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A kind of α-hydroxy thioether and its preparation method and application

A phenyl, ethyl technology, applied in the field of alpha-hydroxy sulfide and its preparation, can solve the problems of poor selectivity, harsh reaction conditions, restricted use, etc., and achieves high atom economy, optimistic application prospect, and easy purification. Effect

Inactive Publication Date: 2016-08-17
RENMIN UNIVERSITY OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

(Gao, P.; Xu, P.F.; Zhai, H.B. Tetrahedron Lett. 2008, 49, 6536.; Movassagh, B.; Navidi, M. Tetrahedron Lett. 2008, 49, 6712.; Surendra, K.; Krishnaveni, N.S. ;Sridhar,R.;Rao,K.R.J.Org.Chem.2006,71,5819.) These methods have great limitations, such as poor selectivity, low yield, harsh reaction conditions, and the reaction process Many side reaction products cannot be controlled
These defects limit the use of existing methods in the synthesis of α-hydroxy thioethers

Method used

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  • A kind of α-hydroxy thioether and its preparation method and application
  • A kind of α-hydroxy thioether and its preparation method and application
  • A kind of α-hydroxy thioether and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Example 1. Preparation of 1-phenyl-2-(p-tolylthio)ethanol (1-phenyl-2-(p-tolylthio)ethanol), the compound represented by formula I

[0036]

[0037] Add 0.025mmol of accelerator copper acetate Cu(OAc) to a 100mL dry Schlenk reaction tube under 1 atmosphere of oxygen atmosphere 2 , 1mmol of promoter p-methoxybenzoic acid, and then evacuated the reaction system to a vacuum with a vacuum pump, and filled the reaction system with oxygen to 1 atmosphere with an oxygen balloon, and 0.5mmol of compound styrene of formula II and 5mL of organic solvent 1,2-Dichloroethane and 2 mmol of p-methylthiophenol compound represented by formula III are sequentially injected into the reaction system. Heat the above mixture at 50°C with continuous stirring for sulfhydryl hydroxylation reaction for 3 hours. After the reaction is completed, a yellow-brown reaction mixture is obtained. Then the mixture is concentrated by rotary evaporation, and then separated by an acid silica gel column (silica g...

Embodiment 2

[0044] Example 2. Preparation of 1-phenyl-2-(p-tolylthio)ethanol (1-phenyl-2-(p-tolylthio)ethanol), the compound represented by formula I

[0045]

[0046] According to the steps of Example 1, only the amount of the accelerator p-methoxybenzoic acid was replaced by 0.5 mmol, and the mercapto hydroxylation reaction was replaced by 1 hour. The resulting product was a colorless oily pure product 1-phenyl-2-(p The yield of methyl phenylthio) ethanol is 65%.

[0047] The infrared, nuclear magnetic and mass spectrum data of the compound are as follows:

[0048] IR(KBr): ν max 3443,3030,2920,1693,1493,1452,1288,1055,804,698cm -1 ;

[0049] 1 H NMR(400MHz, CDCl 3 )δ7.37-7.25(m,7H), 7.15(d,J=7.6Hz,2H), 4.69(ddd,J=9.6Hz,3.6Hz,2.4Hz,1H), 3.29(dd,J=13.6Hz) ,3.6Hz,1H),3.04(dd,J=13.6Hz,9.6Hz,1H),2.97(d,J=2.4Hz1H)2.36(s,3H);

[0050] 13 C NMR(100MHz, CDCl 3 )δ142.1, 137.1, 131.0, 129.9, 128.5, 127.9, 125.8, 71.4, 44.8, 21.0;

[0051] HRMS calcd for C 15 H 16 NaOS(M+Na) + :267.0820;found:267.08114.

...

Embodiment 3

[0053] Example 3: Preparation of 1-phenyl-2-(p-tolylthio)ethanol (1-phenyl-2-(p-tolylthio)ethanol)

[0054]

[0055] According to the steps of Example 1, only the accelerator copper acetate Cu(OAc) 2 The amount of thiophenol was replaced by 0.0125mmol, the amount of p-methylthiophenol represented by formula III was replaced by 1mmol, and the reaction time of sulfhydryl hydroxylation was replaced by 1 hour. The resulting product was a colorless oily pure product 1-phenyl-2- (P-methylphenylthio) ethanol, the yield was 56%.

[0056] The infrared, nuclear magnetic and mass spectrum data of the compound are as follows:

[0057] IR(KBr): ν max 3443,3030,2920,1693,1493,1452,1288,1055,804,698cm -1 ;

[0058] 1 H NMR(400MHz, CDCl 3 )δ7.37-7.25(m,7H), 7.15(d,J=7.6Hz,2H), 4.69(ddd,J=9.6Hz,3.6Hz,2.4Hz,1H), 3.29(dd,J=13.6Hz) ,3.6Hz,1H),3.04(dd,J=13.6Hz,9.6Hz,1H),2.97(d,J=2.4Hz1H)2.36(s,3H);

[0059] 13 C NMR(100MHz, CDCl 3 )δ142.1, 137.1, 131.0, 129.9, 128.5, 127.9, 125.8, 71.4, 44.8, 21.0;

[006...

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Abstract

The invention discloses alpha-hydroxysulfide and a preparation method and application thereof. The alpha-hydroxysulfide has a structure formula as shown in formula I. The polysubstituted alpha-hydroxysulfide structure can be constructed by direct use of industrial raw materials thiophenol and derivatives thereof and the like. The method realizes production of the alpha-hydroxysulfide by use of very cheap metal Cu and a simple organic carboxylic acid used as a promoter and direct use of oxygen to oxidize industrial raw materials thiophenol and derivatives thereof for oxidation hydroxylation reaction with olefins. According to the method, oxygen is used as an oxidant, atomic economy property is high, and the method is environmental friendly. The method is simple in operation, direct high-yield synthesis of alpha-hydroxysulfide compounds can be achieved only by one step, the product is easy to purify, and the method is groundbreaking, is not available in other traditional organic synthesis, and has optimistic application prospects.

Description

Technical field [0001] The invention relates to an α-hydroxy sulfide and a preparation method and application thereof. Background technique [0002] α-Hydroxysulfide compounds, English α-hydroxysulfide, are an important class of heteroatom compounds, which are widely used in the fields of organic chemistry, life sciences and medicine. Many drugs contain the backbone of α-hydroxy sulfide, such as bicalutamide (1), which is a non-steroidal anti-androgen drug used in the treatment of advanced prostate cancer and is well absorbed by oral administration. Leukotriene C-1 (2), it has a therapeutic effect on inflammation of the upper and lower respiratory tract. [0003] [0004] The traditional synthetic methods of α-hydroxy sulfide mainly include: (1) the ring-opening reaction of epoxy compounds. (2) the use of sulfide as a sulfur source to react with olefins. (3) The reaction of thiophenol and olefin under complex conditions. (Gao, P.; Xu, PF; Zhai, HBT Trahedron Lett. 2008, 49, 6536...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C319/14C07C323/16C07C323/56C07C323/52C07C323/14A01N31/14A01N37/36A01P7/04
Inventor 李志平席辉
Owner RENMIN UNIVERSITY OF CHINA