JPS60258150A - Anilide compound, its preparation and herbicide containing same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is halogen, lower alkyl, lower alkoxy, nitro, acyl, phenyl, etc.; n is 1-5; when n is 2-5, plural R may be same or different). EXAMPLE:(2-Methyl-4-chloro)phenoxybutyric acid (4'-methyl)anilide. USE:Herbicide free from phytotoxicity to the gramineous crops even at a high rate of application. PREPARATION:The compound of formula I can be prepared by reacting the carboxylic acid of formula II or its reactive derivative with the aniline compound of formula III. When an acid chloride is used as the reactive derivative, the reaction is carried out preferably in the presence of a proper acid acceptor (e.g. potassium carbonate) in a proper inert solvent (e.g. benzene) usually at 0-40 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (1'J (wherein R is independently a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, an acyl group, a trifluoromethyl group, a dimethyl Amino group.

It represents an alkylthio group, a hydroxyl group, or a phenyl group, and the outside represents an integer of 1 to 5, and when 3 is an integer of 2 to 5, the plurality of R's may be the same or different. ), their production method, and herbicides containing them as active ingredients.

Many herbicides containing phenoxy compounds as active ingredients have been known for a long time, and a large number of them are commercially available. For example, λ4-D; 2,4-dichlorotetraphenoxyacetic acid,
MOP; 4-Rita 4-0-tolyloxyacetic acid, MO
Examples include PP; 27(4-ri-p-0-tolyloxy)purpionic acid; MOPB; 4-(4-lyp-0-tolyloxy)butyric acid. Also, Japanese Patent Publication No. 51-3877. JP-A-54-23125 and JP-A-57-
Similar compounds are described in Japanese Patent No. 171904.

Although these phenoxy compounds exhibit excellent effects on various weeds including broad-leaved weeds, they have the disadvantage of causing unavoidable chemical damage to gramineous crops.

The compound of the present invention represented by the general formula CI) maintains the effects of phenoxy compounds, and on the other hand, it is a unique compound that does not cause any phytotoxicity, especially to grasses, even at high doses.

In general formula (1), R is a hapgen atom, a lower alkyl group,
lower alkoxy group, nitro group, acyl group.

Indicates a group selected from the group consisting of trifluorosomethyl group, dimethylamino group, alkylthio group, hydroxyl group, and phenyl group. The halogen atoms include fluorine, chlorine, bromine,
It represents an iodine atom, and the lower alkyl group is a methyl group,
Ethyl group, purpyl group.

Indicates an alkyl group of 01-04 such as a butyl group, and the lower aj to

It represents an alkoxy group of 01 to C4 such as a psiboxyl group or a butoxy group, and the acyl group is an acetyl group.

A propionyl group or a butyryl group is shown, and the alkylthio group is an alkylthio group of 01 to 03 such as a methylthio group, an ethylthio group, or a propylthio group.

When producing the compound of the present invention represented by the general formula (1), a carboxylic acid represented by the following formula or a reactive derivative thereof is added to the general formula [[] (wherein R and arithmetic have the same meanings as above). ) can be obtained by reacting.

The conditions for carrying out this reaction vary depending on the carboxylic acid or whether its activity is induced.

The reactive derivative mentioned here is, for example, acid p-lide.

ester. It is an acid anhydride.

For example, when using acid p-ride, it is prepared in the presence of a suitable deoxidizing agent such as potassium carbonate, sodium carbonate, potassium chloride, sodium hydroxide, pyridine, triethylamine, etc. in an appropriate inert solvent such as benzene, toluene, etc. It is preferable to react with 1-ene, xylene, methylene chloride, chloroform, acetic acid ethyl ester, dioxane, tetrahydrene, dimethylformamide, and the like. The reaction temperature is usually 0 to 40
'C is suitable, but further heating may be possible depending on the degree of progress of the reaction.

□ □ □ No.

Next, a synthesis example will be given and explained.

Synthesis example.

Synthesis of (2-methyl-4-chloro)phenoxybutyric acid (4'-methyl)anilide (compound number 3) p-) Luedin 1.07P,) Liethylamine 1°4d
40 mJ of an acetic acid ethyl ester solution containing 40 mJ of ethyl acetate was stirred while cooling with ice water, and 2.48 f of (2-methyl-4-chloro)butyric acid anilide was added dropwise to this solution (the reaction temperature was maintained at 10°C). After completion of the dropwise addition, the reaction was continued for 30 minutes under cooling and with stirring at room temperature for 2 hours. Next, water was added to the reaction solution, and the ethyl acetate layer was separated, washed in the order of IN hydrochloric acid, 5% sodium bicarbonate aqueous solution, and water, dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled to form colorless crystals. is precipitated. Recrystallization from a mixed solvent of ethyl acetate and hexane produced the title compound 2.2.
I got 1. Melting point 120-121℃ Elemental analysis value 201BH
2004! Molecular weight as NO2 317.82 0 HN Calculated value (to) 68.02 6.34 4.40 Actual value (to) 6B, 13 6.21 4.32 The compound thus obtained is described below. The compound numbers in the table also apply to test examples and formulation examples.

In Table 1, the positions of substituent holes and outside positions (numbering) are as follows.

Compounds similar to the compound represented by general formula [1] are shown below.

■ Compounds described in Japanese Patent Publication No. 51-38770 Reference compound 1: (2-methyl-4-chloro) phenoxyacetic acid orthoanilide Reference compound 2: (2-methyl-4-chloro) phenoxyacetic acid anilide Reference compound 3: (2-Methyl-4-chloro)phenokidib tetrapionanilide Compound described in JP-A-54-23125 Reference compound 4: 4-(2,4-dimethylphenoxy)butylanilide Reference compound 5: 4-(2 ,4-dimethylphenoxy)-
2'-Chlorbutytetraanilide Reference Compound 6: 4-(2,4-dimethylphenoxy)-
3'-ri Qfip butyroanilide ■ Compound described in JP-A-57-171904 Reference compound 7: 4-(2,4-dicp-3,5-dimethylphenoxy)butyroanilide In actual use of the compound of the present invention Because the compound of the present invention has little phytotoxicity, especially to grass crops, the timing of use can be freely selected, such as 1 wj before sowing, at the time of transplanting, during the seedling stage, or during the growing season. Further, the method of use can be selected as appropriate, such as water surface treatment, soil treatment, foliage treatment, etc.

When actually using the compounds of the present invention, solids commonly used in the preparation of agricultural chemicals,
It can be mixed with various liquid carriers to produce wettable powders, emulsions, oils, powders, fuable tablets, etc. Furthermore, the drugs include dispersants, diluents, emulsifiers, spreading agents, wetting agents, adsorbents, and thickeners.

Defoamers 9 Auxiliary agents such as antifreeze agents can also be added.

The carrier referred to herein may be either solid or liquid, or a combination thereof. Listing these examples,
Talc, clay, bentonite.

Kaori', diatomaceous earth, carbonated wood powder, starch) powder,
Gum arabic, water, alcohol, quercin.

Examples include naphtha, xylene, Schifftetrahexanone, methylnaphthalene, benzene, acetone, dimethylformamide, glycol ether, and N-methylbitetralidone.

Examples of adjuvants include polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan monooleate, ethylene oxide p-pyrene oxide copolymer, lignin sulfonate, sorbitan ester, soaps, and sulfated oils.

Alkyl sulfate ester salts 1 Petroleum sulfonates.

Dioctylsulfosuccinate salts, alkylbenzene sulfonates, aliphatic amine salts, quaternary ammonium salts, alkylpyridinium salts.

Examples include alkylaminoethylglycine, alkyldimethylbetaine, polyglycol sulfate, alkylamine sulfonic acid, isopropyl phosphate, carboxymethylcellulose, polyvinyl alcohol, hydroxypropylcellulose, ethylene glycol, xanthan gum, and the like.

In formulation, the mixing ratio can generally be freely selected within the range of 0.05 to 95% by weight of the compound of the present invention, but preferably 1 to 70%, and 70% by weight as the carrier. ~99% preferably 40-90%, as adjuvants 0-20% preferably 1-7% is optimum. In addition, by mixing with other fungicides, herbicides, plant growth regulators, insecticides, acaricides, and other agricultural chemicals and fertilizers,
A wider range of effects can be expected.

When actually using the compound of the present invention, the timing of use,
Weather conditions, method of use, dosage form, location of use, target weeds,
It goes without saying that the drug should be selected as appropriate depending on the target crop, etc., but the amount used (as the compound of the present invention) is generally 1.
5-500 per 0 are? , preferably 10 to 200 tons per 10 are.

Next, the usefulness of the compounds of the present invention as herbicides will be explained using test examples.

Test Example 1 A polyethylene pot of 115,000 are was filled with paddy soil (clay loam), each weed seed was sown in the surface layer 2, and at the same time paddy rice at the 2-leaf stage was planted with 2cm deep buds. Formulation Example 1 A predetermined amount of a hydrating powder of each test compound prepared according to the recipe was weighed out, diluted in 10 tnl of water per bot, and dropped onto the water surface.

Thereafter, the plants were grown in a glass room, and the herbicidal effect and phytotoxicity of rice were investigated after 3 hours of treatment. The results are shown in Table 2.

In addition, the numerical values in the table indicate paddy rice phytotoxicity and herbicidal effects, and are specifically as follows.

Test Example 2 A 115,000-acre pot was filled with paddy soil, and five tubers each of Urikawa and Cyperus japonica were transplanted and submerged in water to a depth of 36 nm. 2 weeks after transplanting (Urikawa 3-leaf stage).

A wettable powder obtained according to Formulation Example 1 was diluted with water to a predetermined concentration and applied to the water surface. Two weeks after treatment, the degree of herbicidal effect was investigated. The results are shown in Table 3. The numerical values in the table conform to the interpretation shown in Test Example 1.

Table 3 Examples of formulations are shown below.

Formulation Example 1 Wettable powder Compound No. 3 50 parts by weight Sodium alkyl sulfate 2.5 parts by weight Polyoxyethylene alkyl phenyl ether 2.5 parts by weight Ray 45 parts by weight These were mixed well until homogeneous and pulverized. Obtain a hydrating powder.

Formulation Example 2 Granule Compound No. 28 10 parts by weight Sodium ligninsulfonate 2 parts by weight Bentonite
30 parts by weight talc 58 parts by weight These are thoroughly mixed until uniform and granulated to obtain granules.

Applicant: Chugai Pharmaceutical Co., Ltd. Procedural amendment (voluntary) May 28, 1985 Mr. Manabu Shiga, Commissioner of the Patent Office 1.Display of the incident 1981 Patent Application No. 115855 2. Name of the invention Anilide compounds and their production methods and herbicides containing them 3. Person who makes corrections Relationship to the incident: Patent applicant 5-5-1 Ukima, Kita-ku, Tokyo (331) Chugai Pharmaceutical Co., Ltd. Representative - Kimio L Nono Specification 1 Detailed Description of the Invention” Column 0) Contents of correction The description of the description shall be amended as follows.

1) Correct "Synthesis example" on page 7, line 5 to "Synthesis example 1".

2) Change “p-toluezine” on page 7, line 9 to “p-
Toluidine--” I corrected myself.

3) Page 7, line 12, [chloro)butyric acid anilide-1”
is corrected to "chloro)butyric acid chloride."

4) Insert the following between lines 7 and 8 on page 8.

Synthesis Example 2 Synthesis of (2-methyl-4-chloro)phenoxybutyric acid (3'-isopropyl)anilide (Compound No. 63) Ethyl acetate solution containing 1.35 g of m-isopropylaniline, 1.4 ml of IJ ethylamine 40ml was stirred while cooling with ice water, and 2.48g of (2-methyl-4-chloro)butyric acid chloride was added dropwise to this solution (the reaction temperature was maintained at 10°C).After the dropwise addition was completed, the mixture was cooled for 30 minutes. The reaction was continued with stirring at room temperature for 2 hours.Water was then added to the reaction solution, and the ethyl acetate layer was separated, washed in the order of IN hydrochloric acid, 5% aqueous sodium bicarbonate solution, and water, and then washed with anhydrous magnesium sulfate. After drying and distilling off the ethyl acetate, colorless crystals were precipitated.Furthermore, recrystallization from a mixed solvent of ethyl acetate and n-hexane yielded 2.4 g of the target compound.

Melting point 103~104°C Elemental analysis value: Molecular weight as C2oH24CJNO2 3
45.87 CHN Calculated value (%) 69.45 B, 99 4.04 Actual value (%) 1.53 C3,924,15J5) Add a separate table after compound number 60 in the table on page 11 6) Page 12 In the 5th line, "/acetic acid orthoanilide" is corrected to "acetic acid orthochloroanilide".

7) Insert the following table between compound number 60 and MCPB in the table on page 19.

[ ”

Claims (1)

[Scope of Claims] 1) General formula (wherein R each independently represents a halogen atom, a lower alkyl group, a lower alkoxy group, a nido four group, an acyl group, a trifluoroxymethyl group, and a dimethylamine seven group. Alkylthio group, hydroxyl group, or phenyl group. The outside represents an integer from 1 to 5, and when the outside represents an integer from 2 to 5, the plural numbers may be the same or different.) Anilide compound. 2) The carboxylic acid represented by the formula or its reactive derivative has the general formula (wherein R is independently a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, an acyl group, a trifluoromethyl group) , dimethylamino group. Indicates an alkylthio group, hydroxyl group or phenyl group. Deaf indicates an integer from 1 to 5, and if deaf is an integer from 2 to 5, multiple R's may be the same or different. 1. A method for producing an anilide compound represented by the general formula (wherein the inside and outside of the formula have the same meanings as above), the method comprising reacting an aniline represented by the following. 3) General formula (wherein R each independently represents a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, an acyl group, a trifluoromethyl group, a dimethylamino group, an alkylthio group, a hydroxyl group, or a phenyl group). One or two of the anilide compounds represented by (where the outside represents an integer of 1 to 5, and where the outside is an integer of 2 to 5, the plurality of R may be the same or different) A herbicide characterized by containing the above as active ingredients.