JPS59155366A - Amide derivative, its preparation, and herbicide - Google Patents

Abstract

NEW MATERIAL:An amide derivative shown by the formula I [Q is thienyl, furyl, or phenyl; A is group shown by the formula II(R<3> is H, lower alkyl, or lower alkoxycarbonyl), or group shown by the formula III(R<4> and R<5> are H, or lower alkyl; R<6> is H, lower alkyl, or lower alkoxycarbonyl); R<1> is H or lower alkyl; R<2> is H, lower alkyl, or phenyl; R<1> and R<2> are 1-5C alkylene may be linked to form ring; M is imidazole or triazole]. EXAMPLE:N-2-(3-Methylbuten-1-yl)-N-(1-imidazolylcarbonyl)-benzylamine. USE:A herbicide. Effective for weeds such as annual, perennial gramineous weeds, broad-leaved weeds, etc. in paddy fields and plowed fields. PREPARATION:A carbamoyl chloride intermediate shown by the formula IV is reacted with a compound shown by the formula V in the presence of a base, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION This invention is based on the general formula [wherein Q is a chenyl group, furyl group or phenyl group
One or two hydrogen atoms of the phenyl group may be substituted with a lower alkyl group, a lower alkoxy group, or a halogen atom. ) represents a lower alkoxycarbonyl group. ) or alkyl group, R6 is a hydrogen atom,
Indicates a lower alkyl group or a lower alkoxycarbonyl group. ), R1 represents a hydrogen atom or a lower alkyl group, and R2 represents a hydrogen atom, a lower alkyl group, a phenyl group (
The hydrogen atom of the phenyl group may be substituted with a lower alkyl group. ), and R1 and R2 have 1 to 5 carbon atoms.
is a linear or branched alkylene group that 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 amide derivative represented by the following formula, a method for producing the same, and a herbicide containing this novel amide derivative as an active ingredient.

The inventors have conducted various studies with the aim of obtaining industrially useful amide derivatives that have not been previously published in literature.

As a result, a new amide derivative represented by the general formula (in which Q, A, R1, R2 and M each have the same meaning as above) can be synthesized by a new manufacturing method. Furthermore, it was discovered that this new amide derivative has an outstanding herbicidal effect on various weeds, and has no phytotoxicity to various crops, no toxicity to humans, livestock, fish and shellfish, and no odor. Reached.

The amide 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. family weeds,
Effective against a wide range of weeds including broad-leaved weeds.

As shown in the following reaction formula, the amide derivative in this invention combines a carbamoyl chloride intermediate represented by general formula (I) and a compound represented by general formula [II] (specifically, imidazole or triazole). Synthesized by reaction.

(However, in the formula, Q, A, R1, R2 and M each have the same meaning as above.) This reaction is carried out in a reaction-inert solvent such as acetone, dimethylformamide, dimethyl sulfoxide, etc. It is carried out in the presence of a base such as , potassium hydroxide, sodium hydroxide, or pyridine.

This reaction proceeds quantitatively. Therefore, the amount of imidazole or triazole used is preferably 1.0 to 1.2 mol per 1 mol of the carbamoyl chloride intermediate.

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

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, the desired amide derivative represented by the general formula [■] can be obtained by appropriately employing operations such as extraction, water washing, drying, and distillation.

The raw material carbamoyl chloride intermediate represented by the general formula [I] can be obtained by reacting trichloromethyl chloroformate [V] with a compound represented by the general formula (III) as shown in the following reaction formula. It is synthesized by

(However, in the formula, Q, A, R1, and R2 each have the same meaning as above.) This reaction is carried out in a solvent inert to the reaction, such as benzene, toluene, dioxane, dimethylformamide, etc., using pyridine, triethylamine, It is carried out in the presence of a base such as sodium hydroxide or 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 [V] or 1 to 1.2 mol of bosgene 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 carrying out the reaction at a temperature of 0 to 80°C for 0.1 to 1 hour. After the reaction, the carbamoyl chloride intermediate represented by general formula (I) can be isolated by appropriately employing operations such as water washing, dehydration, extraction, and distillation.

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

Example 1 N-2-(3-methylbuten-1-yl)
-N-(1-imidazolylcarbonyl)-benzylamine (Compound No. 2 in Table 1 below) 6.0 g (0.03 mol) of trichloromethyl chloroformate was dissolved in 400 ml of toluene, and triethylamine was added under stirring. 20 g (0.2 mol) was added dropwise. Next, 10.5 g of N-imbutylidene-benzylamine (
0.06 mol) was added dropwise and stirred for 30 minutes. After the reaction, the toluene layer was washed with water, dried over a small amount of anhydrous sodium sulfate, the toluene was distilled off, and the intermediate N-2
-(3-methylbuten-1-yl)-N-benzylcarbamoyl chloride was obtained.

Next, this carbamoyl chloride and imidazole 6.
1 g (0.09 mol) in 50 ml of dimethylformamide
12.4 g of potassium carbonate ((0.09
mol) was added and heated at 60-80°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 then the toluene was distilled off to obtain 9.6 g of a slightly yellow target product (n25D 1.5483).

Example 2 N-2-(3-methyl-benten-1-yl)-N-(imidazolylcarbonyl)-4-methylbenzylamine (compound No. 50 in Table 1 below) Trichloromethylchloroform was added to 400 ml of toluene. 7.9 g (0.039 mol) of 2-(3-methylpentylidene)-4-methylbenzylamine and 20 g (0.20 mol) of triethylamine were dissolved and stirred. ) was added all at once at room temperature, and the reaction was carried out for 30 minutes.

After washing with water and drying the organic layer over anhydrous sodium sulfate, toluene was distilled off to obtain an intermediate carbamoyl chloride. Dissolve this carbamoyl chloride in 50 ml of dimethylformamide, and dissolve 6.8 g of imidazole.
(0.1 mol) and 7.6 g of potassium carbonate,
Heated at 60-80°C for 30 minutes. After the reaction is completed, it is poured into water, extracted with toluene, and concentrated to obtain the target product 5.8.
g (n22D 1.5481) was obtained.

Example 3 N-2-(cyclohexen-1-yl)-N
-(imidazolylcarbonyl)-α-n-propylbenzylamine (compound No. 75 in Table 1 below) 2-cyclohexylidene-α in place of 2-(3-methylpentylidene)-4-methylbenzylamine The reaction was carried out in the same manner as in Example 2, except that 8.9 g (0.039 mol) of -n-propylbenzylamine was used, and 7.2 g (m.p. 86-87 °C) was obtained.

Example 4 N-2-(3-methyl-buten-l-yl)
-N-(imidazolylcarbonyl)-α-ethoxycarbonylbenzylamine (Table 1 below, compound number 147
compound) 2-(3-methylbutylidene)-α-instead of 2-(3-methylpentylidene)-4-methylbenzylamine
Ethoxycarbonylbenzylamine 10.3g (0
．． The reaction was carried out in the same manner as in Example 2, except that 039 mol) was used, and 6.0 g (n2
2D 1.5314) was obtained.

It was manufactured according to Examples 1 to 4. Specific examples of the novel amide derivatives of this invention are listed in Table 1.

In addition, the upper row of the elemental analysis value section in Table 1 shows the theoretical value, and the lower row shows the measured value.

When the amide derivatives of this invention are used as herbicides, they are prepared in granules, powders, emulsions, wettable powders, etc. using inert solid carriers, liquid carriers, emulsifying dispersants, etc., in accordance with the customary practice of agricultural chemical formulations. It can be used in any dosage form such as tablets, oils, aerosols, smokes, etc. Examples of these inert carriers include talc, clay, kaolin,
Diatomaceous earth, calcium carbonate, potassium chlorate, slaked stone,
Wood flour, nitrocellulose, starch, benzene, xylene, n-hexane, gum arabic, vinyl chloride. Examples include carbon gas, freon, propane, and butane. In addition, formulation auxiliaries such as spreading agents, diluents,
Surfactants and the like can be appropriately blended. moreover,
It can also be used in appropriate mixtures with fungicides, insecticides and other agricultural chemicals, urea, ammonium sulfate, ammonium phosphorous, potassium salts and other fertilizer substances, soil conditioners, etc.

The herbicide of this invention has an amide rating of 0.1 as an active ingredient.
It can contain up to 99 wt%. The preferred content differs slightly depending on the dosage form; for example, in the case of granules, it is 1 to 3
5 wt%, 25 to 90 wt% in the case of wettable powders, 5 to 50 wt% in the case of emulsions, and 1 to 25 wt% in the case of powders.
Wt% is good.

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

Next, examples of herbicides used in this research will be given. In addition, parts in each example mean parts by weight.

Example 5 (Granules) 8 parts of Compound No. 2, 30 parts of bentonite, 59 parts of talc, 1 part of Neoperex powder (trade name: Kao Atlas Co., Ltd.), and 2 parts of sodium lignin sulfonate were uniformly mixed and ground. A small amount of water was added and the mixture was kneaded, granulated using a granulator, and dried to obtain granules.

Example 6 (Hydration series) 50 parts of Compound No. 17, 48 parts of kaolin, and 2 parts of Neoperex powder were uniformly mixed and ground to obtain a wettable powder.

Example 7 (Emulsion) 50 parts of compound No. 114, 40 parts of xylene,
An emulsion was obtained by uniformly mixing and dissolving 5 parts of dimethylformamide and 5 parts of toxanone (trade name: manufactured by Sanyo Chemical Industries, Ltd.).

Example 8 (Powder) 5 parts of Compound No. 13, 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. In addition, the test compound number in each experimental example is the same as the compound number in Table 1.

Experimental example 1. Paddy field weeding experiment A Wagner pot of 1/5000 are was filled with Ube soil (alluvial clay loam), and seeds of Japanese millet that had awakened from dormancy.
After sowing the seeds of Firefly and the seeds of Helaomodaka, and lightly covering the top layer with soil containing the seeds of Konagi and Kikashigusa, the seedlings of paddy rice seedlings at the 2- and 3-leaf stage (
Variety: Nipponbare) was transplanted and water was added to create a submerged state at a depth of 3 cm. 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 added with a pipette so that the amount of active ingredient was 50 g per 1 are. The samples were uniformly added dropwise and 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: Major damage 3: Medium damage 2: Minor damage 1: Slight damage 0: Harmless (normal growth) Experimental example 2. Field cultivation soil treatment test A 1/5000 are Wagner pot was filled with Ube soil, and radish (variety: Tokinashi) and sugar beet (variety:
After sowing and covering the soil with seeds of Daisu (variety: Akiyoshi), Daisu (variety: Akiyoshi), and weeds such as Mehishiba, Inubu, Shiroza, and Suberihyu, each chemical agent (an irrigation agent manufactured according to Example 6) was applied as an active ingredient. (diluted with water to a concentration of 1000 ppm) was sprayed under pressure uniformly onto the soil surface so that the amount of 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.

(72) Originator: Nobuyuki Kuroda 5 U, 1978 Oaza Kogushi, Ube City Bukosan Co., Ltd. Central Research Laboratory (72) Initiator: Masanori Sone 5 U, 1978 Oaza Kogushi, Ube City Bukosan Co., Ltd. Central Research Laboratory

Claims (3)

[Claims] (1). General formula [wherein Q is a chenyl group, furyl group or phenyl group (
One or two hydrogen atoms of the phenyl group may be substituted with a lower alkyl group, a lower alkoxy group, or a halogen atom. ) represents a lower alkoxycarbonyl group. ) or alkyl group, R6 is a hydrogen atom,
Indicates a lower alkyl group or a lower alkoxycarbonyl group. ), R1 represents a hydrogen atom or a lower alkyl group, and R2 represents a hydrogen atom, a lower alkyl group, a phenyl group (
The hydrogen atom of the phenyl group may be substituted with a lower alkyl group. ), and R1 and R2 have 1 to 5 carbon atoms.
is a linear or branched alkylene group that can be bonded to each other to form a ring. ), and M represents an imidazole group or a triazole group. ] An amide derivative represented by (2). A compound represented by the general formula (I) and a compound represented by the general formula [II] H-M...[
II] is characterized by reacting the compound represented by the following in the presence of a base. A method for producing an amide derivative represented by general formula (III). However, in the above general formulas (I) to [■], Q is a chenyl group, a furyl group, or a phenyl group (one or two hydrogen atoms of the phenyl group are substituted with a lower alkyl group, a lower alkoxy group, or a halogen atom). R5 represents a hydrogen atom or a lower alkyl group, and R6 represents a hydrogen atom, a lower alkyl group, or a lower alkoxycarbonyl group.
1 represents a hydrogen atom or a lower alkyl group, R2 represents a hydrogen atom, a lower alkyl group, or a phenyl group (the hydrogen atom of the phenyl group may be substituted with a lower alkyl group), and R1 and R2 are It is a linear or branched alkylene group 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. (3). General formula [wherein Q is a chenyl group, furyl group or phenyl group (
One or two hydrogen atoms of the phenyl group may be substituted with a lower alkyl group, a lower alkoxy group, or a halogen atom. ) represents a lower alkoxycarbonyl group. ) or an alkyl group, and R6 represents a hydrogen atom, a lower alkyl group, or a lower alkoxycarbonyl group. ), R1 represents a hydrogen atom or a lower alkyl group, R2 represents a hydrogen atom, a lower alkyl group, a phenyl group (the hydrogen atom of the phenyl group may be substituted with a lower alkyl group), and R1 and R2 have 1 or more carbon atoms
5 linear or branched alkylene groups, which can also 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 amide derivative represented by ] as an active ingredient.