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Trifluoromethylthiolation reagent, and preparation method and application thereof

A technology of trifluoromethylthio group and reagent, applied in the preparation of thioether, organic chemistry, etc., can solve the problems of high toxicity of trifluoromethylthio group reagent, low reactivity, harsh reaction conditions, etc.

Active Publication Date: 2016-10-05
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The technical problem to be solved by the present invention is to overcome the relatively high toxicity of trifluoromethylthiolation reagents in the prior art, limited scope of applicable substrates, low reactivity, harsh reaction conditions, poor reaction effect on aromatics or heteroaromatics, etc. defect, and a trifluoromethylthiolation reagent, preparation method and application thereof are provided

Method used

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  • Trifluoromethylthiolation reagent, and preparation method and application thereof
  • Trifluoromethylthiolation reagent, and preparation method and application thereof
  • Trifluoromethylthiolation reagent, and preparation method and application thereof

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Experimental program
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Effect test

Embodiment 1 3

[0056] The preparation of embodiment 1 trifluoromethylthiolation reagent 1

[0057]

[0058] Under the condition of Ar gas protection, compound 2 (2.0g, 6mmol), AgSCF 3 (1.76g, 8.4mmol) was added to a 50mL dry Schlenk bottle equipped with a stir bar, and 20mL of redistilled dichloromethane was added, and stirred at room temperature (about 25°C) in the dark for 2 hours. After the reaction was finished, the AgCl precipitate was filtered, the sample was mixed with silica gel, and the white solid trifluoromethylthiolation reagent 1 was obtained by column chromatography. (1.50g, yield 65%, purity greater than 98% identified by hydrogen spectrum.).

[0059] N-benzenesulfonyl-N-trifluoromethylthiobenzenesulfonamide (N-(Phenylsulfonyl)-N-((trifluoromethyl)thio)benzenesulfonamide): yield 65%, white solid. 1 H NMR (400MHz, CDCl 3 ,293K,TMS)δ8.05(d,J=8.1Hz,4H),7.71(t,J=7.4Hz,2H),7.58(t,J=7.7Hz,4H); 19 F NMR (376MHz, CDCl 3 )δ-48.20(s,3F); 13 C NMR (126MHz, CDCl 3 , 293K, TMS) δ...

Embodiment 2

[0062] Naphthalene was used as an aromatic hydrocarbon substrate and reacted for 24 hours. The screening conditions for reaction temperature, concentration, reagent equivalent, and acid dosage are shown in Table 1. x represents the charging capacity of substrate naphthalene; y represents the charging capacity of the trifluoromethylthiolation reagent shown in formula 1; z represents the charging capacity of acid; a Indicates that the molar volume ratio of trifluoromethylthiolation reagent 1 to solvent is 0.1mol / L; 19 F NMR yield is internal standard with trifluorotoluene; b Indicates that the molar volume ratio of trifluoromethylthiolation reagent 1 to solvent is 0.5mol / L; NR indicates that no reaction product was detected.

[0063]

[0064] Table 1 Screening table of reaction conditions

[0065]

[0066]

Embodiment 3

[0067] Embodiment 3 The application of the trifluoromethylthiolation reagent shown in formula 1, the specific operating conditions are as follows:

[0068] Indole substrate reaction operation steps: under the condition of argon (Ar) protection, the indole substrate (0.3mmol), the trifluoromethylthiolation reagent 1 (0.36mmol) shown in formula 1 is added to already Add 1.5 mL of redistilled dichloromethane to a 25 mL sealed tube with a stirring bar, and react for 24 hours at room temperature (about 20°C to 25°C). TLC was followed until the reaction was completed, the sample was mixed with silica gel, and the corresponding products (a1-a7) were separated by flash column chromatography.

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Abstract

The invention discloses a trifluoromethylthiolation reagent, and a preparation method and an application thereof. The invention provides the trifluoromethylthiolation reagent represented by a formula 1, and the preparation method thereof. The method comprises the following step: in an organic solvent, a compound represented by a formula 2 is subjected to a nucleophilic substitution reaction with trifluoromethylthio silver. The invention also provides an application of the trifluoromethylthiolation reagent represented by the formula 1 in an electrophilic substitution reaction with RH for preparing a compound containing trifluoromethylthio group. The application comprises the following step: in an organic solvent, the trifluoromethylthiolation reagent represented by the formula 1 is subjected to an electrophilic substitution reaction with a compound represented by a formula 4. The trifluoromethylthiolation reagent preparation method has the advantages of simple method, mild reaction conditions, and inexpensive and easy-to-obtain raw materials. The trifluoromethylthiolation reagent provided by the invention has a wide application range, and is especially suitable for aromatic hydrocarbons. Trifluoromethylthio reaction conversion rate is high, and reaction yield. The prepared product has high purity. The reagent has a good industrialized production prospect.

Description

technical field [0001] The invention specifically relates to a trifluoromethylthiolation reagent, a preparation method and an application thereof. Background technique [0002] Fluorine atoms have small atomic radius, high electronegativity, and low polarizability. Therefore, introducing fluorine atoms or fluorine-containing substituents into molecules can greatly change the physical, chemical, and physiological properties of molecules. As a fluorine-containing substituent, trifluoromethylthio has high electronegativity and fat solubility. Therefore, trifluoromethylthio plays an important role in the fields of medicine, pesticides and materials. [0003] The electrophilic trifluoromethylthiolation reagents reported in the literature mainly include the following categories: trifluoromethylthio chloride, which was widely used in the early stage; the Munavalli group first synthesized (Munavalli, S.Synth.Commun.2000, 30, 2847. ), and developed by the Rueping research group (Ru...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C311/48C07D209/30C07C323/03C07C323/20C07C323/21C07C319/14C07D333/62C07D209/88
Inventor 沈其龙吕龙张盼盼徐春发
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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