CN117603072A - A kind of 2-difluoroacetyl-3-dimethylaminoacrylic acid compound and its preparation method and application - Google Patents

Abstract

The embodiment of the application relates to a 2-difluoroacetyl-3-dimethylamino acrylic acid compound, and a preparation method and application thereof, belonging to the technical field of fine chemical intermediate synthesis. The embodiment of the application aims to solve the technical problems of difficult raw material source, high price, harsh process conditions, large three wastes, low yield, high cost and inapplicability to industrial production in the prior art. The preparation method of the 2-difluoroacetyl-3-dimethylamino acrylic acid compound comprises the following steps: and (3) reacting the dimethylaminoacrylic acid, triethylamine and difluoroacetyl fluoride in a solvent, and separating and purifying a reaction product after the reaction is finished to obtain the 2-difluoroacetyl-3-dimethylaminoacrylic acid. The preparation method provided by the embodiment of the application adopts lower raw material cost, the reaction is converted in one step, the environment is gentle, the yield is higher, and the purity of the prepared 2-difluoro acetyl-3-dimethylamino acrylic acid compound is higher.

Description

A kind of 2-difluoroacetyl-3-dimethylaminoacrylic acid compound and preparation method thereof and application

Technical field

The embodiments of this application relate to the technical field of fine chemical intermediate synthesis, and in particular to a 2-difluoroacetyl-3-dimethylaminoacrylic acid compound and its preparation method and application.

Background technique

2-Difluoroacetyl-3-dimethylaminoacrylic acid, as an intermediate compound, can be used to prepare succinate dehydrogenase inhibitor (SDHI) pesticide and fungicide intermediates, such as triflufenac, benzene Trifluconazole, diphenoxylin, triflufenacil, triflufenacil, triflufenacil, etc.

Related preparation methods in the prior art have problems such as difficult sources of raw materials, high prices, harsh process conditions, large amounts of three wastes, low yields, high costs, and are not suitable for industrial production.

Contents of the invention

In view of this, the embodiments of the present application provide a 2-difluoroacetyl-3-dimethylaminoacrylic acid compound and its preparation method and application. The preparation method of the embodiments of the present application solves the problem of raw material sources in the prior art. Problems such as expensive price, harsh process conditions, large amount of three wastes, low yield, high cost, and unsuitable for industrial production. The preparation method of the embodiment of the present application uses convenient sources of raw materials, low cost, friendly reaction conditions, and greatly reduces by-products. It has high overall yield, high raw material utilization rate and low production cost, and is suitable for large-scale industrial continuous production.

The first aspect of the embodiments of the present application provides a method for preparing 2-difluoroacetyl-3-dimethylaminoacrylic acid compound, which is characterized by comprising the following steps:

Dimethylaminoacrylic acid, triethylamine and difluoroacetyl fluoride react in a solvent. After the reaction, the reaction product is separated and purified to obtain 2-difluoroacetyl-3-dimethylaminoacrylic acid; the reaction equation is as follows:

In some embodiments that may include the above embodiments, the following steps are specifically included:

Step 1: Add dimethylaminoacrylic acid and triethylamine to the solvent, cool down and then pass in difluoroacetyl fluoride gas, and then react after rising to room temperature;

Step 2: Separate and purify the reaction product in Step 1 to obtain 2-difluoroacetyl-3-dimethylaminoacrylic acid.

In some embodiments that may include the above embodiments, in step one, the temperature is lowered to 0-25°C; or the temperature is lowered to 0-5°C.

In some embodiments that may include the above embodiments, in step one, the reaction time is 2 to 10 hours; or the reaction time is 2 to 5 hours.

In some embodiments that may include the above embodiments, in step 2, the separation and purification includes the following steps: adding an appropriate amount of water, after layering, removing the solvent from the organic layer under reduced pressure.

In some embodiments that may include the above embodiments, the yield of 2-difluoroacetyl-3-dimethylaminoacrylic acid is 98%, and the purity detected by GC is 99%.

In some embodiments that may include the above embodiments, the solvent is selected from one or more of toluene, xylene, dichloromethane and dichloroethane; or

The solvent is toluene and/or xylene.

In some embodiments that may include the above embodiments, the weight ratio of the solvent to the dimethylaminoacrylic acid is (50:30) ~ (100:1); or

The weight ratio of the solvent to the dimethylaminoacrylic acid is (20:1) to (30:10); or

The molar ratio of the dimethylaminoacrylic acid, the triethylamine and the difluoroacetyl fluoride is (1:50:100) to (1:20:50); or

The molar ratio of the dimethylaminoacrylic acid, the triethylamine and the difluoroacetyl fluoride is (1:20:30) to (1:10:20).

The second aspect of the embodiment of the present application also provides a 2-difluoroacetyl-3-dimethylaminoacrylic acid compound, which is prepared by the above-mentioned preparation method of the 2-difluoroacetyl-3-dimethylaminoacrylic acid compound. .

The third aspect of the embodiment of the present application also provides a pesticide and fungicide, including the above-mentioned 2-difluoroacetyl-3-dimethylaminoacrylic acid compound, or 2-difluoroacetyl-3-dimethylaminoacrylic acid compound prepared by the above preparation method. -3-Dimethylaminoacrylic acid compound.

Compared with the prior art, the embodiments of the present application have the following beneficial effects:

The preparation method of the embodiment of the present application uses convenient sources of raw materials, low cost, friendly reaction conditions, greatly reduced by-products, high overall yield, high raw material utilization rate, low production cost, and is suitable for large-scale industrial continuous production; and the synthesis method One-step conversion, high conversion rate and purity, mild reaction, green and environmentally friendly.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present application, not all of them. embodiment. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application.

In the following examples and comparative examples, unless otherwise specified, all raw materials can be purchased commercially or prepared by conventional methods.

Example 1

The synthetic method of 2-difluoroacetyl-3-dimethylaminoacrylic acid includes the following steps:

Accurately weigh 300g of toluene into a 500mL four-necked flask, add 115g of dimethylaminoacrylic acid, add 101g of triethylamine, cool to 0°C and slowly add 118g of difluoroacetyl fluoride gas. After the introduction is completed, raise the temperature to room temperature to continue the reaction. After 2 hours, add an appropriate amount of water, separate the layers, and remove the solvent under reduced pressure to obtain 2-difluoroacetyl-3-dimethylaminoacrylic acid. The yield is 97%, and the purity detected by GC is 98%.

Example 2

The synthetic method of 2-difluoroacetyl-3-dimethylaminoacrylic acid includes the following steps:

Accurately weigh 300g of methylene chloride into a 500mL four-necked flask, add 115g of dimethylaminoacrylic acid, add 101g of triethylamine, cool to 0°C and slowly add 118g of difluoroacetyl fluoride gas. After the introduction is completed, warm to room temperature. After continuing the reaction for 2 hours, add an appropriate amount of water, separate the layers, and remove the solvent under reduced pressure to obtain 2-difluoroacetyl-3-dimethylaminoacrylic acid. The yield is 83%, and the purity detected by GC is 91%.

Example 3

The synthetic method of 2-difluoroacetyl-3-dimethylaminoacrylic acid includes the following steps:

Accurately weigh 500g of toluene into a 1000mL four-necked flask, add 230g of dimethylaminoacrylic acid, add 202g of triethylamine, cool to 0°C and slowly introduce 236g of difluoroacetyl fluoride gas. After the introduction is completed, raise the temperature to room temperature to continue the reaction. After 2 hours, add an appropriate amount of water, separate the layers, and remove the solvent under reduced pressure to obtain 2-difluoroacetyl-3-dimethylaminoacrylic acid. The yield is 98%, and the purity detected by GC is 99%.

Example 4

The synthetic method of 2-difluoroacetyl-3-dimethylaminoacrylic acid includes the following steps:

Accurately weigh 500g of dichloroethane into a 1000mL four-necked flask, add 230g of dimethylaminoacrylic acid, and add 202g of triethylamine. Cool to 0°C and slowly add 236g of difluoroacetyl fluoride gas. After the introduction is completed, warm to room temperature. Continue the reaction for 2 hours, add an appropriate amount of water, separate the layers, and remove the solvent under reduced pressure to obtain 2-difluoroacetyl-3-dimethylaminoacrylic acid. The yield is 68%, and the purity detected by GC is 89%.

Example 5

The synthetic method of 2-difluoroacetyl-3-dimethylaminoacrylic acid includes the following steps:

Accurately weigh 600g of xylene into a 1000mL four-necked flask, add 230g of dimethylaminoacrylic acid, and add 202g of triethylamine. After cooling to 10°C, slowly add 236g of difluoroacetyl fluoride gas. After the introduction is completed, raise the temperature to room temperature and continue. React for 5 hours, add an appropriate amount of water, separate layers, and remove the solvent under reduced pressure to obtain 2-difluoroacetyl-3-dimethylaminoacrylic acid. The yield is 91%, and the purity detected by GC is 92%.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features can be equivalently replaced; and these modifications or substitutions do not deviate from the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present application. scope.

Claims (10)

1. A method for preparing a 2-difluoroacetyl-3-dimethylaminoacrylic acid compound, comprising the steps of:

reacting dimethylaminoacrylic acid, triethylamine and difluoroacetyl fluoride in a solvent, and separating and purifying a reaction product after the reaction is finished to obtain 2-difluoroacetyl-3-dimethylaminoacrylic acid; the reaction equation is as follows:

2. the preparation method according to claim 1, comprising the specific steps of:

step one, adding dimethylaminoacrylic acid and triethylamine into a solvent, cooling, introducing difluoroacetyl fluoride gas, and reacting after the temperature is raised to room temperature;

and step two, separating and purifying the reaction product in the step one to obtain the 2-difluoro acetyl-3-dimethylamino acrylic acid.

3. The method according to claim 2, wherein in the first step, the temperature is lowered to 0 to 25 ℃; or (b)

Cooling to 0-5 ℃.

4. The method according to claim 2, wherein in the first step, the reaction time is 2 to 10 hours; or (b)

The reaction time is 2-5 h.

5. The method according to claim 2, wherein in the second step, the separation and purification comprises the steps of: after adding a proper amount of water and layering, the organic layer was decompressed to remove the solvent.

6. The method according to claim 1 or 2, wherein the yield of 2-difluoroacetyl-3-dimethylaminoacrylic acid is 98% and the GC detection purity is 99%.

7. The preparation method according to claim 1 or 2, wherein the solvent is selected from one or more of toluene, xylene, methylene chloride and dichloroethane; or (b)

The solvent is toluene and/or xylene.

8. The production method according to claim 1 or 2, wherein the weight ratio of the solvent to the dimethylaminoacrylic acid is (50:30) to (100:1); or (b)

The weight ratio of the solvent to the dimethylaminoacrylic acid is (20:1) - (30:10); or (b)

The molar ratio of the dimethylamino acrylic acid to the triethylamine to the difluoroacetyl fluoride is (1:50:100) - (1:20:50); or (b)

The molar ratio of the dimethylamino acrylic acid to the triethylamine to the difluoroacetyl fluoride is (1:20:30) - (1:10:20).

9. A2-difluoroacetyl-3-dimethylaminoacrylic acid compound prepared by the process for preparing a 2-difluoroacetyl-3-dimethylaminoacrylic acid compound according to any one of claims 1 to 8.

10. A pesticidal bactericide comprising the 2-difluoroacetyl-3-dimethylaminoacrylic acid compound according to claim 9 or comprising the 2-difluoroacetyl-3-dimethylaminoacrylic acid compound produced by the production process according to any one of claims 1 to 8.