JPS5920270A - Anilide derivative, preparation of anilide derivative, and herbicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is lower alkyl, CF3, lower alkoxy, alkenyloxy, etc.; n is 0-3; when n is 2 or 3, and one of X is substituted at the 2-position of benzene ring, the other Xs are not substituted at the 6- position; R1 is H or lower alkyl, R2 is R1, lower alkenyl or phenyl; M is imidazolyl or triazolyl). EXAMPLE:N-1-(2-methylpropen-1-yl)-N-(1-imidazolylcarbonyl)-2-methylani line. USE:Herbicide having excellent herbicidal effect to various weeds, free from phytotoxicity to crops, toxicity to man, animals, fish and shellfish, nor ill odor, and applicable either by soil treatment or by foliar treatment. PROCESS:The compound of formula I can be prepared by reacting the carbamoyl chloride of formula II with the compound of formula H-M such as imidazole in an inert solvent in the presence of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention is based on the general formula [wherein X is a lower alkyl group, a trinorolomethyl group,
Lower alkoxy group, alkenyloxy group.

lower alkoxyalkoxy group, )-rogen atom, phenyl group, benzyloxy group, or phenoxy group (the hydrogen atom of the phenoxy group is a lower alkyl group).

It may be substituted with a lower alkoxy group or )/rogen atom. ), and n represents 0.1.2 or 3.

However, when n is 2 or 3 and one of X is substituted at the 2-position of the benzene ring, the remaining X is 6 of the benzene ring.
In the formula, RI represents a hydrogen atom or a lower alkyl group, and R2 represents a hydrogen atom or a lower alkyl group. It represents a lower alkenyl group or a phenyl group, and R1 and R2 are linear or branched alkylene groups having 1 to 3 carbon atoms, and can be bonded to each other to form a ring. In the formula, M represents an imidazole group or a triazole group. ] A novel anilide derivative and its production method. The present invention also provides a herbicide containing this novel anilide derivative as an active ingredient.

The inventors. The purpose of this study was to obtain industrially useful anilide derivatives that have not been previously reported in the literature. We conducted various researches. the result.

It is represented by the general formula % (wherein X, n, R (, R2 and M each have the same meaning as above).

We have succeeded in synthesizing a new anilide derivative using a new manufacturing method. Furthermore, this new anilide derivative has an outstanding herbicidal effect on various confections, and has no toxicity to various crops, including toxicity to humans, livestock, fish, and shellfish. We also found that there was no strange odor at all.

We have arrived at this invention.

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 is a carnocumoyl chloride intermediate represented by general formula (1) and a compound represented by general formula (n) (specifically, imidazole or triazole). ) is synthesized by reacting.

1 0 item CD, (n) [+n)
(However, in formula 1, X* ne R,, R2 and M are.

Each has the same meaning as above. ) This reaction involves 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 proceeds quantitatively. Therefore, the amount of imidazole or triazole to be used is preferably from 0 to 1.2 mol per 1 mol of the carbamoyl chloride intermediate.

In addition, the amount of base used is carbamoyl chloride intermediate 1
It is preferably 0.8 to 1.5 moles.

The reaction is completed at a temperature of 0-150'C, preferably 50-100'C, for 0.5-10 hours. After the reaction, the desired anilide derivative represented by the general formula (I[l) can be obtained by appropriately employing operations such as extraction, water washing, drying, and distillation.

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

CrV) [V) [1)
(However, in formula 9, X, n, R1 and R2 each have the same meaning as above.) This reaction is performed on benzene, toluene and dioxane.

It is carried out in a reaction-inert solvent such as dimethylformamide in the presence of a base such as pyridine, triethylamine, sodium hydroxide, or potassium hydroxide.

This reaction proceeds quantitatively. Therefore, the general formula of the raw material C
It is preferable to use 0.5 to 0.6 mol of trichloromethyl chloroformate (V) or 1 to 1.2 mol of phosgene per 1 mol of the compound represented by IV),
Moreover, it is preferable to use 0.8 to 1.5 moles of the base.

The reaction is completed by 2, which is carried out for 0.1 to 1 hour at a temperature of 0 to 80°C. After the reaction, by appropriately employing operations such as water washing, dehydration, extraction, and distillation.

A carbamoyl chloride intermediate represented by general formula [1] can be isolated.

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

Example I N-1-(2-methylpropen-1-yl)
-N-(1-imidazolylcarbonyl)-2-methylaniline (Compound No. 11 in Table 1 below) Toluene 300 m/in, )! Dissolve 5.2 p (0,026 mol) of J dichlorotyl chloroformate.

Under stirring, triethylamine 5.7 p (0,056 mol)
was dripped. Then, 8.1 p (0.05 mol) of N-imbutylidene-2-methylaniline was added dropwise.

Stirring was performed for 15 minutes. After the reaction, the toluene layer was washed with water and diluted with a small amount of anhydrous sulfuric acid.l) After drying with a ram, the toluene was distilled off and the intermediate r*-1-(2-methylproben-1-yl)-N- (2-)f-ruphenyl)-rubamoyl chloride was obtained.

Next, this carbamoyl chloride and imidazole 3
．． After dissolving 8 g, (0,055 mol) in 50 ml of dimethylformamide, 7.6.17 g of potassium carbonate
-' (0,055 mol) was added and stirred at 50 to 70°C for 1 hour. After the reaction, it was poured into water, extracted with toluene, dried over a small amount of anhydrous sodium sulfate, and the toluene was distilled off to obtain 7.4 g of the target product as a pale yellow viscous liquid (yield 56%, n11)'1. 5'613) was obtained.

Example 2N-2-(3-methyl-buten-1-yl)-
N-(imidazolylcarbonyl)-2-fluoro, aniline (Compound No. 49 in Table 1) Internal volume 500m/! 5.8. After preparing y, (0,029 mol) and dissolving it in 400 ml of toluene, while stirring,
2-(3-methylbutylidene)-2-fluoroaniline 77, (o; oz 9 mol) triethylamine 20. y(
0.198 mol) was added at once at room temperature. After the reaction, the organic layer was washed with water and dried over anhydrous sodium sulfate.
6.82 (0.1 mol) imidazole, 30 ml N,N-dimethylformamide and anhydrous potassium carbonate7.
62 (0,055 mol) was added and toluene was distilled off at 50'C.

Heated at 70°C for 30 minutes. After the reaction, 1-1-0O water was added, extracted with toluene, dried over anhydrous sulfuric acid, and the toluene was distilled off. The obtained oil was recrystallized from a mixed solvent of toluene and n-hexane to obtain 3.5 g of the desired product in the form of colorless sand crystals.

Example 3 N'-2-(3-ethyl-buten-1-yl)-N-(imidazolylcarbonyl)-2-fluoroaniline (compound No. 50 in Table 1 of Goshu) 2-(3- Same as Example 2 except that 2-(3-ethylbutylidene)-2,-fluoroaniline 7.5y (0,039 mol) was used instead of methylbutylidene)-2-fluoroaniline. The reaction was carried out by operation to obtain the desired product 4.52 in the form of colorless sandy crystals.

Example 4 N-2-(3-methyl-buten-1-yl)-N-(imidazolylcarbonyl)-2-methyl-5
- Chloraniline (compound No. 85 in Table 1 below) 2-(3-methylbutylidene)-2-methyl-5- in place of 2-(3-methylbutylidene)-2-fluoroaniline The reaction was carried out in the same manner as in Example 2 except that chloroaniline 8.21 (0,039 mol) was used, and the obtained oil was purified by column chromatography to obtain the target product 4.82 as an orange liquid. Obtained.

It was manufactured according to Examples 1 to 4 below. Examples of the novel anilide derivatives in this invention are listed in Table 1.

In addition, in the column of elemental analysis values in Table 1, the upper row (indicates the theoretical value), and the lower row with -1 indicates the measured value.

Table 1 Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 1Continued from Table 11 Continuation of Table Continuation of Table 1 Continuation of Table 1 Continuation of Table 1 Continuation of Table 1 Continuation of Table 1 In this invention. When using anilide derivatives as herbicides, follow the conventions for pesticide formulations.

1 tablet, powder, emulsion, and 9 tablets of wettable powder using an inert solid body, a liquid carrier, an emulsifying dispersant, etc.

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, isocarbonate, freon, bronogun, butane, and the like. 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, agricultural chemicals, urea, ammonium sulfate, ammonium phosphorous, potassium salts, pond fertilizers, soil conditioners, etc.

The herbicide of this invention contains an anilide derivative as an active ingredient at 0.0%.
It can be contained in an amount of 1 to 99 wt%. The preferred amount varies slightly depending on the dosage form. For example, in the case of granules, the amount is 1 to 1.
35 wt%, 25 to 90 wt% in the case of hydrating powders,
In the case of emulsions, it is preferably 5 to 50 wt%, and in the case of powders, it is preferably 1 to 25 wt%.

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

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

Example 5 N-(1-isopropylvinyl), N-(
l-imidazolylcarbonyl)-2-methylaniline (
8 parts of compound number 5), 30 parts of bentonite, 59 parts of talc, 1 part of Neoberesox powder (product name: Kao Atlas Co., Ltd.), and 2 parts of sodium lignin sulfonate were uniformly mixed and ground, and a small amount of water was added. The mixture was kneaded using a granulator, granulated using a granulator, and dried to obtain granules.

Example 6. N-(2,2-dimethylvinyl)-N-(l
-imidazolylcarbonyl)-2-methylaniline (compound No. 11), 48 parts of kaolin, and 2 parts of Neopellex powder were uniformly mixed and ground to obtain an irrigation agent.

Example 7 N-(1-isopropylvinyl) -N-(
An emulsion was obtained by uniformly mixing and dissolving 50 parts of (imidazolylcarbonyl)-2-methoxyaniline (compound No. 23), 40 parts of xylene, 5 parts of dimethylformamide, and 5 parts of toxanone (trade name: manufactured by Sanyo Chemical Industries, Ltd.). .

Example 8”N-(1-isopropylvinyl)-N-(
A powder was obtained by uniformly mixing 5 parts of 1-imidazolylcarbonyl-2-methyl-4-chloroayu (compound wJ number 82), 50 parts of talc, and 45 parts of kaolin.

Next, the effects of the herbicide in this invention will be specifically explained using a series of experiments. Note that the test compound numbers in each experimental row are the same as the compound numbers in Table 1.

Experimental Example 1 Paddy field weeding experiment Ube soil (alluvial clay loam) was placed in a Wagner pot of Fukuri Earl.
After sowing dormant and awakened Japanese millet seeds, firefly seeds, and Helaomodaka seeds, the top layer was lightly covered with soil containing Konagi and Kikashigusa seeds. Young seedlings (variety: Nipponbare) were transplanted, and water was added to create a flooded state with a water depth of 3 CTn. Next, each drug (an aquarium prepared according to Example 6 was diluted with water so that the concentration of the active ingredient was 1000 ppm) was pipetted so that the amount of active ingredient was 502 per are. The specimens were uniformly treated under 7rAr as shown in the figure, and 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 2.

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

5: Complete withering 4: Daikichi 3: Medium-kichi 2: Small 1: Slight damage 0: Harmless (normal growth) Continuation of Table 2 * 1-(N-71J-N-2-methylphenylcarbamoyl)imidazole (% Kaisho, 52-1256
28. Compounds described in the above publication).

Experimental Example 2 Field Crop Soil Treatment Test A 175,000 are Wagner pot was filled with Ube soil, and radish (variety: Tokinashi) and sugar beet (variety:
After sowing and covering the soil with the seeds of Dice (variety: Akiyoshi), Daisu (variety: Akiyoshi), and weeds such as porcupine, inubu, 70za, purslane, and inutade, each chemical agent (an irrigation agent manufactured according to Example 6) was applied. Component concentration is 1000 ppm
It is diluted with water so that ) was uniformly sprayed under pressure onto the soil surface so that the active ingredient was 50 g per 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 3.

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

Table 3 Patent applicant: Ube Industries Co., Ltd. 5 U, 1978 Oaza Kogushi, Ube City Bukosan Co., Ltd. Central Research Laboratory

Claims (3)

[Claims] (1), General formula % Formula % [In the formula, X is a lower alkyl group, a trifluoromethyl group,
Lower alkoxy group, alkenyloxy group. Indicates a lower alkoxyalkoxy group, a halogen atom, a phenyl group, a benzyloxy group, or a phenoxy group (the hydrogen atom of the phenoxy group is a lower alkyl group. It may be substituted with a lower alkoxy group or a halogen atom), and n is 0. , 1.2 or 3. However, when n is 2 or 3 and one of the X's is substituted at the 2-position of the benzene ring, the remaining X is not substituted at the 6-position of the benzene ring. In the formula, RI represents a hydrogen atom or a lower alkyl group, +R2 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, or a phenyl group, and R1 and R2 each have a carbon number of 1
~3 linear or branched alkylene groups which can be bonded to each other to form a ring. Moreover, 1M in the formula represents an imidazole group, a tria, or a zole group. Anilide derivative represented by ]. (2) is characterized by reacting a compound represented by the general formula (1) % formula % with a compound represented by the general formula [■] HM...CI+) in the presence of a base. General formula (III) 0H-R. 11 1] A method for producing an anilide derivative represented by: However, in the above general formulas CI) to [III], X is a di-lower alkyl group, trifluoromethyl group, lower alkoxy group, alkenyloxy group, lower alkoxyalkoxy group, halogen atom, phenyl group, benzyloxy group, or phenoxy group. (The hydrogen atom of the phenoxy group may be substituted with a lower alkyl group, lower alkoxy group, or)-logen atom. ), and n represents 0, 1.2 or 3. However, when n is 2 or 3 and one of X is substituted at the 2-position of the benzene ring, it is not substituted at the remaining or 6-position of the benzene ring. R1 represents a hydrogen atom or a lower alkyl group, R2 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a phenyl group, and R1 and R2 are a linear or branched alkylene group having 1 to 3 carbon atoms. and mutually) (they can also be bonded together to form a ring. M represents an imidazole group or a triazole group. (3) In the general formula C, X is a lower alkyl group, a trifluoromethyl group, a lower alkoxy group, or an alkenyloxy group. Indicates a lower alkoxyalkoxy group, a norogen atom, a phenyl group, a benzyloxy group, or a phenoxy group (the hydrogen atom of the phenoxy group is a lower alkyl group. It may be substituted with a lower alkoxy group or a halogen atom), and n is 0. .1.2 or 3. However, when n is 2 or 3 and one of the X's is substituted at the 2-position of the benzene ring, the remaining X is not substituted at the 6-position of the benzene ring. In the formula, R1 represents a hydrogen atom or a lower alkyl group + R2 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a phenyl group, and R, and R21l
'i is a linear or branched alkylene group having 1 to 3 carbon atoms and can be bonded to each other to form a ring. In the formula, 1M represents an imidazole group or a triazole group. ] A herbicide characterized by containing an anilide derivative represented by the following as an active ingredient.