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CN-121990884-A - Vanilla alcohol ether and preparation method thereof

CN121990884ACN 121990884 ACN121990884 ACN 121990884ACN-121990884-A

Abstract

The invention discloses a vanillyl alcohol ether and a preparation method thereof, wherein the preparation method comprises the following steps of (1) taking vanillin or ethyl vanillin and hydrogen as reactants, taking alcohols or Ethyl Acetate (EA) as solvents, preparing reactant solution, adding Raney nickel catalyst as catalyst, reacting at 40-70 ℃, reacting at 2-3MPa for 8-10h. (2) The vanillyl alcohol or the ethyl vanillyl alcohol and the second alcohol are used as reactants, lewis acid is used as a catalyst (such as Lewis acid of magnesium chloride, aluminum chloride, calcium chloride, ferric chloride, copper sulfate and the like), the reaction temperature is 80-100 ℃, and the vanillyl alcohol ether is obtained by reaction.

Inventors

  • TANG XUCHONG
  • WANG PEIQUAN
  • XIONG JIE

Assignees

  • 八叶草健康产业研究院(厦门)有限公司
  • 厦门八叶草生物医药有限公司

Dates

Publication Date
20260508
Application Date
20251218

Claims (9)

  1. 1. The preparation method of the vanillyl alcohol ether is characterized by comprising the following steps: (1) Adding vanillin or ethyl vanillin and Raney nickel catalyst into alcohol solvent or ethyl acetate solvent, and reacting for 8-10h under the condition of hydrogen pressure of 2-3MPa and 40-70 ℃ to obtain vanillin or ethyl vanillin; (2) Reacting vanillyl alcohol or ethyl vanillyl alcohol with a second alcohol at 80-100 ℃ for 12-18h under the catalysis of Lewis acid to obtain the vanillyl alcohol ether; Wherein the mass ratio of the vanillyl alcohol or the ethyl vanillyl alcohol to the second glycol is 1:1.5-5, and the second glycol is C1-C6 unit alcohol.
  2. 2. The method of claim 1, wherein the concentration of vanillin or ethyl vanillin in step (1) is 0.2-0.5wt%.
  3. 3. The preparation method according to claim 1, wherein the mass ratio of the vanillin or ethyl vanillin to the raney nickel catalyst is 1:0.1-0.05.
  4. 4. The method of claim 1, wherein the lewis acid is selected from at least one of magnesium chloride, aluminum chloride, calcium chloride, ferric chloride, and cupric sulfate.
  5. 5. The process according to claim 1 or 4, wherein the molar ratio of said vanillyl alcohol or said ethyl vanillyl alcohol to said lewis acid is from 1:0.05 to 0.5.
  6. 6. The process of claim 1, wherein step (1) further comprises the steps of removing the Raney nickel catalyst by filtration after the completion of the reaction, followed by sequential rotary evaporation and recrystallization, and finally filtering to obtain a white solid, which is vanillyl alcohol or ethyl vanillyl alcohol.
  7. 7. The method of claim 1, wherein the alcoholic solvent is a C1-C6 monohydric alcohol.
  8. 8. The method of claim 1, wherein the alcoholic solvent is the same as the second alcohol.
  9. 9. A vanillyl alcohol ether, characterized in that it is obtainable by a process according to any one of claims 1 to 8.

Description

Vanilla alcohol ether and preparation method thereof Technical Field The invention belongs to the field of organic chemical synthesis, and particularly relates to vanillyl alcohol ether and a preparation method thereof. Background The vanillyl alcohol ether is also called as capsicum ether, has strong fragrance and smell, and is widely used for essence and spice. The vanillyl butyl ether in the vanillyl alcohol ether is an oil-soluble heat sensing agent, can generate mild and durable heat sensing after being acted on skin, can effectively stimulate subcutaneous fat metabolism and promote blood circulation, and is a safe and stable cosmetic additive with pleasant vanilla taste and certain metabolism promoting effect. The methyldantiglishi in the vanillyl alcohol ether is more and more favored in the cosmetic industry at present, and particularly the vanillyl butyl ether is most widely applied in the fields of foods, cosmetics and the like. CN109942382B provides a method for preparing vanillyl alcohol ether, which uses vanillin as raw material and sodium borohydride as reducing agent, and has the advantages of rapid reaction, mild condition and simple operation, but due to the use of metal complex hydride as reducing agent, byproducts may be generated, and further post-treatment is needed. CN108658734a uses vanillyl alcohol and n-butanol as raw materials, and anhydrous sodium sulfate as catalyst to make stage heating reaction, and it needs long-time step-by-step feeding reaction and after-treatment is complex. CN101165038a employs vanillyl alcohol to react with ethanol under reflux conditions and cation exchange resin or concentrated sulfuric acid as catalyst, the yield is only 70.1% and strong acid catalyst may corrode equipment. Disclosure of Invention The invention aims to provide a vanillyl alcohol ether and a preparation method thereof, and the preparation method has the advantages of simple operation, mild condition and high yield. The technical scheme of the invention is as follows: a preparation method of vanillyl alcohol ether comprises the following steps: (1) Adding vanillin or ethyl vanillin and Raney nickel catalyst into alcohol solvent or ethyl acetate solvent, and reacting for 8-10h under the condition of hydrogen pressure of 2-3MPa and 40-70 ℃ to obtain vanillin or ethyl vanillin; (2) Reacting vanillyl alcohol or ethyl vanillyl alcohol with a second alcohol at 80-100 ℃ for 12-18h under the catalysis of Lewis acid to obtain vanillyl alcohol ether; Wherein the mass ratio of the vanillyl alcohol or the ethyl vanillyl alcohol to the glycol is 1:1.5-5, and the glycol is C1-C6 unit alcohol. In some preferred embodiments, the concentration of vanillin or ethyl vanillin in step (1) is 0.2-0.5wt%. In some preferred embodiments, the mass ratio of vanillin or ethyl vanillin to Raney nickel catalyst is 1:0.1-0.05. In some preferred embodiments, the lewis acid is selected from at least one of magnesium chloride, aluminum chloride, calcium chloride, ferric chloride, and copper sulfate. In some preferred embodiments, the molar ratio of vanillyl alcohol or ethyl vanillyl alcohol to lewis acid is 1:0.05-0.5. In some preferred embodiments, step (1) further comprises the operation of removing the Raney nickel catalyst by filtration after completion of the reaction, followed by sequential spin-steaming and recrystallisation, and finally filtration to give a white solid, either vanillyl alcohol or ethyl vanillyl alcohol. In some preferred embodiments, the alcoholic solvent is a C1-C6 monohydric alcohol. In some preferred embodiments, the alcoholic solvent is the same as the second alcohol. The vanillyl alcohol ether is prepared by the preparation method. The invention has at least the following beneficial effects: (1) The invention adopts a two-step method for synthesis, the step (1) adopts ethyl acetate or alcohol solvent, wherein the ethyl acetate solvent can avoid acetal byproducts, and the step (2) adopts solvent-free Lewis acid catalytic etherification, thereby being capable of reducing the cost of raw materials, being environment-friendly and having higher yield and being beneficial to industrial application. (2) In some preferred embodiments the alcoholic solvent used is the same as the substrate second alcohol of step (2), further reducing possible impurities. Drawings FIG. 1 is a 1 HNMR diagram of vanillyl alcohol prepared in example 1; FIG. 2 is a 1 HNMR diagram of vanillyl methyl ether prepared in example 1; FIG. 3 is a 1 HNMR diagram of ethyl vanillyl alcohol prepared in example 2; FIG. 4 is a 1 HNMR diagram of methyldantirater prepared in example 2; FIG. 5 is a 1 HNMR diagram of vanillyl diethyl ether prepared in example 3; FIG. 6 is a 1 HNMR diagram of vanillyl propyl ether prepared in example 4; FIG. 7 is a 1 HNMR diagram of the vanillyl butyl ether prepared in example 5; FIG. 8 is a 1 HNMR diagram of the vanillyl amyl ether prepared in example 6; FIG. 9 is a 1 HNMR diagram of the vanillyl hexyl eth