Synthesis method of trimethyl phosphoryl acetate
By using a catalyst to carry out Arbuzov rearrangement reaction at a lower temperature, the problems of high energy consumption and low product purity in the prior art were successfully solved, and a high-efficiency and low energy consumption synthesis method was achieved, which was suitable for industrial production.
Patent Information
- Application Number
- CN202411580357.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-07
- Publication Date
- 2025-03-28
AI Technical Summary
In the prior art, the synthesis of trimethyl phosphoryl acetate needs to be carried out at higher temperatures, resulting in high energy consumption, high production costs, and possible side reactions, affecting the purity and yield of the product.
Trimethyl phosphite and methyl chloroacetate were used as raw materials, and Arbuzov rearrangement reaction was carried out at a lower temperature (70-80℃) under the action of a catalyst to produce trimethyl phosphoyl acetate. The process includes mixing methyl chloroacetate and a catalyst, dropping in trimethyl phosphite, and reacting under heating and stirring conditions, followed by purification.
The efficient synthesis of phosphoryl trimethyl acetate at lower temperatures reduces energy consumption and production costs, improves the purity and yield of the product, avoids the occurrence of side reactions, and is conducive to industrial production.
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing trimethyl phosphoacetate. Background Art
[0002] Trimethyl phosphoacetate is mainly used as an activation reagent in organic synthesis. It can react with carbonyl compounds to generate phosphate intermediates, and then participate in a series of organic synthesis reactions. It can also be used in the synthesis of skeleton compounds, regulation of tissue distribution of compounds, metabolic reactions, etc.
[0003] In existing chemical technology, the synthesis of trimethyl phosphoacetate mainly depends on the reaction of trimethyl phosphite and methyl chloroacetate. Traditional synthesis methods are usually carried out at higher temperatures, requiring additional energy input, resulting in higher energy consumption and higher production costs. In addition, high temperature conditions may lead to a series of side reactions, which affect the purity and yield of the product and are not conducive to industrial-scale production.
[0004] Therefore, developing a method for efficiently synthesizing trimethyl phosphoacetate at a relatively low temperature, reducing production costs, and improving product purity and yield has important practical application value for industrial production. Summary of the invention
[0005] In view of the shortcomings of the prior art, the present invention provides a method for synthesizing trimethyl phosphoacetate, the purpose of which is to realize a method for efficiently synthesizing trimethyl phosphoacetate at a relatively low temperature under a catalyst, thereby reducing the reaction energy consumption and improving the purity and yield of the product.
[0006] In order to achieve the above object, the present invention provides a method for synthesizing trimethyl phosphoacetate, which is synthesized according to the following reaction equation:
[0007] (CH3O)3P+ClCH2COOCH3=(CH3O)2POCH2COOCH3+CH3Cl;
[0008] Trimethyl phosphite and methyl chloroacetate are used as raw materials, a phosphorus-containing mixture is used as a catalyst, the mixture is mixed and stirred under heating conditions, and then purified to obtain trimethyl phosphoacetate.
[0009] Further, the synthesis method comprises the following steps:
[0010] Step 1, mixing methyl chloroacetate and a phosphorus-containing mixture catalyst into a reactor;
[0011] Step 2, add trimethyl phosphite dropwise into the reaction kettle and stir evenly under heating conditions;
[0012] Step 3, continuously heating and stirring the reaction mixture until the reaction is completed, and refluxing during the reaction;
[0013] Furthermore, the catalyst is a phosphorus-containing mixture obtained by reacting acrylic emulsion and phosphorus pentoxide or polyphosphoric acid at 50-70° C. and cooling, solidifying and crushing the mixture.
[0014] Furthermore, the weight ratio of methyl chloroacetate, catalyst and trimethyl phosphite is between 1:0.01:1.05 and 1:0.01:1.15.
[0015] Furthermore, in step 2, the temperature in the reactor is set to 70-80°C.
[0016] Furthermore, in step 3, the reflux temperature of trimethyl phosphite is 110-115°C
[0017] Furthermore, the reaction time in step 3 is 3-4 hours.
[0018] Furthermore, the stirring speed is controlled at 60-80 r / min.
[0019] Furthermore, the reaction temperature is controlled by a PLC program.
[0020] Furthermore, in step 4, the reaction product is placed in a distillation tower for purification.
[0021] It can be seen from the above technical solution that the present invention has the following beneficial effects:
[0022] A synthesis method of trimethyl phosphoacetate of the present invention adopts the reflux temperature of trimethyl phosphite to react, which greatly reduces energy consumption compared with traditional high-temperature reaction conditions. By adding a specific catalyst to the raw material, the type and amount of the catalyst after optimization make the reaction more efficient, improve the yield of the product, and then by controlling key factors such as reaction temperature and time, the efficient synthesis of trimethyl phosphoacetate is achieved at a relatively low temperature, avoiding the occurrence of side reactions under high temperature conditions, thereby reducing production difficulty and energy consumption, and improving the purity and yield of the product. In addition, the synthesis method of the present invention has simple steps, is easy to operate, and is conducive to industrial production. DETAILED DESCRIPTION
[0023] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and intended to be used to explain the present invention, but should not be construed as limiting the present invention.
[0024] Example 1
[0025] A mixture of 1000g of methyl chloroacetate and 10g of a catalyst (a phosphorus-containing mixture obtained by cooling, solidifying, and crushing a reaction product of acrylic emulsion and phosphorus pentoxide or polyphosphoric acid at 50-70°C) was placed in a 5000ml reactor, wherein the reactor temperature was controlled between 70 and 80°C, and then 1050g of trimethyl phosphite was dripped in, and the dripping was completed in 3.5 hours, and the mixture was stirred evenly, and then the reactor temperature was controlled to 80-90°C for insulation reaction for 2 hours. During this period, the reaction was completed below the reflux temperature of trimethyl phosphite to generate a reaction liquid, and then the reaction liquid obtained by the reaction was transferred to a distillation tower for purification, and 1528.8g of trimethyl phosphoacetate (purity: 99.82%, yield: 99.20%) was obtained. Among them, the stirring speed was controlled at 60-80r / min, and the reaction temperature was accurately controlled by a PLC program.
[0026] Example 2
[0027] A mixture of 1000g of methyl chloroacetate and 10g of a catalyst (a phosphorus-containing mixture obtained by cooling, solidifying, and crushing a reaction product of acrylic emulsion and phosphorus pentoxide or polyphosphoric acid at 50-70°C) was placed in a 5000ml reactor, wherein the reactor temperature was controlled between 70 and 80°C, and then 1150g of trimethyl phosphite was dripped in, and the dripping was completed in 3 hours, and the mixture was stirred evenly, and then the reactor temperature was controlled to 80-90°C for insulation reaction for 2 hours. During this period, the reaction was completed below the reflux temperature of trimethyl phosphite to generate a reaction liquid, and then the reaction liquid obtained by the reaction was transferred to a distillation tower for purification, and 1676.0g of trimethyl phosphoacetate (purity: 99.80%, yield: 99.30%) was obtained. Among them, the stirring speed was controlled at 60-80r / min, and the reaction temperature was accurately controlled by a PLC program.
[0028] Comparative Example 1
[0029] A mixture of 1000g of methyl chloroacetate and a catalyst (tetrabutylammonium iodide) was placed in a 5000ml reactor, wherein the reactor temperature was controlled between 110 and 115°C, and then 1150g of trimethyl phosphite was dripped in, and the dripping was completed within 3 hours, and the mixture was stirred evenly, and then the reactor temperature was controlled to be 80 to 90°C for insulation reaction for 2 hours. During this period, the reaction was completed below the reflux temperature of trimethyl phosphite to generate a reaction liquid, and then the reaction liquid obtained by the reaction was transferred to a distillation tower for purification to obtain a fine product of trimethyl phosphoacetate (purity: 98.8%, yield: 96.6%).
[0030] Table 1
[0031] Method of the present invention Existing traditional methods Temperature(℃) 70-80 110-115 catalyst Phosphorus mixture Tetrabutylammonium iodide Steam consumption per ton of product (tons) 0.364 1.342 Product purity (%) ≥99.80 98.40-99.50 Yield (%) ≥99.2 94-97
[0032] Under the traditional method, after adding trimethyl phosphite and methyl chloroacetate to form a reaction mixture, the reaction mixture is added to a reactor maintained at a temperature of 110-115°C, and a catalyst (tetrabutylammonium iodide) is added to promote the reaction. 1.342 tons of steam are consumed per ton of product to obtain fine trimethyl phosphoacetate (purity: 98.40-99.50%, yield: 94-97%).
[0033] The method for synthesizing trimethyl phosphoacetate of the present invention comprises the following steps: trimethyl phosphite and methyl chloroacetate are mixed in a certain ratio to form a reaction mixture, the reaction mixture is added into a reactor maintained at a temperature of 70-80° C., a catalyst (phosphorus-containing mixture) is added to promote the reaction, 0.364 tons of steam is consumed per ton of product, and a fine product of trimethyl phosphoacetate (purity: ≥99.80%, yield: ≥99.2%) is obtained.
[0034] The temperature of the method of the present invention is much lower than that of the existing traditional method, and the amount of steam consumed per ton of product is relatively reduced by about three quarters, which reduces energy consumption and saves resources required for production. The catalyst of the method of the present invention is a phosphorus-containing mixture, which is a reaction product of acrylic emulsion and phosphorus pentoxide or polyphosphoric acid at 50-70°C, and the phosphorus-containing mixture is obtained after cooling, solidification and crushing. Methyl chloroacetate and trimethyl phosphite undergo Arbuzov rearrangement reaction under the action of the catalyst. The intermediate product generated by the catalyst and methyl chloroacetate under the condition of maintaining the temperature at 70-80°C can quickly react with trimethyl phosphite to obtain the final product, which is more conducive to the reaction than the tetrabutylammonium iodide catalyst of the existing traditional method. The traditional synthesis method requires additional energy input due to being carried out at a higher temperature, resulting in higher energy consumption, and may also cause the occurrence of side reactions, affecting the purity and yield of the product. The synthesis method of the present application realizes the efficient synthesis of trimethyl phosphoacetate at a relatively low temperature, avoids the occurrence of side reactions, reduces the production difficulty and energy consumption, improves the purity and yield of the product, and is conducive to industrial-scale production.
[0035] The above embodiments are only used to illustrate the present invention and do not constitute a limitation on the scope of the claims. Other alternative means that can be thought of by those skilled in the art are all within the scope of the claims of the present invention.
Claims
1. A method for synthesizing trimethyl phosphoacetate, characterized in that: Synthesized according to the following reaction formula: (CH3O)3P+ClCH2COOCH3= (CH3O)2POCH2COOCH3+CH3Cl; Trimethyl phosphite and methyl chloroacetate are used as raw materials and a phosphorus-containing mixture is used as a catalyst to react under heating conditions to generate trimethyl phosphoacetate.
2. A method for synthesizing trimethyl phosphoacetate according to claim 1, characterized in that: The synthesis method comprises the following steps: Step 1, mixing methyl chloroacetate and a phosphorus-containing mixture catalyst into a reactor; Step 2, add trimethyl phosphite dropwise into the reaction kettle and stir evenly under heating conditions; Step 3, continuously heating and stirring the reaction mixture until the reaction is completed, and refluxing during the reaction; Step 4: purifying the reaction product to obtain trimethyl phosphoacetate.
3. A method for synthesizing trimethyl phosphoacetate according to claim 2, characterized in that: The catalyst is a phosphorus-containing mixture obtained by reacting acrylic emulsion with phosphorus pentoxide or polyphosphoric acid at 50-70° C. and cooling, solidifying and crushing the mixture.
4. A method for synthesizing trimethyl phosphoacetate according to claim 2, characterized in that: The weight ratio of the methyl chloroacetate, the catalyst and trimethyl phosphite is between 1:0.01:1.05 and 1:0.01:1.
15.
5. A method for synthesizing trimethyl phosphoacetate according to claim 2, characterized in that: In step 2, the temperature in the reactor is set to 70-80°C.
6. A method for synthesizing trimethyl phosphoacetate according to claim 2, characterized in that: The reflux temperature of trimethyl phosphite in step 3 is 110-115°C.
7. A method for synthesizing trimethyl phosphoacetate according to claim 2, characterized in that: The reaction time in step 3 is 3-4 hours.
8. A method for synthesizing trimethyl phosphoacetate according to claim 2, characterized in that: The stirring speed is controlled at 60-80 r / min.
9. A method for synthesizing trimethyl phosphoacetate according to claim 2, characterized in that: The reaction temperature is controlled by a PLC program.
10. The method for synthesizing trimethyl phosphoacetate according to claim 2, characterized in that: In step 4, the reaction product is placed in a distillation tower for purification.