulsion prepared according to Example 8 was diluted with water to a predetermined amount, and the resulting spray solution was diluted with 10 ml per pot.
It was dropped. This test is carried out in duplicate for each chemical concentration group,
Twenty-one days after the treatment, the herbicidal effect and the phytotoxicity of paddy rice were investigated based on the same evaluation index as in Test Example 1. The results are shown in Table 3.
It is as follows.

[0064]

[Table 10]

[0065]

INDUSTRIAL APPLICABILITY The compound of the present invention has an excellent herbicidal effect as compared with known similar compounds, and exhibits excellent selectivity between crops and weeds. That is, in flooding treatment of paddy fields, various weeds that are problematic, for example, grass weeds such as Taenia japonicus, azena, yellow grass, broad-leaved weeds such as Mizochabe,
It can act on a wide range of weeds such as firefly, Cyperaceae, and almost completely weed it, and it has no phytotoxic effect on rice. Moreover, there is no animal or fish toxicity. Therefore, it can be used safely.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hirokazu Yoshizawa 2190-1 Toda, Atsugi, Kanagawa Prefecture Clover Heights 303 (72) Inventor Yoshihisa Watanabe 1 at 2352, Toda, Atsugi, Kanagawa Prefecture

Claims (2)

[Claims] 1. A compound of the general formula [In the formula, R ¹ represents a lower alkyl group, a lower alkoxy group, a lower alkylamino group, a lower dialkylamino group or an aryl group which may be substituted, R ² represents a lower alkyl group, and R ³ is substituted. Represents an aryl group,
X represents an oxygen atom or a group = NOR ⁴ , and R ⁴ represents a lower alkyl group. ] The isoxazoline derivative represented by these. 2. A herbicide containing the isoxazoline derivative according to claim 1 as an active ingredient.