阅读说明：本技术 一种通过漆酶生物合成异丙胺盐酸盐的方法 (Method for biosynthesizing isopropyl amine hydrochloride by laccase ) 是由 张红夺 金峰 金涛 王雯 金成福 李仙洛 于 2020-12-22 设计创作，主要内容包括：为了实现上述目的,本发明提供了一种通过漆酶生物合成异丙胺盐酸盐的方法,所述的方法,以异丙醇、氨水为起始物,以漆酶为催化剂,经过两步反应,得到异丙胺盐酸盐。本发明利用漆酶的对胺和醇类的降解特性,意外发现其具有合成异丙胺的功能。同时,本发明具有反应条件温和,收率高,能耗低等特点。本发明对环境无污染,是一条绿色环保的合成线路。(In order to achieve the aim, the invention provides a method for biosynthesizing isopropyl amine hydrochloride by laccase, which takes isopropanol and ammonia water as starting materials and laccase as a catalyst to obtain isopropyl amine hydrochloride through two-step reaction. The invention utilizes the degradation characteristic of laccase on amine and alcohol, and unexpectedly finds that the laccase has the function of synthesizing isopropylamine. Meanwhile, the method has the characteristics of mild reaction conditions, high yield, low energy consumption and the like. The invention has no pollution to the environment and is a green and environment-friendly synthesis line.)

1. A method for biosynthesizing isopropyl amine hydrochloride by laccase is characterized in that isopropyl alcohol and ammonia water are used as starting materials, laccase is used as a catalyst, and the isopropyl amine hydrochloride is obtained through two-step reaction.

2. The method for the biosynthesis of isopropylamine hydrochloride by laccase of claim 1, characterized in that it is carried out according to the following steps:

step 1, isopropanol and ammonia water are used as raw materials, laccase is used as a catalyst, and the reaction is carried out at the temperature of 38-40 ℃ to obtain a mixed product of isopropylamine and isopropyl ether;

and 2, distilling at 55-60 ℃ to obtain isopropylamine, directly putting the isopropylamine into an ethyl acetate or methyl tert-butyl ether system, cooling to 0-5 ℃, introducing hydrogen chloride gas to generate isopropylamine hydrochloride, filtering, and drying to obtain the final product.

3. The method of claim 1, wherein the ammonia concentration is 10% ammonia.

4. The method for biosynthesis of isopropylamine hydrochloride by a laccase according to claim 1, wherein in step 1 the volume ratio of isopropanol to 10% ammonia is 1: 5.

5. the method of claim 1, wherein the laccase is a polyphenol oxidase containing four copper ions, which is extracted from raw lacquer.

6. The method of claim 1, wherein the laccase is used in an amount of one percent by volume of isopropanol.

7. The method for biosynthesis of isopropylamine hydrochloride by a laccase of claim 1, wherein in step 1 the reaction time is 16-24 hours.

8. The method for biosynthesis of isopropylamine hydrochloride by laccase of claim 1, wherein in step 2, the reaction time with hydrogen chloride is 4-6 hours.

Technical Field

The application relates to the technical field of organic synthesis, in particular to a method for biosynthesizing isopropyl amine hydrochloride by laccase.

Background

Isopropylamine, also known as 2-aminopropane, is a widely used lower aliphatic alcohol amine, mainly used in the field of medicine, and the demand for isopropylamine is becoming more and more extensive with the development of some downstream products, but the preparation of isopropylamine is carried out by a chemical synthesis method.

1. The acetone hydrogenating and ammoniating process includes feeding acetone material into reactor with Cu-Ni-clay as catalyst, introducing hydrogen and ammonia to react at normal pressure and 220 deg.c, and rectifying and purifying the reaction product to obtain monoisopropylamine and simultaneously produce diisopropylamine. The conversion rate of acetone is up to 98%, and the total yield of diisopropylamine and mono-isopropyl amine is up to above 90%. Raw material consumption quota: 1390kg/t acetone and 450kg/t liquid ammonia.

2. The isopropanol hydroammonation method is characterized in that isopropanol reacts with ammonia and hydrogen at 195 ℃ and 1.72MPa by a porous nickel-aluminum catalyst activated by barium hydroxide to generate monoisopropylamine and diisopropylamine. The total conversion rate of the reaction can reach 86 percent, the product yield (calculated by isopropanol) reaches 96 percent, and the product comprises 37 percent of monoisopropylamine, 33 percent of diisopropylamine, 12 percent of isopropanol and 18 percent of water.

The refining method comprises the following steps: isopropylamine is prepared by reacting bromoisopropane with an alcoholic solution of ammonia, or acetone with ammonia and hydrogen under the catalysis of nickel-copper-clay. And thus may contain impurities such as acetone, bromoisopropane, isopropanol, and other various propylamines. Can be refined by rectification method. To obtain high purity isopropylamine, anhydrous barium oxide can be added and left for several days, then distillation is carried out in the presence of sodium, and the fraction at 31.4 ℃ under 131.961Pa is collected and redistilled.

Both methods have harsh conditions and high energy consumption, and pollute the environment, so a green and environment-friendly synthesis process with low energy consumption needs to be developed.

Disclosure of Invention

The main purpose of the application is to provide a method for biosynthesis of isopropylamine hydrochloride, in particular a method for biosynthesis of isopropylamine hydrochloride by laccase.

In order to achieve the aim, the invention provides a method for biosynthesizing isopropyl amine hydrochloride by laccase, which takes isopropanol and ammonia water as starting materials and laccase as a catalyst to obtain isopropyl amine hydrochloride through two-step reaction.

Specifically, the method comprises the following steps:

step 1, isopropanol and ammonia water are used as raw materials, laccase is used as a catalyst, and the reaction is carried out at the temperature of 38-40 ℃ to obtain a mixed product of isopropylamine and isopropyl ether;

and 2, distilling at 55-60 ℃ to obtain isopropylamine, directly putting the isopropylamine into an ethyl acetate or methyl tert-butyl ether system, cooling to 0-5 ℃, introducing hydrogen chloride gas to generate isopropylamine hydrochloride, filtering, and drying to obtain the final product.

Specifically, in the step 1, the concentration of the ammonia water is 10%. The volume ratio of the isopropanol to the 10% ammonia water is 1: 5.

specifically, in the step 1, the laccase is laccase extracted from raw lacquer. Polyphenol oxidase containing four copper ions. The laccase is used in an amount of one percent of the volume of the isopropanol.

Specifically, in the step 1, the reaction time is 16 to 24 hours.

Specifically, in the step 2, hydrogen chloride is introduced for reaction for 4-6 hours.

Has the advantages that: the invention creatively utilizes the degradation characteristic of laccase to amine and alcohol, and unexpectedly finds that the laccase has the function of synthesizing isopropylamine.

The invention has the characteristics of mild reaction conditions, high yield, low energy consumption and the like.

The invention has no pollution to the environment and is a green and environment-friendly synthesis line.

Detailed Description

In order to make the technical solutions of the present application better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments.

Examples 1 to 3 are examples of the production of isopropylamine

Example 1

Adding 10 ml of isopropanol and 50 ml of 10% ammonia water into a 100 ml single-neck flask, stirring, raising the temperature of the system to 35-37 ℃, adding 0.1 g of laccase, reacting for 16-18 hours, filtering out the laccase after the reaction is finished, and refrigerating for storage, and preparing for next use. The filtrate was directly distilled and dehydrated to give isopropylamine 4.2 g. The yield was 42% by volume of isopropanol.

Example 2

Adding 10 ml of isopropanol and 50 ml of 10% ammonia water into a 100 ml single-neck flask, stirring, raising the temperature of the system to 38-40 ℃, adding 0.1 g of laccase, reacting for 16-18 hours, filtering out the laccase after the reaction is finished, and refrigerating for storage, and preparing for next use. The filtrate was directly distilled and dehydrated to give isopropylamine 5.6 g. The yield was 56% by volume of isopropanol.

Example 3

Adding 10 ml of isopropanol and 50 ml of 10% ammonia water into a 100 ml single-neck flask, stirring, raising the temperature of the system to 41-43 ℃, adding 0.1 g of laccase, reacting for 16-18 hours, filtering out the laccase after the reaction is finished, and refrigerating for storage, and preparing for next use. The filtrate was directly distilled and dehydrated to give isopropylamine 4.8 g. The yield was 48% by volume of isopropanol.

Examples 4 to 5 examples of preparation of isopropylamine hydrochloride

The structural formula of isopropylamine hydrochloride is:

example 4

5 g of isopropylamine and 20 ml of ethyl acetate are added into a 100 ml single-neck flask, hydrogen chloride is introduced when the temperature is reduced to 0-5 ℃ until the pH value of the system is 1-2, the mixture is stirred for 4 hours at normal temperature, and after the reaction is finished, the mixture is filtered and dried under reduced pressure to obtain 7.6 g of isopropylamine hydrochloride. The yield thereof was found to be 96%.

Example 5

5 g of isopropylamine and 20 ml of methyl tert-butyl ether are added into a 100 ml single-neck flask, hydrogen chloride is introduced when the temperature is reduced to 0-5 ℃ until the pH value of the system is 1-2, the introduction is stopped, the mixture is stirred for 4 hours at normal temperature, and after the reaction is finished, the mixture is filtered and dried under reduced pressure to obtain 7.7 g of isopropylamine hydrochloride. The yield thereof was found to be 97%.

The above description is only a preferred embodiment of the present application and is not intended to limit the present application.