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Synthesis method of heteroaryl thioether

A technology of a heteroaryl sulfide and a synthesis method, applied in the direction of organic chemistry and the like, can solve problems such as multiple wastes, achieve good selectivity, improve synthesis efficiency, and shorten synthesis steps.

Active Publication Date: 2020-08-21
YANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] However, in the preliminary work, catalysts, additives, or additives need to be added to the reaction system, resulting in a lot of waste

Method used

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  • Synthesis method of heteroaryl thioether
  • Synthesis method of heteroaryl thioether
  • Synthesis method of heteroaryl thioether

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Preparation of 2-pyridylanisole sulfide from 2-bromopyridine, thiourea and benzyl bromide

[0021]

[0022] Add 2-bromopyridine (158.0mg, 1.0mmol) and thiourea (91.3mg, 1.2mmol, 1.2equiv.) to the high-pressure sealed tube successively, seal it under air, heat at 80°C for 1h without solvent, and then add benzyl Bromine (205.2mg, 1.20mmol, 1.2equiv.) continued to react at 140°C for 23h. After the complete 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 ): δ8.47(d, J=4.3Hz, 1H), 7.47-7.41 (m, 3H), 7.31(t, J=7.4Hz, 2H), 7.28-7.25(m, 1H), 7.15(d, J=8.1Hz, 1H), 6.99-6.94(m, 1H), 4.46(s, 2H). 13 C NMR (100MHz, CDCl 3 ): δ158.4, 149.3, 135.9, 128.9, 128.4, 127.1, 122.0, 119.5, 34.4. MS (EI): m / z (%) 201 (48), 168 (100), 154 (2), 124 ( 10), 121(4), 91(58), 65(24), 51(8). This compound was known: Jia X, Yu L, Liu J, Xu Q, Sickert M, Chen L, Lautens M, Green Chem, 2014, 16...

Embodiment 2

[0024] Preparation of 2-pyridyl(4-methyl)-anisole sulfide from 2-bromopyridine, thiourea and 4-methylbenzyl bromide

[0025]

[0026] Add 2-bromopyridine (158.0mg, 1.0mmol) and thiourea (91.3mg, 1.2mmol, 1.2equiv.) successively into the high-pressure sealed tube, seal it directly under air, react at 80°C for 1h under solvent-free conditions, and then add 4- Methyl benzyl bromide continued to react at 140°C for 23h. After the complete reaction was monitored by TLC, the product was separated and purified by column chromatography. The isolated yield is 63%. 1 H NMR (400MHz, CDCl 3 ): δ8.46(d, J=4.7Hz, 1H), 7.44(t, J=7.7Hz, 1H), 7.31(d, J=7.7 Hz, 2H), 7.13(dd, J=14.9, 7.9Hz ,3H),6.99-6.95(m,1H),4.42(s,2H),2.33(s,3H). 13 C NMR (100MHz, CDCl 3 ): δ159.0, 149.3, 135.9, 134.7, 129.1, 128.8, 122.0, 119.5, 34.2, 21.1. MS (EI): m / z (%) 215 (68), 182 (85), 167 (30), 105 ( 100), 79(45), 51(15). This compound was known: Pathak AK, Pathak V, Seitz LE, Suling WJ, Reynolds RC, J Med C...

Embodiment 3

[0028] Preparation of 2-pyridyl(3-methyl)-anisole sulfide from 2-bromopyridine, thiourea and 3-methylbenzyl bromide

[0029]

[0030] Add thiourea (91.3mg, 1.2mmol, 1.2equiv.) and 3-methylbenzyl bromide (222.1mg, 1.20mmol, 1.2equiv.) sequentially into the high-pressure sealed tube, seal it directly under air, and react at 80°C without solvent 1h, then added 2-bromopyridine to continue the reaction at 170°C for 23h. After the complete reaction was monitored by TLC, the product was separated and purified by column chromatography. The isolated yield was 72%. 1 H NMR (400MHz, CDCl 3 ):δ8.46(d,J=4.6Hz,1H),7.48-7.44(m,1H), 7.24-7.13(m,4H),7.05(d,J=6.7Hz,1H),7.01-6.95( m,1H),4.41(s,2H),2.32(s,3H). 13 C NMR (100MHz, CDCl 3 ): δ158.9, 149.3, 138.1, 137.6, 135.9, 129.6, 128.3, 127.8, 125.9, 122.0, 119.5, 34.4, 21.3. MS (EI): m / z (%) 215 (30), 181 (68), 167 (23), 105 (100), 79 (68), 51 (32). This compound was known: Pathak AK, Pathak V, Seitz LE, Suling WJ, Reynolds RC, J MedChe...

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Abstract

The invention discloses a synthesis method of heteroaryl thioether. Under the conditions of no catalyst, no solvent, no additive and the like, aryl halide / 2-bromopyridine, thiourea and substituted benzyl bromide which are directly taken as raw materials to selectively synthesize asymmetric heteroaryl thioether in one step without using conventional organic sulfides such as mercaptan or thiophenol.The use of organic sulfides with high toxicity and heavy odor, such as mercaptan or thiophenol, is avoided, and the synthesis steps are shortened, so that the synthesis efficiency is improved, the reaction has good selectivity, and the asymmetric thioether can be preferentially obtained.

Description

technical field [0001] The invention relates to a synthesis method of heteroaryl sulfide, which belongs to the technical field of synthesis of organic sulfur compounds. Background technique [0002] Organosulfur compounds are a very important class of compounds. As important intermediates in 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, such as the treatment of inflammation, antidepression, human immunodeficiency virus, asthma, and Alzheimer's disease. [0003] However, in the preliminary work, catalysts, additives, or additives need to be added to the reaction system, resulting in a lot of waste. Therefore, it is of great significance for organic synthesis, biochemistry, and medicinal chemists to find new green and concise methods to synthesize unsymmetric...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/70C07D213/60
CPCC07D213/70C07D213/60
Inventor 徐清王琦章小兰赵霖昱
Owner YANGZHOU UNIV