阅读说明：本技术 一种新型除草安全剂双苯噁唑酸的制备方法 (Preparation method of novel weeding safener isoxadifen ) 是由 孔繁蕾 王小兵 韩建平 李逸峰 张旺庚 于 2020-07-18 设计创作，主要内容包括：本发明涉及双苯噁唑酸制备技术领域,公开了一种新型除草安全剂双苯噁唑酸的制备方法,由1,1-二苯基乙烯与氯代肟基乙酸乙酯在有机酸和有机碱作用下充分混合,并在40～60℃的环境下与催化剂以及反应溶剂反应后,制得双苯噁唑酸,其中,所述1,1-二苯基乙烯与氯代肟基乙酸乙酯、有机酸和有机碱的摩尔比为(0.4～0.9)∶(1～1.8)∶(1.3～2.0)。通过该方法制备的新型除草安全剂双苯噁唑酸,采用甲醇钠作为有机碱、氨基磺酸为有机酸,反应后可以大大减少副产物的生成,提高了反应的精准性和选择性,明显提高了收率,而且反应过程较为平稳,条件温和,操作较为简单,原材料较为廉价、易得,污染程度小,可大面积推广生产。(The invention relates to the technical field of bisbenzoxazole acid preparation, and discloses a preparation method of a novel weeding safety agent bisbenzoxazole acid, which is characterized in that 1, 1-diphenylethylene and chlorooximido ethyl acetate are fully mixed under the action of organic acid and organic base, and react with a catalyst and a reaction solvent at the temperature of 40-60 ℃ to prepare the bisbenzoxazole acid, wherein the molar ratio of the 1, 1-diphenylethylene to the chlorooximido ethyl acetate to the organic acid to the organic base is (0.4-0.9) to (1-1.8) to (1.3-2.0). The novel weeding safety agent bisoxazole acid prepared by the method adopts sodium methoxide as organic base and sulfamic acid as organic acid, can greatly reduce the generation of byproducts after reaction, improves the accuracy and selectivity of the reaction, obviously improves the yield, has stable reaction process, mild conditions, simple operation, cheap and easily obtained raw materials, small pollution degree and large-area popularization and production.)

1. A preparation method of a novel weeding safener bisbenzoxazole acid is characterized in that 1, 1-diphenylethylene and chlorooximido ethyl acetate are fully mixed under the action of organic acid and organic base, and react with a catalyst and a reaction solvent at the temperature of 40-60 ℃ to prepare the bisbenzoxazole acid, wherein the molar ratio of the 1, 1-diphenylethylene to the chlorooximido ethyl acetate to the organic acid to the organic base is (0.4-0.9) to (1-1.8) to (1.3-2.0).

2. The method for preparing a novel herbicidal safener bisbenzoxazole acid according to claim 1, wherein the organic base is any one of sodium methoxide, potassium ethoxide, potassium tert-butoxide, alkyl lithium reagent, grignard reagent, quaternary ammonium hydroxide, Lithium Diisopropylamide (LDA) or lithium hexamethyldisilazide.

3. The preparation method of the novel herbicidal safener bisbenzoxazole acid as claimed in claim 1, wherein said organic acid is any one of sulfamic acid, glycolic acid, citric acid, acetic acid, benzoic acid, oxalic acid or succinic acid.

4. The preparation method of the novel herbicidal safener isoxadifen acid as claimed in claim 1, wherein the catalyst is any one of sodium hydroxide, barium hydroxide, hydrochloric acid, ammonia water, oxalic acid, acetic acid, formic acid, sulfuric acid, phosphoric acid or magnesium oxide.

5. The method for preparing a novel herbicidal safener bisbenzoxazole acid as claimed in claim 1, wherein said reaction solvent is any one of petroleum ether, diethyl ether, propylene glycol, tetrahydropyran or methyl 2-methylpentanoate.

6. The process for preparing bisbenzoxazole acid as herbicide safener according to claim 1, wherein the weight ratio of ethyl chlorohydroxyimino acetate to solvent is 1: 4.

7. The preparation method of the novel herbicidal safener isoxadifen as claimed in claim 1, which is characterized by comprising the following steps:

a: sequentially pouring organic acid and organic base into a container 1 according to the weight ratio of 1:1, and mixing for later use to obtain a mixture a;

b: taking 50% of chlorooximido ethyl acetate according to the weight parts, pouring 1, 1-diphenylethylene and 50% of chlorooximido ethyl acetate into a container 2 containing a catalyst and a reaction solvent for mixing for later use to obtain a mixture b;

c: and B, fully reacting the mixture a in the step A and the mixture B in the step B at the temperature of 40-60 ℃ to obtain the bisbenzoxazole acid.

8. The method for preparing the novel herbicidal safener isoxadifen acid as claimed in claim 7, wherein the mixture a and the mixture b in step C are fully reacted, and the pH value of the new mixture is adjusted to be neutral, and the new mixture is allowed to stand for 20min at normal temperature to obtain the final product isoxadifen acid.

Technical Field

The invention relates to the technical field of preparation of isoxadifen acid, in particular to a preparation method of isoxadifen acid serving as a novel weeding safety agent.

Background

The isoxadifen is an additive for reducing or eliminating phytotoxicity of herbicide to crops, and is also called herbicide safener. The special safener for weeding in the nicosulfuron corn field can enhance the pesticide effect of nicosulfuron while reducing the pesticide damage under adverse weather conditions.

However, triethylamine is mostly used as an organic base in the existing preparation method, so that a part of byproducts are generated, the yield is low, and the actual production is not facilitated. Therefore, the person skilled in the art provides a preparation method of a novel herbicide safener isoxadifen to solve the problems in the background art.

Disclosure of Invention

The invention aims to provide a preparation method of a novel herbicide safener isoxadifen acid, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme:

a preparation method of novel weeding safener-bisbenzoxazole acid comprises the steps of fully mixing 1, 1-diphenylethylene and chlorooximido ethyl acetate under the action of organic acid and organic base, and reacting with a catalyst and a reaction solvent at 40-60 ℃ to obtain the bisbenzoxazole acid, wherein the molar ratio of the 1, 1-diphenylethylene to the chlorooximido ethyl acetate to the organic acid to the organic base is (0.4-0.9): (1-1.8): (1.3-2.0).

As a still further scheme of the invention: the organic base is any one of sodium methoxide, potassium ethoxide, potassium tert-butoxide, alkyl lithium reagent, Grignard reagent, quaternary ammonium hydroxide, Lithium Diisopropylamide (LDA) or lithium hexamethyldisilazide.

As a still further scheme of the invention: the organic acid is any one of sulfamic acid, glycolic acid, citric acid, acetic acid, benzoic acid, oxalic acid or succinic acid.

As a still further scheme of the invention: the catalyst is any one of sodium hydroxide, barium hydroxide, hydrochloric acid, ammonia water, oxalic acid, acetic acid, formic acid, sulfuric acid, phosphoric acid or magnesium oxide.

As a still further scheme of the invention: the reaction solvent is any one of petroleum ether, diethyl ether, propylene glycol, tetrahydropyran or 2-methyl valerate.

As a still further scheme of the invention: the weight ratio of the chlorooximido ethyl acetate to the solvent is 1: 4.

A preparation method of a novel weeding safener-bisbenzoxazole acid comprises the following steps: the method specifically comprises the following steps:

a: sequentially pouring organic acid and organic base into a container 1 according to the weight ratio of 1:1, and mixing for later use to obtain a mixture a;

b: taking 50% of chlorooximido ethyl acetate according to the weight parts, pouring 1, 1-diphenylethylene and 50% of chlorooximido ethyl acetate into a container 2 containing a catalyst and a reaction solvent for mixing for later use to obtain a mixture b;

c: and B, fully reacting the mixture a in the step A and the mixture B in the step B at the temperature of 40-60 ℃ to obtain the bisbenzoxazole acid.

As a still further scheme of the invention: and C, after the mixture a and the mixture b in the step C are fully reacted, adjusting the pH value of the new mixture to be neutral, and standing for 20min at normal temperature to obtain the finished product of the bisoxazole acid.

Compared with the prior art, the invention has the beneficial effects that: the novel weeding safety agent bisoxazole acid prepared by the method adopts sodium methoxide as organic base and sulfamic acid as organic acid, can greatly reduce the generation of byproducts after reaction, improves the accuracy and selectivity of the reaction, obviously improves the yield, has stable reaction process, mild conditions, simple operation, cheap and easily obtained raw materials, small pollution degree and large-area popularization and production.

Detailed Description

In embodiment 1 of the present invention, a method for preparing a novel herbicide safener, bisbenzoxazole acid, comprises the steps of fully mixing 1, 1-diphenylethylene and chlorohydroxyimino ethyl acetate under the action of an organic acid and an organic base, and reacting with a catalyst and a reaction solvent at 45 ℃ to obtain the bisbenzoxazole acid, wherein the molar ratio of the 1, 1-diphenylethylene to the chlorohydroxyimino ethyl acetate to the organic acid to the organic base is 0.6: 1.2: 1.4.

preferably: the organic base is sodium methoxide.

Preferably: the organic acid is sulfamic acid.

Preferably: the catalyst is sodium hydroxide.

Preferably: the reaction solvent is 2-methyl pentanoic acid methyl ester.

Preferably: the weight ratio of the chlorooximidoethyl acetate to the solvent is 1: 4.

A preparation method of a novel weeding safener-bisbenzoxazole acid comprises the following steps: the method specifically comprises the following steps:

a: sequentially pouring organic acid and organic base into a container 1 according to the weight ratio of 1:1, and mixing for later use to obtain a mixture a;

b: taking 50% of chlorooximido ethyl acetate according to the weight parts, pouring 1, 1-diphenylethylene and 50% of chlorooximido ethyl acetate into a container 2 containing a catalyst and a reaction solvent for mixing for later use to obtain a mixture b;

c: and B, fully reacting the mixture a in the step A and the mixture B in the step B at the temperature of 50 ℃ to obtain the bisbenzoxazole acid.

Preferably: and C, after the mixture a and the mixture b in the step C are fully reacted, adjusting the pH value of the new mixture to be neutral, and standing for 20min at normal temperature to obtain the finished product of the bisoxazole acid.

In embodiment 2 of the present invention, a method for preparing a novel herbicide safener, bisbenzoxazole acid, comprises the steps of fully mixing 1, 1-diphenylethylene and chlorohydroxyimino ethyl acetate under the action of an organic acid and an organic base, and reacting with a catalyst and a reaction solvent at 50 ℃ to obtain the bisbenzoxazole acid, wherein the molar ratio of the 1, 1-diphenylethylene to the chlorohydroxyimino ethyl acetate to the organic acid to the organic base is 0.8: 1.7: 1.8.

preferably: the organic base is sodium methoxide.

Preferably: the organic acid is sulfamic acid.

Preferably: the catalyst is sodium hydroxide.

Preferably: the reaction solvent is 2-methyl pentanoic acid methyl ester.

Preferably: the weight ratio of the chlorooximidoethyl acetate to the solvent is 1: 4.

A preparation method of a novel weeding safener-bisbenzoxazole acid comprises the following steps: the method specifically comprises the following steps:

a: sequentially pouring organic acid and organic base into a container 1 according to the weight ratio of 1:1, and mixing for later use to obtain a mixture a;

b: taking 50% of chlorooximido ethyl acetate according to the weight parts, pouring 1, 1-diphenylethylene and 50% of chlorooximido ethyl acetate into a container 2 containing a catalyst and a reaction solvent for mixing for later use to obtain a mixture b;

c: and B, fully reacting the mixture a in the step A and the mixture B in the step B at 55 ℃ to obtain the bisbenzoxazole acid.

Preferably: and C, after the mixture a and the mixture b in the step C are fully reacted, adjusting the pH value of the new mixture to be neutral, and standing for 20min at normal temperature to obtain the finished product of the bisoxazole acid.

The novel weeding safety agent bisoxazole acid prepared by the method adopts sodium methoxide as organic base and sulfamic acid as organic acid, can greatly reduce the generation of byproducts after reaction, improves the accuracy and selectivity of the reaction, obviously improves the yield, has stable reaction process, mild conditions, simple operation, cheap and easily obtained raw materials, small pollution degree and large-area popularization and production.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the technical scope of the present invention.