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Aryl-alkyl asymmetric persulfide compounds and their synthesis method and application

A synthetic method and asymmetric technology, applied in the field of organic compound process application, can solve the problems of poor selectivity, easy oxidation, environmental and human harm, etc.

Active Publication Date: 2018-02-23
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In this method, the organic mercaptan or thiophenol compounds used are easily oxidized, and the selectivity in the oxidation process is poor, which is poisonous to the metal catalyst; the raw material tastes too heavy, and has different degrees of damage to the environment and human body ; so that the application of such methods is restricted

Method used

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  • Aryl-alkyl asymmetric persulfide compounds and their synthesis method and application
  • Aryl-alkyl asymmetric persulfide compounds and their synthesis method and application
  • Aryl-alkyl asymmetric persulfide compounds and their synthesis method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0083] Synthesis of SS-benzylacetyl dithioester:

[0084]

[0085] Under nitrogen atmosphere, add TolSO 2 SNa (150mmol, 31.54g, 1equiv.), BnCl (180mmol, 20.7mL, 1.2equiv.), TBAI (7.5mmol, 2.77g, 5mol%) and MeCN (400mL), the reaction system was reacted at 50°C for 10h , adding silica gel, removing the solvent under reduced pressure, and purifying by column chromatography to obtain the thiosulfonate compound. Add the thiosulfonate compound (125mmol, 1equiv, 34.8g) obtained in the flask, KSAc (162.5mmol, 1.3equiv, 18.5g) and DCM (500mL), the reaction system was reacted at room temperature for 6h, and then The reaction solution was filtered, and KSAc (62.5mmol, 0.5equiv., 7.137g) was added to the obtained filtrate to continue the reaction. After the reaction was detected by TLC, after the solvent was removed under reduced pressure, petroleum ether was recrystallized to obtain the product 2a (22.32g ,90%). 1 H NMR (400MHz, CDCl 3 )δ7.54(d,J=7.8Hz,1H),7.33(m,4H),4.02(s,3H). ...

Embodiment 2

[0087] Synthesis of SS-(4-methylthiobenzyl)acetyl dithioester:

[0088]

[0089] Under nitrogen atmosphere, add TolSO 2 SNa (5mmol, 1.051g, 1equiv.), p-methylthiobenzyl chloride (6mmol, 1.036g, 1.2equiv.), TBAI (0.25mmol, 92.4mg, 5mol%) and MeCN (20mL), the reaction system at 50 After reacting at ℃ for 10 h, adding silica gel, removing the solvent under reduced pressure, and purifying by column chromatography, the thiosulfonate compound was obtained. The obtained thiosulfonate compound (3mmol, 1equiv, 972mg), KSAc (3.9mmol, 1.3equiv, 445mg) and DCM (20mL) were added to the flask, and the reaction system was reacted at room temperature for 6h, and the reaction was detected by TLC. Finally, the solvent was removed under reduced pressure and purified by column chromatography to obtain product 2b (689 mg, 94%). (Eluant polarity: PE:EA 50:1). 1 H NMR (400MHz, CDCl 3 )δ7.20(m,4H),3.88(s,2H),2.47(s,3H),2.36(s,3H). 13 C NMR (100MHz, CDCl 3 )δ 194.93, 138.18, 132.59, 129.83, 1...

Embodiment 3

[0091] Synthesis of SS-(4-methoxybenzyl)acetyl dithioester:

[0092]

[0093] Under nitrogen atmosphere, add TolSO 2 SNa (5mmol, 1.051g, 1equiv.), p-methoxybenzyl chloride (6mmol, 939.7mg, 1.2equiv.), TBAI (0.25mmol, 92.4mg, 5mol%) and MeCN (20mL), the reaction system at 50 After reacting at ℃ for 10 h, adding silica gel, removing the solvent under reduced pressure, and purifying by column chromatography, the thiosulfonate compound was obtained. The obtained thiosulfonate compound (3mmol, 1equiv, 972mg), KSAc (3.9mmol, 1.3equiv, 445mg) and DCM (20mL) were added to the flask, and the reaction system was reacted at room temperature for 6h, and the reaction was detected by TLC. Finally, the solvent was removed under reduced pressure and purified by column chromatography to obtain product 2c (664 mg, 96%). (Eluant polarity: PE:EA 100:1). 1 H NMR (400MHz, CDCl 3 )δ7.23(d, J=8.7Hz, 2H), 6.85(d, J=8.7Hz, 2H), 3.89(s, 2H), 3.79(s, 3H), 2.35(s, 3H). 13 C NMR (100MHz, CDCl 3 )δ...

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Abstract

Disclosed is an asymmetric aryl-alkyl persulfate compound as represented by formula (3) and a synthesis method therefor, in which an arylboronic acid of formula (1) and R2SSCOR3 of formula (2) serve as reaction raw materials and, under the effect of copper metal catalyst, react to produce the asymmetric aryl-alkyl persulfate compound. The present invention has mild reaction conditions, inexpensive and readily available raw materials, a simple reaction operation, high yield, and an inexpensive metal serving as the catalyst in the reaction, is economical, practical, and environmentally friendly, has a reaction substrate that can be prepared easily, and provides high reaction efficiency when the reaction is magnified. The asymmetric aryl-alkyl persulfate compound as represented by formula (3) prepared in the present invention is applicable in further synthesis of C-S bond-containing compounds such as benzyl(phenyl)sulfide and benzyl(4-methoxyphenyl)sulfide in a potential medicament. The present invention has broad application prospects and practical value.

Description

technical field [0001] The invention belongs to the technical field of organic compound technology application, and specifically relates to a class of aryl-alkyl asymmetric persulfide compounds and an efficient and convenient synthesis method thereof. Background technique [0002] Organic compounds containing persulfur structures are a very important class of compounds, which widely exist in natural products, drugs, materials, and food additives (as shown below), so constructing persulfur compounds from some simple and commercially available compounds Compounds are particularly important. [0003] [0004] In the prior art, the traditional method of synthesizing asymmetric persulfide compounds through asymmetric persulfurization reaction is mainly to combine a mercaptan or thiophenol compound with another mercaptan or thiophenol compound and its derivatives. preparation. In this method, the organic mercaptan or thiophenol compounds used are easily oxidized, and the sele...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C319/22C07C321/28C07C321/20C07C323/20C07C323/09C07C323/63C07C323/62C07C323/22C07C323/07C07C323/16C07C323/52C07C323/65C07D317/62C07D333/34C07D307/64C07H13/06C07H1/00C07D493/04C07C381/00
CPCC07C319/22C07C321/20C07C321/28C07C323/09C07C323/20C07C381/00C07D307/64C07D317/62C07D493/04C07H1/00C07H13/06
Inventor 姜雪峰肖霄冯明昊
Owner EAST CHINA NORMAL UNIV