JP2745737B2 - Benzylideneaminooxyalkanoic acid amide derivatives, their production and herbicides - Google Patents

Description

The present invention relates to a benzylideneaminooxyalkanoic acid amide derivative useful as a herbicide, a method for producing the same and a use thereof.

(Prior Art) Conventionally, many phenoxyalkanoic acid amide derivatives are known as herbicides, but no benzylideneaminooxyalkanoic acid amide derivatives are known.

(Problems to be Solved by the Invention) The present invention has a broad herbicidal activity against grasses and broadleaf weeds, and has a high herbicidal activity on weeds that are difficult to remove with conventional herbicides. It is an object of the present invention to provide a highly selective herbicidal compound having no phytotoxicity to seedling rice, wheat, soybean, corn and the like.

(Means for Solving the Problems) The benzylideneaminooxyalkanoic acid amide derivative of the present invention is represented by the following formula.

(Wherein R ¹ is halo-lower alkyl, halo-lower alkoxy,
Halo-lower alkylthio, halo-lower alkylsulfonyl,
Cyano, or a phenyl group substituted with a halogen and a halo-lower alkyl, or a thienyl group or a furyl group which may have a lower alkyl or halogen substituent, R ² represents a lower alkyl group, and R ³ represents Represents a phenyl group, a cycloalkyl group, a thienyl group or a furyl group which may have one or two substituents selected from lower alkyl, halogen, halo-lower alkyl and lower alkoxy, and n is 0 or 1 Wherein, when R ¹ represents a furyl group, n represents 1.) A benzylideneaminooxyalkanoic acid amide derivative represented by the formula:

In the above formula, the lower alkyl group as a substituent of the phenyl group, thienyl group and furyl group includes, for example, methyl, ethyl, propyl, isopropyl, butyl and t-butyl, especially methyl. The lower alkoxy group as a substituent includes, for example, methoxy and ethoxy, particularly methoxy. Examples of the halogen atom as a substituent include chloro, bromo and fluoro, with chloro and fluoro being preferred. Examples of the substituted halo-lower alkyl group include trifluoromethyl, difluoromethyl, 1,1-difluoroethyl, 1,1,
Examples include 2,2-tetrafluoroethyl and pentafluoroethyl, with trifluoromethyl being preferred. Examples of the halo-lower alkoxy group as a substituent include difluoromethoxy, trifluoromethoxy and 1,1,2-
Trifluoro-2-chloroethoxy is mentioned, and trifluoromethoxy is preferable. Examples of the halo-lower alkylthio group as a substituent include trifluoromethylthio, difluorochloromethylthio, and difluorobromomethylthio. Examples of the halo-lower alkylsulfonyl group as a substituent include trifluoromethylsulfonyl. Examples of the lower alkyl group for R ² include methyl and ethyl, with ethyl being particularly preferred.

Preferred compounds in the above formula (I) are those wherein R ¹ is a phenyl group substituted by trifluoromethyl, trifluoromethoxy or cyano, R ² is ethyl, and R ³ is substituted by methyl, halogen or trifluoromethyl. A phenyl or thienyl group which may be substituted.

Preferred compounds included in Formula (I) are as shown in Table I.

The compound of the formula (I) is produced by any one of the methods A to D shown below.

(In the formula, R ¹ , R ² , R ³ and n are the same as those described above; X represents a halogen atom.) The above-mentioned method comprises the steps of converting an oxime compound (II) and a 2-halogenoalkanoic acid amide (III) The reaction is carried out in a suitable solvent in the presence of a base. The solvent is not particularly limited as long as it does not participate in the reaction, and examples thereof include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; dipolar aprotic solvents such as dimethylformamide and dimethyl sulfoxide; and ethers such as tetrahydrofuran. Can be As the base, potassium carbonate, sodium carbonate and the like are used. Reaction is 20
It is almost completed by stirring at ~ 150 ° C for 1-10 hours.

(Wherein, R ¹ , R ² , R ³ and n are the same as those described above; Y represents a halogen atom) The above-mentioned method comprises reacting an acid halide (IV) and an amine (V) with a base in a suitable solvent. The reaction is carried out in the presence of The solvent is not particularly limited as long as it does not participate in the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; diethyl ether, 1,4-
Ethers such as dioxane and tetrahydrofuran; aliphatic hydrocarbons such as n-hexane; and halogenated hydrocarbons such as chloroform and methylene chloride are used. As the base, amine (V) plays the role, but pyridine, triethylamine and the like may be used. The reaction is performed at
It is almost completed by stirring for 5 hours.

(Wherein R ¹ , R ² , R ³ and n are the same as described above) In the above method, the aldehyde (VI) is reacted with the aminooxyalkanoic acid amide (VII) in the absence or presence of a solvent. This is done by: The solvent is not particularly limited as long as it does not participate in the reaction. For example, alcohols such as methanol and ethanol; diethyl ether;
Ethers such as tetrahydrofuran and 1,4-dioxane;
Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as benzene, toluene and xylene are used. The reaction is almost complete by stirring at 0-50 ° C for 1-5 hours.

(In the formula, R ¹ , R ² , R ³ and n are the same as described above. Z represents a lower alkyl group.) The above-mentioned method comprises reacting the ester (VIII) and the amine (IX) with a base in a suitable solvent. By reacting in the presence of The solvent is not particularly limited as long as it does not participate in the reaction, and aromatic hydrocarbons such as benzene, toluene and xylene; and alcohols such as methanol and ethanol are used. As the base, an alkali metal salt of an alcohol such as sodium methoxide is used. The reaction is almost completed by stirring at 10-100 ° C for 1-20 hours.

(Examples) Production examples of the compound of the present invention are shown below.

Example 1 (Synthesis Method A) Synthesis of N-benzyl-2- (3-chlorobenzylideneaminooxy) butanoic acid amide (Compound No. 40) 1.7 g (0.011 mol) of m-chlorobenzaldoxime and N-benzyl-2 2.6 g of bromobutanoic acid amide (0.01 g
mol) in 30 ml of acetone, and 1.51 g of anhydrous potassium carbonate
(0.011 mol) was added and the mixture was heated under reflux for 4 hours. After completion of the reaction, the reaction solution was added to water, and the liberated oil was extracted with ethyl acetate. The ethyl acetate was washed with water, dried over magnesium sulfate, and evaporated under reduced pressure. The resulting residue was subjected to column chromatography (Wakogel C-200, toluene: ethyl acetate = 4: 1).
Purification by elution), the desired product of mp 75-78 ° C 2.
3 g (yield 69%) was obtained.

Example 2 (Synthesis method B) Synthesis of N- (2,5-difluorobenzyl) -2- (3-trifluoromethylbenzylideneaminooxy) butanoic acid amide (Compound No. 64) 2,5-difluorobenzyl in 20 ml of toluene Amine 2.9g
(0.02 mol) and 2.2 g (0.22 mol) of triethylamine were added, and after cooling to 5 ° C., 6.0 g (0.02 mol) of 3-trifluoromethylbenzylideneaminooxybutanoic acid chloride was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, the reaction solution was washed with water, the toluene layer was dried over anhydrous sodium sulfate, and the residue obtained by distilling off toluene under reduced pressure was treated in the same manner as in Example 1. n ^26.9 _D ▼ 7.0 g of the target product of 1.5069 (yield 89
%).

Example 3 (Synthesis Method C) Synthesis of N- (2,4-difluorophenyl) -2- (3-nitrobenzylideneaminooxy) butanoic acid amide (Compound No. 156) To 1.51 g (0.01 mol) of m-nitrobenzaldehyde N-
2.3 g (0.01 mol) of (2,4-difluorophenyl) -2-aminooxybutanoic acid amide was dissolved in 20 ml of ethanol and reacted at 60 ° C. for 2 hours. After completion of the reaction, ethanol was distilled off under reduced pressure, and the residue was purified by column chromatography (Wakogel C-200, toluene: ethyl acetate = 4: 1 elution) to obtain a white powder of the target compound having a mp of 87 to 88 ° C.
3.0 g (83% yield) was obtained.

Example 4 (Synthesis method D) N-benzyl-2- (3-trifluoromethylbenzylideneaminooxy) butanoic acid amide (Compound No. 58)
After dissolving 3.0 g (0.01 mol) of ethyl 2- (3-trifluoromethylbenzylideneaminooxy) butanoate and 1.1 g (0.01 mol) of benzylamine in 15 ml of methanol, sodium methoxide (28% methanol solution) was used. ) 1.
0 g (0.005 mol) was added, and the mixture was stirred at 50 ° C. for 5 hours. After completion of the stirring, water was added, and the liberated oil was extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over magnesium sulfate, and evaporated under reduced pressure. The obtained residue was treated in the same manner as in Example 1.
2.9 g (79% yield) of the desired product having a refractive index of ｎn ^26.5 _D 1.51.5321 was obtained.

In order to use the compound (I) of the present invention as a herbicide, it is admixed with a carrier and, if necessary, other adjuvants to prepare a preparation usually used as a herbicide, for example, powders, fine granules, granules, water, It can be used in any dosage form such as a sump, emulsion, suspension, paste, tablet, aerosol, smoking agent and the like.

These carriers include kaolin, clay, talc,
Inorganic substances such as mica, diatomaceous earth, vermiculite, gypsum, calcium carbonate, dolomite, magnesium lime, phosphorus lime, zeolite, silicic anhydride, synthetic calcium silicate; plant substances such as wood flour, starch, cellulose; liquid carriers , Kerosene, mineral oil, toluene, xylene, ethylbenzene, cumene, methylnaphthalene,
Examples include carbon tetrachloride, chloroform, dioxane, tetrahydrofuran, cyclohexane, isophorone, n-hexanol, cyclohexanol, ethylene glycol phenyl ether, dimethylformamide and the like.

For the purpose of emulsification, dispersion, wetting, spreading, stabilization of active ingredients, etc., one to several kinds selected from nonionic, anionic, cationic, and zwitterionic surfactants are mixed as an auxiliary agent. be able to.

In addition, fungicides, insecticides and other pesticides, urea,
Ammonium sulfate, ammonium phosphate, potassium salt and other fertilizer substances, soil conditioners and the like can be appropriately mixed and used. It can also be used by appropriately mixing with other herbicides.

Next, formulation examples of the herbicide according to the present invention will be given. Parts mean parts by weight.

Formulation Example 1 N-benzyl-2- (3-trifluoromethylbenzylideneaminooxy) butanoic acid amide (compound of compound No. 58) 8 parts, bentonite 30 parts, talc 59 parts, neoperex powder Trade name: Kao Atlas Co., Ltd. 1) and 2 parts of sodium ninsulfonate were uniformly mixed, and then a small amount of water was added and kneaded, followed by granulation and drying to obtain granules.

Formulation Example 2 50 parts of N- (2-chlorobenzyl) -2- (3-trifluoromethylbenzylideneaminooxy) butanoic acid amide (compound of compound No. 60), 48 parts of kaolin, and 2 parts of neoperex powder are homogeneously prepared. And then pulverized to obtain a wettable powder.

Formulation Example 3 N- (2-chlorobenzyl) -2- (3-methylbenzylideneaminooxy) butanoic acid amide (Compound No. 13)
30 parts, xylene 60 parts, dimethylformamide 5 parts and toxanone (trade name: Sanyo Chemical Industry Co., Ltd.) 5
Parts were uniformly mixed and dissolved to obtain an emulsion.

Formulation Example 4 N-benzyl-2- (3-trifluoromethylbenzylideneaminooxy) butanoic acid amide (compound No. 60) (5 parts), talc (50 parts), and kaolin (45 parts) were uniformly mixed to obtain a powder. .

The herbicide of the present invention can be expected to have a selective effect without harm to rice, soybean, corn and wheat as a pre-emergence soil treatment agent for paddy fields and upland crops, or is also effective as a foliage treatment agent. is there. The amount of drug used is 5-
100 g can be used.

 Next, test examples of the herbicide according to the present invention will be described.

Test Example 1 (paddy field weeding test) A 1/5000 arel Wagner pot is filled with Ube soil (alluvial clay loam), and seeds or tubers of nobies, oaks, pine trees and fireflies are planted, and rice seedlings in the 1.8 to 2 leaf stage Was transplanted, and water was added thereto to make a flooded state at a depth of 3 cm. Each drug was dropped at the first leaf stage of Nobie with a pipette so that the active ingredient became 20 g / a, and was controlled in a glass room at an average temperature of 25 ° C. Three weeks after the chemical treatment, the herbicidal effect of each test compound was investigated. Table 2 shows the results.

 The herbicidal effects in Table 2 were based on the following criteria.

5: Complete mortality 4: Major harm 3: Moderate harm 2: Minor harm 1: Minor harm 0: Harmless (normal growth) Test Example 2 (Upland soil treatment test) A 1/4000 arel Wagner pot was filled with Ube soil (heavy soil), and seeds of corn, soybean, wheat, mehisiba, nobie, inubeyu, shiroza, pureruhiyu, and cedar were sown. After covering the soil, spray each agent uniformly under pressure so that the active ingredient becomes 20 g / a on the soil surface layer, and the average temperature is 25 ° C.
In the glass room. Three weeks after the chemical treatment, the herbicidal effect of each test compound was investigated. Table 3 shows the results.

 The herbicidal effects in Table 3 were based on the following criteria.

5: Complete mortality 4: Major harm 3: Moderate harm 2: Minor harm 1: Minor harm 0: Harmless (normal growth) Test Example 3 (Field foliage treatment test) A 1/5000 arel Wagner pot was filled with volcanic ash soil, and plants of Meishiba, Nobie, Shiroza, Inubiyu and Onamomino were grown until the time indicated by.

2000 ppm of water containing 500 ppm of the spreading agent Neoesulin (trade name: Kumiai Chemical Co., Ltd.)
After diluting the mixture, it was sprayed under pressure onto foliage and maintained in a glass room at an average temperature of 25 ° C.

Three weeks after the chemical treatment, the herbicidal effect of each test compound was investigated. Table 4 shows the results.

 The herbicidal effect in Table 4 was based on the following criteria.

5: Complete mortality 4: Major harm 3: Moderate harm 2: Minor harm 1: Minor harm 0: Harmless (normal growth) (Effects of the Invention) As shown in Table 2 above, when the compound of the present invention is used as a herbicide for soil treatment before germination of paddy rice, the rice seedling has no phytotoxicity and shows medicinal properties against various weeds. As shown in Table 1, soil treatment before germination of field crops showed selectivity with no phytotoxicity to soybean, corn, and wheat, and showed excellent effects on other grasses and broadleaf weeds. In addition, as shown in Table-4, the field treatment with foliage also showed an excellent effect on various weeds.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 317/32 C07C 317/32 323/47 323/47 C07D 307/52 C07D 307/52 333/20 333/20 333/22 333/22 333 / 28 333/28 (72) Inventor Yasushi Shiraishi 1978 Kobe, Ogushi, Ube City, Yamaguchi Prefecture Inside Ube Research Laboratories, Ltd. (72) Inventor Kaoru Yamamoto 578, 1978 Kogushi, Ube City, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Ube Laboratory Co., Ltd. (56) References JP-A-50-84539 (JP, A)

Claims (6)

(57) [Claims] (1) (Wherein R ¹ is halo-lower alkyl, halo-lower alkoxy,
Halo-lower alkylthio, halo-lower alkylsulfonyl,
Cyano, or a phenyl group substituted with a halogen and a halo-lower alkyl, or a thienyl group or a furyl group which may have a lower alkyl or halogen substituent, R ² represents a lower alkyl group, and R ³ represents Represents a phenyl group, a cycloalkyl group, a thienyl group or a furyl group which may have one or two substituents selected from lower alkyl, halogen, halo-lower alkyl and lower alkoxy, and n is 0 or 1 Represents Provided that when R ¹ represents a furyl group, n represents 1.) A benzylideneaminooxyalkanoic acid amide derivative represented by the following formula: 2. An oxime compound represented by the formula: R ¹ —CH ＝ N—OH (II) wherein R ¹ is the same as defined in claim 1. Wherein R ² , R ³ and n are the same as described in claim 1 and X represents a halogen atom. 2-halogenoalkanoic acid amide represented by the following formula: Of a benzylideneaminooxyalkanoic acid amide derivative of the formula (I) (3) (Wherein, R ¹ and R ² are the same as described in claim 1, and Y represents a halogen atom), and a benzylideneaminooxyalkanoic acid halide represented by the formula: NH ₂ — (CH ₂ ) _n —R ³ (formula Wherein R ³ and n are the same as defined in claim 1). ^3. A process for producing a benzylideneaminooxyalkanoic acid amide derivative of the formula (I) according to claim 1, wherein 4. An aldehyde of the formula R ¹ -CHO, wherein R ¹ is as defined in claim 1, (Wherein R ² , R ³ and n are the same as defined in claim 1), wherein the benzylideneaminooxy of the formula (I) is reacted with an aminooxyalkanoic acid amide represented by the following formula: Production method of alkanoic acid amide derivative. (5) (Wherein, R ¹ and R ² are the same as described in claim 1, and Z represents a lower alkyl group), and a compound represented by the formula NH ₂ — (CH ₂ ) _n —R ³ ( Wherein R ³ and n are the same as defined in claim 1). A process for producing a benzylideneaminooxyalkanoic acid amide derivative of formula (I) according to claim 1, wherein 6. A herbicide comprising the benzylideneaminooxyalkanoic acid amide derivative of the formula (I) according to claim 1 as an active ingredient.