阅读说明：本技术 一种超细三氯化铝催化制备佳乐麝香的方法 (Method for preparing galaxolide musk by using superfine aluminum trichloride as catalyst ) 是由 易健康 傅绪飞 胡青阳 于 2019-08-15 设计创作，主要内容包括：本发明涉及一种超细三氯化铝催化制备佳乐麝香的方法,其特征在于：1.将五甲基茚满与粒径5目以下的无水三氯化铝加入到溶剂中,五甲基茚满与无水三氯化铝质量比1.5-2：1,冷却到-30~-20℃；2.搅拌滴加环氧丙烷溶于溶剂中的溶液,环氧丙烷与五甲基茚满质量比为0.3-0.5：1,于-30~-5℃下反应1-2小时,生成六甲基茚满醇；3.继续加入失活剂、甲醛或甲醛等价物,其中失活剂、甲醛或甲醛等价物与五甲基茚满的摩尔比分别为1-2:1、0.5-1:1,升温到5~65℃,反应0.5-4小时即可生成佳乐麝香；4.提纯。本发明优点：用超细粒径的三氯化铝粉末,显著提高了原料转化率和产物收率、缩短了反应时间、反应具有良好重现性,节约了能源,提高了生产效率,降低了生产成本。(the invention relates ~ a method for preparing galaxolide by catalyzing ultrafine aluminum trichloride, which is characterized by comprising the steps of 1, adding pentamethyl indane and anhydrous aluminum trichloride with the particle size of less than 5 meshes into a solvent, wherein the mass ratio of the pentamethyl indane ~ the anhydrous aluminum trichloride is 1.5-2: 1, cooling ~ -30 ~ -20 ℃, 2, stirring and dropwise adding a solution of propylene oxide dissolved in the solvent, wherein the mass ratio of the propylene oxide ~ the pentamethyl indane is 0.3-0.5: 1, reacting for 1-2 hours at-30 ~ -5 ℃ ~ generate hexamethyl indanol, 3, continuously adding an inactivating agent and formaldehyde or a formaldehyde equivalent, wherein the molar ratios of the inactivating agent, the formaldehyde or the formaldehyde equivalent and the pentamethyl indane are 1-2:1 and 0.5-1:1 respectively, heating ~ 5-65 ℃, reacting for 0.5-4 hours ~ generate galaxolide, and 4, purifying.)

1. A method for preparing galaxolide by using superfine aluminum trichloride as a catalyst is characterized by comprising the following steps:

(1) adding pentamethyl indan with purity not lower than 80% and anhydrous aluminum trichloride with particle size less than 5 meshes into halogenated hydrocarbon or a mixture of pentamethyl indan and halogenated hydrocarbon, controlling the mass ratio of pentamethyl indan to anhydrous aluminum trichloride to be 1.5 ~ -2:1, and cooling to ~ -30 ~ -20 ℃;

(2) dropwise adding propylene oxide solution into the solution in the step (1) while stirring, and controlling the mass ratio of the propylene oxide ~ the pentamethyl indane ~ be 0.3-0.5: 1 and reacting at-30 ~ -5 ℃ ~ generate hexamethyl indanol;

(3) adding water or alcohols or carboxylic ester compounds into the hexamethyl indanol generated in the step (2) as a deactivator, wherein the molar ratio of the deactivator to the pentamethyl indanol is 1 ~ 2:1, deactivating the anhydrous aluminum trichloride, adding formaldehyde or a formaldehyde equivalent, wherein the molar ratio of the formaldehyde or the formaldehyde equivalent to the pentamethyl indanol is 0.5 ~ 1:1, heating to 5 ~ 65 ℃, and continuing to react for 0.5 ~ 4 hours to generate the galaxolide;

(4) the galaxolide is purified to obtain galaxolide with purity not lower than 70%.

2. the method for preparing galaxolide by using the ultrafine aluminum trichloride as a catalyst according to claim 1, wherein the particle size of the anhydrous aluminum trichloride in the step (1) is 40 ~ 100 meshes.

3. the method for preparing galaxolide by using the ultrafine aluminum trichloride as a catalyst according to claim 1, wherein the particle size of the anhydrous aluminum trichloride in the step (1) is 60 ~ 80 meshes.

4. The method for preparing galaxolide by using the ultrafine aluminum trichloride as the catalyst in claim 1, which comprises the following steps: the solvent used in the reaction is dichloromethane, chlorobenzene or pentamethyl indane.

5. the method for preparing galaxolide by using the ultrafine aluminum trichloride as the catalyst in claim 1, which comprises the following steps: the solvent used for the reaction is preferably dichloromethane or chlorobenzene.

6. The method for preparing galaxolide by using the ultrafine aluminum trichloride as the catalyst in claim 1, which comprises the following steps: the deactivator in the step (3) is water, alcohol or diol containing 1-4 carbon atoms, and carboxylic ester formed by carboxylic acid containing 1-2 carbon atoms and alcohol containing 1-4 carbon atoms.

7. the method for preparing galaxolide by using the ultrafine aluminum trichloride as the catalyst in claim 1, which comprises the following steps: the deactivator in the step (3) is preferably water, methanol or ethyl acetate.

8. The method for preparing galaxolide by using the ultrafine aluminum trichloride as the catalyst in claim 1, which comprises the following steps: the formaldehyde equivalent in the step (3) is formaldehyde aqueous solution, paraformaldehyde, trioxymethylene or dimethoxymethane.

Technical Field

The invention belongs to the field of preparation of essence and spice, relates to preparation of galaxolide, and particularly relates to a method for preparing galaxolide by catalysis of ultrafine aluminum trichloride.

background

Jiale musk (Galaxolide)^®) The chemical name of the perfume is 1, 3, 4, 6, 7, 8-hexahydro-4, 6, 6, 7, 8, 8-hexamethylcyclopenta-gamma-2-benzopyran, the perfume is a tricyclic isochroman perfume successfully developed by International essence perfume company (IFF) in the 60 th 20 th century, has strong musk smell, and is widely applied to the industries of daily chemicals, perfumes and the like.

There are several synthetic routes to galaxolide (patent publication US 3360530), and so far the most direct and economical route is: pentamethyl indane (I) and propylene oxide are subjected to Friedel-Crafts alkylation (Friedel-Crafts alkylation) under the action of Lewis acid (usually aluminum trichloride) to generate hexamethyl indanol (II), and the hexamethyl indanol (II) is continuously subjected to cyclization reaction with formaldehyde or formaldehyde equivalent to generate galaxolide (III) (as shown in figure 1). Depending on whether the hexamethylindanol (II) formed is separated or not, there are further two methods: separating the generated hexamethylindanol (II), and then putting the separated hexamethylindanol (II) into the next step of cyclization reaction to synthesize the hexamethylindanol (patent publication Nos. US3360530 and US 4315951A) by a fractional step method; the hexamethyl indanol (II) is not separated, and is directly subjected to the next cyclization reaction by adding a deactivator into a reaction system, namely the synthesis by a one-pot method (patent publication numbers US3532719A and CN 1072179A). The synthesis process of the 'one-pot method' has the advantages of convenient operation, short production period, low cost and the like, is more concerned by people, but the comprehensive examination of the prior art finds that the synthesis process still has some defects, particularly poor reaction reproducibility, low reaction conversion rate and yield, long reaction time and the like.

disclosure of Invention

the invention aims to solve the problems of poor reaction reproducibility, low reaction conversion rate and yield, long reaction time and the like in the existing 'one-pot' synthesis process of galaxolide, and provides a method for preparing galaxolide by using superfine aluminum trichloride as a catalyst.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

A method for preparing galaxolide by using superfine aluminum trichloride as a catalyst is characterized by comprising the following steps:

(1) adding pentamethyl indane (purity is not lower than 80%) and anhydrous aluminum trichloride with the particle size of less than 5 meshes (4 mm) into a solvent (halogenated hydrocarbon or a mixture of pentamethyl indane and halogenated hydrocarbon), controlling the mass ratio of pentamethyl indane ~ anhydrous aluminum trichloride ~ be 1.5-2: 1, and cooling ~ -30 ~ -20 ℃;

(2) dropwise adding propylene oxide while stirring ~ dissolve in the solvent in the step (1), and controlling the mass ratio of the propylene oxide ~ the pentamethyl indane ~ be 0.3-0.5: 1 and reacting at-30 ~ -5 ℃ ~ generate hexamethyl indanol;

(3) adding a deactivator (water, alcohols or carboxylic ester compounds) into the hexamethylindanol generated in the step (2) to partially deactivate anhydrous aluminum trichloride, wherein the molar ratio of the deactivator to the pentamethyl indane is 1 ~ 2:1, adding formaldehyde or a formaldehyde equivalent, wherein the molar ratio of the aldehyde or the formaldehyde equivalent to the pentamethyl indane is 0.5 ~ 1:1, heating to 5 ~ 65 ℃, and continuing to react for 0.5 ~ 4 hours to generate the galaxolide;

(4) The galaxolide can be prepared with purity not less than 70% by purifying galaxolide (extraction, column chromatography, rectification or crystallization).

further, the particle size of the anhydrous aluminum trichloride in the step (1) is 40 ~ 100 meshes.

further, the particle size of the anhydrous aluminum trichloride in the step (1) is 60 ~ 80 meshes.

Further, the solvent used for the reaction is dichloromethane, chlorobenzene or pentamethyl indane.

further, the solvent used for the reaction is preferably dichloromethane or chlorobenzene.

further, the deactivator in step (3) is water, alcohol or diol containing 1-4 carbon atoms, or carboxylate of carboxylic acid containing 1-2 carbon atoms and alcohol containing 1-4 carbon atoms.

Further, the step (3) deactivator is preferably water, methanol or ethyl acetate.

further, the formaldehyde equivalent in the step (3) is formaldehyde aqueous solution, paraformaldehyde, trioxymethylene or dimethoxymethane.

Through careful research, the Friedel-crafts alkylation reaction catalyzed by anhydrous aluminum trichloride in the synthesis process is used as heterogeneous reaction, the shape of the anhydrous aluminum trichloride solid, especially the particle size, has great influence on the reaction effect, and through careful research, the use of the aluminum trichloride powder with superfine particle size can obviously improve the conversion rate of raw materials and the yield of products, shorten the reaction time and ensure that the reaction has good reproducibility.

The invention has the advantages that: by using the aluminum trichloride powder with the superfine particle size, the conversion rate of raw materials and the yield of products are obviously improved, the reaction time is shortened, the reaction has good reproducibility, the production period is shortened, the energy consumption is reduced, the production efficiency is improved, the production cost is reduced, and the aluminum trichloride powder has obvious advantages in the aspect of economic benefit.

drawings

Fig. 1 is a synthesis process diagram of galaxolide in the current production.

Detailed Description

A method for preparing galaxolide by using superfine aluminum trichloride as a catalyst comprises the following specific implementation steps: