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CN-122011012-A - (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenyl silane and synthesis method and application thereof

CN122011012ACN 122011012 ACN122011012 ACN 122011012ACN-122011012-A

Abstract

The application discloses (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenyl silane and a synthesis method and application thereof, and relates to the technical field of biological pesticides. The application takes (R) -3-hydroxy-2-methyl propionate as an initial raw material, firstly reacts with imidazole and tributyl diphenyl chlorosilane to protect hydroxy, then reacts with DIBAL-H to generate reduction reaction, then reacts with TsCl to generate sulfonylation reaction, and then reacts with Grignard reagent containing alkynyl to generate coupling reaction, thus synthesizing (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenyl silane. The optical purity of the (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenyl silane synthesized by the application reaches 98 percent.

Inventors

  • ZHOU YUN
  • ZHANG YUERU
  • SHAN CHENGGANG
  • HAN JINLONG
  • ZHU YANWEI
  • WANG XIANCHANG
  • Tian beijing
  • LIU LI

Assignees

  • 山东省农业科学院

Dates

Publication Date
20260512
Application Date
20260213

Claims (10)

  1. 1. The (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane is characterized by having the following structural formula: 。
  2. 2. A method for synthesizing (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane, characterized in that (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane is (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane according to claim 1; The synthesis method of the (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenylsilane comprises the following steps of taking (R) -3-hydroxy-2-methylpropionate as a starting material, reacting with imidazole and tributyl diphenylchlorosilane to protect hydroxyl, then reacting with DIBAL-H to generate reduction reaction, then reacting with TsCl to generate sulfonylation reaction, and then reacting with an alkynyl-containing Grignard reagent in a coupling way to synthesize the (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenylsilane.
  3. 3. A process for synthesizing (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane according to claim 2, wherein the Grignard reagent containing alkynyl groups is prepared by mixing magnesium chips with tetrahydrofuran under the protection of argon, adding iodine and a part of (4-bromobut-1-yn-1-yl) trimethylsilane to initiate reaction, heating the reaction solution until the redness of the reaction solution is completely removed, then adding another part of (4-bromobut-1-yn-1-yl) trimethylsilane dropwise, obtaining the reaction solution, heating the reaction solution to reflux, stirring for 30-45 minutes, and cooling to room temperature to obtain the tetrahydrofuran solution of (4- (trimethylsilyl) but-3-yn-1-yl) magnesium bromide, namely the Grignard reagent containing alkynyl groups.
  4. 4. A method for synthesizing (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane according to claim 3, wherein the mass of the first added (4-bromobut-1-yn-1-yl) trimethylsilane is 20% -30% of the sum of the mass of the first added (4-bromobut-1-yn-1-yl) trimethylsilane and the mass of the second added (4-bromobut-1-yn-1-yl) trimethylsilane.
  5. 5. A process for the synthesis of (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane according to claim 2, characterized in that said process for the synthesis of (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane comprises the steps of: S1, taking (R) -3-hydroxy-2-methyl propionate as a starting material, and reacting with imidazole and tributyl diphenylchlorosilane to synthesize (R) -3- ((tert-butyldiphenylsilyl) oxy) -2-methyl propionate so as to protect hydroxy; s2, (R) -3- ((tert-butyl diphenyl silicon base) oxy) -2-methyl propionate and DIBAL-H undergo a reduction reaction to synthesize (S) -3- ((tert-butyl diphenyl silicon base) oxy) -2-methylpropan-1-ol; s3, carrying out sulfonylation reaction on (S) -3- ((tert-butyl diphenyl silicon base) oxy) -2-methylpropan-1-ol and TsCl to synthesize (R) -3- ((tert-butyl diphenyl silicon base) oxy) -2-methylpropyl 4-methylbenzenesulfonate; S4, performing a coupling reaction on (R) -3- ((tert-butyl diphenyl silicon base) oxy) -2-methylpropyl 4-methylbenzenesulfonate and an alkynyl-containing Grignard reagent to synthesize (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenyl silane.
  6. 6. A process for synthesizing (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane using (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane, wherein the (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane is (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane of claim 1; A process for synthesizing (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane from (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane includes such steps as reacting (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane with methanol and potassium carbonate to remove trimethylsilyl protecting group.
  7. 7. A process for the synthesis of (S, E) -8- ((tert-butyldiphenylsilyl) oxy) -3, 7-dimethyl-2-octen-1-ol using (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane, characterized in that the (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane is (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane according to claim 6; A process for synthesizing (S, E) -8- ((tert-butyldiphenylsilyl) oxy) -3, 7-dimethyl-2-octen-1-ol from (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane comprises alkylating (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane with trimethylaluminum and then nucleophilic addition extension of carbon chain by n-butyllithium and paraformaldehyde to synthesize (S, E) -8- ((tert-butyldiphenylsilyl) oxy) -3, 7-dimethyl-2-octen-1-ol.
  8. 8. A process for the synthesis of (S, E) -3, 7-dimethyl-2-octen-1, 8-diol using (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane, characterized in that (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane is (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane according to claim 6; A process for synthesizing (S, E) -3, 7-dimethyl-2-octen-1, 8-diol from (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane includes alkylating (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane with trimethylaluminum, nucleophilic addition of n-butyllithium and paraformaldehyde to lengthen carbon chain, synthesizing (S, E) -8- ((tert-butyldiphenylsilyl) oxy) -3, 7-dimethyl-2-octen-1-ol, and removing protecting group from (S, E) -8- ((tert-butyldiphenylsilyl) oxy) -3, 7-dimethyl-2-octen-1-ol by TBAF to synthesize (S, E) -3, 7-dimethyl-2-octen-1, 8-diol.
  9. 9. A method for synthesizing (S, E) -8- ((tert-butyldiphenylsilyl) oxy) -3, 7-dimethyl-2-octen-1-ol by using (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane, wherein (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane is (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane according to claim 1; A method for synthesizing (S, E) -8- ((tert-butyldiphenylsilyl) oxy) -3, 7-dimethyl-2-octen-1-ol using (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane, comprising the steps of: Firstly, taking (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenyl silane as a raw material to synthesize (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenyl silane; Then (S, E) -8- ((tert-butyldiphenylsilyl) oxy) -3, 7-dimethyl-2-octen-1-ol is synthesized by taking (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane as a raw material.
  10. 10. A process for synthesizing (S, E) -3, 7-dimethyl-2-octene-1, 8-diol from (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane, wherein (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane is (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane according to claim 1; a process for the synthesis of (S, E) -3, 7-dimethyl-2-octene-1, 8-diol using (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane comprising the steps of: Firstly, taking (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenyl silane as a raw material to synthesize (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenyl silane; Then (S, E) -8- ((tert-butyldiphenylsilyl) oxy) -3, 7-dimethyl-2-octen-1-ol is synthesized by taking (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane as a raw material; finally, (S, E) -8- ((tert-butyl diphenyl silicon base) oxy) -3, 7-dimethyl-2-octene-1-alcohol is taken as a raw material to synthesize (S, E) -3, 7-dimethyl-2-octene-1, 8-diol.

Description

(S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenyl silane and synthesis method and application thereof Technical Field The invention belongs to the technical field of biological pesticides, and particularly relates to (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yne-1-yl) oxy) diphenylsilane and a synthesis method and application thereof. Background Insect pheromones play a vital role in species-specific communications, mating behavior and ecological interactions. Therefore, insect pheromones have long been an important research goal in the fields of organic synthesis and chemical ecology. Prior studies have found that (S, E) -3, 7-dimethyl-2-octene-1, 8-diol is the major component of the secretion of the junior plaque butterfly, (S, E) -3, 7-dimethyl-2-octene-1, 8-diol is thought to play a role in the coupling behavior and chemical defenses of the junior plaque butterfly, however, the content of (S, E) -3, 7-dimethyl-2-octene-1, 8-diol in nature is extremely low. Accordingly, researchers have begun focusing on the synthesis of (S, E) -3, 7-dimethyl-2-octen-1, 8-diol, and among numerous intermediates for the synthesis of (S, E) -3, 7-dimethyl-2-octen-1, 8-diol, an intermediate of (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane has not been reported in the prior art. Therefore, the application provides (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenyl silane, and a synthesis method and application thereof. Disclosure of Invention In order to make up the defects of the prior art, the invention provides (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenyl silane, and a synthesis method and application thereof. The technical scheme of the invention is as follows: (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane having the structural formula shown below: 。 A process for synthesizing (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenyl silane includes such steps as reaction of methyl (R) -3-hydroxy-2-methylpropionate as initial raw material with imidazole and tributyl diphenyl chlorosilane to protect hydroxy, reduction reaction with DIBAL-H, sulfonylation reaction with TsCl, and coupling reaction with Grignard reagent containing alkynyl to obtain (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenyl silane. Preferably, the alkynyl group-containing Grignard reagent is synthesized by mixing magnesium chips and tetrahydrofuran under the protection of argon, adding iodine and a part of (4-bromobut-1-yn-1-yl) trimethylsilane to initiate the reaction, wherein the part of (4-bromobut-1-yn-1-yl) trimethylsilane is called first added (4-bromobut-1-yn-1-yl) trimethylsilane, heating the reaction solution until the redness of the reaction solution is completely removed, then dropwise adding another part of (4-bromobut-1-yn-1-yl) trimethylsilane, wherein the part of (4-bromobut-1-yn-1-yl) trimethylsilane is called second added (4-bromobut-1-yn-1-yl) trimethylsilane, after the dropwise adding is completed, obtaining the reaction solution, heating the reaction solution to reflux, stirring for 30-45 minutes, and cooling to room temperature to obtain the (4- (trimethylsilyl) but-3-1-yl) magnesium bromide solution, namely the Grignard reagent is the tetra-hydro-1-ethynyl group-containing Grignard reagent. Preferably, the mass of the (4-bromobut-1-yn-1-yl) trimethylsilane added for the first time accounts for 20% -30% of the sum of the mass of the (4-bromobut-1-yn-1-yl) trimethylsilane added for the first time and the mass of the (4-bromobut-1-yn-1-yl) trimethylsilane added for the second time. Preferably, the synthesis method of the (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) diphenylsilane comprises the following steps: S1, taking (R) -3-hydroxy-2-methyl propionate as a starting material, and reacting with imidazole and tributyl diphenylchlorosilane to synthesize (R) -3- ((tert-butyldiphenylsilyl) oxy) -2-methyl propionate so as to protect hydroxy; s2, (R) -3- ((tert-butyl diphenyl silicon base) oxy) -2-methyl propionate and DIBAL-H undergo a reduction reaction to synthesize (S) -3- ((tert-butyl diphenyl silicon base) oxy) -2-methylpropan-1-ol; s3, carrying out sulfonylation reaction on (S) -3- ((tert-butyl diphenyl silicon base) oxy) -2-methylpropan-1-ol and TsCl to synthesize (R) -3- ((tert-butyl diphenyl silicon base) oxy) -2-methylpropyl 4-methylbenzenesulfonate; S4, performing a coupling reaction on (R) -3- ((tert-butyl diphenyl silicon base) oxy) -2-methylpropyl 4-methylbenzenesulfonate and an alkynyl-containing Grignard reagent to synthesize (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-alkyne-1-yl) oxy) diphenyl silane. A method for synthesizing (S) -tert-butyl ((2-methylhept-6-yn-1-yl) oxy) diphenylsilane from (S) -tert-butyl ((2-methyl-7- (trimethylsilyl) hept-6-yn-1-yl) oxy) di