阅读说明：本技术 一种3-氯-1，2-丙二醇脂肪酸二酯的合成方法 (Synthetic method of 3-chloro-1, 2-propanediol fatty acid diester ) 是由 郭会 陈武炼 于 2019-12-12 设计创作，主要内容包括：本发明公开了一种3-氯-1,2-丙二醇脂肪酸二酯的合成方法。该合成方法是将3-氯-1,2-丙二醇和脂肪酸酰氯在固定化脂肪酶催化作用下反应得到3-氯-1,2-丙二醇脂肪酸二酯。与现有技术相比,本发明的合成方法所得到的3-氯-1,2-丙二醇脂肪酸二酯的收率显著提高,而且合成工艺条件温和,过程简单,工艺路线短,产品容易分离提纯,得到的产品纯度高,可作为检测分析的对照品及毒理学评价实验的原料。(The invention discloses a synthetic method of 3-chloro-1, 2-propylene glycol fatty acid diester. The synthesis method comprises the step of reacting 3-chloro-1, 2-propanediol with fatty acid chloride under the catalytic action of immobilized lipase to obtain 3-chloro-1, 2-propanediol fatty acid diester. Compared with the prior art, the yield of the 3-chloro-1, 2-propylene glycol fatty acid diester obtained by the synthesis method is obviously improved, the synthesis process condition is mild, the process is simple, the process route is short, the product is easy to separate and purify, the purity of the obtained product is high, and the product can be used as a reference substance for detection and analysis and a raw material for toxicological evaluation experiments.)

1. A synthetic method of 3-chloro-1, 2-propylene glycol fatty acid diester is characterized in that: 3-chlorine-1, 2-propylene glycol and fatty acid chloride react under the catalysis of immobilized lipase to obtain 3-chlorine-1, 2-propylene glycol fatty acid diester.

2. The method of synthesis according to claim 1, characterized in that: the mol ratio of the 3-chlorine-1, 2-propanediol to the fatty acid chloride is 1: 2.5 to 3.0; the mass ratio of the 3-chloro-1, 2-propanediol to the immobilized lipase is 1: 0.2 to 0.4.

3. The method of synthesis according to claim 1, characterized in that: the reaction temperature is 25-30 ℃; the reaction time is 2-10 hours.

4. The method of synthesis according to claim 1, characterized in that: the fatty acid chloride is any one of palmitoyl chloride, stearoyl chloride, lauric acid acyl chloride, myristic acid acyl chloride, oleoyl chloride, linoleoyl chloride and linolenoyl chloride.

5. The method of synthesis according to claim 1, characterized in that: the immobilized lipase is one or a mixture of Novozym435, Lipozyme RM IM and Lipozyme TL IM.

Technical Field

The invention relates to a synthesis method of 3-chloro-1, 2-propylene glycol fatty acid diester, belonging to the technical field of fine chemical synthesis.

Background

Chloropropanol esters are a new class of carcinogens found in food products, especially refined vegetable oils. Chloropropanol esters release free chloropropanol by intestinal pancreatic lipase, which is reproductive and neurotoxic and can cause renal tumors. At present, the attention on chloropropanol ester is increasing at home and abroad, 3-chloro-1, 2-propanediol fatty acid diester is one of chloropropanol ester, and high-purity 3-chloro-1, 2-propanediol fatty acid diester is required to be used as a reference substance for detecting the chloropropanol ester, so that the development of a synthetic method of the 3-chloro-1, 2-propanediol fatty acid diester is very important.

The existing literature (J Am Oil Chem Soc, 2011, 88: 1143-.

Disclosure of Invention

The invention overcomes the defects in the prior art and provides a high-yield synthesis method of 3-chloro-1, 2-propylene glycol fatty acid diester.

In order to solve the technical problems, the invention is realized by the following technical scheme: 3-chlorine-1, 2-propylene glycol and fatty acid chloride react under the catalysis of immobilized lipase to obtain 3-chlorine-1, 2-propylene glycol fatty acid diester.

Further, the molar ratio of the 3-chloro-1, 2-propanediol to the fatty acid chloride is 1: 2.5 to 3.0; the mass ratio of the 3-chloro-1, 2-propanediol to the immobilized lipase is 1: 0.2 to 0.4.

Further, the reaction temperature is 25-30 ℃; the reaction time is 2-10 hours.

Further, the fatty acid chloride is any one of palmitoyl chloride, stearoyl chloride, lauroyl chloride, myristoyl chloride, oleoyl chloride, linoleoyl chloride, and linolenoyl chloride.

Further, the immobilized lipase is one or a mixture of Novozym435, Lipozyme RM IM and Lipozyme TL IM.

Compared with the prior art, the invention has the following advantages:

(1) the synthesis process has the advantages of mild conditions, simple process, short process route and high yield of the 3-chloro-1, 2-propylene glycol fatty acid diester.

(2) The product of the invention is easy to separate and purify, has high chemical purity, and can meet the requirement of being used as a standard reagent for detecting the 3-chloro-1, 2-propylene glycol fatty acid diester.

(3) The invention has high use value and good economical efficiency.

Detailed Description

The invention is further described in the following examples, which should not be construed as limiting the invention.

The invention provides a synthesis method of 3-chloro-1, 2-propanediol fatty acid diester, which comprises the steps of reacting 3-chloro-1, 2-propanediol with fatty acid chloride under the catalysis of immobilized lipase to obtain 3-chloro-1, 2-propanediol fatty acid diester; the process is simple, the process route is short, the product is easy to separate and purify, and the obtained product has high purity.

The invention provides a synthesis method of 3-chloro-1, 2-propanediol fatty acid diester, wherein the molar ratio of 3-chloro-1, 2-propanediol to fatty acid chloride is 1: 2.5-3.0, wherein the proportion range can ensure that the 3-chloro-1, 2-propanediol is completely reacted, so that the 3-chloro-1, 2-propanediol fatty acid diester is fully obtained, and meanwhile, the dosage of the fatty acid chloride is saved; the mass ratio of the 3-chloro-1, 2-propanediol to the immobilized lipase is 1: 0.2-0.4, and the dosage of the immobilized lipase is saved under the condition of ensuring the catalytic effect. The reaction temperature is 25-30 ℃, and the energy consumption is reduced under the condition of ensuring the reaction; the reaction time is 2-10 hours.

Example 1

Adding 3-chloro-1, 2-propanediol (9.0mmol, 1.0g), palmitoyl chloride (25mmol, 6.9g) and Novozym435 immobilized lipase (300mg) into a reaction vessel, reacting at 25-30 ℃ for 2.5 hours, filtering to remove the immobilized lipase, washing filter cake with n-hexane, concentrating the filtrate, and performing column chromatography to obtain 3-chloro-1, 2-propanediol palmitate diester with the yield of 60%.

Example 2

Adding 3-chloro-1, 2-propanediol (9.0mmol, 1.0g), palmitoyl chloride (25mmol, 6.9g) and Lipozyme RM IM immobilized lipase (300mg) into a reaction vessel, reacting at 25-30 ℃ for 4 hours, filtering to remove the immobilized lipase, washing a filter cake with n-hexane, concentrating a filtrate, and performing column chromatography to obtain 3-chloro-1, 2-propanediol palmitate diester with the yield of 65%.

Example 3

Adding 3-chloro-1, 2-propanediol (9.0mmol, 1.0g), palmitoyl chloride (25mmol, 6.9g) and Lipozyme TL IM immobilized lipase (300mg) into a reaction vessel, reacting at the temperature of 25-30 ℃ for 3 hours, filtering to remove the immobilized lipase, washing a filter cake with n-hexane, concentrating a filtrate, and performing column chromatography to obtain 3-chloro-1, 2-propanediol palmitate diester with the yield of 62%.

Example 4

Adding 3-chloro-1, 2-propanediol (9.0mmol, 1.0g), palmitoyl chloride (25mmol, 6.9g) and immobilized lipase (300 mg: 100mg Novozym435, 100mg lipozyme RM IM, 100mg lipozyme TL IM) into a reaction vessel, reacting at the temperature of 25-30 ℃ for 2 hours, filtering to remove the immobilized lipase, washing a filter cake by using n-hexane, concentrating the filtrate, and performing column chromatography to obtain 3-chloro-1, 2-propanediol palmitate diester with the yield of 65%.

Example 5

In the synthesis method for preparing 3-chloro-1, 2-propanediol fatty acid diester in this example, the specific preparation steps are the same as those in any of examples 1 to 4, except that the fatty acid chloride is stearoyl chloride.

Example 6

In the synthesis method for preparing 3-chloro-1, 2-propanediol fatty acid diester in this example, the specific preparation steps are the same as those in any of examples 1 to 4, except that the fatty acid chloride is lauroyl chloride.

Example 7

In the synthesis method for preparing 3-chloro-1, 2-propanediol fatty acid diester in this example, the specific preparation steps are the same as those in any of examples 1 to 4 except that the fatty acid chloride is myristoyl chloride.

Example 8

In the synthesis method for preparing 3-chloro-1, 2-propanediol fatty acid diester in this example, the specific preparation steps are the same as those in any of examples 1 to 4, except that the fatty acid chloride is oleoyl chloride.

Example 9

In the synthesis method for preparing 3-chloro-1, 2-propanediol fatty acid diester in this example, the specific preparation steps are the same as those in any of examples 1 to 4, except that the fatty acid chloride is linoleoyl chloride.

Example 10

In the synthesis method for preparing the 3-chloro-1, 2-propanediol fatty acid diester in this embodiment, the specific preparation steps are the same as those in any one of embodiments 1 to 4, except that the fatty acid chloride is linolenoyl chloride.

Although the present invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.