阅读说明：本技术 一种丙位内酯副产物叔丁醇-水共沸物合成酮麝香的方法 (Method for synthesizing musk ketone by using propyl lactone byproduct tert-butyl alcohol-water azeotrope ) 是由 王天义 范一义 汪洋 张政 吴旭 何云飞 于 2020-12-25 设计创作，主要内容包括：本发明公开一种丙位内酯副产物叔丁醇-水共沸物合成酮麝香的方法,以丙位内酯生产过程中的副产物叔丁醇为起始原料,与盐酸经氯代反应得到氯代叔丁烷；在三氯化铝的存在下,氯代叔丁烷与间二甲苯进行缩合反应,经中和水洗和蒸馏回收间二甲苯后,得到1,3-二甲基-5-叔丁基苯；以三氯甲烷为溶剂,在三氯化铝的催化作用下,1,3-二甲基-5-叔丁基苯与乙酰氯进行酰基化反应,得到2,6-二甲基-4-叔丁基苯乙酮；以硫酸为催化剂,2,6-二甲基-4-叔丁基苯乙酮与硝酸进行硝化反应,得到酮麝香粗品,经中和洗涤、结晶、离心等一系列分离提纯后得到99％的酮麝香产品,实现副产物资源综合利用。(The invention discloses a method for synthesizing musk ketone by using a propyl lactone byproduct tert-butyl alcohol-water azeotrope, wherein the method comprises the steps of taking the byproduct tert-butyl alcohol in the production process of propyl lactone as an initial raw material, and carrying out chlorination reaction on the initial raw material and hydrochloric acid to obtain chloro tert-butyl alcohol; in the presence of aluminum trichloride, carrying out condensation reaction on chlorinated tert-butane and m-xylene, and carrying out neutralization washing and distillation to recover the m-xylene to obtain 1, 3-dimethyl-5-tert-butyl benzene; using trichloromethane as a solvent, and carrying out an acylation reaction on 1, 3-dimethyl-5-tert-butyl benzene and acetyl chloride under the catalytic action of aluminum trichloride to obtain 2, 6-dimethyl-4-tert-butyl acetophenone; the method comprises the steps of carrying out nitration reaction on 2, 6-dimethyl-4-tert-butyl acetophenone and nitric acid by using sulfuric acid as a catalyst to obtain a musk ketone crude product, and carrying out neutralization washing, crystallization, centrifugation and other series of separation and purification to obtain a musk ketone product with the concentration of 99%, thereby realizing comprehensive utilization of byproduct resources.)

1. A method for synthesizing ketone musk from a propyl lactone byproduct tert-butyl alcohol-water azeotrope is characterized by comprising the following steps:

step S1, adding the collected by-product tert-butyl alcohol-water azeotrope generated in the production process of the propiolactone into a separating funnel, standing for layering, and separating out the lower layer water to obtain an azeotrope of the tert-butyl alcohol and the water, wherein the content of the tert-butyl alcohol is 80 +/-5%;

step S2, controlling the temperature at 15-25 ℃, starting magnetic stirring, and adding hydrochloric acid into a three-neck flask with a reflux device; dropwise adding the tert-butyl alcohol-water azeotrope obtained in the step S1 into a flask through a peristaltic pump, keeping reflux in the dropwise adding process, controlling the dropwise adding time to be 4-8h, keeping the temperature unchanged after dropwise adding, stirring and refluxing for 30min, transferring the reaction liquid into a separating funnel, standing, and separating out a lower-layer dilute hydrochloric acid aqueous solution to obtain chloro-tert-butane;

s3, controlling the temperature to be-5-0 ℃, starting a magnetic stirrer, adding m-xylene into a three-neck flask with a reflux device, adding aluminum trichloride into the three-neck flask, dropwise adding the chloro-tert-butane obtained in the step S2 into the flask through a peristaltic pump, controlling the reaction temperature to be 10-15 ℃ and the dropwise adding time to be 4-8 hours; after the dropwise addition is finished, keeping the temperature unchanged, stirring for 1h, sampling, carrying out gas chromatography detection, and stopping the reaction when the content of the chloro-tert-butane is below 0.5%; after the reaction is finished, adjusting the pH value to 8 by using a sodium hydroxide solution with the mass fraction of 20%, standing and layering for 1h, separating out a water layer, washing an organic layer for 2-4 times by using deionized water, standing and layering for 1h, separating out the water layer to obtain a 1, 3-dimethyl-5-tert-butyl benzene crude product, and transferring the crude product to a rotary evaporator; starting a rotary evaporator, starting vacuum, heating, distilling under reduced pressure, and collecting distillate to obtain 1, 3-dimethyl-5-tert-butyl benzene;

step S4, after chloroform is added into a four-neck flask with a reflux device, the temperature is controlled to be 40 ℃, aluminum trichloride is added into the four-neck flask, acetyl chloride is dropwise added into the flask through a peristaltic pump, the dropwise adding temperature is controlled to be 40 +/-5 ℃, the dropwise adding time is controlled to be 2-4 hours, the temperature is kept unchanged, 1, 3-dimethyl-5-tert-butyl benzene obtained in the step S3 is dropwise added into the flask, the dropwise adding time is controlled to be 4-8 hours, after the dropwise adding is finished, the reaction is continued for 2 hours under heat preservation and stirring, a dilute hydrochloric acid solution is added into the reaction liquid to terminate the reaction, and the acidification is carried out for 1-2 hours; standing and layering the acidified reaction liquid, separating lower aluminum-containing wastewater, adding a sodium hydroxide solution with the mass fraction of 20% into an organic layer, adjusting the pH value to 7.0-8.5, adding deionized water, washing for 2 times, and transferring to a rotary evaporator; starting a rotary evaporator, distilling at normal pressure to recover the trichloromethane, starting vacuum, raising the temperature and the vacuum degree, and collecting distillate to obtain 2, 6-dimethyl-4-tert-butyl acetophenone;

s5, controlling the temperature to be minus 10 +/-5 ℃, starting a magnetic stirrer, slowly adding concentrated sulfuric acid and nitric acid into a three-neck flask at one time, then dropwise adding the 2, 6-dimethyl-4-tert-butyl acetophenone obtained in the step S4 into the three-neck flask, controlling the reaction temperature to be minus 10 +/-2 ℃, controlling the dropwise adding time to be 4-8h, continuing stirring for 1h after the dropwise adding is finished, standing for layering, and separating a water layer; adding 20% sodium hydroxide solution into the organic layer for neutralization until the pH value is 8, standing for layering for 1h, separating out a water layer, adding deionized water into the organic layer for washing, standing for layering for 1h, and separating out the water layer to obtain a musk ketone crude product;

and S6, adding N, N-dimethylformamide into the flask, starting a magnetic stirrer, adding the crude musk ketone obtained in the step S5 under the stirring condition, dissolving crystals, filtering while the solution is hot, transferring the filtrate into a centrifugal machine, recovering the N, N-dimethylformamide from the separated mother solution to obtain crystals of musk ketone, and drying to obtain the musk ketone.

2. The method for synthesizing musk ketone from a propiolactone by-product tert-butyl alcohol-water azeotrope, as claimed in claim 1, wherein the molar ratio of tert-butyl alcohol to hydrochloric acid in the tert-butyl alcohol-water azeotrope added dropwise in step S2 is 1: 1-5.

3. The method for synthesizing musk ketone from a tertiary butanol-water azeotrope as a by-product of propiolactone according to claim 1, wherein the conditions for collecting 1, 3-dimethyl-5-tert-butylbenzene by reduced pressure distillation in step S3 are as follows: the temperature is 150-; the mol ratio of the m-xylene to the chloro-tert-butane is 1-5: 1, the mass ratio of the aluminum trichloride to the chloro-tert-butane is 0.1-1: 1.

4. the method for synthesizing musk ketone from a propyl lactone by-product tert-butyl alcohol-water azeotrope according to claim 1, wherein the molar ratio of acetyl chloride to 1, 3-dimethyl-5-tert-butyl benzene in step S4 is 1-5: 1; the mass ratio of the trichloromethane to the aluminum trichloride to the 1, 3-dimethyl-5-tert-butyl benzene is 10: 0.1-1: 1, the mass fraction of the dilute hydrochloric acid solution is 7 percent; the mass ratio of the dilute hydrochloric acid solution to the trichloromethane is 1: 10; the conditions for collecting the 2, 6-dimethyl-4-tert-butyl acetophenone by reduced pressure distillation are as follows: the temperature is 107-109 ℃, and the vacuum pressure is 3330 Pa.

5. The method for synthesizing the ketone musk as the propyl lactone byproduct tert-butyl alcohol-water azeotrope, as claimed in claim 1, wherein the concentration of nitric acid in step S5 is 8mol/L, the concentration of concentrated sulfuric acid is 98%, and the molar ratio of nitric acid to 2, 6-dimethyl-4-tert-butyl acetophenone is 1-5: 1, the volume ratio of concentrated sulfuric acid to nitric acid is 0.1: 1-2.5.

Technical Field

The invention belongs to the technical field of synthesis of musk ketone, and particularly relates to a method for synthesizing musk ketone by using a propyl lactone byproduct tert-butyl alcohol-water azeotrope.

Background

The musk ketone is light yellow solid, has elegant and strong musk fragrance, sweet and musk-like animal fragrance, mild fragrance, lasting fragrance and powder fragrance, is widely used in cosmetic essence and soap essence and is mainly used as a fragrance fixative. The musk ketone is one of important nitro musk, can produce powder fragrance when used together with methylionone, cinnamyl alcohol, benzyl salicylate and the like in sweet, oriental and heavy fragrance type essences, and can also be used in a proper amount of 1-5% in perfumed soap essences and 0.2-1.5% in top-grade perfumes, incense powders and cream essences.

The ketone musk is prepared by tert-butyl reaction, acetylation and nitration of m-xylene. When isobutene is used for alkylation, aluminum trichloride is used as a catalyst to generate 1, 3-dimethyl-5-tert-butyl benzene, aluminum trichloride is used as a catalyst for acetylation, ferric trichloride or zinc chloride can also be used, during nitration reaction, nitric acid is firstly cooled, 2, 6-dimethyl-4-tert-butyl acetophenone is added, reaction is carried out at low temperature, a nitration product is washed by water, and an obtained crude product is recrystallized by ethanol to obtain musk ketone.

The propiolactone belongs to a large amount of products in the field of spices, the annual demand is more than 10000 tons, therefore, the byproduct tertiary butanol-water azeotrope of 1500-:

firstly, the waste liquid is sent into a waste liquid incinerator for incineration, the method is adopted for treatment, the load of a pollution treatment facility is increased, resources are wasted, and new pollutants can still be generated after incineration.

And secondly, the valuable units are directly delivered to be used as hazardous wastes for disposal, so that the hazardous waste disposal cost with a high value is generated while the resources are wasted, and the operation cost of an enterprise is increased.

And thirdly, purifying the content of the tertiary butanol in the tertiary butanol-water azeotrope to 95% by adopting a combined separation technology, and then using the purified tertiary butanol-water azeotrope for producing tertiary butyl peroxide, but the separation and purification cost is very high by adopting the method, and the method is not beneficial to industrial application.

Disclosure of Invention

In order to overcome the technical problems, the invention provides a method for synthesizing musk ketone by using a propyl lactone byproduct, namely tertiary butanol-water azeotrope.

The technical problems to be solved by the invention are as follows:

the propiolactone belongs to a large amount of products in the field of spices, and the annual demand is more than 10000 tons, so that a byproduct of tert-butyl alcohol-water azeotrope of 1500-1800 tons can be generated, and new pollutants can be generated by incineration treatment; the qualified units are delivered as hazardous wastes to be treated, so that the operation cost is increased; the combined separation technology is not beneficial to industrial application.

The purpose of the invention can be realized by the following technical scheme:

a method for synthesizing ketone musk from a propyl lactone byproduct tert-butyl alcohol-water azeotrope comprises the following steps:

step S1, adding the collected by-product tert-butyl alcohol-water azeotrope generated in the production process of the propiolactone into a separating funnel, standing for layering, and separating out the lower layer water to obtain an azeotrope of the tert-butyl alcohol and the water, wherein the content of the tert-butyl alcohol is 80 +/-5%;

step S2, controlling the temperature at 15-25 ℃, starting magnetic stirring, and then adding hydrochloric acid into a three-neck flask with a reflux device; slowly dripping the tert-butyl alcohol-water azeotrope obtained in the step S1 into a flask through a peristaltic pump, keeping reflux in the dripping process, controlling the dripping time to be 4-8h, keeping the temperature unchanged after dripping, stirring and refluxing for 30min, transferring the reaction liquid into a separating funnel, standing, and separating out a lower-layer dilute hydrochloric acid aqueous solution to obtain chloro-tert-butane;

s3, controlling the temperature to be-5-0 ℃, starting a magnetic stirrer, adding m-xylene into a three-neck flask with a reflux device, adding aluminum trichloride into the three-neck flask, dropwise adding the chloro-tert-butane obtained in the step S2 into the flask through a peristaltic pump, controlling the reaction temperature to be 10-15 ℃ and the dropwise adding time to be 4-8 hours; after the dropwise addition is finished, keeping the temperature unchanged, stirring for 1h, sampling, carrying out gas chromatography detection, and stopping the reaction when the content of the chloro-tert-butane is below 0.5%; after the reaction is finished, adjusting the pH value to 8 by using a sodium hydroxide solution with the mass fraction of 20%, standing and layering for 1h, separating out a water layer, washing an organic layer for 2-4 times by using deionized water, standing and layering for 1h, separating out the water layer to obtain a 1, 3-dimethyl-5-tert-butyl benzene crude product, and transferring the crude product to a rotary evaporator; starting a rotary evaporator, starting vacuum, heating, distilling under reduced pressure, and collecting distillate to obtain 1, 3-dimethyl-5-tert-butyl benzene;

step S4, starting a cold and hot integrated exchanger, adding trichloromethane into a four-neck flask with a reflux device, controlling the temperature at 40 ℃, adding aluminum trichloride into the four-neck flask, dropwise adding acetyl chloride into the flask through a peristaltic pump, controlling the dropwise adding temperature at 40 +/-5 ℃, controlling the dropwise adding time at 2-4h, keeping the temperature unchanged, dropwise adding the 1, 3-dimethyl-5-tert-butyl benzene obtained in the step S3 into the flask, controlling the dropwise adding time at 4-8h, keeping the temperature and stirring to continue reacting for 2h after the dropwise adding is finished, adding a dilute hydrochloric acid solution into the reaction liquid to terminate the reaction, and acidifying for 1-2 h; standing and layering the acidified reaction liquid, separating lower aluminum-containing wastewater, adding a sodium hydroxide solution with the mass fraction of 20% into an organic layer, adjusting the pH value to 7.0-8.5, adding deionized water, washing for 2 times, and transferring to a rotary evaporator; starting a rotary evaporator, heating, raising the temperature, distilling at normal pressure to recover the trichloromethane, starting vacuum, raising the temperature and the vacuum degree, and collecting distillate to obtain 2, 6-dimethyl-4-tert-butyl acetophenone;

step S5, starting cooling water of a cold and hot integrated exchanger, controlling the temperature to be-10 +/-5 ℃, starting a magnetic stirrer, slowly adding concentrated sulfuric acid and nitric acid into a three-neck flask at one time, then dropwise adding the 2, 6-dimethyl-4-tert-butyl acetophenone obtained in the step S4 into the three-neck flask, controlling the reaction temperature to be-10 +/-2 ℃, controlling the dropwise adding time to be 4-8 hours, after the dropwise adding is finished, continuously stirring for 1 hour, standing for layering, and separating out a water layer; adding 20% sodium hydroxide solution into the organic layer for neutralization until the pH value is 8, standing for layering for 1h, separating out a water layer, adding deionized water into the organic layer for washing, standing for layering for 1h, and separating out the water layer to obtain a musk ketone crude product;

and S6, adding N, N-dimethylformamide into the flask, starting a magnetic stirrer, adding the crude musk ketone obtained in the step S5 under the stirring condition, starting a cold and hot integrated exchanger, dissolving crystals, filtering while hot, transferring the filtrate into a centrifugal machine, recovering the N, N-dimethylformamide from the separated mother liquor to obtain crystals of musk ketone, and drying to obtain the musk ketone.

Further, in step S2, the molar ratio of the tertiary butanol to the hydrochloric acid in the tertiary butanol-water azeotrope is 1: 1-5.

Further, the conditions for collecting 1, 3-dimethyl-5-tert-butylbenzene by distillation under reduced pressure in step S3 are as follows: the temperature is 150-; the mol ratio of the m-xylene to the chloro-tert-butane is 1-5: 1, the mass ratio of the aluminum trichloride to the chloro-tert-butane is 0.1-1: 1.

further, the molar ratio of acetyl chloride to 1, 3-dimethyl-5-tert-butyl benzene in step S4 is 1-5: 1; the mass ratio of the trichloromethane to the aluminum trichloride to the 1, 3-dimethyl-5-tert-butyl benzene is 10: 0.1-1: 1, the mass fraction of the dilute hydrochloric acid solution is 7 percent; the mass ratio of the dilute hydrochloric acid solution to the trichloromethane is 1: 10; the conditions for collecting the 2, 6-dimethyl-4-tert-butyl acetophenone by reduced pressure distillation are as follows: the temperature is 107-109 ℃, and the vacuum pressure is 3330 Pa.

Further, the concentration of the nitric acid in the step S5 is 8mol/L, the concentration of the concentrated sulfuric acid is 98%, and the molar ratio of the nitric acid to the 2, 6-dimethyl-4-tert-butyl acetophenone is 1-5: 1, the volume ratio of concentrated sulfuric acid to nitric acid is 0.1: 1-2.5.

The invention has the beneficial effects that:

in the production process of the propiolactone, di-tert-butyl peroxide is used as an initiator for the addition reaction of acrylic acid and fatty alcohol, the di-tert-butyl peroxide is hydrolyzed to generate a by-product tert-butyl alcohol, a 30% tert-butyl alcohol-water mixture is formed with water generated in the reaction process, the tert-butyl alcohol-water mixture is separated from a reaction system after being condensed by an overhead condenser arranged on a reaction kettle, and an 80% tert-butyl alcohol-water azeotrope is obtained after water diversion operation. Uses tert-butyl alcohol-water azeotrope as initial raw material, and makes it undergo the processes of chlorination, condensation, acetylation and nitration reaction so as to obtain the invented musk ketone.

The invention relates to a method for synthesizing musk ketone by using a propyl lactone byproduct tert-butyl alcohol-water azeotrope, which comprises the steps of taking the tert-butyl alcohol as a by-product in the production process of the propyl lactone as an initial raw material, carrying out chlorination reaction on the tert-butyl alcohol and hydrochloric acid to obtain chloro-tert-butyl alcohol, carrying out condensation reaction on the chloro-tert-butyl alcohol and m-xylene in the presence of aluminum trichloride, and carrying out neutralization washing and distillation to recover the m-xylene to obtain 1, 3-dimethyl-5-tert-butyl benzene; using aluminum trichloride as a catalyst, using trichloromethane as a solvent, carrying out acylation reaction on 1, 3-dimethyl-5-tert-butyl benzene and acetyl chloride to obtain 2, 6-dimethyl-4-tert-butyl acetophenone, then using sulfuric acid as a catalyst, carrying out nitration reaction to obtain a musk ketone crude product, and carrying out a series of separation and purification such as neutralization washing, crystallization, centrifugation and the like to obtain a musk ketone product with the purity of 99%. Reducing the generation of new pollutants; the cost is reduced; is beneficial to industrial application.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A method for synthesizing ketone musk from a propyl lactone byproduct tert-butyl alcohol-water azeotrope comprises the following steps:

step S1, adding the collected by-product tert-butyl alcohol-water azeotrope generated in the production process of the propiolactone into a separating funnel, standing for layering, and separating out the lower layer water to obtain an azeotrope of the tert-butyl alcohol and the water, wherein the content of the tert-butyl alcohol is 80 +/-5%;

step S2, controlling the temperature at 15 ℃, starting magnetic stirring, and adding hydrochloric acid into a three-neck flask with a reflux device; dropwise adding the tert-butyl alcohol-water azeotrope obtained in the step S1 into a flask through a peristaltic pump, keeping reflux in the dropwise adding process, controlling the dropwise adding time to be 4h, keeping the temperature unchanged after dropwise adding, stirring and refluxing for 30min, transferring the reaction liquid into a separating funnel, and standing to separate out a lower-layer dilute hydrochloric acid aqueous solution to obtain chloro-tert-butane;

s3, controlling the temperature to be-5 ℃, starting a magnetic stirrer, adding m-xylene into a three-neck flask with a reflux device, adding aluminum trichloride into the three-neck flask, dropwise adding the chloro-tert-butane obtained in the step S2 into the flask through a peristaltic pump, controlling the reaction temperature to be 10 ℃ and the dropwise adding time to be 4 hours; after the dropwise addition is finished, keeping the temperature unchanged, stirring for 1h, sampling, carrying out gas chromatography detection, and stopping the reaction when the content of the chloro-tert-butane is below 0.5%; after the reaction is finished, adjusting the pH value to 8 by using a sodium hydroxide solution with the mass fraction of 20%, standing and layering for 1h, separating out a water layer, washing an organic layer for 2 times by using deionized water, standing and layering for 1h, separating out the water layer to obtain a 1, 3-dimethyl-5-tert-butyl benzene crude product, and transferring the crude product to a rotary evaporator; starting a rotary evaporator, starting vacuum, heating, distilling under reduced pressure, and collecting distillate to obtain 1, 3-dimethyl-5-tert-butyl benzene;

step S4, after chloroform is added into a four-neck flask with a reflux device, the temperature is controlled to be 40 ℃, aluminum trichloride is added into the four-neck flask, acetyl chloride is dropwise added into the flask through a peristaltic pump, the dropwise adding temperature is controlled to be 40 +/-5 ℃, the dropwise adding time is controlled to be 2 hours, the temperature is kept unchanged, 1, 3-dimethyl-5-tert-butyl benzene obtained in the step S3 is dropwise added into the flask, the dropwise adding time is controlled to be 4 hours, after the dropwise adding is finished, the reaction is continued for 2 hours under heat preservation and stirring, a dilute hydrochloric acid solution is added into the reaction liquid to terminate the reaction, and the reaction is acidified for 1 hour; standing and layering the acidified reaction liquid, separating lower aluminum-containing wastewater, adding a sodium hydroxide solution with the mass fraction of 20% into an organic layer, adjusting the pH value to 7.0, adding deionized water, washing for 2 times, and transferring to a rotary evaporator; starting a rotary evaporator, distilling at normal pressure to recover the trichloromethane, starting vacuum, raising the temperature and the vacuum degree, and collecting distillate to obtain 2, 6-dimethyl-4-tert-butyl acetophenone;

s5, controlling the temperature to be minus 10 +/-5 ℃, starting a magnetic stirrer, slowly adding concentrated sulfuric acid and nitric acid into a three-neck flask at one time, then dropwise adding the 2, 6-dimethyl-4-tert-butyl acetophenone obtained in the step S4 into the three-neck flask, controlling the reaction temperature to be minus 10 +/-2 ℃, controlling the dropwise adding time to be 4 hours, after the dropwise adding is finished, continuously stirring for 1 hour, standing for layering, and separating a water layer; adding 20% sodium hydroxide solution into the organic layer for neutralization until the pH value is 8, standing for layering for 1h, separating out a water layer, adding deionized water into the organic layer for washing, standing for layering for 1h, and separating out the water layer to obtain a musk ketone crude product;

and S6, adding N, N-dimethylformamide into the flask, starting a magnetic stirrer, adding the crude musk ketone obtained in the step S5 under the stirring condition, dissolving crystals, filtering while the solution is hot, transferring the filtrate into a centrifugal machine, recovering the N, N-dimethylformamide from the separated mother solution to obtain crystals of musk ketone, and drying to obtain the musk ketone. The purity of the musk ketone was 99%.

Wherein, in the step S2, the molar ratio of the tertiary butanol to the hydrochloric acid in the tertiary butanol-water azeotrope is 1: 1.

wherein the conditions for collecting 1, 3-dimethyl-5-tert-butylbenzene by vacuum distillation in step S3 are as follows: the temperature is 150-; the mol ratio of the m-xylene to the chloro-tert-butane is 1: 1, the mass ratio of the aluminum trichloride to the chloro-tert-butane is 0.1: 1.

wherein, in the step S4, the molar ratio of acetyl chloride to 1, 3-dimethyl-5-tert-butyl benzene is 1: 1; the mass ratio of the trichloromethane to the aluminum trichloride to the 1, 3-dimethyl-5-tert-butyl benzene is 10: 0.1: 1, the mass fraction of the dilute hydrochloric acid solution is 7 percent; the mass ratio of the dilute hydrochloric acid solution to the trichloromethane is 1: 10; the conditions for collecting the 2, 6-dimethyl-4-tert-butyl acetophenone by reduced pressure distillation are as follows: the temperature is 107-109 ℃, and the vacuum pressure is 3330 Pa.

Wherein the concentration of the nitric acid in the step S5 is 8mol/L, the concentration of the concentrated sulfuric acid is 98%, and the molar ratio of the nitric acid to the 2, 6-dimethyl-4-tert-butyl acetophenone is 1: 1, the volume ratio of concentrated sulfuric acid to nitric acid is 0.1: 1.

example 2

A method for synthesizing ketone musk from a propyl lactone byproduct tert-butyl alcohol-water azeotrope comprises the following steps:

step S1, adding the collected by-product tert-butyl alcohol-water azeotrope generated in the production process of the propiolactone into a separating funnel, standing for layering, and separating out the lower layer water to obtain an azeotrope of the tert-butyl alcohol and the water, wherein the content of the tert-butyl alcohol is 80 +/-5%;

step S2, controlling the temperature at 20 ℃, starting magnetic stirring, and adding hydrochloric acid into a three-neck flask with a reflux device; dropwise adding the tert-butyl alcohol-water azeotrope obtained in the step S1 into a flask through a peristaltic pump, keeping reflux in the dropwise adding process, controlling the dropwise adding time to be 6h, keeping the temperature unchanged after dropwise adding, stirring and refluxing for 30min, transferring the reaction liquid into a separating funnel, and standing to separate out a lower-layer dilute hydrochloric acid aqueous solution to obtain chloro-tert-butane;

s3, controlling the temperature to be-2 ℃, starting a magnetic stirrer, adding m-xylene into a three-neck flask with a reflux device, adding aluminum trichloride into the three-neck flask, dropwise adding the chloro-tert-butane obtained in the step S2 into the flask through a peristaltic pump, controlling the reaction temperature to be 12 ℃ and controlling the dropwise adding time to be 6 hours; after the dropwise addition is finished, keeping the temperature unchanged, stirring for 1h, sampling, carrying out gas chromatography detection, and stopping the reaction when the content of the chloro-tert-butane is below 0.5%; after the reaction is finished, adjusting the pH value to 8 by using a sodium hydroxide solution with the mass fraction of 20%, standing and layering for 1h, separating out a water layer, washing an organic layer for 3 times by using deionized water, standing and layering for 1h, separating out the water layer to obtain a 1, 3-dimethyl-5-tert-butyl benzene crude product, and transferring the crude product to a rotary evaporator; starting a rotary evaporator, starting vacuum, heating, distilling under reduced pressure, and collecting distillate to obtain 1, 3-dimethyl-5-tert-butyl benzene;

step S4, after chloroform is added into a four-neck flask with a reflux device, the temperature is controlled to be 40 ℃, aluminum trichloride is added into the four-neck flask, acetyl chloride is dropwise added into the flask through a peristaltic pump, the dropwise adding temperature is controlled to be 40 +/-5 ℃, the dropwise adding time is controlled to be 3 hours, the temperature is kept unchanged, 1, 3-dimethyl-5-tert-butyl benzene obtained in the step S3 is dropwise added into the flask, the dropwise adding time is controlled to be 6 hours, after the dropwise adding is finished, the reaction is continued for 2 hours under heat preservation and stirring, a dilute hydrochloric acid solution is added into the reaction liquid to terminate the reaction, and the acidification is carried out for 1.5 hours; standing and layering the acidified reaction liquid, separating lower aluminum-containing wastewater, adding a sodium hydroxide solution with the mass fraction of 20% into an organic layer, adjusting the pH value to 8, adding deionized water, washing for 2 times, and transferring to a rotary evaporator; starting a rotary evaporator, distilling at normal pressure to recover the trichloromethane, starting vacuum, raising the temperature and the vacuum degree, and collecting distillate to obtain 2, 6-dimethyl-4-tert-butyl acetophenone;

s5, controlling the temperature to be minus 10 +/-5 ℃, starting a magnetic stirrer, slowly adding concentrated sulfuric acid and nitric acid into a three-neck flask at one time, then dropwise adding the 2, 6-dimethyl-4-tert-butyl acetophenone obtained in the step S4 into the three-neck flask, controlling the reaction temperature to be minus 10 +/-2 ℃, controlling the dropwise adding time to be 6 hours, after the dropwise adding is finished, continuously stirring for 1 hour, standing for layering, and separating a water layer; adding 20% sodium hydroxide solution into the organic layer for neutralization until the pH value is 8, standing for layering for 1h, separating out a water layer, adding deionized water into the organic layer for washing, standing for layering for 1h, and separating out the water layer to obtain a musk ketone crude product;

and S6, adding N, N-dimethylformamide into the flask, starting a magnetic stirrer, adding the crude musk ketone obtained in the step S5 under the stirring condition, dissolving crystals, filtering while the solution is hot, transferring the filtrate into a centrifugal machine, recovering the N, N-dimethylformamide from the separated mother solution to obtain crystals of musk ketone, and drying to obtain the musk ketone. The purity of the musk ketone was 99%.

Wherein, in the step S2, the molar ratio of the tertiary butanol to the hydrochloric acid in the tertiary butanol-water azeotrope is 1: 2.

wherein the conditions for collecting 1, 3-dimethyl-5-tert-butylbenzene by vacuum distillation in step S3 are as follows: the temperature is 152 ℃, and the vacuum pressure is 4000 Pa; the mol ratio of the m-xylene to the chloro-tert-butane is 3: 1, the mass ratio of the aluminum trichloride to the chloro-tert-butane is 0.6: 1.

wherein, in the step S4, the molar ratio of acetyl chloride to 1, 3-dimethyl-5-tert-butyl benzene is 1-5: 1; the mass ratio of the trichloromethane to the aluminum trichloride to the 1, 3-dimethyl-5-tert-butyl benzene is 10: 0.6: 1, the mass fraction of the dilute hydrochloric acid solution is 7 percent; the mass ratio of the dilute hydrochloric acid solution to the trichloromethane is 1: 10; the conditions for collecting the 2, 6-dimethyl-4-tert-butyl acetophenone by reduced pressure distillation are as follows: the temperature is 107-109 ℃, and the vacuum pressure is 3330 Pa.

Wherein the concentration of the nitric acid in the step S5 is 8mol/L, the concentration of the concentrated sulfuric acid is 98%, and the molar ratio of the nitric acid to the 2, 6-dimethyl-4-tert-butyl acetophenone is 1: 3, the volume ratio of concentrated sulfuric acid to nitric acid is 0.1: 1.8.

example 3

A method for synthesizing ketone musk from a propyl lactone byproduct tert-butyl alcohol-water azeotrope comprises the following steps:

step S1, adding the collected by-product tert-butyl alcohol-water azeotrope generated in the production process of the propiolactone into a separating funnel, standing for layering, and separating out the lower layer water to obtain an azeotrope of the tert-butyl alcohol and the water, wherein the content of the tert-butyl alcohol is 80 +/-5%;

step S2, controlling the temperature at 25 ℃, starting magnetic stirring, and adding hydrochloric acid into a three-neck flask with a reflux device; dropwise adding the tert-butyl alcohol-water azeotrope obtained in the step S1 into a flask through a peristaltic pump, keeping reflux in the dropwise adding process, controlling the dropwise adding time to be 8h, keeping the temperature unchanged after dropwise adding, stirring and refluxing for 30min, transferring the reaction liquid into a separating funnel, and standing to separate out a lower-layer dilute hydrochloric acid aqueous solution to obtain chloro-tert-butane;

s3, controlling the temperature to be 0 ℃, starting a magnetic stirrer, adding m-xylene into a three-neck flask with a reflux device, adding aluminum trichloride into the three-neck flask, dropwise adding the chloro-tert-butane obtained in the step S2 into the flask through a peristaltic pump, controlling the reaction temperature to be 15 ℃ and controlling the dropwise adding time to be 8 hours; after the dropwise addition is finished, keeping the temperature unchanged, stirring for 1h, sampling, carrying out gas chromatography detection, and stopping the reaction when the content of the chloro-tert-butane is below 0.5%; after the reaction is finished, adjusting the pH value to 8 by using a sodium hydroxide solution with the mass fraction of 20%, standing and layering for 1h, separating out a water layer, washing an organic layer for 4 times by using deionized water, standing and layering for 1h, separating out the water layer to obtain a 1, 3-dimethyl-5-tert-butyl benzene crude product, and transferring the crude product to a rotary evaporator; starting a rotary evaporator, starting vacuum, heating, distilling under reduced pressure, and collecting distillate to obtain 1, 3-dimethyl-5-tert-butyl benzene;

step S4, after chloroform is added into a four-neck flask with a reflux device, the temperature is controlled to be 40 ℃, aluminum trichloride is added into the four-neck flask, acetyl chloride is dropwise added into the flask through a peristaltic pump, the dropwise adding temperature is controlled to be 40 +/-5 ℃, the dropwise adding time is controlled to be 4 hours, the temperature is kept unchanged, 1, 3-dimethyl-5-tert-butyl benzene obtained in the step S3 is dropwise added into the flask, the dropwise adding time is controlled to be 8 hours, after the dropwise adding is finished, the reaction is continued for 2 hours under heat preservation and stirring, a dilute hydrochloric acid solution is added into the reaction liquid to terminate the reaction, and the reaction is acidified for 2 hours; standing and layering the acidified reaction liquid, separating lower aluminum-containing wastewater, adding a sodium hydroxide solution with the mass fraction of 20% into an organic layer, adjusting the pH value to 8.5, adding deionized water, washing for 2 times, and transferring to a rotary evaporator; starting a rotary evaporator, distilling at normal pressure to recover the trichloromethane, starting vacuum, raising the temperature and the vacuum degree, and collecting distillate to obtain 2, 6-dimethyl-4-tert-butyl acetophenone;

s5, controlling the temperature to be minus 10 +/-5 ℃, starting a magnetic stirrer, slowly adding concentrated sulfuric acid and nitric acid into a three-neck flask at one time, then dropwise adding the 2, 6-dimethyl-4-tert-butyl acetophenone obtained in the step S4 into the three-neck flask, controlling the reaction temperature to be minus 10 +/-2 ℃, controlling the dropwise adding time to be 8 hours, after the dropwise adding is finished, continuously stirring for 1 hour, standing for layering, and separating a water layer; adding 20% sodium hydroxide solution into the organic layer for neutralization until the pH value is 8, standing for layering for 1h, separating out a water layer, adding deionized water into the organic layer for washing, standing for layering for 1h, and separating out the water layer to obtain a musk ketone crude product;

and S6, adding N, N-dimethylformamide into the flask, starting a magnetic stirrer, adding the crude musk ketone obtained in the step S5 under the stirring condition, dissolving crystals, filtering while the solution is hot, transferring the filtrate into a centrifugal machine, recovering the N, N-dimethylformamide from the separated mother solution to obtain crystals of musk ketone, and drying to obtain the musk ketone. The purity of the musk ketone was 99%.

Wherein, in the step S2, the molar ratio of the tertiary butanol to the hydrochloric acid in the tertiary butanol-water azeotrope is 1: 5.

wherein the conditions for collecting 1, 3-dimethyl-5-tert-butylbenzene by vacuum distillation in step S3 are as follows: the temperature is 150-; the mol ratio of the m-xylene to the chloro-tert-butane is 5: 1, the mass ratio of the aluminum trichloride to the chloro-tert-butane is 1: 1.

wherein, in the step S4, the molar ratio of acetyl chloride to 1, 3-dimethyl-5-tert-butyl benzene is 1-5: 1; the mass ratio of the trichloromethane to the aluminum trichloride to the 1, 3-dimethyl-5-tert-butyl benzene is 10: 1: 1, the mass fraction of the dilute hydrochloric acid solution is 7 percent; the mass ratio of the dilute hydrochloric acid solution to the trichloromethane is 1: 10; the conditions for collecting the 2, 6-dimethyl-4-tert-butyl acetophenone by reduced pressure distillation are as follows: the temperature was 109 ℃ and the vacuum pressure was 3330 Pa.

Wherein the concentration of the nitric acid in the step S5 is 8mol/L, the concentration of the concentrated sulfuric acid is 98%, and the molar ratio of the nitric acid to the 2, 6-dimethyl-4-tert-butyl acetophenone is 1: 5, the volume ratio of concentrated sulfuric acid to nitric acid is 0.1: 2.5.

in the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.