Search

CN-121974947-A - 8-Tert-butyl diphenyl silanyloxy-7-methyl octyl tosylate and synthetic method and application thereof

CN121974947ACN 121974947 ACN121974947 ACN 121974947ACN-121974947-A

Abstract

The application discloses 8-tert-butyl diphenyl silanyloxy-7-methyl octyl p-toluenesulfonate and a synthetic method and application thereof, and relates to the technical field of biological pesticides. The application takes 8-bromooctanoic acid as a starting material, firstly reacts with t-BuOK and 18-crown ether-6, then reacts with pivaloyl chloride to generate acid anhydride, then reacts with 4-benzyl oxazolidine-2-ketone for acylation, then carries out diastereoselective methylation, then carries out NaBH 4 reduction, then carries out hydroxyl protection, then carries out hydroboration oxidation, and then carries out TsCl sulfonylation to synthesize the p-toluenesulfonic acid-8-tert-butyl diphenyl silanyloxy 7-methyl octyl ester. The optical purity of the (S) -8-tert-butyl diphenyl silanyloxy-7-methyl octyl tosylate synthesized by the application reaches 98 percent, and the optical purity of the (R) -8-tert-butyl diphenyl silanyloxy-7-methyl octyl tosylate synthesized by the application also reaches 98 percent.

Inventors

  • ZHOU YUN
  • ZHANG YUERU
  • SHAN CHENGGANG
  • ZHANG JIANHUA
  • HAN JINLONG
  • ZHU YANWEI
  • ZHANG FENG
  • WANG XIANCHANG

Assignees

  • 山东省农业科学院

Dates

Publication Date
20260505
Application Date
20260129

Claims (10)

  1. 1. The p-toluenesulfonic acid 8-tert-butyl diphenyl silanyloxy-7-methyl octyl ester is characterized by having the following structural formula: 。
  2. 2. The 8-tert-butyldiphenylsilanyloxy-7-methyloctyl p-toluenesulfonate according to claim 1, wherein the 8-tert-butyldiphenylsilanyloxy-7-methyloctyl p-toluenesulfonate has an S configuration, and the structural formula of the 8-tert-butyldiphenylsilanyloxy-7-methyloctyl p-toluenesulfonate having the S configuration is shown in the formula (S) -10: 。
  3. 3. The 8-tert-butyldiphenylsilanyloxy-7-methyloctyl p-toluenesulfonate according to claim 1, wherein the 8-tert-butyldiphenylsilanyloxy-7-methyloctyl p-toluenesulfonate has the R configuration, and the structural formula of the 8-tert-butyldiphenylsilanyloxy-7-methyloctyl p-toluenesulfonate with the R configuration is shown as formula (R) -10: 。
  4. 4. a method for synthesizing 8-tert-butyldiphenylsilyloxy-7-methyloctyl tosylate is characterized in that the 8-tert-butyldiphenylsilyloxy-7-methyloctyl tosylate is the 8-tert-butyldiphenylsilyloxy-7-methyloctyl tosylate according to claim 1, and the method for synthesizing 8-tert-butyldiphenylsilyloxy-7-methyloctyl tosylate comprises the following steps: The 8-bromooctanoic acid is used as a starting material, and is reacted with t-BuOK and 18-crown ether-6 to generate acid anhydride, then is reacted with pivaloyl chloride to generate acid anhydride, then is subjected to acylation reaction with 4-benzyl oxazolidine-2-ketone, then is subjected to diastereoselective methylation, then is subjected to NaBH 4 reduction, then is subjected to hydroxyl protection by TBDPSCl, then is subjected to hydroboration reaction to oxidize olefin into alcohol, and then is subjected to TsCl sulfonylation to synthesize the p-toluenesulfonic acid-8-tert-butyl diphenylsilanyloxy 7-methyl octyl ester.
  5. 5. The method for synthesizing p-toluenesulfonic acid-8-tert-butyldiphenylsilanyloxy-7-methyloctyl ester according to claim 4, wherein when 4-benzyl oxazolidine-2-one is (S) -4-benzyl oxazolidine-2-one, S7 is performed to obtain p-toluenesulfonic acid-8-tert-butyldiphenylsilanyloxy-7-methyloctyl ester with S configuration.
  6. 6. The method for synthesizing p-toluenesulfonic acid-8-tert-butyldiphenylsilanyloxy-7-methyloctyl ester according to claim 4, wherein when 4-benzyl oxazolidine-2-one is (R) -4-benzyl oxazolidine-2-one, the step S7 is to obtain the p-toluenesulfonic acid-8-tert-butyldiphenylsilanyloxy-7-methyloctyl ester with R configuration.
  7. 7. A method for synthesizing 2, 10-dimethyldodecyloxy tert-butyldiphenylsilane based on p-toluenesulfonic acid-8-tert-butyldiphenylsilanyloxy-7-methyloctyl ester, which is characterized in that p-toluenesulfonic acid-8-tert-butyldiphenylsilanyloxy-7-methyloctyl ester is p-toluenesulfonic acid-8-tert-butyldiphenylsilanyloxy-7-methyloctyl ester, and the method for synthesizing 2, 10-dimethyldodecyloxy tert-butyldiphenylsilane comprises the following steps: Nucleophilic substitution reaction of p-toluenesulfonic acid-8-tert-butyldiphenylsilyloxy-7-methyl octyl ester with Grignard reagent prepared from bromo-and Mg to obtain 2, 10-dimethyldodecyloxy tert-butyldiphenylsilane.
  8. 8. A method for synthesizing 3, 11-dimethyl icosacarbon-12-alkene based on 2, 10-dimethyl dodecyloxy tertiary butyl diphenyl silane is characterized in that the 2, 10-dimethyl dodecyloxy tertiary butyl diphenyl silane is the 2, 10-dimethyl dodecyloxy tertiary butyl diphenyl silane, and the method for synthesizing 3, 11-dimethyl icosacarbon-12-alkene comprises the following steps: A. removing the TBDPS protecting group from 2, 10-dimethyldodecyloxy tertiary butyl diphenylsilane by using TBAF to prepare 2, 10-dimethyldodecyl-1-ol; B. 2, 10-dimethyl dodeca-1-ol is converted into aldehyde group through Dess-Martin reaction, and then the aldehyde group and bromine (heptadecyl) triphenylphosphine are subjected to Wittig reaction to prolong carbon chain, so as to synthesize 3, 11-dimethyl icosahedron-12-ene.
  9. 9. A method for synthesizing 3, 11-dimethyl icosahederane based on 3, 11-dimethyl icosahederane, which is characterized in that the 3, 11-dimethyl icosahederane-12-alkene is the 3, 11-dimethyl icosahederane-12-alkene of claim 8, and the method for synthesizing 3, 11-dimethyl icosahederane comprises the following steps: Pd/C reduction is carried out on 3, 11-dimethyl icosacarbon-12-alkene to synthesize 3, 11-dimethyl icosaalkane.
  10. 10. A method for synthesizing 3, 11-dimethyl icosahederane based on p-toluenesulfonic acid-8-tertiary butyl diphenyl silanyloxy-7-methyl octyl ester is characterized in that the p-toluenesulfonic acid-8-tertiary butyl diphenyl silanyloxy-7-methyl octyl ester is p-toluenesulfonic acid-8-tertiary butyl diphenyl silanyloxy-7-methyl octyl ester, and the method for synthesizing 3, 11-dimethyl icosahederane comprises the following steps: Firstly, synthesizing 2, 10-dimethyl dodecyl oxy tertiary butyl diphenyl silane by taking p-toluenesulfonic acid-8-tertiary butyl diphenyl silyl oxy-7-methyl octyl ester as a raw material; then, 2, 10-dimethyl dodecyl oxy tertiary butyl diphenyl silane is taken as a raw material to synthesize 3, 11-dimethyl icosacarbon-12-alkene; Finally, 3, 11-dimethyl icosahederane is synthesized by taking 3, 11-dimethyl icosahederane-12-alkene as a raw material.

Description

8-Tert-butyl diphenyl silanyloxy-7-methyl octyl tosylate and synthetic method and application thereof Technical Field The invention belongs to the technical field of biological pesticides, and in particular relates to 8-tert-butyl diphenyl silanyloxy-7-methyl octyl tosylate, a synthetic method and application thereof. Background German cockroach (Blattella germanica) is a widely distributed and difficult to treat sanitary insect pests in the global area, and is not only an important medium for transmitting various diseases, but also an important indoor allergen. At present, the use of high-efficiency poison bait has become a main method for preventing and curing the German cockroaches, but the long-term use of single pesticide for preventing and curing the German cockroaches can lead the German cockroaches to generate stronger resistance, and the German cockroaches are not ideal in killing effect due to the passive contact with chemical pesticide. For this reason, research and development personnel begin to consider that the aggregation pheromone is used as an attractant, and the aggregation pheromone is combined with the pesticide to control the German cockroach, so that the pesticide consumption is small, and the trapping and killing effect is obvious. The aggregation pheromone of the German cockroach has complex components, the German cockroach body surface extract is analyzed in the paper "Are Differences in Hydrocarbon Profiles Able to Mediate Strain Recognition in German Cockroaches (Dictyoptera: Blattellidae)? European Journal of Entomology, 2002, 99(4): 437-444." by Rivault and the team thereof in 2002, and the 3, 11-dimethyl icosahederane is found to be the substance with the highest content in the aggregation pheromone of the German cockroach. At present, the synthesis research of 8-tert-butyl diphenyl silanyloxy-7-methyl octyl p-toluenesulfonate, which is an important intermediate for synthesizing 3, 11-dimethyl icosahederane, has not been reported in the literature. In addition, the asymmetric synthesis research of the 8-tert-butyldiphenylsilanyloxy-7-methyl octyl tosylate is developed, the bottleneck of natural extraction yield can be broken through, a compound is provided for further researching the biological activity of the compound, theoretical support is provided for the molecular design of a novel aggregation behavior interfering agent, and the development of the environment-compatible German sickle prevention and control technology is further promoted. Therefore, the application provides 8-tert-butyl diphenyl silanyloxy-7-methyl octyl tosylate and a synthetic method and application thereof. Disclosure of Invention In order to make up the defects of the prior art, the invention provides 8-tert-butyl diphenyl silanyloxy-7-methyl octyl tosylate, and a synthetic method and application thereof. The technical scheme of the invention is as follows: 8-tert-butyldiphenylsilyloxy-7-methyloctyl p-toluenesulfonate has the structural formula shown below: 。 Preferably, the 8-tert-butyldiphenylsilanyloxy-7-methyloctyl p-toluenesulfonate is in S configuration, and the structural formula of the 8-tert-butyldiphenylsilanyloxy-7-methyloctyl p-toluenesulfonate in S configuration is shown as formula (S) -10: 。 preferably, the 8-tert-butyldiphenylsilanyloxy-7-methyloctyl p-toluenesulfonate is in an R configuration, and the structural formula of the 8-tert-butyldiphenylsilanyloxy-7-methyloctyl p-toluenesulfonate in the R configuration is shown as formula (R) -10: 。 A process for synthesizing p-toluenesulfonic acid-8-tert-butyl diphenyl silanyloxy-7-methyl octyl ester includes such steps as reaction of 8-bromooctanoic acid with t-BuOK and 18-crown ether-6 to generate acid anhydride, acylation reaction with 4-benzyl oxazolidine-2-one, diastereoselective methylation, reduction with NaBH 4, hydroxy protection with TBDPSCl, hydroboration to oxidize olefin to alcohol, and TsCl sulfonylation to obtain p-toluenesulfonic acid-8-tert-butyl diphenyl silanyloxy-7-methyl octyl ester. Preferably, the synthesis method of the p-toluenesulfonic acid-8-tert-butyl diphenyl silanyloxy-7-methyl octyl ester comprises the following steps: S1, 8-bromooctanoic acid is used as a starting material, and reacts with t-BuOK and 18-crown ether-6 to synthesize oct-7-enoic acid; s2, reacting octyl-7-enoate with pivaloyl chloride to generate anhydride, and then carrying out acylation reaction with 4-benzyl oxazolidine-2-ketone to synthesize 4-benzyl-3-octyl-7-enoyl oxazolidine-2-ketone; S3, synthesizing 4-benzyl-3- (2-methyloctan-7-enoyl) oxazolidin-2-one by diastereoselective methylation of 4-benzyl-3-oct-7-enoyl oxazolidin-2-one; S4, reducing 4-benzyl-3- (2-methyloctan-7-enoyl) oxazolidin-2-ketone by NaBH4 to obtain 2-methyloctan-7-en-1-ol; s5, performing hydroxyl protection on 2-methyloctan-7-en-1-ol by utilizing TBDPSCl to obtain tert-butyl (2-methyloctan-7-en-1-yloxy) diphenylsilane; S6, oxidizing the para-tertiary butyl (2-methyl octyl-7