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Electrophilic fluoroform sulfenyl reagent and synthetic method and application thereof

A technology of trifluoromethylthio group and synthesis method, which is applied in sulfide preparation, organic chemistry and other directions, can solve the problems of low substrate tolerance, high reagent toxicity, difficult operation and the like, and achieves simple method, easy synthesis and operation. Effect

Active Publication Date: 2014-05-21
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] Summarizing the indirect introduction method, it is not difficult to find that it has some disadvantages: 1. The reaction conditions of the nucleophilic fluorination method are harsh, the substrate tolerance is low, and the reagent toxicity is high; 2. The single electron transfer method solves the reagent toxicity to a certain extent. However, the help of free radical initiators such as ultraviolet light must be used; 3. The toxicity and source of thiophenol or disulfide compounds are also one of the limiting factors
CF 3 SCl has a low boiling point and high toxicity, making it difficult to handle

Method used

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  • Electrophilic fluoroform sulfenyl reagent and synthetic method and application thereof
  • Electrophilic fluoroform sulfenyl reagent and synthetic method and application thereof
  • Electrophilic fluoroform sulfenyl reagent and synthetic method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0027] Example 1 Synthesis of Electrophilic Trifluoromethylthiolation Reagent

[0028] (1) Add 0.208g (10mmol) AgSCF to an oven-dried 100ml Schlenk tube equipped with a stirrer in an argon atmosphere. 3and 0.296 g (10 mmol) of starting material P-152, and 50 ml of freshly purified tetrahydrofuran was added. After preheating at 50°C, the reaction was stirred at this temperature for 1 hour, and AgSCF was detected by fluorine spectroscopy. 3 Completely disappeared, filtered through celite and concentrated to minimum volume in vacuo. The products were separated by flash column chromatography (wet loading). Eluent: 30-60°C petroleum ether, Rf: 0.95. Yield: 30%. The product was further purified using Kugelrohr distillation.

[0029] 1 H NMR (300MHz, CDCl 3 ,293K,TMS)δ8.05(d,J=7.8Hz,1H),7.42-7.32(m,1H),6.97(t,J=7.2Hz,1H),1.86(s,6H)ppm; 19 F NMR (375MHz, CDCl 3 )δ-51.2(s,3F)ppm;IR(KBr):ν=3057,2976,2930,1583,1560,1464,1428,1384,1366,1262,1230,1174,1087,1048,10104,952,904,855,7...

Embodiment 2

[0040] Example 2 Application of electrophilic trifluoromethylthio reagent

[0041] The electrophilic trifluoromethylthio reagent is S1.

[0042] p-tert-butylphenyl trifluoromethyl sulfide

[0043] 1-tert-Butyl-4-[(trifluoromethyl)thio]benzene 3-a

[0044] To an oven-dried sealed tube equipped with a stirring bar was sequentially added 0.0185 g (0.05 mmol) Cu(MeCN) under an argon atmosphere 4 PF 6 , 0.0160g (0.1mmol) 2,2'-bipyridine, 0.138g (1.0mmol) anhydrous potassium carbonate, 0.3620g (0.5mmol) electrophilic trifluoromethylthio reagent and 0.1157g (0.65mmol) 4-tertiary butylphenylboronic acid, and 2.5 ml of freshly purified diethylene glycol dimethyl ether was added. The reaction was stirred at 35°C and detected by fluorine spectrum until the electrophile completely disappeared, which generally took 15 hours. 25ml of distilled water and 20ml of anhydrous ether were added to the reaction system for extraction, the organic phase was separated, the aqueous phase was extra...

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Abstract

The invention relates to an electrophilic fluoroform sulfenyl reagent and a synthetic method and application thereof. The structural formula of the electrophilic fluoroform sulfenyl reagent is shown in the specification. The synthetic method disclosed by the invention is simple and convenient and can be used for preparing a fluoroform sulfenyl product by reacting the electrophilic fluoroform sulfenyl reagent with a nucleophilic reagent.

Description

[0001] reduce the field [0002] The invention relates to an electrophilic trifluoromethylthio reagent, a synthesis method and applications thereof. It can be used for the reaction of electrophilic trifluoromethylthiolation reagents with a nucleophile to prepare trifluoromethylthiolated products. Background technique [0003] Trifluoromethylthio (SCF 3 ) has high lipid solubility (π=1.44) [Okano, T.Eguchi, N.S.Syntlett.2001, 1449-1451.], small organic molecules are introduced into SCF 3 After the group, the lipid solubility of the whole molecule can be significantly improved, and the transmembrane absorption of the compound can be directly improved. At the same time, the bond energy of the C-F bond is much larger than that of the C-H bond, and the trifluoromethylthio group is a strong electron withdrawing group, which reduces the electron cloud density of small molecules and makes it difficult to be metabolized in vivo. The combined effect of these factors greatly increases...

Claims

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Application Information

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IPC IPC(8): C07D347/00C07C319/14C07C323/03C07C323/20C07C323/22C07C323/09C07C323/21C07C323/62C07C323/16C07C323/07C07C323/56C07C323/14C07C323/61C07D215/36C07D213/70C07D333/18
CPCC07C319/14C07C323/03C07C323/07C07C323/09C07C323/14C07C323/16C07C323/20C07C323/21C07C323/22C07C323/56C07C323/61C07C323/62C07D213/70C07D215/36C07D333/18C07D347/00
Inventor 沈其龙吕龙邵欣欣王雪强杨涛
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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