JPS5874670A - Anilide derivative, its preparation, and herbicide - Google Patents

Abstract

NEW MATERIAL:An anilide derivative shown by the formula III[X is lower alkyl or halogen; R is lower alkyl, cycloalkyl, methyl-substituted cycloalkyl, benzyl, alpha-phenethyl which may have lower alkyl or a group shown by the formula IV(R1-R3 are H, lower alkyl, further R1 is phenyl or toluyl, R2 is halogen, R1 and R2 may be linked with 1-5C alkylene to form a ring); M is imidazole or triazole]. EXAMPLE: N-Benzyl-N-(1-imidazolylcarbonyl)-2,4,6-trimethylaniline. USE:A herbicide having both soil treatment ability and foliar treatment ability, having excellent herbicidal effect, having no phytotoxicity to crops, no toxicity to men and beasts, and fishes and shellfishes, and no offensive smell at all. PROCESS:A compound shown by the formula I is reacted with a compound shown by the formula II in the presence of a base, to give a compound shown by the formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention is based on the general formula [1, in which X represents a lower alkyl group or a halogen atom, R represents a lower alkyl group, a cycloalkyl group, a methyl group-substituted cycloalkyl group, and pen R1 represents a hydrogen atom, a lower alkyl group, a phenyl group or a tolyl group, and R2
represents a hydrogen atom, a lower alkyl group or a halogen atom; R3 represents a hydrogen atom or a lower alkyl group;
1 and R2 are linear or branched alkylene groups having 1 to 5 carbon atoms, and can be bonded to each other to form a ring. ), and M represents an imidazole group or a triazole group. The present invention provides a novel anilide derivative represented by the following formula, a method for producing the same, and a herbicide containing this novel anilide derivative as an active ingredient.

The inventors have conducted various studies with the aim of obtaining an industrially useful anilide sieve conductor that has not been previously described in any literature. the result.

It is represented by the general formula (wherein X, R and M each have the same meaning as above). Schiff succeeded in synthesizing an anilide derivative of the :lr order using a new production method, and furthermore, this new anilide derivative.

This invention was achieved by discovering that it has excellent herbicidal effects against various weeds, and also has no chemical damage to various crops, no toxicity to humans, livestock, fish and shellfish, and no odor.

The anilide derivative of this invention has the ability to wither weeds before and after they emerge when sprayed on the soil, which is the ability to treat both soil and foliage. It is effective against a wide range of weeds including family weeds and broad-leaved weeds.

As shown in the first reaction formula, the anilide derivative in this invention combines a carbamoyl chloride intermediate represented by general formula (1) and a compound represented by general formula [IJ] (specifically, imidazole or triazole). Synthesized by reaction.

(1) (ff) [[) (X, R and M in the formula 1 each have the same meanings as above.) This reaction is performed using acetone and dimethylformamide.

It is carried out in a reaction-inert solvent such as dimethyl sulfoxide or water in the presence of a base such as potassium carbonate, potassium hydroxide, sodium hydroxide, or pyridine.

This reaction also proceeds quantitatively. Therefore, the amount of imidazole or 1.2.4-) riazole to be used is.

per mole of carbamoyl chloride intermediate.

1.0-1.2 mol is preferred. Also, the amount of base used.

per mole of carbamoyl chloride intermediate.

0.8 to 1.5 mol is preferred.

The reaction is completed at a temperature of 0 to 150°C, preferably 50 to 100°C, for 0.5 to 10 hours.

After the reaction, by appropriately employing operations such as extraction, washing with water, drying, distillation, etc., it is possible to obtain the target ani-IJ derivative represented by general formula (III).

In addition, as shown in the second reaction formula, the carbamoyl chloride intermediate of the raw material represented by the general formula (1) is mixed with a compound represented by the general formula (IV) or [v] and trichloromethyl chloroformate or phosgene. It is synthesized by reacting.

(X in formula 1; R1, R2, R3p and R are
Each has the same meaning as above, and R4 represents a lower alkyl group, a cycloalkyl group, a methyl-substituted cycloalkyl group, a benzyl group, an α-7enethyl group, or a lower alkyl-substituted α-phenethyl group. ) This reaction consists of benzene, toluene, di-t-y'.

In a reaction-inert solvent such as dimethylformamide, pyridine? , in the presence of a base such as triethylamine, sodium hydroxide, potassium hydroxide.

This reaction proceeds quantitatively. Therefore, the general formula of the raw material [
It is preferable to use 0.5 to 0.6 mol of trichloromethyl chloroformate or 1 to 1.2 mol of phosgene per 1 mol of the compound represented by [2] or [v], and the base is preferably 0.5 to 0.6 mol, or 1 to 1.2 mol of phosgene. Preferably, 8 to 1.5 moles are used.

The reaction is completed by running at a temperature of 0-80°C for 0.1-1 hour. After the reaction, by appropriately employing operations such as water washing, dehydration, extraction, and distillation.

A carbamoyl chloride intermediate of general formula m can be isolated.

Next, examples of the manufacturing method according to the present invention will be given.

Example 1'N-benzyl-N-(1-imidazolylcarbonyl)-2,4,6-) +7 methylanidine (compound No. 5 in Table 1 below) In an Erlenmeyer flask with an internal volume of 500, 4.6#(0,02
After charging 3 mol) of trichloromethyl chloroformate and dissolving it in 350 ml of benzene.

While stirring under water cooling, 7 g (0,031 mol) of N-
A mixture of benzyl-2,4,6-dolinothylaniline and 25-triethylamine was added all at once, and the reaction was carried out for 610 minutes. After the reaction, 80% of water was added at room temperature, stirred, allowed to stand to separate the layers, and anhydrous sodium sulfate was added to the organic layer.
Dry. Then, the solvent was distilled off to quantitatively obtain the intermediate N-benzyl N-2,4,6-)rimethylrubamoyl chloride.

Next, this carbamoyl chloride was dissolved in 30 g of dimethylformamide, and 6 g of imidazole and 10♂
of potassium carbonate was added, and the reaction was carried out at 70 to 80° C. for 1 hour while stirring. After the reaction, it was poured into 200-g water,
The extract was extracted with 300% benzene, dried over anhydrous sodium sulfate, and then the solvent was distilled off. The obtained crystals were mixed with benzene and n-
Recrystallization from a mixed solvent of hexane gave the desired product 3.21 (m, pl 87-88°C) as colorless sandy crystals.

Actual 11 cases 2. N-(1-inglobylvinyl)-N
-(1-imidazolylcarbonyl)-2°4.6-trimethylaniline (see Table 1 below).

Compound No. 7) 12. After charging @(0,061 mol) of trichloromethyl chloroformate and dissolving it in 700% of benzene, 17 p(o,'os 4 mol) of N-(l-methylisobutylidene) was dissolved while stirring under water cooling. A mixture of )-2,4,6-trimethylaniline and 50'-triethylamine was added, and the reaction was carried out for 30 minutes. After the reaction, 150-7! The mixture was added to the mixture for 1 minute, and after drying, the solvent was distilled off to quantitatively obtain the intermediate N-(1-isopropylvinyl)-N-(2,4,6-)limethylphenyl)carbamoyl chloride.

Next, this carbamoyl chloride was dissolved in dimethylformamide of 80-ff, imidazole of 15f and potassium carbonate of zoli were added, and the reaction was carried out at 70 to 80°C for 2 hours.

After the reaction, the mixture was poured into δOOd water, extracted with benzene, separated into 1 portion, dried, and the solvent was distilled off. Add n-hexane to the obtained crystals, recrystallize them, and obtain colorless prismatic crystals of target object 1.
1.9y (rn, p, 92-93°C) was obtained.

Example 3. N -(1-isopropylvinyl) -N-
(1,2,4-)riazol-1-yl-carbonyl)
-z, 4,6741J/Tylaniline (Compound No. 12 in Table 1 below) An experiment was conducted using the same machine as in Example 2, except that imidazole was replaced with 1.2.4-) lyazole, and colorless sand was used. N-(1-isopropylvinyl)-N-(1,2,4
-) lyazol-1-yl-carbonyl) -2,4,
6-) Limethylaniline 13.2y (m, p, 132
~134°C) was obtained.

Actual 11/m Example 4. N-(2-methylcyclohexyl)-N-(1-imidazolylcarbonyl)-2,4,
6-Trimethylaniline (Compound No. 4 in Table 1 below) Place 500 g of benzene in a 1 ton Erlenmeyer flask.

10.9 y (0.11 mol) of phosgene gas was blown into the solution to dissolve it. While stirring this solution under water cooling, add pyridine 8
．． After dropping 7'y (0.11 mol), N-(2-
A benzene solution of methylcyclohexyl)-2,4,6-)limethylaniline 2a, 911 (0.1 mol) was added and stirred for 30 minutes.

The subsequent operations were performed in the same manner as in Example 1 to quantitatively obtain N-(2-methylcyclohexyl)-N-(2,4,6-trimethylphenyl)-rubamoyl chloride.

Next, the reaction between this carbamoyl chloride and imidazole was carried out in the same manner as in Example 1.

16.2. Obtained the target of P.

Example 5. N-(1-isopropylvinyl)-N-(1
-imidazolylcarbonyl)-2,6-dimether-4-
Bromoaniline (compound No. 33 in Table 1 below) N-(2-methylcyclohexyl)-2,4,6-trimethylaniline in place 9, N-(1-methylinbutylidene)-2,6 -cymethyl-4-promanili726
．． 8 g (0.1 mol) was used.

The reaction was carried out in the same manner as in Example 4, and N-(1-isopropylvinyl)-N-(2,6-dimethyl-4-bromphenyl)-rubamoyl chlorite was quantitatively obtained.

Next, the reaction between this carbamoyl chloride and imidazole was carried out in the same manner as in Example 1, resulting in 18.47
Obtained the object F.

It was manufactured according to Examples 1 to 5 above. Examples of the novel anilide derivatives of this invention are listed in Table 1.

In Table 1, the upper row of the elemental analysis values section shows theoretical values, and the lower row shows actual measured values.

Table 1 continued Table 1 continued Table 1 continued Table 1 continued Table 1 continued Table 1 continued In this invention. When using anilide derivatives as herbicides, follow the conventions for pesticide formulations.

Using an inert solid carrier, liquid carrier, emulsifying dispersant, etc., 1 granule, powder, emulsion, or 1 tablet of aquarium.

It can be used in any dosage form such as oil, aerosol, or smoke. These inert carriers include, for example, talc, clay, kaolin, diatomaceous earth, calcium carbonate, potassium chlorate, saltpeter.

Wood flour, nitrocellulose, starch, benzene.

Examples include xylene, n-hexane, gum arabic, vinyl chloride, carbon dioxide, 7 leone, propane, and butane. Also a pharmaceutical adjuvant.

For example, a spreading agent, a diluent, a surfactant, etc. can be appropriately added. Furthermore, it can be used by appropriately mixing with fungicides, insecticides, other agricultural chemicals, urea, ammonium sulfate, ammonium phosphorus, potassium salts, pond fertilizers, soil conditioners, and the like.

The herbicide of this invention contains an anilide derivative as an active ingredient at 0.0%.
It can contain 1 to 99 wt%. The preferable content differs slightly depending on the dosage form. For example, in the case of granules, it is 1
~35 wt%, 25-90 it for irrigation agents
%, in the case of an emulsion, 5 to 50 wt%J, and in the case of a powder, 1 to 25 wt%.

The herbicide of the present invention is preferably used in an amount of 1 to 100 JF of the anilide derivative as the active ingredient.

Next, examples of the herbicide according to the present invention will be given. In addition, parts in each example mean parts by weight.

Example 6 N-benzyl-Nm(1-imidazolylcarbonyl)-2,4,6'-)'J) fk aniline (compound No. 5) 8 parts, bentonite) 30
part, 59 parts of talc, Neoperex powder (product name:
(manufactured by Kako Atlas Co., Ltd.) and 2 parts of lignin sulfonic acid sodium were uniformly mixed, kneaded with a small amount of water, granulated using a granulator, and dried to obtain granules.

Example 7 N-(isopropylvinyl)-N-(1-
imidazolylcarbonyl) -2,4,6-)limethylaniline (compound with compound number 〒) 50 parts, kaolin 4
8 parts and 2 parts of Neoberex Pakgu were uniformly mixed and pulverized to obtain an irrigation agent.

Example s, N-(6-methylcyclohexyl)-
N-(1,2,4-)lyazol-1-ylcarbonyl)-2,6-cyJthyl-3-bromoaniline (compound No. 32) 50 parts, xylene 40 parts, dimethylformamide 5 parts, toxanone (Product name: Sanyo Chemical Industries, Ltd.) 5 parts were uniformly mixed and dissolved to obtain an emulsion.

Example 9 N-(cyclohexen-1-yl)-N
-(1-imidazolylcarbonyl)-2,6-dimethyl-3-chloroaniline (compound No. 17), 5
1 part, 50 parts of talc, and 45 parts of kaolin were uniformly mixed to obtain a powder.

Next, the effects of the herbicide in this invention will be specifically explained using experimental examples. The test compound numbers in each experimental example are the same as the compound numbers in Table 1.

Experimental Example 1 Paddy field weeding experience ゛'' - Earl's Wagner pot was filled with Ube soil 000 (alluvial clay loam), seeds of Japanese millet that had awakened from dormancy, seeds of bulrush and seeds of Helaomodaka were sown.
After lightly covering the upper layer with soil containing the seeds of Konagi and Kikashigusa, we transplanted paddy rice seedlings (variety: Nipponbare) at the 2.3 leaf stage and then added water to create a flooded state at a depth of 3 m. And so. Next, each drug (an aquarium prepared according to Example 7) was added to a solution with an active ingredient concentration of 10 Q Oppm.
It is diluted with water so that ) was uniformly added dropwise with a pipette so that the amount of active ingredient was 50 f/1A, and the mixture was kept in a glass room with an average temperature of 25°C.

Three weeks after the chemical treatment, the herbicidal effects of each test compound were investigated. The results are shown in Table 2.

In addition, the herbicidal effects in Table 2 were based on the following criteria.

5: Complete withering 4: Daikichi 3: Chukichi 2: Small damage 0: No harm (normal growth) Table 2 Continuation of Table 2 Experimental example 2 Paddy weed growing season treatment test Ube in a 115,000 are Wagner pot The soil was filled with upper IK (alluvial clay loam), and the dormant and awakened seeds of Japanese grasshopper, firefly, and Helaomodaka were sown, and the soil was lightly covered with soil containing seeds of Japanese staghorn and Kikashigusa seeds. Next, paddy rice seedlings (variety: Nipponbare) at the 2.3-leaf stage were transplanted and submerged in water at a depth of 3 cIn. Grow for 2 weeks in a glass room with an average temperature of 25°C. When the Japanese millet reaches 1.5 leaf age, each chemical (watering agent manufactured according to Example 7) was added to the water so that the active ingredient concentration was 1000 ppm. (diluted)) was uniformly dropped in a predetermined amount using a pipette.

It was maintained in a glass room with an average temperature of 25°C. After drug treatment, 2
The herbicidal effect of each test compound was investigated every week. The results are shown in Table 3.

Note that the criteria for the herbicidal effect in Table 3 are the same as in Experimental Example 1.

Table 3 Experimental Example 3. Field cultivation soil treatment test A 175,000 are Wagner Ponot was filled with Ube soil, and radish (variety: Tokinashi) and seager beet (variety 1)
After sowing and covering the soil with seeds of soybean (variety: Akiyoshi), soybean (variety: Akiyoshi), and weeds such as mehishiba, inubu, 70za, purslane, and inutade, a hydrating agent manufactured according to Example 7 was applied. Active ingredient concentration is 1000 ppm
It is diluted with water so that ) was sprayed under pressure uniformly onto the soil surface so that the amount of active ingredient was 50 f/are, and the mixture was maintained in a glass room with an average temperature of 25°C.

Three weeks after the chemical treatment, the herbicidal effects of each test compound were investigated. The results are shown in Table 4.

Note that the criteria for the herbicidal effect in Table 4 are the same as in Experimental Example 1.

Table 4 t8) Procedural Amendment July 13, 1980 Director General of the Patent Office 1 Indication of the Case Japanese Patent Application No. 1983-1'71998 2 Name of the Invention Anilide Derivatives, Process for Producing Anilide Derivatives, and Herbicides 3 Relationship with the case of the person making the amendment Patent applicant postal code 755 1-12-32 Nishihonmachi, Ube City, Yamaguchi Prefecture Telephone: 03
(58J) 3311 4 Kusunoki 7. Detailed description of the invention in the statement of date of amendment order. Contents of amendment (1), page 20 of the specification, next to the last column of the continuation of Table 1, the following matters are amended.

Record [Continuation of Table 1] (2), page 26 of the specification, a continuation of Table 2.

Correct as follows.

[Continuation of Table 2*: 1-(N-allyl-N-2-methylquenylcarpamoyl)imidazole (JP-A-52-12562
Compounds listed in No. 8 Common Axis).

=779

Claims (3)

[Claims] (1), General formula [However, in formula 1, X represents a lower alkyl group or a halogen atom, R is a lower alkyl group, cycloalkyl group, or methyl-substituted cycloalkyl group, and pen represents a hydrogen atom, a lower alkyl group, or a phenyl group. or a tolyl group, Rt represents a hydrogen atom, a lower alkyl group, or a halogen atom, and R3 represents a hydrogen atom or a lower alkyl group, and R1 and R6 have a straight chain or a branched atom number of 1 to 5. They are alkylene groups and can also be bonded to each other to form a ring. ), and M represents an imidazole group or a triazole group. Anilide derivative represented by ]. (2), a compound represented by general formula (,1) and general formula (II) H-M...
・It is characterized by reacting the compound represented by (n) in the presence of a base. A method for producing an anilide derivative represented by general formula (III) H3. However, in the above general formulas (1) to (fil), X represents a lower alkyl group or a halogen atom gold, and R represents a lower alkyl group, a cycloalkyl group, a methyl group-substituted cycloalkyl group, a benzyl group, an α-phenetelkyl group, Indicates a phenyl group or tolyl group. R2 represents a hydrogen atom, a lower alkyl group or a halogen atom, R8 represents a hydrogen atom or a lower alkyl group, and R3 and R2 are linear or branched alkylene groups having 1 to 5 carbon atoms and are bonded to each other. It is also possible to form a ring. ), and M represents an imidazole group or a triazole group. (3), General formula [However, in formula 2, X represents a lower alkyl group or a halogen atom, R is a lower alkyl group, a cycloalkyl group, a methyl group-substituted cycloalkyl group, and pen R1 is a hydrogen atom, a lower alkyl group, or a phenyl group. group or toluyl group, R2
represents a hydrogen atom, a lower alkyl group or a halogen atom, R3 represents a hydrogen atom or a lower alkyl group, and R
I and R2 are linear or branched alkylene groups having 1 to 5 carbon atoms, and can be bonded to each other to form a ring. ), and M represents an imidazole group or a triazole group. ] A herbicide characterized by containing an anilide derivative represented by the following as an active ingredient.