Synthetic method of asymmetrical thioether

A synthetic method and asymmetric technology, applied in the formation/introduction of thiol/thioether group, thioether preparation, chemical instruments and methods, etc., can solve problems such as restricting practical application

Active Publication Date: 2016-11-16
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] It can be seen that the current method for synthesizing asymmetric thioethers inevitably uses highly toxic, foul-smelling, sensitive and perishable thiol compounds in the reacti...

Method used

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  • Synthetic method of asymmetrical thioether
  • Synthetic method of asymmetrical thioether
  • Synthetic method of asymmetrical thioether

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[0034] The invention provides a kind of synthetic method of unsymmetrical thioether, comprises the following steps:

[0035] a), under the catalytic conditions of tetrabutylammonium halide, the compound of formula (I), the compound of formula (II) and oxysulfide are reacted in a solvent to obtain the asymmetric thioether with the structure of formula (III);

[0036]

[0037] Among them, R 1 selected from phenyl, substituted phenyl, naphthyl, substituted naphthyl, thienyl or substituted thienyl, R 2 selected from hydrogen, phenyl, substituted phenyl, naphthyl, substituted naphthyl, thienyl, or substituted thienyl; or R 1 , R 2 Form a fluorene ring or a thioxanthene ring with the C connected to it;

[0038] R 3 selected from hydrogen or alkyl;

[0039] R 4 selected from hydrogen, phenyl, substituted phenyl, naphthyl, substituted naphthyl, thienyl or substituted thienyl, R 5 selected from hydrogen; or R 4 , R 5 Form a fluorene ring or a thioxanthene ring with the C conn...

Embodiment 1

[0066] Synthesis of 4-((3,3-diarylallylthio)methyl)benzonitrile

[0067] Weigh 0.3mmol 1,1-diphenylprop-2-enyl-1-ol (0.0631 grams), 0.6mmol p-cyanobenzyl chloride (0.0910 grams), 0.72mmol sodium thiosulfate (0.1138 grams), 0.06 Mmol tetrabutylammonium iodide (0.0222 grams), in a 20mL test tube reaction tube, add 1mL water as a solvent, seal and seal, stir and react at 80°C for 5 hours; Sodium sulfate water drying and column chromatography separation (column chromatography separation conditions: the stationary phase is 300-400 mesh silica gel powder, the mobile phase is ethyl acetate (A) and petroleum ether (B), the mobile phase change program (A:B ) was 1:20→1:6), and 0.0778 gram of reaction product was obtained.

[0068] The above-mentioned reaction product is characterized, and the result is:

[0069] 1 H NMR (400MHz, CDCl 3 ):δ=7.49–7.42(m,2H),7.38–7.33(m,3H),7.29–7.25(m,3H),7.22–7.18(m,2H),7.18–7.13(m,4H),6.08 (t, J=7.8Hz, 1H), 3.63(s, 2H), 3.18(d, J=7.8Hz, 2H)ppm;

...

Embodiment 2

[0072] Synthesis of 4-((3,3-bis(4-fluorophenyl)allylthio)methyl)benzonitrile

[0073] Weigh 0.3mmol 1,1-bis(4-fluorophenyl)prop-2-enyl-1-ol (0.0739 grams), 0.6mmol p-cyanobenzyl chloride (0.0910 grams), 0.72mmol sodium thiosulfate ( 0.1138 grams), 0.06mmol tetrabutylammonium iodide (0.0222 grams), in a 20mL test tube reaction tube, add 1mL water as a solvent, seal and seal, stir and react at 80°C for 5 hours; after the reaction, the reaction solution is passed through Ethyl acetate, anhydrous sodium sulfate drying and column chromatography separation (column chromatography separation conditions: the stationary phase is 300-400 mesh silica gel powder, the mobile phase is ethyl acetate (A) and petroleum ether (B), the mobile phase changes The procedure (A:B) is 1:20 → 1:6), yielding 0.0932 g of reaction product.

[0074] The above-mentioned reaction product is characterized, and the result is:

[0075] 1 H NMR (400MHz, CDCl 3 ):δ=7.51(d, J=8.3Hz, 2H), 7.24(d, J=8.2Hz, 2H), 7...

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Abstract

The invention belongs to the field of chemistry, and relates to a synthetic method of asymmetrical thioether. The synthetic method comprises the following steps of (a) under the condition of catalysis of tetrabutyl ammonium halide, enabling a structural compound as shown in a formula (I), a structural compound as shown in a formula (II) and sulfur oxonium salt to react in a solvent so as to obtain the asymmetrical thioether with a structure as shown in formula (III), wherein R1 is selected from phenyl, substituted phenyl, naphtyl, substituted naphtyl, thienyl, or substituted thienyl; R2 is selected from hydrogen, phenyl, substituted phenyl, naphtyl, substituted naphtyl, thienyl or substituted thienyl; or R1, R2 and C connected with R1 and R2 form fluorene or thioxanthene; R3 is selected from hydrogen or an alkyl group; R4 is selected from hydrogen, phenyl, substituted phenyl, naphtyl, substituted naphtyl, thienyl or substituted thienyl; R5 is selected from hydrogen; or R4, R5 and C connected with R4 and R5 form the fluorene or the thioxanthene; R6 is selected form the alkyl group or the substituted alkyl group; and X is selected from C1, Br or I.

Description

technical field [0001] The invention belongs to the field of organic chemistry, in particular to a method for synthesizing an unsymmetrical thioether. Background technique [0002] Asymmetric thioethers are an important class of sulfur-containing compounds. Their skeletons not only widely exist in natural products and active pharmaceutical molecules, but also can be used as advanced materials and metal ligands, and are also important intermediates in organic synthesis. [0003] Asymmetric thioether compounds are widely used in biomedicine, such as: [0004] Methionine (Methionine) is one of the essential amino acids that make up the human body. It is involved in protein synthesis. Because it cannot be produced in the body itself, it must be obtained from the outside. The lack of methionine will lead to the blockage of protein synthesis in the body and cause damage to the body. . At present, methionine is mostly synthesized by the coupling reaction of halides, thiols and re...

Claims

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Application Information

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IPC IPC(8): C07C319/14C07C323/56C07D335/12C07D333/16C07C323/07C07C321/20C07C321/22C07D209/08C07H9/04C07H1/00C07C323/52C07C323/54
CPCC07C319/14C07D209/08C07D333/16C07D335/12C07H1/00C07H9/04C07C323/56C07C323/07C07C321/20C07C321/22C07C323/52C07C323/54C07D333/18C07C323/60C07B45/06C07C321/12C07C319/28C07C321/18C07C2527/12C07F11/005
Inventor 纪顺俊褚雪强徐小平曹文斌
Owner SUZHOU UNIV
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