阅读说明：本技术 一种法尼基丙酮的合成方法 (Synthesis method of farnesyl acetone ) 是由 张建洋 刘晓涛 王�锋 刘海兵 刘金海 谈磊 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种法尼基丙酮的合成方法,包括以下步骤：将橙花叔醇与三氧化二铝混合,升温,滴加乙酰乙酸甲酯,滴完后保温反应,反应过程中蒸出产生的甲醇,收集产生的二氧化碳气体；反应结束后,过滤分离出三氧化二铝,滤液减压蒸馏收集产物法尼基丙酮。该方法反应产率高,催化剂通过过滤即可分离、并重复利用,避免对反应物料的洗涤,不产生废水,不产生含金属离子的废料,避免对环境的污染,产生的副产物甲醇和二氧化碳都可回收利用。(The invention discloses a method for synthesizing farnesyl acetone, which comprises the following steps: mixing nerolidol and aluminum oxide, heating, dropwise adding methyl acetoacetate, reacting under heat preservation after dropwise adding, evaporating generated methanol in the reaction process, and collecting generated carbon dioxide gas; and after the reaction is finished, filtering and separating out aluminum oxide, and distilling the filtrate under reduced pressure to collect the product of farnesyl acetone. The method has high reaction yield, the catalyst can be separated and reused by filtering, the washing of reaction materials is avoided, no wastewater is generated, no waste material containing metal ions is generated, the pollution to the environment is avoided, and the generated by-products, namely methanol and carbon dioxide can be recycled.)

1. A method for synthesizing farnesyl acetone is characterized by comprising the following steps:

mixing nerolidol and aluminum oxide, heating, dropwise adding methyl acetoacetate, reacting under heat preservation after dropwise adding, evaporating generated methanol in the reaction process, and collecting generated carbon dioxide gas; and after the reaction is finished, filtering and separating out aluminum oxide, and distilling the filtrate under reduced pressure to collect the product of farnesyl acetone.

2. The method for synthesizing farnesyl acetone according to claim 1, wherein the method comprises the following steps: the mol ratio of the nerolidol to the methyl acetoacetate to the aluminum oxide is 1: 0.99-1.29: 0.04 to 0.044.

3. The method for synthesizing farnesyl acetone according to claim 1, wherein the method comprises the following steps: heating to 160-180 ℃, and dropwise adding methyl acetoacetate.

4. The method for synthesizing farnesyl acetone according to claim 1, wherein the method comprises the following steps: the temperature of the heat preservation reaction is 160-180 ℃.

5. The method for synthesizing farnesyl acetone according to claim 1, wherein the method comprises the following steps: the separated aluminum oxide can be recycled.

6. The method for synthesizing farnesyl acetone according to claim 1, wherein the method comprises the following steps: the front distillation sleeve of the reduced pressure distillation is used for the next feeding.

Technical Field

The invention belongs to the technical field of organic synthesis, relates to synthesis of an organic intermediate, and particularly relates to a method for synthesizing farnesyl acetone.

Background

Farnesyl acetone, chemically known as 6,10, 14-trimethyl-5, 9, 13-pentadecatrien-2-one, is an isomer of farnesyl acetone. Farnesyl acetone has wide application in fields such as perfume and medicine, and can be used as perfume fixative of flower fragrance essence, and can be made into hard capsule with microcrystalline cellulose, starch, lactose, polyethylene pyrrolidone, etc. for treating gastritis. The farnesyl acetone is used as a raw material to prepare geranyl linalool, which is an important intermediate for synthesizing the anti-peptic gastric ulcer drug teprenone. In recent years, the demand of vitamin E in the market is continuously increased, the isophytol is an important raw material for synthesizing the vitamin E, and the demand of farnesyl acetone as an intermediate for synthesizing the isophytol is increased.

At present, the synthesis method of farnesyl acetone mainly uses nerolidol and methyl acetoacetate as raw materials and aluminum isopropoxide as a catalyst to synthesize the nerolidol and the methyl acetoacetate through a Carlo reaction. The method has high yield, but the method needs water washing during the post-treatment, can generate a large amount of waste water, has heavy pollution, high industrialization cost and large environmental protection pressure.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a method for synthesizing farnesyl acetone, wherein nerolidol is used as a raw material, aluminum oxide is used as a catalyst, and the nerolidol and the aluminum oxide react with methyl acetoacetate to generate the farnesyl acetone.

The invention is realized by the following technical scheme:

a method for synthesizing farnesyl acetone comprises the following steps:

mixing nerolidol and aluminum oxide, heating, dropwise adding methyl acetoacetate, reacting under heat preservation after dropwise adding, evaporating generated methanol in the reaction process, and collecting generated carbon dioxide gas; and after the reaction is finished, filtering and separating out aluminum oxide, and distilling the filtrate under reduced pressure to collect the product of farnesyl acetone.

The reaction equation is as follows:

further, the mol ratio of the nerolidol to the methyl acetoacetate to the aluminum oxide is 1: 0.99-1.29: 0.04 to 0.044.

Further, heating to 160-180 ℃, and dropwise adding methyl acetoacetate.

Further, the temperature of the heat preservation reaction is 160-180 ℃.

Further, the separated aluminum oxide is recycled.

Further, the front distillation sleeve of the reduced pressure distillation is used for the next feeding.

The invention has the beneficial effects that:

according to the method, the aluminum oxide is used as the catalyst, and the catalyst can be separated out through filtering after the reaction is finished and can be recycled; no waste material containing metal ions is generated in the reaction process; during the reaction process and the post-treatment, water is not needed, no waste water is generated, and the environmental protection pressure of industrial production is reduced.

Detailed Description

Example 1

Adding 600g of nerolidol and 12g of aluminum oxide into a 2000ml reaction kettle with mechanical stirring, starting mechanical stirring, heating to 160 ℃, starting dropwise adding 340g of methyl acetoacetate, dropwise adding for 4h, keeping the temperature for 7h after dropwise adding, finishing reaction, filtering out 11.8g of catalyst after the reaction is finished, recycling the catalyst, and carrying out reduced pressure distillation to obtain 561.62g of farnesyl acetone with the content of 99%. The yield thereof was found to be 80.5%.

Example 2

Adding 600g of nerolidol and 11.8g of aluminum oxide into a 2000ml reaction kettle with mechanical stirring, starting mechanical stirring, heating to 170 ℃, beginning to dropwise add 340g of methyl acetoacetate, dropwise adding for 4h, keeping the temperature for 5h after dropwise adding, finishing the reaction, filtering out 11.5g of catalyst after the reaction is finished, recycling the catalyst, and carrying out reduced pressure distillation to obtain 583.3g of farnesyl acetone with the content of 99%. The yield thereof was found to be 83.6%.

Example 3

Adding 600g of nerolidol and 11.5g of aluminum oxide into a 2000ml reaction kettle with mechanical stirring, starting mechanical stirring, heating to 180 ℃, starting to dropwise add 340g of methyl acetoacetate, dropwise adding for 4h, keeping the temperature for 2h after dropwise adding, finishing the reaction, filtering out 11.3g of catalyst after the reaction is finished, recycling the catalyst, and carrying out reduced pressure distillation to obtain 578.4g of farnesyl acetone with the content of 99%. The yield thereof was found to be 83.0%.

Example 4

Adding 600g of nerolidol and 11.3g of aluminum oxide into a 2000ml reaction kettle with mechanical stirring, starting mechanical stirring, heating to 170 ℃, starting to dropwise add 340g of methyl acetoacetate, dropwise adding for 4h, heating to 180 ℃ after dropwise adding, keeping the temperature for 2h, finishing reaction, filtering out 11.2g of catalyst after the reaction is finished, recycling the catalyst, and carrying out reduced pressure distillation to obtain 598.6g of farnesyl acetone with the content of 99%. The yield thereof was found to be 85.8%.

Example 5

Adding 600g of nerolidol and 11.2g of aluminum oxide into a 2000ml reaction kettle with mechanical stirring, starting mechanical stirring, heating to 170 ℃, beginning to dropwise add 402.3g of methyl acetoacetate, dropwise adding for 4h, heating to 180 ℃, keeping the temperature for 2h after the dropwise adding is finished, finishing the reaction, filtering out 11g of catalyst after the reaction is finished, recycling the catalyst, and carrying out reduced pressure distillation to obtain 600g of farnesyl acetone with the content of 99%. The yield thereof was found to be 86.0%.

Example 6

Adding 600g of nerolidol and 12g of aluminum oxide (1 g of new catalyst is supplemented) into a 2000ml reaction kettle with mechanical stirring, starting mechanical stirring, heating to 170 ℃, starting to dropwise add 309.5g of methyl acetoacetate, dropwise adding for 4h, heating to 180 ℃ after dropwise addition, keeping the temperature for 2h, finishing reaction, filtering out 11.6g of catalyst after the reaction is finished, recycling the catalyst, and carrying out reduced pressure distillation to obtain 583.3g of farnesyl acetone with the content of 99%. The yield thereof was found to be 83.6%.