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Diaryl sulfide compounds and preparation method thereof

A technology of diaryl sulfide and diaryl disulfide, which is applied in the field of preparation of diaryl sulfide compounds, can solve problems such as long time, high cost, and danger of aryl diazonium compounds, and meet the reaction conditions Mild, easy to operate, safe and economical

Active Publication Date: 2019-05-03
ZHENGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

On the one hand, the cost of transition metals (especially noble metal catalysts) is relatively high, and on the other hand, the synthesis products are prone to metal residues, which also increases the cost of subsequent purification
In addition, although the coupling reaction of aryl diazonium compound and diaryl disulfide can be realized by microwave reaction to synthesize diaryl sulfide compounds (Green Chem., 2012, 14, 2024), but the reaction requires The time is long, and the reaction raw material aryl diazonium compound has certain dangers, which limits its application to a certain extent
The method disclosed in the present invention for synthesizing diaryl sulfide compounds from arylhydrazine compounds and diaryl disulfides under visible light irradiation has no relevant literature and patent reports

Method used

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  • Diaryl sulfide compounds and preparation method thereof
  • Diaryl sulfide compounds and preparation method thereof
  • Diaryl sulfide compounds and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] The preparation method of diaryl sulfide compound, the steps are as follows:

[0023] In a 25 mL reaction tube, add photosensitizer Eosin Y disodium salt (5 mol%), hydrogen peroxide (1 equiv), solvent dimethyl sulfoxide 1.5 mL, phenylhydrazine 0.5 mmol, diphenyl disulfide 4.0 mmol, stirring in the air to control the reaction temperature to 45 °C, and reacting under blue light for 8 hours, the final product was separated by silica gel column chromatography, and the yield of the final product was 68% based on the molar amount of phenylhydrazine as 100%.

[0024] The specific results are as follows:

[0025]

[0026] 1 H NMR (400 MHz, CDCl 3 ): δ 7.48 – 7.43 (m, 4H), 7.42 – 7.36 (m, 4H), 7.36– 7.30 (m, 2H). 13 C NMR (101 MHz, CDCl 3 ): δ 135.90, 131.15, 129.32, 127.16.

Embodiment 2

[0028] The preparation method of diaryl sulfide compound, the steps are as follows:

[0029] Add photosensitizer Eosin Y disodium salt (5 mol%), hydrogen peroxide (1 equiv), solvent dimethyl sulfoxide 1.5 mL, 4-methoxyphenylhydrazine 0.5 mmol, diphenyl 2.0 mmol of yl disulfide, stirred in the air to control the reaction temperature to 25 °C, reacted under blue light irradiation for 8 hours, and separated by silica gel column chromatography to obtain the final product.

[0030] The specific results are as follows:

[0031]

[0032] 1 H NMR (400 MHz, CDCl 3 ) δ 7.50 (d, J = 2.1 Hz, 1H), 7.48 (d, J = 2.2 Hz,1H), 7.33 – 7.27 (m, 2H), 7.26 – 7.18 (m, 3H), 6.97 (d, J = 2.2 Hz, 1H), 6.96(d, J = 2.1 Hz, 1H), 3.87 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ): δ 159.91, 138.73, 135.49, 129.02, 128.23, 125.83, 124.31, 115.07, 55.42.

Embodiment 3

[0034] The preparation method of diaryl sulfide compound, the steps are as follows:

[0035] Add photosensitizer Eosin Y disodium salt (5 mol%), hydrogen peroxide (1 equiv), solvent dimethyl sulfoxide 1.5 mL, 4-nitrophenylhydrazine 0.5 mmol, diphenyl 2.0 mmol of disulfide was stirred in the air to control the reaction temperature to 35 °C, reacted under blue light irradiation for 8 hours, and separated by silica gel column chromatography to obtain the final product.

[0036] The specific results are as follows:

[0037]

[0038] 1 H NMR (400 MHz, CDCl 3 ): δ 8.26 (dd, J = 8.3, 1.5 Hz, 1H), 7.66 – 7.59(m, 2H), 7.52 (dd, J = 5.0, 1.9 Hz, 3H), 7.36 (m, 1H), 7.24 (m ,1H), 6.89 (dd,J = 8.2, 1.3 Hz, 1H). 13 C NMR (101 MHz, CDCl 3 ): δ145.00, 139.50, 135.92, 133.41, 131.02, 130.12, 130.02, 128.32, 125.76, 124.94.

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Abstract

The invention discloses diaryl sulfide compounds and a preparation method thereof. The method uses an organic dye as a photosensitizer, an equivalent weight of an oxidant is added, an aryl hydrazine and a diaryl disulfide are used as reactants, dimethyl sulfoxide is used as a solvent, a temperature is controlled at 25-45 DEG C, a reaction is performed for 5-12 h under visible light irradiation, column chromatography separation is performed, and therefore the product sulfide compounds are obtained. The invention provides the novel method for synthesizing the diaryl sulfide target compounds by using the cheap readily-available aryl hydrazine and diaryl disulfide compounds as starting raw materials for the first time. The method provided by the invention has the advantages of mild reaction conditions, simple operation and the like, and can also conveniently synthesize the asymmetric diaryl sulfide compounds; in drug synthesis, a metal catalyst is difficult to remove, so that drug production and applications are limited; therefore, in the method provided by the invention, the metal-free catalytic system shows huge potential application value.

Description

technical field [0001] The invention relates to the field of chemical synthesis, in particular to a preparation method of diaryl sulfide compounds. Background technique [0002] Organic compounds containing carbon-sulfur bonds, such as thioether compounds, widely exist in natural products, drugs, and material molecules, and have extensive and important application values ​​in many fields. In addition, many other sulfur-containing compounds have shown promising application prospects in the treatment of human immunodeficiency virus (HIV), cancer, Alzheimer's disease, and Parkinson's disease. Generally, diaryl sulfide compounds can be catalyzed by transition metals under the coupling reaction of halogenated compounds or diazonium salt compounds and sulfur-containing reagents such as thiophenols or disulfides (Chem. Commun., 2015, 51, 5890 and J. Org. Chem., 2013, 78, 11110), because these synthesis methods usually require the use of transition metals as catalysts or acid, base...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C319/20C07C321/30C07C323/20C07C323/09C07D213/70
Inventor 陈晓岚李瑞石韬於兵屈凌波
Owner ZHENGZHOU UNIV
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