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CN-122010669-A - Preparation method of (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -alkene

CN122010669ACN 122010669 ACN122010669 ACN 122010669ACN-122010669-A

Abstract

The invention provides a preparation method of (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -alkene, belonging to the technical field of organic synthesis. The invention mixes (1R, 2S,8R, 11R) -7-methylene-3,3,11-trimethyl tricyclo [6.3.0.02.4] undecane with a catalyst, and carries out isomerization reaction under the condition of hydrogen and pressurization to obtain (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -alkene. The invention adopts chemical synthesis method to prepare, solves the problem that the target product can only be extracted from natural plants, and has the advantages of environment protection, high efficiency and no industrial three wastes.

Inventors

  • MAO JIANMING

Assignees

  • 茅健明

Dates

Publication Date
20260512
Application Date
20260202

Claims (9)

  1. 1. A method for preparing (2 s,4r,7r,8 r) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -ene, comprising the steps of: (1R, 2S,8R, 11R) -7-methylene-3,3,11-trimethyl tricyclo [6.3.0.02.4] undecane is mixed with a catalyst, and isomerization reaction is carried out under the condition of hydrogen and pressurization to obtain (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -alkene.
  2. 2. The method of claim 1, wherein the catalyst comprises one or more of a ruthenium/alumina catalyst, a palladium/silica catalyst, and a palladium carbon catalyst.
  3. 3. The preparation method according to claim 2, wherein the mass content of ruthenium in the ruthenium/alumina catalyst is 3-6%, and the mass content of palladium in the palladium/silica catalyst is 3-6%.
  4. 4. The preparation method according to claim 1 or 2, wherein the mass ratio of (1 r,2s,8r,11 r) -7-methylene-3,3,11-trimethyltricyclo [6.3.0.02.4] undecane to the catalyst is 100:1.2-1.8.
  5. 5. The method according to claim 1, wherein the isomerization reaction temperature is 145 to 170 ℃.
  6. 6. The method according to claim 1 or 5, wherein the pressure of the isomerization reaction is 0.5 to 0.7mpa.
  7. 7. The method according to claim 1 or 5, wherein the isomerization reaction time is 8 to 12 hours.
  8. 8. The method of claim 1, further comprising, after the isomerization reaction, post-treating the resulting isomerization reaction product, the post-treatment comprising the steps of: And (3) carrying out solid-liquid separation on the isomerization reaction product, and carrying out vacuum fractionation on the obtained liquid phase.
  9. 9. The process according to claim 8, wherein the vacuum degree of the vacuum fractionation is 3 mmhg, and the fraction having a top temperature of 76 to 77 ℃ is heated and collected.

Description

Preparation method of (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -alkene Technical Field The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -ene. Background (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -ene exists in natural plant volatile oil, and the substance has a unique methyl cyclic terpene structure, and the S phase progress of keratinocytes is prolonged by regulating the crosstalk work of epidermal stem cells Notch and Wnt/beta-catenin transmembrane signal channels, so that the promotion of the reconstruction rate of collagen fibers is promoted. According to the report of the International journal 'Natural product research', the superoxide dismutase has important biochemical functions, can promote the catalytic activity index of the superoxide dismutase, directly target and clear HO-free radical chain reaction, can form a stable quinone structure body, and can inhibit mitochondrial membrane potential unbalance. The existing (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -alkene can only be extracted from plants, no artificial synthetic cases are reported in the literature at present, The content of (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -ene in the natural vegetable oil is limited, and only accounts for 0.2-0.3% of the effective components of the volatile oil, and the natural vegetable oil mainly comes from the vegetable volatile oil or the resin. There are two main extraction methods at present, one is steam distillation, which collects the evaporated oil by heating the plant material containing it, and then cooling to obtain liquid oil. Alternatively, organic solvents (e.g., hexane or ethanol) are used to dissolve the alkene in the plant material and then recovered by evaporation of the solvent. However, the products obtained by the two methods also contain other components with similar properties, and are difficult to separate, so that the purity of the target product is low, and is only 30-35%. In addition, the repeated distillation and extraction purification modes can lead to the reduction of the yield and the increase of the emission of three industrial wastes, and do not accord with the concept of green environmental protection. Disclosure of Invention In view of the above, an object of the present invention is to provide a method for producing (2 s,4r,7r,8 r) -3,3,7,11-tetramethyltricyclo [6.3.0.02.4] undec-1 (11) -ene. The invention adopts molecular isomerization path to prepare (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -alkene, which has the advantages of environmental protection and high efficiency. In order to achieve the above object, the present invention provides the following technical solutions: the invention provides a preparation method of (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -alkene, which comprises the following steps: (1R, 2S,8R, 11R) -7-methylene-3,3,11-trimethyl tricyclo [6.3.0.02.4] undecane is mixed with a catalyst, and isomerization reaction is carried out under the condition of hydrogen and pressurization to obtain (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -alkene. Preferably, the catalyst comprises one or more of ruthenium/alumina catalyst, palladium/silica catalyst and palladium carbon catalyst. Preferably, the mass content of ruthenium in the ruthenium/alumina catalyst is 3-6%, and the mass content of palladium in the palladium/silica catalyst is 3-6%. Preferably, the mass ratio of the (1R, 2S,8R, 11R) -7-methylene-3,3,11-trimethyl tricyclo [6.3.0.02.4] undecane to the catalyst is 100:1.2-1.8. Preferably, the isomerization reaction temperature is 145-170 ℃. Preferably, the pressure of the isomerization reaction is 0.5-0.7 MPa. Preferably, the isomerization reaction time is 8-12 hours. Preferably, after the isomerization reaction, the method further comprises the step of carrying out post-treatment on the obtained isomerization reaction product, wherein the post-treatment comprises the following steps: And (3) carrying out solid-liquid separation on the isomerization reaction product, and carrying out vacuum fractionation on the obtained liquid phase. Preferably, the vacuum degree of the vacuum fractionation is 3 mmHg, and the fraction with the top temperature of 76-77 ℃ is heated and collected. The invention provides a preparation method of (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4] undec-1 (11) -alkene, which comprises the following steps of mixing (1R, 2S,8R, 11R) -7-methylene-3,3,11-trimethyl tricyclo [6.3.0.02.4] undecane with a catalyst, and carrying out isomerization reaction under the condition of hydrogen and pressurization to obtain (2S, 4R,7R, 8R) -3,3,7,11-tetramethyl tricyclo [6.3.0.02.4]