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Synthetic method of asymmetric thioether

A synthetic method and asymmetric technology, applied in the formation/introduction of mercapto/thioether groups, thioether preparation, organic chemistry, etc., can solve the problems of limited application range, large amount of waste, poor stability, etc., and shorten the synthesis steps , easy to operate, good selective effect

Pending Publication Date: 2021-03-19
YANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But above-mentioned method all needs to use excessive alkali to convert thiophenol or mercaptan into stronger nucleophilic sulfide anion to participate in reaction, causes a large amount of wastes to be produced after reaction, or uses metal catalyst, for example copper (Xu, H.- J.; Zhao, Y.-Q.; Feng, T.; Feng, Y.-S.J.Org.Chem.2012, 77, 2878), nickel (Lee, P.H.; Park, Y.; Park, S.; Lee , E.; Kim, S.J.Org.Chem.2011,76,760.), palladium (Jammi,S.; Barua,P.; Rout,L.; Saha,P.; Punniyamurthy,T.Tetrahedron Lett.2008,49, 1484.) etc.
The second method also needs to use an alkyl halide compound with high toxicity and poor stability as an alkylating agent. Under alkaline conditions, this method is mainly suitable for primary halogenated hydrocarbons, because secondary halogenated hydrocarbons and tertiary halogenated hydrocarbons are prone to Elimination reaction produces non-target products, the scope of application is very limited

Method used

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  • Synthetic method of asymmetric thioether
  • Synthetic method of asymmetric thioether
  • Synthetic method of asymmetric thioether

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Preparation of p-methylphenyl benzyl sulfide with benzyl alcohol and p-cresyl thiophenol

[0021]

[0022] Benzyl alcohol (108.1mg, 1.0mmol), p-cresylthiophenol (149.0mg, 1.2equiv.) and bromotrimethylsilane (30.6mg, 20mol%) were added successively to the tubular reactor, and it was directly sealed under air without Under solvent conditions, heat at 120°C for 24h. After the completion of the reaction was monitored by TLC, the product was separated and purified by column chromatography. The isolated yield was 86%. 1 H NMR (400MHz, CDCl 3 ):δ7.27-7.18(m,4H),7.18-7.08(m,3H),7.00(s,2H),4.00(s,2H),2.24(s,3H). 13 C NMR (101MHz, CDCl 3 ): δ137.82, 136.56, 132.51, 130.72, 129.63, 128.85, 128.44, 127.08, 39.81, 21.08.

Embodiment 2

[0024] Preparation of p-methylphenyl benzyl sulfide with benzyl alcohol and p-cresyl thiophenol

[0025]

[0026] Benzyl alcohol (108.1mg, 1.0mmol), p-cresylthiophenol (149.0mg, 1.2equiv.) and trimethylchlorosilane (21.7mg, 20mol%) were successively added into the tubular reactor, and it was directly sealed under air without Under solvent conditions, heat at 120°C for 24h. After the completion of the reaction was monitored by TLC, the product was separated and purified by column chromatography. The isolated yield was 41%. 1 H NMR (400MHz, CDCl 3 ):δ7.27-7.18(m,4H),7.18-7.08(m,3H),7.00(s,2H),4.00(s,2H),2.24(s,3H). 13 C NMR (101MHz, CDCl 3 ): δ137.82, 136.56, 132.51, 130.72, 129.63, 128.85, 128.44, 127.08, 39.81, 21.08.

Embodiment 3

[0028] Preparation of p-methylphenyl benzyl sulfide with benzyl alcohol and p-cresyl thiophenol

[0029]

[0030] Benzyl alcohol (108.1mg, 1.0mmol), p-cresylthiophenol (149.0mg, 1.2equiv.) and bromotrimethylsilane (30.6mg, 20mol%) were added successively in the tubular reactor, and the 2 Under the condition of sealed and solvent-free heating at 120 ° C for 24 hours. After the completion of the reaction was monitored by TLC, the product was separated and purified by column chromatography. The isolated yield was 76%. 1 H NMR (400MHz, CDCl 3 ):δ7.27-7.18(m,4H),7.18-7.08(m,3H),7.00(s,2H),4.00(s,2H),2.24(s,3H). 13 CNMR (101MHz, CDCl 3 ): δ137.82, 136.56, 132.51, 130.72, 129.63, 128.85, 128.44, 127.08, 39.81, 21.08.

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Abstract

The invention discloses a synthetic method of asymmetric thioether. According to the method, alcohol which is cheap, easy to obtain, wide in source, stable and low in toxicity is used as an alkylationreagent, trimethyl halosilane is used as a non-transition metal catalyst, a solvent is not needed, and an asymmetric thioether compound is directly synthesized through a high-selectivity dehydrationSalkylation reaction. According to the method, the use of a transition metal catalyst and alkali is avoided, the catalytic method is simple, the condition is simple, the operation is easy, the byproduct is water, the synthesis efficiency is high, and the selectivity is good.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis and relates to a synthesis method of an asymmetric thioether. Background technique [0002] Organosulfur compounds are a very important class of compounds. As catalysts or ligands for organic and pharmaceutical synthesis, they have important uses in the fields of catalysis, polymer materials, natural products, and pesticides. In addition, various thioether structures widely exist in molecules with various biological and pharmaceutical activities. The biological effects of organosulfur compounds are mainly cancer suppression and sterilization, and can treat inflammation, antidepression, human immunodeficiency virus, asthma and other diseases , can also be used as a preventive anti-aging agent. [0003] In known synthetic methods, asymmetric thioether compounds can be prepared by the reduction reaction of sulfoxide and sulfone (Hua, G.; Woollins, J.D. Tetrahedron Lett. 2007, 48, 3677.) A...

Claims

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Application Information

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IPC IPC(8): C07B45/06C07C319/14C07C321/28C07C323/16C07C323/07C07C323/20C07C323/09C07D333/18C07D317/56C07D213/70
CPCC07B45/06C07C319/14C07D333/18C07D317/56C07D213/70C07C321/28C07C323/16C07C323/07C07C323/20C07C323/09
Inventor 徐清章小兰王琦
Owner YANGZHOU UNIV
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