阅读说明：本技术 一种路易斯碱催化合成烯酰吗啉的方法 (Method for synthesizing dimethomorph under catalysis of Lewis base ) 是由 李凯 杨光富 于 2019-09-16 设计创作，主要内容包括：本发明涉及烯酰吗啉生产技术领域,特别公开了一种路易斯碱催化合成烯酰吗啉的方法。本发明通过二苯酮与乙酰吗啉低温反应,在溶剂、路易斯碱存在下制得中间态产物,然后在高温条件下进行消除反应脱一分子水得到产物。本发明合成路线简洁、可靠,原料乙酰吗啉消耗低,反应比较容易控制,所得产品成本低,三废产生量少,具有较高的经济和环保价值。(The invention relates to the technical field of dimethomorph production, and particularly discloses a method for synthesizing dimethomorph under the catalysis of Lewis base. The invention prepares an intermediate product by reacting benzophenone with acetyl morpholine at low temperature in the presence of a solvent and Lewis base, and then carries out elimination reaction at high temperature to remove molecular water to obtain the product. The method has the advantages of simple and reliable synthetic route, low consumption of raw material acetylmorpholine, easy control of reaction, low cost of obtained products, less generation of three wastes and higher economic and environmental protection values.)

1. A method for synthesizing dimethomorph catalyzed by Lewis base is characterized by comprising the following steps: (1) under the catalysis of Lewis base, benzophenone and acetyl morpholine react for 1 to 5 hours in a solvent at the temperature of between 40 and 80 ℃ to obtain an intermediate product 3- (4-chlorphenyl) -3- (3, 4-dimethoxyphenyl) -3-hydroxy-1-morpholinopropane-1-ketone; (2) heating to 90-115 ℃ for dehydration reaction, cooling to room temperature after the reaction is finished, adding water into the reaction liquid for extraction, standing for layering, heating the separated organic phase for desolventizing distillation, concentrating, adsorbing by active carbon, crystallizing the concentrated liquid, and filtering to obtain the dimethomorph product.

2. The process for the catalytic synthesis of dimethomorph, catalysed by a lewis base according to claim 1, characterized in that: in the step (1), the molar ratio of the benzophenone, the acetyl morpholine and the Lewis base is 1:1-2: 3-1.

3. The process for the catalytic synthesis of dimethomorph, catalysed by a lewis base according to claim 1, characterized in that: in the step (1), the Lewis base is sodium methoxide, sodium ethoxide, sodium amide or sodium tert-butoxide.

4. The process for the catalytic synthesis of dimethomorph, catalysed by a lewis base according to claim 1, characterized in that: in the step (1), the solvent is toluene, xylene or trimethylbenzene.

5. The process for the catalytic synthesis of dimethomorph, catalysed by a lewis base according to claim 1, characterized in that: in the step (1), benzophenone and acetyl morpholine react for 3.5 to 4 hours in a solvent at 60 ℃.

6. The process for the catalytic synthesis of dimethomorph, catalysed by a lewis base according to claim 1, characterized in that: in the step (2), the temperature is raised to 110 ℃ for dehydration reaction.

7. The process for the catalytic synthesis of dimethomorph, catalysed by a lewis base according to claim 1, characterized in that: standing and layering, separating a wastewater layer and a solvent organic layer, and collecting wastewater for unified treatment; and concentrating the organic layer of the solvent, and adsorbing and recovering the organic solvent by adopting activated carbon for recycling.

(I) technical field

The invention relates to the technical field of dimethomorph production, in particular to a method for synthesizing dimethomorph under the catalysis of Lewis base.

(II) background of the invention

Dimethomorph is a derivative of cinnamic acid, has unique effect on downy mildew of phycomycetes and phytophthora fungi, and can be used for preventing and treating germs on grapes, cucumbers and potatoes; and has low toxicity and good effect, so the medicine is generally concerned and applied. China is the most populated country in the world, and the requirement on the agricultural output is high every year, so that a large number of greenhouse vegetables are adopted for cultivation, and the disease prevention management of crops cultivated in the greenhouse is very important because the diseases of vegetables, melons and fruits are serious, particularly the diseases are serious because the temperature in the greenhouse is relatively proper.

The traditional aniline bactericides have certain drug resistance to pathogenic bacteria due to long-term and large-scale use, so the research on developing novel antibacterial agents such as dimethomorph is in line with the situation of China and has great significance. At present, the dimethomorph synthesized in China is obtained by one-step reaction of sodium tert-butoxide at high temperature, and water generated by the reaction can decompose raw material acetyl morpholine, so that more raw materials are consumed by the reaction, and more three wastes are generated.

Disclosure of the invention

The invention provides a method for synthesizing dimethomorph by catalyzing Lewis base, which has low three-waste generation amount and raw material cost and is economic and environment-friendly, so as to make up the defects of the prior art.

The invention is realized by the following technical scheme:

a method for synthesizing dimethomorph under catalysis of Lewis base comprises the following steps:

(1) under the catalysis of Lewis base, benzophenone and acetyl morpholine react for 1 to 5 hours in a solvent at the temperature of between 40 and 80 ℃ to obtain an intermediate product 3- (4-chlorphenyl) -3- (3, 4-dimethoxyphenyl) -3-hydroxy-1-morpholinopropane-1-ketone;

(2) heating to 90-115 ℃ for dehydration reaction, cooling to room temperature after the reaction is finished, adding water into the reaction liquid for extraction, standing for layering, heating the separated organic phase for desolventizing distillation, concentrating, adsorbing by active carbon, crystallizing the concentrated liquid, and filtering to obtain the dimethomorph product.

The invention prepares an intermediate product by reacting benzophenone with acetyl morpholine at low temperature in the presence of a solvent and Lewis base, and then carries out elimination reaction at high temperature to remove molecular water to obtain the product.

The more preferable technical scheme of the invention is as follows:

in the step (1), the molar ratio of the benzophenone, the acetyl morpholine and the Lewis base is 1:1-2: 3-1.

The lewis base is sodium methoxide, sodium ethoxide, sodium amide or sodium tert-butoxide.

The solvent is toluene, xylene or trimethylbenzene.

Benzophenone and acetyl morpholine are reacted in solvent at 60 deg.c for 3.5-4 hr, and this is the preferred reaction condition.

In the step (2), the temperature is raised to 110 ℃ for dehydration reaction, which is a better high-temperature reaction condition.

Standing for layering, separating a wastewater layer and a solvent organic layer, and collecting wastewater for unified treatment; and concentrating the organic layer of the solvent, and adsorbing and recovering the organic solvent by adopting activated carbon for recycling.

The reaction equation of the present invention is as follows:

；

。

the method has the advantages of simple and reliable synthetic route, low consumption of raw material acetylmorpholine, easy control of reaction, low cost of obtained products, less generation of three wastes and higher economic and environmental protection values.

(IV) detailed description of the preferred embodiments

The present invention will be further explained with reference to specific examples for easy understanding.

Example 1: preparation of dimethomorph

Reacting benzophenone with acetyl morpholine in a solvent toluene at 60 ℃ for 3-4h under the catalysis of sodium methoxide to obtain an intermediate product 3- (4-chlorphenyl) -3- (3, 4-dimethoxyphenyl) -3-hydroxy-1-morpholinopropane-1-ketone; and then heating to 110 ℃ for dehydration reaction, cooling to room temperature after the reaction is finished, adding water into the reaction liquid for extraction, standing for layering, separating a waste water layer and a solvent toluene organic layer, heating the organic layer for desolventizing, distilling and concentrating, adsorbing and recovering the organic solvent by activated carbon for recycling, and treating waste water. Crystallizing the concentrated solution and filtering to obtain the dimethomorph product. Yield: 71.6 percent and the content is 96.6 percent.

Example 2: preparation of dimethomorph

Reacting benzophenone with acetyl morpholine in a solvent toluene at 60 ℃ for 3-4h under the catalysis of sodium ethoxide to obtain an intermediate product 3- (4-chlorphenyl) -3- (3, 4-dimethoxyphenyl) -3-hydroxy-1-morpholinopropane-1-ketone; and then heating to 110 ℃ for dehydration reaction, cooling to room temperature after the reaction is finished, adding water into the reaction liquid for extraction, standing for layering, separating a waste water layer and a solvent toluene organic layer, heating the organic layer for desolventizing, distilling and concentrating, adsorbing and recovering the organic solvent by activated carbon for recycling, and treating waste water. Crystallizing the concentrated solution and filtering to obtain the dimethomorph product. Yield: 72.5 percent and the content is 97.9 percent.

Example 3: preparation of dimethomorph

Reacting benzophenone with acetyl morpholine in a solvent toluene at 40 ℃ for 5h under the catalysis of sodium tert-butoxide to obtain an intermediate product 3- (4-chlorphenyl) -3- (3, 4-dimethoxyphenyl) -3-hydroxy-1-morpholinopropane-1-ketone; and then heating to 95 ℃ for dehydration reaction, cooling to room temperature after the reaction is finished, adding water into the reaction liquid for extraction, standing for layering, separating a waste water layer and a toluene organic solvent layer, heating the organic layer for desolventizing, distilling and concentrating, adsorbing and recovering the organic solvent by activated carbon for recycling, and treating waste water. Crystallizing the concentrated solution and filtering to obtain the dimethomorph product. Yield: 74.8 percent and the content is 98.0 percent.

Example 4: preparation of dimethomorph

Reacting benzophenone with acetyl morpholine in solvent xylene at 80 ℃ for 2h under the catalysis of sodium tert-butoxide to obtain an intermediate product 3- (4-chlorphenyl) -3- (3, 4-dimethoxyphenyl) -3-hydroxy-1-morpholinopropane-1-ketone. And then heating to 115 ℃ for dehydration reaction, cooling to room temperature after the reaction is finished, adding water into the reaction liquid for extraction, standing for layering, separating a wastewater layer and a xylene organic layer serving as a solvent, heating, desolventizing, distilling and concentrating the organic layer, adsorbing and recovering the organic solvent by activated carbon for recycling, and treating wastewater. Crystallizing the concentrated solution and filtering to obtain the dimethomorph product. Yield: 76.3 percent and the content is 97.1 percent.