阅读说明：本技术 一种烷基羧酸糠酯的制备方法 (Preparation method of alkyl carboxylic acid furfuryl ester ) 是由 徐志强 田振峰 贺增洋 黄兰 陈开波 于 2021-09-29 设计创作，主要内容包括：本发明公开了一种烷基羧酸糠酯的制备方法,是将糠醇、催化剂、酰基化试剂、缚酸剂和溶剂混匀后反应,即得到烷基羧酸糠酯化合物。本发明选择性高、副产物少、反应条件温和,具有一定的工业应用前景。(The invention discloses a preparation method of alkyl carboxylic acid furfuryl ester, which is to mix furfuryl alcohol, a catalyst, an acylation reagent, an acid-binding agent and a solvent uniformly and react to obtain the alkyl carboxylic acid furfuryl ester compound. The method has the advantages of high selectivity, few byproducts, mild reaction conditions and certain industrial application prospect.)

1. A preparation method of alkyl carboxylic acid furfuryl ester is characterized by comprising the following steps: the furfuryl alcohol, the catalyst, the acylation reagent, the acid-binding agent and the solvent are mixed uniformly and then react to obtain the alkyl carboxylic acid furfuryl ester compound.

2. The method for producing furfuryl alkylcarboxylate according to claim 1, characterized in that: the catalyst is at least one of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid.

3. The method for producing furfuryl alkylcarboxylate according to claim 1 or 2, characterized in that: the acylation reagent is at least one of saturated carboxylic acid, anhydride and acyl chloride with less than five carbons.

4. The method for producing furfuryl alkylcarboxylate according to claim 3, characterized in that: the structure of the acylation reagent is any one of the following structures:

5. the method for producing furfuryl alkylcarboxylate according to claim 1 or 2, characterized in that: the solvent is at least one of acetonitrile, dichloroethane, chloroform and n-hexane.

6. The method for producing furfuryl alkylcarboxylate according to claim 1 or 2, characterized in that: the acid-binding agent is at least one of triethylamine, pyridine and potassium carbonate.

7. The method for producing furfuryl alkylcarboxylate according to claim 1 or 2, characterized in that: the reaction temperature is 0-100 ℃ and the reaction time is 1-72 h.

8. The method for producing furfuryl alkylcarboxylate according to claim 1 or 2, characterized in that: the mass ratio of the catalyst to the furfuryl alcohol is 0.1-1: 1.

9. the method for producing furfuryl alkylcarboxylate according to claim 1 or 2, characterized in that: the molar ratio of the acylation reagent to the furfuryl alcohol is 1-10: 1.

10. the method for producing furfuryl alkylcarboxylate according to claim 1 or 2, characterized in that: the molar ratio of the acid-binding agent to the acylation reagent is 1-10: 1.

Technical Field

The invention relates to the technical field of chemical substance preparation, in particular to a preparation method of alkyl carboxylic acid furfuryl ester.

Background

The alkyl carboxylic acid furfuryl ester is an important biomass-derived chemical and can be used as a biomass-based platform compound to prepare various important chemicals. Useful in the plastics industry as plasticizers, thermosetting resins, and the like; as a preservative in the food industry; also useful as an intermediate for paint additives, medicines, perfumes, etc. The furfuryl ester spice is taken as a downstream product of the furfuryl aldehyde and is a food spice approved by China.

The synthesis method of the alkyl carboxylic acid furfuryl ester comprises the following steps: 1. furfuryl alcohol is reacted with the corresponding anhydride in the presence of a carboxylate, but the yield is not high; 2. acyl chloride is used as an acylation reagent to react with furfuryl ester in the presence of pyridine, but the yield and the aroma quality of the product are not ideal due to unstable acyl chloride, difficult pyridine removal and the like; 3. 4-dimethylamino pyridine is used as a catalyst, sodium bicarbonate is used as an acid-binding agent, and the reaction of the catalytic conversion anhydride and the furfuryl alcohol is catalyzed, so that the yield of the product is high, but the cost of the catalyst is high.

Therefore, the development of a catalytic system with high selectivity and good effect is of great significance.

Disclosure of Invention

Based on the technical problems in the prior art, the invention provides a preparation method of alkyl carboxylic acid furfuryl ester, aiming at improving the product yield.

In order to solve the technical problem, the invention adopts the following technical scheme:

a preparation method of alkyl carboxylic acid furfuryl ester is characterized by comprising the following steps: the furfuryl alcohol, the catalyst, the acylation reagent, the acid-binding agent and the solvent are mixed uniformly and then react to obtain the alkyl carboxylic acid furfuryl ester compound. The reaction formula is as follows:

preferably, the catalyst is at least one of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and silicomolybdic acid.

Preferably, the acylating agent is at least one of saturated carboxylic acid, anhydride and acyl chloride with five carbons or less, and the specific structure is any one of the following structures:

preferably, the solvent is at least one of acetonitrile, dichloroethane, chloroform, and n-hexane.

Preferably, the acid-binding agent is at least one of triethylamine, pyridine and potassium carbonate.

Preferably, the reaction temperature is 0-100 ℃ and the reaction time is 1-72 h. More preferably 0-50 ℃ for 10-24 h.

Preferably, the mass ratio of the catalyst to the furfuryl alcohol is 0.1-1: 1.

preferably, the molar ratio of the acylation agent to the furfuryl alcohol is 1-10: 1, preferably 2-5: 1.

Preferably, the molar ratio of the acid-binding agent to the acylation agent is 1-10: 1, preferably 1:1 to 5: 1.

Compared with the prior art, the invention has the beneficial effects that:

the method increases the selectivity of the reaction and improves the yield of the alkyl carboxylic acid furfuryl ester by selecting a proper catalyst, an acylation reagent and a solvent, and has few byproducts, mild reaction conditions and a certain industrial application prospect.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of furfuryl propionate obtained in example 1.

FIG. 2 is a nuclear magnetic carbon spectrum of furfuryl propionate obtained in example 1.

FIG. 3 is a nuclear magnetic hydrogen spectrum of furfuryl acetate obtained in example 6.

FIG. 4 is a nuclear magnetic carbon spectrum of furfuryl acetate obtained in example 6.

Detailed Description

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.

The catalysts, acid-binding agents and solvents used in the following examples were purchased from the national pharmaceutical industries.

Example 1

The preparation method of the alkyl carboxylic acid furfuryl ester comprises the following steps:

adding 1mmol of furfuryl alcohol, 10mL of acetonitrile, 100mg of phosphotungstic acid catalyst and 2mmol of potassium carbonate into a 50mL three-neck flask, slowly adding 10mL of acetonitrile solvent containing 2mmol of propionic anhydride at room temperature under the condition of nitrogen, heating to 50 ℃, and stirring for reacting for 15 hours. After the reaction is finished, cooling to room temperature, concentrating the solvent to be dry30mL of CH was added₂Cl₂And (4) extracting. Washing the organic layer twice with brine, the organic layer containing anhydrous Na₂SO₄Drying, filtering and concentrating the solvent gave furfuryl propionate in 83% yield.

Example 2

This example prepared furfuryl alkylcarboxylate in the same manner as in example 1 except that potassium carbonate was changed to pyridine. The yield of furfuryl propionate of this example was 87%.

Example 3

This example prepared furfuryl alkylcarboxylate in the same manner as in example 1 except that acetonitrile was changed to dichloroethane. The yield of furfuryl propionate of this example was 78%.

Example 4

This example prepared furfuryl alkylcarboxylate in the same manner as in example 1 except that acetonitrile was changed to chloroform. The yield of furfuryl propionate of this example was 79%.

Example 5

This example was carried out in the same manner as in example 1 except that phosphotungstic acid was changed to phosphomolybdic acid to prepare an alkylcarboxylic acid furfuryl ester. The yield of furfuryl propionate of this example was 81%.

Example 6

This example produced furfuryl alkylcarboxylate in the same manner as in example 1 except that propionic anhydride was changed to acetic anhydride. The yield of furfuryl acetate in this example was 90%.

Example 7

This example prepared furfuryl alkylcarboxylate in the same manner as in example 1, except that propionic anhydride was changed to acetyl chloride. The yield of furfuryl acetate in this example was 80%.

Example 8

This example prepared furfuryl alkylcarboxylate in the same manner as in example 1, except that propionic anhydride was changed to acetic acid. The yield of furfuryl acetate in this example was 81%.

Example 9

This example prepared furfuryl alkylcarboxylate in the same manner as in example 1, except that propionic anhydride was changed to propionic acid. The yield of furfuryl propionate of this example was 72%.

Example 10

This example produced furfuryl alkylcarboxylate in the same manner as in example 1 except that the reaction time was changed to 20 hours. The yield of furfuryl propionate of this example was 78%.

Example 11

This example produced furfuryl alkylcarboxylate in the same manner as in example 1 except that the reaction time was changed to 5 hours. The yield of furfuryl propionate of this example was 73%.

Example 12

This example prepared furfuryl alkylcarboxylate in the same manner as in example 1 except that 2mmol of propionic anhydride was changed to 4mmol of propionic anhydride and 2mmol of potassium carbonate was changed to 4mmol of potassium carbonate. The yield of furfuryl propionate of this example was 83%.

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 should be equivalent or changed within the scope of the present invention.