KR820000938B1 - Process for preparing of acetanilides - Google Patents

Abstract

Acetanilides I (R = H, C1-5 alkyl, alkoxy; R1, R2 = H, halogen, C1-5 alkyl or alkoxy, 1-alkoxyalkyl; X = Cl, Br, I; A = azole or substituted azoles), useful as selective herbicide, were prepd. by the reaction of 2-halo-N-halomethylacetanilide (II) and monohydrogene azole (H-A) at 0≰C-200≰C. Thus, a mixt. of 16.5 2-chloro-2',6'-dimethyl-N-chloroacetanilide and 9.3wt. % 1,2,4-triazole was refluxed in 60wt.% THF for 8hr, cooled, filtrated, and condensed to give 21.0 wt.% 2-chloro-2',6'-dimethyl-N-(1,2,4-triazole-1-yl-methyl) acetanilide (m.p.115-118≰C).

Description

Method for preparing acetanilide

The present invention relates to a process for preparing herbicides containing new and useful acetanilides and to methods for controlling weed growth. It is already known in the literature that haloacetanilides have herbicidal or growth-controlling action.

Particularly important active ingredients are 2-chloro-N-isopropylacet anilide (German Patent No. 1,014,380) and 2-chloro-2 ', 6'-diethyl-N-methoxymethyl-acetanilide (US patent). 3,547,620) and compounds having a 1,3-dioxolan-2-yl methyl group bonded to a nitrogen atom which is a haloacet anhydride having a heterocyclic substituent (see German Patent Publication No. 2,405,510).

However, weeds that can be easily weeded with the above compounds are limited to a few and have a disadvantage of using a relatively large amount due to their low herbicidal activity. U. S. Patent No. 3,637, 847 also describes a process for the preparation of N-haloalkyl anilides.

The present invention relates to the preparation of acet anilide of formula (I) which overcomes the above disadvantages and has a very strong selective herbicidal action.

Wherein group R is hydrogen or alkyl containing up to 5 carbon atoms or -alkoxy containing up to 5 carbon atoms; R ¹ is hydrogen, halogen, alkyl containing up to 5 carbon atoms, alkoxy containing up to 5 carbon atoms, perhaloalkyl containing up to 4 carbon atoms or 1-alkoxy containing up to 5 carbon atoms Alkyl, R ² is formed with hydrogen, halogen, alkyl or alkoxy each containing up to 5 carbon atoms, perhaloalkyl having up to 4 carbon atoms, or alkoxyalkyl having up to 5 carbon atoms, or R and When attached to a position represents an alkylene chain of up to 6 carbon atoms optionally substituted by an alkyl group having up to 4 carbon atoms; X is chlorine, cancelled or iodine; A is carboalkoxy having up to 4 carbon atoms in a halogen, phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl (each having 4 carbon atoms), cyano, carboxy or alkoxy groups, linked by a ring nitrogen atom Or an azole salt which represents an azole which is substituted one or more times or at all by an alkanoyl having a maximum of 4 carbon atoms and also contains 2-3 nitrogen atoms.

Heterocyclic substituted acetanilides according to the present invention exhibit excellent and potent herbicidal activity against numerous types of weeds, in particular to remove any plant growth or to selectively weed in certain herbaceous or herbaceous crops. The new active ingredient has a surprising effect in removing bays or controlling growth.

When the compound such as Structural Formula (I) according to the present invention is used as a herbicide, weeds can be weeded only by selecting weeds and crops in a very small amount. Wherein R and R ¹ in the formula (I) are substituted at the 2- and 6- positions of the phenyl nucleus and have an alkyl group having a maximum number of 5 carbon atoms.

R, R ¹ , R ² , X and A in the general formula (I) are mainly used as the following groups. In other words,

R is hydrogen, an alkyl group having up to 5 carbon atoms (e.g., methyl, ethyl, n-furophyl isofurophyll, n-butyl, secondary-butyl, isobutyne, tert-butyl, straight and branched pentyl), max Alkoxy having 5 carbon atoms (e.g., methoxy, ethoxy, furoxy, butoxy and pentyloxy),

R ¹ is hydrogen, halogen, alkyl having up to 5 carbon atoms (e.g., methyl, ethyl, n-furophyl isofurophyll, n-butyl, secondary-butyl, isobutyl, tert-butyl, straight and branched pentyl) , Alkoxy alkyl having up to 5 carbon atoms (eg methoxy methyl and ethoxyethyl),

R ² is hydrogen, halogen, alkyl having up to 5 carbon atoms (e.g. methyl, ethyl, n-furophyll, isofurophyll, n-butyl, secondary-butyl, isobutyl, tert-butyl, straight and Branched pentyl), alkoxy having up to 5 carbon atoms (e.g. methoxy, ethoxy, furoxy, butoxy, pentyloxy), perhaloalkyl having up to 4 carbon atoms (e.g. trifluoromethyl, triclo) Rhomethyl, pentafluoroethyl, heptafluoroisofurophyll alkoxy alkyl having up to 5 carbon atoms (e.g., methoxymethyl and ethoxymethyl), and together with R, R ² is attached to the orzo-position and Alkylene chains having up to 6 carbon atoms which may be substituted by alkyl having 4 carbon atoms (e.g. ethylene, trimethylene, tetramethylene, 1-methyltrimethylene, 1,1-dimethyltrimethylene, 1,1-dimethylde Trimethylene).

X is mainly chlorine, but can also be canceled and oxo.

A is an azole bound by a nitrogen atom ring (e.g., pyrrole, pyrazole, 1,2,4-triazole, 1,2,3-triazole or tetrazole), the azole having a maximum number of carbon atoms of 4 Mono- or multiple by groups such as phosphorus halogen, phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl groups, cyano, carboxy, alkoxy groups having a maximum of 4 carbon atoms, or alkanoyl having a maximum of 4 carbon atoms Substituted or unsubstituted examples of the substituent include 2,6-dimethylpyrazole, tetramethylpyrazole, 3 (5) -methylpyrazole, 4-methylpyrazole, 3 (5) -ethylpyrazole , 4-ethylpyrazole, 3 (5) -isopurophanpyrazole, 4-isopurophilpyrazole, 3,5-dimethylpyrazole, 3,5-dimethyl-4-acetylpyrazole, 3,5- Dimethyl, 4-propionylpyrazole, 3,4,5-trimethylpyrazole, 3 (5) -phenylpyrazole, 4-phenylpyrazole, 3,5-diphenylpyrazole, 3 (5) -phenyl -5 (3) -methylpyrazole, 3 (5) -chloropyrazole, 4-chloro Pyrazole, 4-bromopyrazole, 4-iodopyrazole, 3,4,5-trichloropyrazole, 3,4,5-tribromopyrazole, 3,5-dimethyl-4-chloropyrazole, 3,5-dimethyl-4-bromopyrazole, 4-chloro-3 (5) -methylpyrazole, 4-bromo-3 (5) -methylpyrazole, 4-methyl-3,5-dichloropyrazole , 3 (5) -methyl-4,5 (3) -dichloropyrazole, 3 (5) -chloro-5 (3) -methylpyrazole, 4-methoxypyrazole, 3 (5) -methyl-5 (3) -methoxypyrazole, 3 (5) -ethoxy-4,5 (3) -dimethylpyrazole, 3 (5) -methyl-5 (3) -trifluoromethylpyrazole, 3,5 -Bis-trifluoromethylpyrazole, 3 (5) -methyl-5 (3) -caraethoxypyrazole, 3,5-bis-caraethoxypyrazole, 3,4,5-triscarab Ethoxypyrazole, 3 (5) -methyl-5 (3) -methylthio-4-caraethoxypyrazole, 4-methyl, 3,5-bis-caraethoxypyrazole, 4-cyano Pyrazole, 4-methoxy-3,5-dichloropyrazole, 3 (5) -methyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3 (5 ) -Chloro-1,2,4-triazole-3 (5) -bromo-1,2,4-tri Azole, 3 (5) -chloro-5 (3) methyl-1,2,4-triazole, 3,5-dichloro-1,2,4-triazole, 3,5-dibromo-1,2 , 4-triazole, 3 (5) -chloro-5 (3) -cyano-1,2,4-triazole, 3 (5) -chloro-5 (3) -phenyl-1,2,4- Triazole, 3 (5) -chloro-5 (3) -carbomethoxy-1,2,4-triazole, 3 (5) -methylthio-1,2,4-triazole, 4 (5)- Methyl-1,2,3-triazole, 4,5-dimethyl-1,2,3-triazole, 4 (5) -phenyl-1,2,3-triazole, 4 (5) -chloro-1 , 2,3-triazole, 1,2,3-triazole-4 (5) ylcarboxylic acid ethyl ester, 1,2,3-triazole-4,5-yldicarboxylic acid dimethyl ester, 5 -Methyltetrazole, 5-chlorotetrazole, tetrazolyl-5-carboxylic acid ethyl ester, imidazole, 2-methylimidazole, 4,5-chloroimidazole, 2-methyl-4,5-dichloroimid With diazole, 2-ethyl-4,5-dichloroimidazole, 2-isopropyl-4,5-dichloroimidazole, 2,4,5-trichloroimidazole, 2,4,5-tribromoimidazole 2-bromo-4,5-dichloroimidazole have.

In addition, when the optionally substituted azole contains 2 or 3 nitrogen atoms, A is usually selected from inorganic acids or organic acids of strong acids which are used well to form salts. Examples of strong acids include hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, tetrafluoroboric acid, fluoroboric acid, fluoroboric acid and formic acid, halogenated carboxylic acids (e.g. trichloroacetic acid), alkanesulfonic acid (e.g. methanesulfonic acid), Halogenated alkanesulfonic acids such as trifluoromethane sulfonic acid and perfluorohexanesulfonic acid, and arylsulfonic acids such as dodecylbenzenesulfonic acid.

Asymmetric substituted azoles (e.g. pyrazole, 1,2,3-triazole and 1,2,4-triazole) have two isomers in the starting material due to their automeric structure. Two isomers of pyrazole are as follows.

In this case, two isomers appear in the compound of general formula (I), and the abundance of these isomers varies depending on B, C and D and is an important factor for herbicidal properties.

The new acet anilide according to the present invention is obtained by reacting 2-halo-N-halomethyl (formula (II)) with monohydrogenazole (expressed by formula H-A) as shown in the following scheme.

Substituents R ¹ , R ² , R and X have the same meanings as described above, A is an azole attached through a ring of nitrogen atom, halogen, phenyl, alkyl, alkoxy, alkylthio having 4 maximum carbon atoms, Substituents that are not substituted with any of a perfluoroalkyl group, a carboxyalkoxy, cyano, carboxy or alkanoyl group, or a mono- or polysubstituted substituent.

Some of the 2-halo-N-halomethylacetanilides of the formula (II) may be obtained by reaction with haloacetylhalide with the reaction according to German Patent Publication No. 1,542,950 or similarly.

At least one mole of 2-halo-N-halomethylacet anilide is reacted with monohydrogen to add acetanilide of the present invention. The hydrogen halide liberated during the reaction is easily obtained by using organic bases such as tertiary amines, alkali metals, alkaline earth metal carbonates, or bicarbonates as appropriate binders, which are formulated at least relative to the amount of one hydrogen azole reacted. Add more than

It is preferable to react 2-halo-N-halomethylacetanilide in an inert solvent, and suitable solvents include hydrocarbons such as petroleum ether, ligroin, cyclohexane, toluene and xylene, diethyl ether, diisofurophyll ether, Ethers such as dimethoxyethane, tetrahydrofuran, dioxane and anisol, dichloromethane, chloroform, 1,2-dichloroethane, halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene, ketones such as acetone and methyl ethyl ketone, ethyl acetate and Esters such as butyl acetate and sulfones such as dimethyl soloxide and tetrahydrothiophene-1 and 1-side. These solvents may be used alone or in combination.

This reaction can be carried out at a temperature of 0 ° C. or higher. The reaction is carried out at the boiling point of the solvent or the solvent mixture to promote the reaction, but not at a temperature of 200 ° C. or higher. Usually, reaction is performed between 50-150 degreeC. After completion of the reaction, the mixture is filtered and washed as necessary and the product is isolated from the filtrate according to conventional methods.

If a solvent is soluble in water, it is usually advantageous to filter off the solvent after evaporation and replace it with a solvent insoluble in water.

A

형태의 화학식을 갖는 아졸염과 반응시켜 얻을 수 있다.In addition, the structural formula (I) and the new acetanilide M are 2-halo-N-halomethylacetanilide of the structural formula (II).

A

It can be obtained by reaction with an azole salt having the chemical formula in the form.

는 음이온, 알칼리금속이온, 혹은 알칼리토금속 이온의 등가물을 의미하고, A는 질소원자고리를 통해 부착되고 전혀 치환되지 않거나 또는 할로겐, 페닐, 알킬, 알콕시, 최대 수용 탄소수가 4인 알킬티오, 퍼플루오로알킬, 시아노, 카아복시, 또는 알카노일과 같은 기에 의해 모노-또는 다중치환된 아졸을 나타낸다.Substituents R, R ¹ , R ² and X have the same meanings as described above and M

Is an equivalent of an anion, an alkali metal ion, or an alkaline earth metal ion, and A is attached through a nitrogen atom ring and is not substituted at all or halogen, phenyl, alkyl, alkoxy, alkylthio, perfluorinated having 4 carbon atoms. Azoles mono- or polysubstituted by groups such as roalkyl, cyano, carboxy, or alkanoyl.

는 일 수소아졸 H-A를 알칼리금속 또는 강염기와 반응시켜 수소 혹은 알코올 혹은 암모니아를 유리시킴으로서 얻는데, 이때의 알칼리 금속이나 강염기로는 알칼리 금속의 수산화물, 알칼리금속의 알코올 염, 알칼리금속아미드, 알칼리금속하이드라이드 및 수산화은 등이 있다.Alkali metal, alkaline earth metal, or silver azole

Is obtained by reacting one hydrogen azole HA with an alkali metal or strong base to liberate hydrogen, alcohol or ammonia, wherein the alkali metal or strong base includes hydroxides of alkali metals, alcohol salts of alkali metals, alkali metal amides and alkali metal hydrides. And silver hydroxide.

와 일반식(Ⅱ)의 2-할로-N-할로메틸아세트아닐 라이드와의 반응은 -30-50℃, 대개는 실온에서 다음과 같은 극성중성 용매내에서 더 반응이 잘된다. 아세토니트릴, 디메틸포름아미드, 디메틸렌글리콜 디메틸에테르 및 트리에틸렌 글리콜 디메틸에테르, 테트라 하이드로 티오펜-1, 1-디옥사이드, 디메틸슬퍼옥사이드, 아세톤, 메틸에테르 케톤, 디이소프로필 케톤, 염

와 2-할로-N-할로메틸아세트 아닐라이드는 서로 같은 몰수로 반응을 시키는데, 반응 생성물은 필요에 따라 무기염

을 분리시키고 필요에 따라 극성중성 용매를 물과 혼화할 수 없는 용매로 대체한 후 단리시킨다.salt

And 2-halo-N-halomethylacetanilide of general formula (II) are better reacted at -30-50 DEG C, usually at room temperature in the following polar neutral solvent. Acetonitrile, dimethylformamide, dimethylene glycol dimethyl ether and triethylene glycol dimethyl ether, tetrahydro thiophene-1, 1-dioxide, dimethylsulfoxide, acetone, methyl ether ketone, diisopropyl ketone, salt

And 2-halo-N-halomethylacetanilide are reacted with the same mole number as each other, and the reaction product is an inorganic salt if necessary.

Are separated and, if necessary, the polar neutral solvent is replaced with a solvent that is incompatible with water and then isolated.

In the preparation of acetanilides of formula (I), the substituted aniline of formula (R) is reacted with a hydrohalide of halomethylazole such as X-CH ₂ -A to formula (IV). Obtain a second aniline and react it again with haloacetylhalide with the structural formula X-CO-CH ₂ -X as in the scheme below.

(Wherein R, R ¹ , R ² and X have the same meaning as described above, A is attached to the nitrogen atom ring (2 or 3 nitrogen atoms in the ring), unsubstituted or halogen, phenyl, alkyl , Alkoxy, alkylthio or perfluoroalkyl cyano with a maximum of 4 carbon atoms, carboxy, carboxyl, with a maximum of 4 carbon atoms, azoles mono- or polysubstituted by alkanoyl groups with a maximum of 4 carbon atoms Indicates.

As halomethylazole (X-CH ₂ -A), chloromethylazole in which X is Cl (chlorine) is used well, and chloromethyl azole is used in J. Chem. Soc., 1960, 5272-3. There are a number of ways to obtain similarly, mainly available ones.

In chloromethylazole (Cl-CH ₂ -A), A is pyrazole, 1,2,3-triazole, or 1,2,4-triazole, which is asymmetrically substituted, and is known as automerism. Because of its structure, two isomers are formed.

The above two reactions require a binder to bind hydrogen halide (HX), and the binders required for the first reaction include triethylamine, ethyldiisopropylamine, diazabicyclo- (2,2,2) -octane, di Tertiary organic amines such as ethylcyclohexylamine, pyridine and alkyl pyridine, alkali groups, or alkaline earth metal carbonates or bicarbonates, or substituted anilines of the formula (II). In addition to the substituted aniline, mention may be made of bases.

Both reactions were acetonitrile, dimethylformamide, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, tetra hydrothiophene-1,1-dioxide, dimethyl sulfoxide, acetone, methyl ethyl ketone and diisopuropin. Better in polar neutral solvents such as ketones.

The reaction for obtaining the secondary aniline of formula (IV) is in the temperature range between 20 ° C. and 150 ° C., and further reaction with haloacetyl halide is carried out at a temperature between −20 + 100 ° C.

Starting materials are used in the same molar amount. If desired, the secondary aniline of formula (IV) can be further reacted with haloacetylhalide without separation.

Acetanilide of formula (I) also reacts 2-halo-N-halomethylacetanilide of formula (II) with an alkali metal azide and obtains 2-halo-N-azido of formula (V) It can be obtained by reaction of methylacetanilide with acetylene, whose hydrogen atom can be substituted with a substituent such as triazolyl group.

In the above, R, R ¹ , R ² and X are the same groups as described above, A is attached via nitrogen atom weight and is not substituted at all or mono by any of phenyl, alkyl, carboxy or alkoxy having 4 maximum carbon atoms. Or multiple substituted 1,2,3-triazoles.

The reaction can be represented by the following formula.

는 알칼리금속 이온을 나타내고, R³및 R⁴는 서로 동일하거나 또한 상이한 수소, 페닐, 최대 수용탄소수가 4인 알킬, 카아복시, 카아브알콕시 또는 알카노일 등과 같은 기이다.In the above scheme, R, R ¹ , R ² and X are the same groups as described above, M

Represents an alkali metal ion, and R ³ and R ⁴ are the same or different hydrogen, phenyl, alkyl having a maximum number of carbon atoms of 4, carboxy, carbalkoxy or alkanoyl and the like.

2-halo-N-halomethylacetanilide of formula (II), such as alkali metal azide such as sodium azide, in the presence of a polar neutral solvent at temperatures between -30- + 50 ° C., typically at room temperature React in molar amounts.

Particularly well used polar polar solvents required for the reaction are tertiary amides such as dimethylformamide and N, N-dimethyl acetamide or nitriles such as acetonitrile and tetrahydrothiophene-1,1-dioxide and dimethylsulfoxide. Sponges, such as a side, are mentioned.

2-halo-N-azidomethylacetanilide of formula (V) is reacted with at least the molar amount of acetylene or acetylene derivative in a solvent inert to the reactants to produce crude 2-halo-N- (1,2 , 3-triazol-1-yl-methyl) -acetanilide can easily be obtained, which is advantageous to wash off the alkali metal azide still present before the reaction with water to remove it. Reaction with acetylene or acetylene derivatives proceeds at temperatures between 0-150 ° C. and pressures above atmospheric or atmospheric pressure, depending on the reactivity of the reactants, and suitable chlorinated aliphatic and aromatic hydrocarbons (eg; Non-polar neutral solvents such as dichloromethane, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene and ethers (eg diethyl ether, dioxane, tetrahydrofuran and anisol) are mainly used.

Salts of acetanilide of formula (I) wherein A is an azole having two or three nitrogen atoms (generally pyrazole, 1,2,3-triazole, 1,2,4-triazole, etc.) It can be obtained from acetanilide of formula (I) by the method of any one of the above-mentioned methods, i.e., at least one mole or more of an inorganic or organic acid (e.g. hydrochloric acid, hydrobromic acid, nitric acid, tetrafluoro sulfate) Boric acid, fluorosulfonic acid and formic acid), halogenated carboxylic acids (e.g. trichloroacetic acid), alkanesulfonic acid (e.g. methanesulfonic acid), halogenated alkansulfonic acid (e.g. trifluoromethanesulfonic acid and perfluorohexanesulfonic acid Or arylsulfonic acid (e.g., dodecylbenzenesulfonic acid).

The preparation of the new acetanilides and salts thereof is explained in more detail by the following examples. Here, parts means parts by weight and have the same relationship as volume parts in which kg is replaced by l (liter). For convenience of description, parts are expressed in% and explained.

Example 1

16,5% by weight of 2-chloro-2 ', 6'-dimethyl-N-chloromethylacetanilide and 9.3% by weight of 1,2,4-triazole were refluxed in 60% by weight of anhydrous tetrahydrofuran for 8 hours. The resulting mixture is cooled, filtered and the residue, which is concentrated in vacuo, is dissolved in chloroform having a volume ratio of 60%, washed three times with 40% volume ratio of water each time and dried over sodium sulfate. 21.0 weight of 2-chloro-2 ', 6'-dimethyl-N- (1,2,4-triazol-1-yl-methyl) acetanilide (melting point; 115-118 ° C.) after evaporation of the solvent under vacuum The% is separated and recrystallized from ethanol and then melted at 120 ° C.

Example 2

43.9% by weight of 2-chloro-2 ', 6'-dimethyl-N-chloromethylacetanilide and 25.8% of pyrazole were stirred at 90 ° C. for 7 hours in 120% volume ratio of toluene to cool and filter The filtrate was then washed three times with 50% volumetric water each time and dried by passing through sodium sulfate.

The solvent was evaporated and the residue was triturated with 50% by volume petroleum ether to yield 2-chloro-2 ', 6'-dimethyl-N- (pyrazol-1-yl-methyl) -acetanilide (melting point; 81 ° C.). ) 39.1% by weight.

Example 3

68.5% by weight of 2-chloro-2 ', 6'-diethyl-N-chloromethylacetanilide and 50.4% by weight of 3,5-dimethylpyrazole were stirred in toluene at 100% volume ratio for 8 hours at 90-95 ° C. The resulting mixture was cooled to room temperature, filtered and the filtrate was washed three times with 100% volumetric water each time and dried by passing through sodium sulfate. After evaporation of the solvent in vacuo, the residue was triturated with 70% by volume petroleum ether to afford 2-chloro-2 ', 6'-diethyl-N- (3,5-dimethylpyrazol-1-yl-methyl)- Obtained by separating 42.5% by weight of acetanilide (melting point; 107-109 ° C.).

Example 4

21.4% by weight of 2-chloro-2'-methyl-6'-ethyl-N-ethylchloromethylacetanilide and 20.2% by weight of 4-chloro-3,5-dimethylpyrazole were dissolved in 100% by volume glycol dimethylether. The mixture obtained by refluxing for 10 hours was cooled to 0 ° C., filtered, and the filtrate concentrated to 23.8% by weight was passed through 50% by weight of silica gel and filtered through 600% by volume of chloroform. 20.4% by weight of 2-chloro-2'-methyl-6'-ethyl-N- (4-chloro-3,5-dimethylpyrazol-1-yl-methyl) -acetanilide as an oil from the concentrated chloroform filtrate Was separated and triturated with 50 ml of petroleum ether and completely crystallized (melting point 66 ° C. in petroleum ether).

Example 5

28.5% by weight of 2-chloro-N-chloromethyl-2'-methyl-6'-ethylacetanilide and 17.4% by weight of 3 (5) -methyl-1,2,4-triazole were 150% by volume anhydrous tetra The mixture obtained by refluxing for 6 hours in hydrofuran was cooled to 0 ° C., then filtered and the filtrate was concentrated in vacuo. The residue was triturated thoroughly with 200% volume ratio and water, filtered off with suction and dried. 20.5% by weight of 2-chloro-2'-methyl-6'-ethyl-N-3 (5) -methyl-1,2,4-triazol-1-yl-methyl) -acetanilide as a crystalline powder (Melting point 89-91 ° C.) This was recrystallized from a mixture of toluene and petroleum ether 3: 1. It melts at 90-93 ° C. with a 3 (5) -position isomer ratio of 3: 1.

Example 6

The solution obtained by dissolving 3.5% by weight of 1,2,4-triazole in 8.8% by weight of 30% sodium methylate solution was evaporated to dryness in vacuo at 50 ° C. This crystalline residue was introduced into the solution of 13.0% by weight of 2-chloro-2'-methyl-6'-ethyl-N-chloro methyl acetanilide dissolved in anhydrous acetonitrile in 80% by volume, gradually stirring at room temperature with one hand stirring. did. After 24 hours the undissolved material was filtered off and the filtrate was concentrated in vacuo. The residue was passed through 60% by weight of silica gel and filtered through 300% by volume of chloroform to elute the developer, followed by 2-chloro-2'-methyl-6'-ethyl-N- (1,2,4-triazole 8.0 wt% of 1-yl-methyl) -acetanilide was obtained (melting point: 84 ° C.).

Example 7

To a solution of 26.1% by weight of 2-chloro-2'-methyl-6'-ethyl-N-chloromethylacetanilide in which 6.5% by weight of sodium azide was dissolved in 100% by volume anhydrous dimethylformamide at 25-30 ° C. The whole mixture introduced little by little was stirred for 2 hours. After adding 200% by volume water, the organic phase was separated, dissolved in 200% by volume methylene chloride, washed three times with 50% by volume water each time and dried by passing through sodium sulfate. After filtering this, 14.2 volume% of dimethyl esters of acetylenedicarboxylic acid were dripped, and the temperature was raised to 30 degreeC. After 2 hours the mixture was concentrated in vacuo and triturated with methanol and then from the residue 2-chloro-2'-methyl-6'-ethyl-N- (4,5-bis-carbomethoxy-1,2,3 21.5 weight% of -triazol-1-yl-methyl) -acetanilide was obtained (melting point: 103-105 ° C).

Example 8

10.0% by weight of 2-chloro-2'-methyl-6'-ethyl-N- (1,2,4-triazol-1-yl-methyl) -acetaryl chloride with anhydrous dichloromethane and ether (1: 1) After dissolving in 50% by weight of the mixture, the mixture was passed through dry hydrogen chloride and cooled for 15 minutes, followed by dropwise addition of anhydrous ether in a 55% by volume ratio to 2-chloro-2'-methyl-6'-ethyl-N- (1, 7.5 wt% of 2,4-triazol-1-yl-methyl) acetanilide hydrochloride (melting point: 148 ° C.) was obtained.

The following compounds were also obtained in a similar manner to the above.

The active ingredients of the present invention may be directly sprayed into solutions, powders, suspensions (including large amounts of aqueous solutions, emulsions or other suspensions), dispersants, emulsions, oil dispersants, pastes, dusting agents, spreading agents or sprays, agricultural sprays, It can be formulated as a spray, spread or fountain granules. The form of use depends entirely on the reagents used, and uses the active ingredients as finely as possible.

Mineral oils such as kerosene or diesel oil or coultar and vegetable or animal oils, benzene, toluene, xylene, paraffin, tetrahydronaphthalene and derivatives thereof, for preparing direct sprayable emulsions, pastes and phase dispersants (e.g. methanol Fatty or cyclic and aromatic hydrocarbons such as ethanol, propanol, butanol, chloroform, carbon tetrachloride and strong polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone and water. The effect can be obtained.

The aqueous solution may be prepared by adding water to an emulsion, a paste, an oil dispersant or a hydrate. Active ingredients dissolved in oils or solvents for the preparation of emulsions, pastes and oil dispersants are homogenized in water with a hydrating or dispersing agent, an adhesive or an emulsifier to dilute the active ingredient wetting agent adhesive, emulsifying or dispersing agent and possibly a solvent or oil with water. This possible thickener can be obtained.

Surfactants include the following: alkali metals of alkaline lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, alkyl arylsulfonates, alkylsulfonates and alkynsulfonates, alkaline earth metals and ammonium salts, alkalis of dibutylnaphthalenesulfonic acid Earth and alkaline earth metal salts, lauryl ether sulfate, aliphatic alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, sulfated hexadecanol, heptadecanol and salts of octadecanol, sulfated aliphatic alcohol glycol ether salts, sla Phenolized naphthalene and naphthalene derivatization products with formaldehyde, naphthalene or naphthalene sulfonic acids with phenols and formaldehyde concentrates, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenols, ethoxylated octylphenols and ethoxylated nonylphenols, Alkylphenol polyglycol ether, tributyl phenol polyglycol ether , Alkylaryl polyester alcohol, isotridecyl alcohol, aliphatic alcohol ethylene oxide concentrate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxyfuropropylene, lauryl alcohol polyglycoether ether acetyl, sorbitol ester, lignin , Sulfite waste liquor and methyl cellulose.

Powders, dispersants and dusting agents can be prepared by mixing or grinding the active ingredient with the solid carrier.

Coating, impregnation or homogeneous granules can be formulated by combining the active ingredient with a solid carrier. Solid carriers include silicic acid, silcagel, silicates, actives, kaolin, atacclay, limestone, chalk, bowls, clay, clay, rholomite diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide and ground plastics. Mineral soils or fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and urea and vegetable materials such as cereal flour, wood flour, bark flour and nuts, and cellulose powder are mainly used.

The formulation contains 0.1-95, suitably 0.5-90% by weight of active ingredient.

The new herbicidal anilide according to the invention can be used in admixture with a number of other herbicides or growth-controlling active ingredients, including diazines, benzothiadiazines, 2,6-dinitroanilines, N-phenyls Carbamates, bis-carbamates, thiocarbamates, halocarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, Benzofuran derivatives are mainly used. By using in combination with other components in this way, not only widens the range of action, but also sometimes excellent effects such as synergism can be obtained. The following are a number of active ingredients that have compositions with very wide application in combination with new compounds.

It is useful to use the new compounds of the invention alone or in admixture with other crop protection agents, such as pests, plant pathogens or bactericidal agents. In addition, the compound can be obtained by mixing with a light solution that is useful for preventing malnutrition and trace element deficiency.

The specific effect of the compound of the present invention and the compound obtained by the prior art were investigated by comparing the effect on the growth of weed crops as in the following experiment.

1. Greenhouse Experiment

Plastic pots having a volume of 300 cm ³ were filled with sandy soil containing approximately 1.5% of the soil, and the seeds of the test plants (see Table I) were shallowly planted and separated according to the type.

In the case of edible cypress, pre-germinated bulbs were transplanted. In the case of pre-germination treatment, the active ingredient is used directly on the soil surface, which is usually suspended or emulsified in the field and sprayed through spray nozzles. After administering herbicides, the sown seeds are germinated to grow and watered gently with a sprayer to activate the chemicals. The plant is covered with a clear plastic cover over the pot until the roots emerge, which uniformly germinate the test plant to prevent the plant from being injured by chemicals and prevent the volatiles from easily evaporating.

In the case of treatment after germination, the plants were grown to a height of 3-10 cm before treatment with chemicals. The planter is not covered. Experiments are carried out in greenhouses at 25-40 ° C and for plants in temperate climates at 15-30 ° C. This experiment relates to observation of the plant's response to various treatments for 4-6 weeks, and the following table shows the test substance, the active ingredient (kg / ha) and the plant species under test. The assessment was graded C-100, where 0 means no injury or normal germination, 100 means no germination or at least the thorny part of the plant is completely destroyed.

[Outdoor experiment]

The experiment was done in a small field. Sandy soil of pH 5-6 containing 1-1.5% of humus was used. In the case of treatment before germination, the active ingredient was administered immediately after sowing or up to 3 days after sowing. Crops were sown in line. The most widespread and common weed ploora in nature is the weed, which depends on the season of the year and partly on crops (eg spring-germination, summer-germination). The chemically active component emulsified or suspended in water is administered with a motor-actuated nebulizer fitted to the hitch.

When there is no rainfall, water the fields so that there is no problem with the growth of crops or weeds. After several weeks of experiments, the results were evaluated by dividing them into 0-100.

[result]

The results are shown in Table 2-15. It has been found that the anilide of the present invention clearly shows a very strong herbicidal effect even at very fine contents (see Tables 2 and 10). The new compounds have also been shown to exhibit potent herbicidal action against unwanted mining plants.

In this respect it can be seen that the active ingredients of the present invention have obvious advantages over conventional compounds (see Tables 3, 4, 5, 9, 10).

Sufficient labeling was provided to allow anyone to recognize the herbicidal action of the new compound or selective herbicidal action on safety (Table 3,5,6,7,8,9,10,12,13,14). , 15).

In the case of treatment after germination, the plants can be completely killed according to the usage of the compound (see Table 4). In case of dosing dose, only growth inhibitory effect occurred in the treatment area and did not harm the edges, plantation areas and grasses, and showed only growth-controlling action on unnecessary plants.

The herbicidal action of the new compounds of the present invention is potent enough to completely moisten all plants in excess of use than for selective herbicidal use. Amounts available here are suitable for removing unnecessary weeds such as shrubs, crops, industrial drinking trees on railroad tracks, and playgrounds on squares.

The use of the compounds for treatment before or after germination is indicated in the table, where the herbicides can be combined not only on the soil surface, but also inside the soil, and the herbicide can be used before or after sowing or on already germinated crops.

Other uses include post-treatment or spraying, which spray directly onto the surface of weeds or soil without sacrificing chemical-sensitive crops.

There are several possible methods of use, the compounds of the present invention or herbicides incorporating these compounds can be used in numerous crops in addition to those exemplified in the table for removing weeds or inhibiting growth. The amount can be used between 0.1-15 kg / ha depending on the purpose of use.

The crops used in the experiments are listed in the table below.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

TABLE 6

TABLE 7

TABLE 8

TABLE 9

TABLE 10

TABLE 11

TABLE 12

TABLE 13

TABLE 14

TABLE 15

Claims (1)

Monohydrogen azole at a temperature of 0 ° C to 200 ° C, HA) a process for the preparation of acetanilide of formula (I)

In the formula, the group R in the formula represents hydrogen, alkyl having 5 maximum carbons, alkoxy having 5 maximum carbons, and the group R ¹ is hydrogen, halogen, alkyl or alkoxy having 5 maximum carbons Or 1-alkoxyalkyl, pihaloalkyl having 4 maximum carbons, group R ² is hydrogen, halogen, alkyl having 5 maximum carbons or alkoxy or alkoxyalkyl, perhalo having 4 maximum carbons A group having an alkylene chain having up to 6 carbon atoms optionally substituted by alkyl or a group having up to 4 carbon atoms formed together with the group R and attached to the ortho position, wherein X represents chlorine, The same halogen, and 4 is attached via a nitrogen atom ring, which is an unsubstituted azole or halogen, phenyl, alkyl, alkoxy, alkylthionaperfluoroalkyl having 4 carbon atoms Or salts of azoles containing one or two-substituted azoles with groups such as carabalkoxy or alkanoyl, cyano, carboxy, and containing two or three nitrogen atoms.