CN1634874A

CN1634874A - N-methyl (p-phenoxy, phenoxy) acetamide and its preparation method

Info

Publication number: CN1634874A
Application number: CN 200410084390
Authority: CN
Inventors: 金东元; 顾建生; 陶建伟; 陆庆宁
Original assignee: Shanghai Institute of Technology
Current assignee: Shanghai Institute of Technology
Priority date: 2004-11-22
Filing date: 2004-11-22
Publication date: 2005-07-06
Anticipated expiration: 2024-11-22
Also published as: CN1281579C

Abstract

The invention discloses a novel N-methyl (p-phenoxy,phenoxy) acetamide and its preparation method. The preparation process comprises the following steps: a. aminolysis reaction between methyl chloroacetate and Methylamine alcohol solution at low temperature, and separating to intermediate 2-chloracetyl methylamine; b. heating phenoxy phenol and anhydrous potassium carbonate in organic solvent N,N-dimethylformamide(DMF) to produce phenolate; c. reaction between said phenolate and said 2-chloracetyl methylamine in DMF to produce product N-methyl (p-phenoxy,phenoxy) acetamide in yield between 85% and 88% and purity over 99%.

Description

N-methyl (p-phenoxy, phenoxy) acetamide and preparation method thereof

Technical Field

The present invention relates to a carboxylic acid amide compound having at least one singly-bound oxygen atom further bonded to a carbon atom of a six-membered aromatic ring, such as phenoxyacetamide, and more particularly to a novel compound N-methyl (p-phenoxyphenoxy) acetamide and a process for the preparation thereof.

Background

The pesticide for preventing and controlling agricultural pests has high activity and good function, and can meet the requirements of ecological environment. Therefore, high-efficiency and low-toxicity organic pesticides are developed by competition among countries to replace traditional pesticides with strong toxicity and long residual period. 2- (p-phenoxy) ethyl carbamate is a high-efficiency low-toxicity pesticide discovered by DR.R. MAAG company of Switzerland in 1982, has stomach toxicity and contact poisoning effects, is high-efficiency in poisoning pests, is low in toxicity to mammals, has long validity period, does not pollute the environment and the like. However, the raw materials used in the method have high toxicity, the manufacturing method is complex and the cost is high.

Disclosure of Invention

The invention aims to overcome the defects of the existing pesticide for preventing and controlling agricultural pests and provides a novel carboxylic acid amide compound, namely N-methyl (p-phenoxy) acetamide and a preparation method thereof.

The technical scheme adopted by the invention is as follows: a novel compound, N-methyl (p-phenoxy) acetamide, having the formula of formula (I):

the preparation method of the N-methyl (p-phenoxy) acetamide comprises the following steps: a. performing aminolysis reaction of ester by using methyl chloroacetate and methylamine alcohol solution at low temperature, and separating to obtain an intermediate 2-chloroacetylmethylamine; b. heating phenoxyphenol and anhydrous potassium carbonate inan organic solvent N, N-Dimethylformamide (DMF) to react to generate phenolate; c. the above phenoxide and the above 2-chloroacetylmethylamine react in an organic solvent, N-Dimethylformamide (DMF), to give the product, N-methyl (p-phenoxyphenoxy) acetamide.

And (b) controlling the aminolysis reaction temperature of the ester in the step a to be-10-0 ℃.

The concentration of the methylamine alcohol solution in the step a is 27-32%.

And c, heating the DMF solution of the phenoxyphenol and the potassium carbonate to 50-80 ℃ in the step b.

And (c) dropwise adding the DMF solution of the 2-chloroacetylmethylamine into the phenolic salt solution for 0.5-1 h, and carrying out heat preservation reaction at 80-110 ℃ for 2-5 h.

And (c) recrystallizing the crude product N-methyl (p-phenoxy) acetamide obtained in the step (c) in an alkaline aqueous solution, and then carrying out suction filtration, washing and drying to obtain an N-methyl (p-phenoxy) acetamide product with the purity of more than or equal to 99%.

The invention has the beneficial effects that: the invention provides a new compound N-methyl (p-phenoxy) acetamide and a preparation method thereof, the product cost is lower, the method steps are less, the operation is simple, the yield of the product (calculated by p-phenoxy phenol) reaches 88%, and the purity of the product is more than or equal to 99%.

Detailed Description

The invention is described in further detail below by means of specific examples: a new compound N-methyl (p-phenoxy) acetamide. The preparation method of the compound N-methyl (p-phenoxy) acetamide comprises the following steps:

a. reacting excessive methyl chloroacetate with methylamine alcohol solution at low temperature to obtain 2-chloroacetylmethylamine, wherein the chemical reaction formula is as follows:

b. dissolving phenoxy phenol in an organic solvent N, N-Dimethylformamide (DMF), heating, and then adding anhydrous potassium carbonate to generate corresponding phenolate, wherein the chemical reaction formula is as follows:

c. dissolving the 2-chloroacetylmethylamine prepared in the step a in an organic solvent N, N-Dimethylformamide (DMF), then dropwise adding the solution into the phenolate prepared in the step b, and reacting to obtain a product N-methyl (p-phenoxy) acetamide, wherein the chemical reaction formula is as follows:

preparation example 1:

adding 120 g of methyl chloroacetate into a three-neck flask with stirring, cooling to below-8 ℃, dropwise adding 62 g of methylamine alcohol solution (27-32%) while stirring, wherein the reaction temperature does not exceed-5 ℃, and then reacting for 2.5 hours at the temperature. After the reaction is finished, evaporating methanol and ethanol, recovering excessive methyl chloroacetate, cooling the distillate to below 70 ℃ when the methyl chloroacetate cannot be distilled out of solution, and then carrying out reduced pressure distillation to collect a fraction at 90-92 ℃/1.8KPa to obtain 62.5 g of white crystal 2-chloroacetylmethylamine.

20 g of phenoxyphenol were added to a stirred four-neck flask, followed by 30 g of freshly dried K₂CO₃And 100ml of DMF, heating to 80 ℃ with stirring, dropwise adding a mixed solution of 12 g of 2-chloroacetylmethylamine and 50ml of DMF with stirring at the temperature for about 30min, and then heating to 85 ℃ for reaction for 3 hours. After distilling and separating DMF, recrystallizing with alkaline water solution, filtering, washing and drying to obtain 24 g of N-methyl (p-phenoxy) acetamide.

Preparation example 2:

80 g of methyl chloroacetate is added into a three-neck flask with stirring, 62 g of methylamine alcohol solution (27-32%) is dropwise added with stirring, the reaction temperature is 0 ℃, and then the reaction is carried out for 2.5 hours at the temperature. After the reaction is finished, evaporating methanol and ethanol, recovering excessive methyl chloroacetate, cooling the distillate to below 70 ℃ when the methyl chloroacetate cannot be distilled, and then carrying out reduced pressure distillation to collect a fraction at 90-92 ℃/1.8KPa to obtain 52 g of white crystal 2-chloroacetylmethylamine.

20 g of phenoxyphenol were added to a stirred four-neck flask, followed by 30 g of freshly dried K₂CO₃And 100ml of DMF, heating to 50 ℃ with stirring, dropwise adding a mixed solution of 12 g of 2-chloroacetylmethylamine and 50ml of DMF with stirring at the temperature for about 30min, and then heating to 70 ℃ for reaction for 2 hours. After distilling and separating DMF, recrystallizing with alkaline aqueous solution, filtering, washing and drying to obtain 19 g of N-methyl (p-phenoxy) acetamide.

In preparation examples 1 and 2, the yield of 2-chloroacetylmethylamine was 80 to 97% (based on methylamine), the yield of N-methyl (p-phenoxyphenoxy) acetamide was 69 to 88% (based on p-phenoxyphenol), and the purity of N-methyl (p-phenoxyphenoxy) acetamide was more than 99%.

The above description isonly a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.

Claims

An N-methyl (p-phenoxy) acetamide of the formula (I):
2. the process for producing N-methyl (p-phenoxyphenoxy) acetamide as claimed in claim 1, which comprises:

a. performing aminolysis reaction of ester by using methyl chloroacetate and methylamine alcohol solution at low temperature, and separating to obtain an intermediate 2-chloroacetylmethylamine;

b. heating phenoxyphenol and anhydrous potassium carbonate in an organic solvent N, N-Dimethylformamide (DMF) to react to generate phenolate;

c. the above phenoxide and the above 2-chloroacetylmethylamine react in an organic solvent, N-Dimethylformamide (DMF), to give the product, N-methyl (p-phenoxyphenoxy) acetamide.
3. The process for producing N-methyl (p-phenoxyphenoxy) acetamide according to claim 2, wherein: and (b) controlling the aminolysis reaction temperature of the ester in the step a to be-10-0 ℃.
4. The process for producing N-methyl (p-phenoxyphenoxy) acetamide according to claim 2, wherein: the concentration of the methylamine alcohol solution in the step a is 27-32%.
5. The process for producing N-methyl (p-phenoxyphenoxy) acetamide according to claim 2, wherein: and c, heating the DMF solution of the phenoxyphenol and the potassium carbonate to 50-80 ℃ in the step b.
6. The process for producing N-methyl (p-phenoxyphenoxy) acetamide according to claim 2, wherein: and (c) dropwise adding the DMF solution of the 2-chloroacetylmethylamine into the phenolic salt solution for 0.5-1 h, and carrying out heat preservation reaction at 80-110 ℃ for 2-5 h.
7. The process for producing N-methyl (p-phenoxy, phenoxy) acetamide according to claim 2 or 6, which comprises: and (c) recrystallizing the crude product N-methyl (p-phenoxy) acetamide obtained in the step (c) in an alkaline aqueous solution, and then carrying out suction filtration, washing and drying to obtain an N-methyl (p-phenoxy) acetamide product with the purity of more than or equal to 99%.