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CN-121974878-A - Preparation method of sclareolide and catalyst

CN121974878ACN 121974878 ACN121974878 ACN 121974878ACN-121974878-A

Abstract

The invention provides a preparation method of sclareolide and a catalyst, belonging to the technical field of organic catalysis. Dissolving sclareol with a first solvent, adding a catalyst, regulating the pH value of the solution under a microwave condition, dropwise adding hydrogen peroxide, heating and stirring for reaction, separating the catalyst, repeatedly using, extracting the product with a second solvent, and heating and refluxing to obtain sclareolide, wherein the catalyst is imidazolyl ionic liquid/polyethylene glycol/maleic acid modified graphene oxide loaded with the absent heteropolyacid salt. The preparation method of sclareolide adopts microwave-assisted reaction, so that the yield of sclareolide products is greatly improved. The reaction system adopts two mutually compatible reaction systems of alcohol and water, so that the environmental protection of the process is greatly improved, and meanwhile, under the action of the catalyst, the catalyst has the effect of phase catalytic transfer, the reaction efficiency is improved, the reaction condition is mild, the product yield is high, and the application prospect is wide.

Inventors

  • LIAO XINGRONG
  • WANG BOGUO
  • CHEN HONGYI
  • WANG SIJIE
  • GUO XIANGLIN
  • SHI HAILIN

Assignees

  • 绵阳市斯麦尔顾生物科技有限公司

Dates

Publication Date
20260505
Application Date
20251118

Claims (10)

  1. 1. A preparation method of sclareolide is characterized by dissolving sclareolide with a first solvent, adding a catalyst, regulating the pH value of the solution under a microwave condition, dropwise adding hydrogen peroxide, heating and stirring for reaction, separating the catalyst, repeatedly using, extracting the product with a second solvent, and heating and refluxing to obtain sclareolide, wherein the catalyst is imidazolyl ionic liquid/polyethylene glycol/maleic acid modified graphene oxide loaded with an absent heteropolyacid salt.
  2. 2. The preparation method of claim 1, wherein the first solvent is ethanol or methanol, the second solvent is toluene, the molar volume of sclareol and hydrogen peroxide is 1mol:250-300mL, the addition amount of the catalyst is 2-4wt% of sclareol, the temperature of the heating and stirring reaction is 55-65 ℃ for 0.5-1.5h, the heating and refluxing time is 0.5-1.5h, the power of microwaves is 200-400W, and the pH value of the regulating solution is 2-2.5.
  3. 3. The preparation method according to claim 1, wherein the preparation method of the catalyst is as follows: S1, adding graphene oxide into N, N-dimethylformamide, adding maleic anhydride, heating, stirring, reacting, centrifuging, washing, and drying to obtain modified graphene oxide; s2, adding the modified graphene oxide and polyethylene glycol into toluene, adding a catalyst, heating, refluxing, stirring, reacting, filtering, washing and drying to obtain polyethylene glycol/maleic acid modified graphene oxide; S3, adding the imidazolyl ionic liquid with double bonds and the polyethylene glycol/maleic acid modified graphene oxide into a solvent, adding an initiator under the protection of inert gas, heating, stirring, reacting, filtering, washing and drying to obtain the imidazolyl ionic liquid/polyethylene glycol/maleic acid modified graphene oxide; s4, dissolving phosphotungstic acid in water, regulating the pH value of the solution, heating and stirring for reaction, removing the solvent under reduced pressure, and drying to obtain the absent heteropolyacid salt; S5, dissolving the absent heteropolyacid salt in water, adding imidazolyl ionic liquid/polyethylene glycol/maleic acid modified graphene oxide, heating, stirring, reacting, filtering, washing and drying to obtain the catalyst.
  4. 4. The preparation method according to claim 3, wherein the mass ratio of graphene oxide to maleic anhydride in the step S1 is 1-3:10-15, the temperature of the heating and stirring reaction is 80-90 ℃ and the time is 1-2h.
  5. 5. The preparation method of claim 3, wherein in the step S2, the mass ratio of the modified graphene oxide to the polyethylene glycol to the catalyst is 10:3-5:0.5-1, the catalyst is concentrated sulfuric acid or p-toluenesulfonic acid, the polyethylene glycol is polyethylene glycol 400, polyethylene glycol 600 or polyethylene glycol 1000, and the heating reflux stirring reaction time is 5-7h.
  6. 6. The preparation method according to claim 3, wherein in the step S3, the mass ratio of the imidazolyl ionic liquid with double bonds, the polyethylene glycol/maleic acid modified graphene oxide and the initiator is 3-4:10-12:0.1-0.15, the imidazolyl ionic liquid with double bonds is at least one selected from 1-vinyl-3-butylimidazole chloride salt, 1-vinyl-3-benzylimidazole chloride salt and 1-allyl-3-methylimidazole chloride, the temperature of the heating and stirring reaction is 60-70 ℃ and the time is 3-5h, and the initiator is at least one selected from ammonium persulfate, potassium persulfate and sodium persulfate.
  7. 7. The method according to claim 3, wherein the pH of the solution is adjusted to 5-5.5 in the step S4, the temperature of the heating and stirring reaction is 55-65 ℃ and the time is 2-4 hours.
  8. 8. The preparation method according to claim 3, wherein the mass ratio of the short-site heteropolyacid salt to the imidazolyl ionic liquid/the polyethylene glycol/the maleic acid modified graphene oxide in the step S5 is 2-5:8-12, the temperature of the heating and stirring reaction is 55-65 ℃ and the time is 20-50min.
  9. 9. A catalyst for use in the production process according to claim 1, characterized in that the production process comprises the steps of: s1, adding 1-3 parts by weight of graphene oxide into N, N-dimethylformamide, adding 10-15 parts by weight of maleic anhydride, heating to 80-90 ℃, stirring and reacting for 1-2 hours, centrifuging, washing and drying to obtain modified graphene oxide; S2, adding 10 parts by weight of modified graphene oxide and 3-5 parts by weight of polyethylene glycol into toluene, adding 0.5-1 parts by weight of concentrated sulfuric acid or p-toluenesulfonic acid, heating, refluxing, stirring, reacting for 5-7 hours, filtering, washing and drying to obtain polyethylene glycol/maleic acid modified graphene oxide; S3, adding 3-4 parts by weight of imidazolyl ionic liquid with double bonds and 10-12 parts by weight of polyethylene glycol/maleic acid modified graphene oxide into a solvent, adding 0.1-0.15 part by weight of an initiator under the protection of inert gas, heating to 60-70 ℃, stirring and reacting for 3-5 hours, filtering, washing and drying to obtain imidazolyl ionic liquid/polyethylene glycol/maleic acid modified graphene oxide; S4, dissolving phosphotungstic acid in water, regulating the pH value of the solution to be 5-5.5, heating to 55-65 ℃, stirring and reacting for 2-4 hours, removing the solvent under reduced pressure, and drying to obtain the absent heteropolyacid salt; S5, dissolving 2-5 parts by weight of the absent heteropolyacid salt in water, adding 8-12 parts by weight of imidazolyl ionic liquid/polyethylene glycol/maleic acid modified graphene oxide, heating to 55-65 ℃, stirring and reacting for 20-50min, filtering, washing and drying to obtain the catalyst.
  10. 10. Use of the catalyst prepared by the preparation method of claim 9 in hydrogen peroxide catalytic oxidation reaction.

Description

Preparation method of sclareolide and catalyst Technical Field The invention relates to the technical field of organic catalysis, in particular to a preparation method of sclareolide and a catalyst. Background Sclareol is a raw material for a series of artificial synthetic fragrances such as sclareolide, is also an important raw material for synthesizing a number of compounds with important pharmacological activities, and has important applications in the fragrance industry, pharmacy and food additives. Currently, sclareolide is obtained mainly by chemical methods, such as a series of redox reactions using sclareol as a substrate, or by extraction from SALVIA SCLAREA flowers. The traditional method used in the chemical synthesis at present is a chromic anhydride oxidation method, namely, sclareol is oxidized by chromic anhydride for synthesis, the process operation is easy, but the yield is lower, in addition, the chromium-containing wastewater generated in the production process has great environmental pollution, and the method is basically not adopted. Ozonization methods developed by swiss Fenmeiyi corporation have harsh reaction conditions, expensive reagents, and carry many hazards, and are not suitable for modern production. While the currently developed methods such as sodium periodate and osmium tetroxide are used for oxidizing sclareol in tetrahydrofuran, the potassium permanganate two-part oxidation method of Reynolds company in U.S. and the low-temperature oxidation process of potassium permanganate developed by Shanghai flavor in China are all used for oxidizing sclareol by chemical reagents to obtain sclareolide. However, the use of sclareolide is greatly limited by the residual and poor stereoselectivity of these chemicals. Therefore, the development of a high-efficiency catalyst to improve the production process of sclareolide has attracted great attention from researchers. Disclosure of Invention The invention aims to provide a preparation method of sclareolide and a catalyst, which adopt microwave-assisted reaction to greatly improve the product yield of sclareolide. The reaction system adopts two mutually compatible reaction systems of alcohol and water, so that the environmental protection of the process is greatly improved, and meanwhile, under the action of the catalyst, the catalyst has the effect of phase catalytic transfer, the reaction efficiency is improved, the reaction condition is mild, the product yield is high, and the application prospect is wide. The technical scheme of the invention is realized as follows: The invention provides a preparation method of sclareolide, which comprises the steps of dissolving sclareolide with a first solvent, adding a catalyst, regulating the pH value of the solution under a microwave condition, dropwise adding hydrogen peroxide, heating and stirring for reaction, separating the catalyst, repeatedly using, extracting the product with a second solvent, and heating and refluxing to obtain sclareolide, wherein the catalyst is imidazolyl ionic liquid/polyethylene glycol/maleic acid modified graphene oxide loaded with absent heteropolyacid salt. The invention is further improved, wherein the first solvent is ethanol or methanol, the second solvent is toluene, the mole of sclareol and hydrogen peroxide is 1mol:250-300mL, the addition amount of the catalyst is 2-4wt% of sclareol, the temperature of the heating and stirring reaction is 55-65 ℃ for 0.5-1.5h, the heating and refluxing time is 0.5-1.5h, the power of microwaves is 200-400W, and the pH value of the regulating solution is 2-2.5. As a further improvement of the present invention, the catalyst is prepared as follows: S1, adding graphene oxide into N, N-dimethylformamide, adding maleic anhydride, heating, stirring, reacting, centrifuging, washing, and drying to obtain modified graphene oxide; s2, adding the modified graphene oxide and polyethylene glycol into toluene, adding a catalyst, heating, refluxing, stirring, reacting, filtering, washing and drying to obtain polyethylene glycol/maleic acid modified graphene oxide; S3, adding the imidazolyl ionic liquid with double bonds and the polyethylene glycol/maleic acid modified graphene oxide into a solvent, adding an initiator under the protection of inert gas, heating, stirring, reacting, filtering, washing and drying to obtain the imidazolyl ionic liquid/polyethylene glycol/maleic acid modified graphene oxide; s4, dissolving phosphotungstic acid in water, regulating the pH value of the solution, heating and stirring for reaction, removing the solvent under reduced pressure, and drying to obtain the absent heteropolyacid salt; S5, dissolving the absent heteropolyacid salt in water, adding imidazolyl ionic liquid/polyethylene glycol/maleic acid modified graphene oxide, heating, stirring, reacting, filtering, washing and drying to obtain the catalyst. As a further improvement of the invention, the mass ratio of graphene oxide to maleic anhydride in