阅读说明：本技术 一种合成爱德万甜的方法 (Method for synthesizing Edwarden sweet ) 是由 任世阔 韩子明 楚志强 李�荣 于 2020-07-07 设计创作，主要内容包括：本发明公开了一种合成爱德万甜的方法,属于食品化工技术领域。首先3-羟基-4-甲氧基苯丙烯醛或3-羟基-4-甲氧基苯丙醛和阿斯巴甜在溶剂中发生缩合反应,在脱水剂作用下转化生成亚胺中间体；然后再进行氢化还原反应,纯化精制处理后得到爱德万甜。本发明工艺简单,原料易得,改进了现有的爱德万甜的合成工艺,有效转化率达到85％以上,产品纯度达95％以上,收率达70％以上,经精制纯化爱德万甜的纯度达到99％以上。(The invention discloses a method for synthesizing Edwardsient, belonging to the technical field of food chemical industry. Firstly, 3-hydroxy-4-methoxy phenylpropyl olefine aldehyde or 3-hydroxy-4-methoxy phenylpropyl olefine aldehyde and aspartame are subjected to condensation reaction in a solvent, and are converted into imine intermediates under the action of a dehydrating agent; then carrying out hydrogenation reduction reaction, and carrying out purification and refining treatment to obtain the Edwardsient. The invention has simple process and easily obtained raw materials, improves the prior synthesis process of the Edwardsient, has the effective conversion rate of more than 85 percent, the product purity of more than 95 percent and the yield of more than 70 percent, and has the purity of the refined and purified Edwardsient of more than 99 percent.)

1. A method for synthesizing Edwardsient is characterized in that 3-hydroxy-4-methoxy phenylpropyl olefine aldehyde or 3-hydroxy-4-methoxy phenylpropyl olefine aldehyde and aspartame are subjected to condensation reaction in a solvent and are converted into imine intermediates under the action of a dehydrating agent; then carrying out hydrogenation reduction reaction, and carrying out purification and refining treatment to obtain the Edwardsient.

2. The method for synthesizing edmuntin according to claim 1, which comprises the following steps:

(1) adding a solvent, aspartame, 3-hydroxy-4-methoxy phenylpropyl enal or 3-hydroxy-4-methoxy phenylpropyl aldehyde, a dehydrating agent and palladium carbon washed by methanol to perform condensation reaction at 0-50 ℃ for 0.5-10h, and performing the step (2) after the reaction is finished;

(2) replacing air in the reaction system with nitrogen, and introducing hydrogen to perform pressurized hydrogenation reduction reaction;

(3) and filtering and concentrating the reaction solution, recovering methanol and palladium carbon, and crystallizing and purifying the crude product by using methanol/water to obtain the Edwardsient.

3. The method for synthesizing edmuntin according to claim 1 or 2, wherein the dehydrating agent is any one or a combination of more of anhydrous ferric chloride, anhydrous ferrous chloride, anhydrous magnesium chloride, anhydrous calcium chloride, anhydrous lithium chloride, anhydrous potassium chloride, anhydrous sodium bicarbonate, anhydrous potassium bicarbonate, anhydrous lithium bicarbonate, anhydrous potassium acetate, anhydrous sodium acetate, anhydrous lithium acetate, anhydrous calcium acetate, anhydrous magnesium acetate, anhydrous ferrous acetate, anhydrous sodium sulfate, anhydrous potassium sulfate, anhydrous magnesium sulfate, anhydrous lithium sulfate, anhydrous sodium dihydrogen phosphate, anhydrous disodium hydrogen phosphate and anhydrous potassium hydrogen phosphate, and the molar ratio of the dehydrating agent to aspartame is 1:1-10: 1.

4. The method for synthesizing edmuntin according to claim 1 or 2, wherein the molar ratio of 3-hydroxy-4-methoxyphenylenal or 3-hydroxy-4-methoxyphenylenal to aspartame is 2:1 to 1: 2.

5. The method for synthesizing edmuntin according to claim 2, wherein the mass ratio of palladium on carbon to aspartame is 1:100-1: 2; the water content of the palladium-carbon is 40-60%, and the weight ratio of palladium-carbon after water removal is 5-10%.

6. The method for synthesizing edmuntin according to claim 2, wherein the mass ratio of palladium on carbon to aspartame is 1: 10.

7. The method for synthesizing edmuntin according to claim 1 or 2, wherein the solvent is methanol, and the amount ratio of methanol to aspartame is 5-30mL:1 g.

8. The method for synthesizing edmuntin according to claim 1 or 2, wherein the molar ratio of 3-hydroxy-4-methoxyphenylenal or 3-hydroxy-4-methoxyphenylenal to aspartame is 1: 1.

9. The method for synthesizing edmuntan according to claim 1 or 2, wherein the pressure of the hydrogenation reduction reaction is 15-300psi, the temperature is 0-50 ℃, and the time is 2-20 h.

10. The method for synthesizing edwantan according to claim 1 or 2, wherein the pressure of the hydrogenation reduction reaction is 120psi, and the temperature is 35-45 ℃.

Technical Field

The invention belongs to the technical field of food chemical industry, and particularly relates to a method for synthesizing Edwardsient.

Background

The sweetener has very important function in food additives, and has various types and different functions. For example, sucrose, which is used as a main sweet ingredient in the food industry, has excellent mouthfeel, but has high calorie, and can cause diseases such as dental caries, diabetes and the like when being eaten excessively; for example, the psicose is used as natural rare sugar, has good taste and low calorie, has special functions of regulating blood sugar and the like beneficial to human health, and is evaluated as the most potential sucrose substitute by the American food navigation network. The functional sweetener can replace sucrose to a certain extent, on one hand, the functional sweetener meets the preference of human beings on sweet food, on the other hand, the functional sweetener can reduce the harm of the sweet food to human bodies, and even has a certain adjuvant therapy effect on patients with diabetes and the like. Therefore, the development of functional sweeteners with good taste is currently an important trend in the development of food additives.

The sweetness of the Edwardsient (ADM) can reach 20000 times of that of cane sugar, and is a sweetener with the highest sweetness which is approved to be put on the market by a plurality of countries at present. The Edwardsient can be added into various foods to improve the taste sweetness, and has extremely high market development value. However, as the artificial sweetener, synthetic methods such as: US2002133037A1 is mainly generated by condensing 3-hydroxy-4-methoxy phenylpropyl enal (HMCA) or 3-hydroxy-4-methoxy phenylpropyl aldehyde and Aspartame (APM) into imine and then reducing the imine; the method has the main problems that methanol and water are used as solvents during hydrogenation reduction, which is not beneficial to the generation of imine, and the generated raw materials are reduced into 3-hydroxy-4-methoxyphenylpropanol (HMPA) without complete reaction, so that the generation conversion rate of the Edwardsient is greatly reduced; in 2011, the journal of science and technology in food industry reported a method for synthesizing edmuntin, alkali was added into a reaction system to promote dissolution, acid was added to carry out hydrogenation reduction, so that aspartame was partially decomposed, and 3-hydroxy-4-methoxyphenylene aldehyde (HMCA) or 3-hydroxy-4-methoxyphenylene aldehyde could not be completely converted into imine but was reduced into 3-hydroxy-4-methoxyphenylpropanol (HMPA), so that the yield of edmuntin was not high. By adopting the method, the yield of the Edwardsient is generally lower than 70%, the dosage of the catalyst is large, the synthesis process is complex, and the cost is high. The reaction process is as follows:

disclosure of Invention

Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide a method for synthesizing Edwardsient, which uses a process method of firstly condensing a dehydrating agent and then reducing, greatly improves the reaction conversion rate, reduces the using amount and cost of a catalyst, and realizes industrial production.

In order to solve the problems, the technical scheme adopted by the invention is as follows:

a method for synthesizing Edwardsient comprises the steps of firstly carrying out condensation reaction on 3-hydroxy-4-methoxy phenylpropyl olefine aldehyde or 3-hydroxy-4-methoxy phenylpropyl aldehyde and aspartame in a solvent, and converting into an imine intermediate under the action of a dehydrating agent; then carrying out hydrogenation reduction reaction, and carrying out purification and refining treatment to obtain the Edwardsient; the reaction formula is shown as follows:

the method specifically comprises the following steps:

(1) adding a solvent, aspartame, 3-hydroxy-4-methoxy phenylpropyl enal or 3-hydroxy-4-methoxy phenylpropyl aldehyde, a dehydrating agent and palladium carbon washed by methanol to perform condensation reaction at 0-50 ℃ for 0.5-10h, and performing the step (2) after the reaction is finished;

(2) replacing air in the reaction system with nitrogen, and introducing hydrogen to perform pressurized hydrogenation reduction reaction;

(3) and filtering and concentrating the reaction solution, recovering methanol and palladium carbon, and crystallizing and purifying the crude product by using methanol/water to obtain the Edwardsient.

The method for synthesizing the Edwardsiene comprises the steps of using a dehydrating agent which is any one or combination of more of anhydrous ferric chloride, anhydrous ferrous chloride, anhydrous magnesium chloride, anhydrous calcium chloride, anhydrous lithium chloride, anhydrous potassium chloride, anhydrous sodium bicarbonate, anhydrous potassium bicarbonate, anhydrous lithium bicarbonate, anhydrous potassium acetate, anhydrous sodium acetate, anhydrous lithium acetate, anhydrous calcium acetate, anhydrous magnesium acetate, anhydrous ferrous acetate, anhydrous sodium sulfate, anhydrous potassium sulfate, anhydrous magnesium sulfate, anhydrous lithium sulfate, anhydrous sodium dihydrogen phosphate, anhydrous disodium hydrogen phosphate and anhydrous potassium hydrogen phosphate, wherein the molar ratio of the dehydrating agent to the aspartame is 1:1-10:1, the using amount of the dehydrating agent is determined according to the water content of a reaction system and the dehydrating capacity of the dehydrating agent, if the sum of the water content in a solvent and the water content in a reagent is a, the dehydrating capacity of the dehydrating agent is b, it is required that a always be less than b. The purpose of the dehydrating agent added in the reaction is mainly to combine water in the reaction system, including water generated in the reaction, so as to promote the condensation reaction to fully proceed, therefore, the amount of the dehydrating agent added in the reaction system is generally more than the total amount of water in the reaction system.

According to the method for synthesizing the Edwardsient, the molar ratio of the 3-hydroxy-4-methoxy phenylpropyl olefine aldehyde or the 3-hydroxy-4-methoxy phenylpropyl aldehyde to the aspartame is 2:1-1: 2.

According to the method for synthesizing the Edwardsient, the mass ratio of the palladium carbon to the aspartame is 1:100-1:2, wherein the dosage of the palladium carbon refers to the mass of directly purchased water-containing palladium carbon; the water content of the palladium-carbon is 40-60%, the weight ratio of palladium in the palladium-carbon after water removal is 5-10%, and more than 90% of water is removed by washing with methanol before use.

According to the method for synthesizing the Edwardsient, the mass ratio of the palladium carbon to the aspartame is 1: 10.

According to the method for synthesizing the Edwardsient, the solvent is methanol, and the dosage ratio of the methanol to the aspartame is 5-30mL:1 g.

According to the method for synthesizing the Edwardsient, the molar ratio of the 3-hydroxy-4-methoxy phenylpropyl enal or the 3-hydroxy-4-methoxy phenylpropyl aldehyde to the aspartame is 1: 1.

The method for synthesizing the Edwardsient has the pressure of hydrogenation reduction reaction of 15-300psi, the temperature of 0-50 ℃ and the time of 2-20 h. If the reaction pressure is low, the reaction time is prolonged, and if the pressure is too high, the by-products increase. If the reaction temperature is low, the reaction time is prolonged, and if the temperature is too high, the by-products increase. The time of the hydrogenation reaction is determined according to the HPLC detection result; the end point is that the generation and conversion of the Edwardsient are not increased any more, and the time is mainly related to the temperature, the pressure and the dosage of the catalyst.

According to the method for synthesizing the Edwardsient, the pressure of the hydrogenation reduction reaction is 120psi, and the temperature is 35-45 ℃.

Has the advantages that: compared with the prior art, the invention has the advantages that:

(1) the invention uses the technological method of dehydrating agent condensation and then reduction, greatly improves the reaction conversion rate, reduces the catalyst dosage and cost, realizes industrial production, and mainly uses 3-hydroxy-4-methoxy phenylpropyl aldehyde and aspartame as the cost is increased when synthesizing 3-hydroxy-4-methoxy phenylpropyl aldehyde.

(2) The method has the advantages of simple process, easily obtained raw materials, improvement on the synthesis process of the Edwardsient, effective conversion rate of more than 85 percent, product purity of more than 95 percent, yield of more than 70 percent, and refined and purified Edwardsient purity of more than 99 percent.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.