Trifluoromethylthio reagent as well as synthetic method and application thereof

A technology of trifluoromethylthio group and reagent, applied in the field of trifluoromethylthio group reagent, can solve the problems of harsh reaction conditions, low conversion rate, unsuitable for industrial production and the like

Active Publication Date: 2015-09-30
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
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  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The technical problem to be solved by the present invention is to overcome the disadvantages of harsh reaction conditions, low conversion rate, low yield, high production cost, limited applicable substrates and unsuitability for industrial production in the prior art for introducing trifluoromethylthio. , and provides trifluoromethylthiolation reagents, synthesis methods and applications

Method used

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  • Trifluoromethylthio reagent as well as synthetic method and application thereof
  • Trifluoromethylthio reagent as well as synthetic method and application thereof
  • Trifluoromethylthio reagent as well as synthetic method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0085] Example 1 Synthesis of trifluoromethylthiolation reagent 1.

[0086] Saccharin (6.0g) was reacted with tert-butyl hypochlorite (5ml) in methanol (120ml) at room temperature for 5 minutes to obtain compound chlorosaccharin 1a (6.0g, 84%); Silver fluoromethylthio (3.6g) was reacted in acetonitrile (40ml) at room temperature for 10 minutes to obtain compound 1 (3.3g, 86%). Reagent 1 is a white solid at room temperature, soluble in dichloromethane, chloroform, acetone, acetonitrile and other organic solvents.

[0087]

[0088] Nitrogen-trifluoromethylthiosaccharin (2-((Trifluoromethyl)thio)benzo[d]isothiazol-3(2H)-one1,1-dioxide): 1 H NMR (400MHz, cdcl 3 )δ8.20(d,J=7.6Hz,1H),8.06-7.97(m,2H),7.96-7.90(m,1H); 19 F NMR (376MHz, CDCl 3 )δ-47.34(s,3F); 13 C (126MHz, CDCl 3 )δ158.50,138.08,136.50,135.12,127.42(q,J=31.6Hz),126.67,126.30,122.12ppm.MS(DART POS):283.97(M+H);HRMS(DART POS):C 8 h 5 o 3 NF 3 S 2 (M+H) calculated value: 283.9657, experimental value: 283.965...

Embodiment 2

[0091]

[0092] Dissolve 1-methylbenzylamine (37mg, 0.3mmol) and trifluoromethylthiolation reagent (100mg, 0.36mmol) in dichloromethane (6.0mL) under air condition, stir at room temperature for 1 hour, then add 100μl triethyl The amine was evaporated under reduced pressure to remove the solvent, and the residue was purified by a flash silica gel column to obtain the corresponding nitrogen trifluoromethylthioated product a1 (60 mg, 90%). The purity is greater than 95% identified by hydrogen spectrum.

[0093] Nitrogen-trifluoromethylthio-1-phenyl-ethylamine ((S)-N-(1-Phenylethyl)-S-(trifluoromethyl)thiohydroxylamine): 1 H NMR (400MHz, CDCl 3 )δ7.39–7.36(m,2H),7.33–7.30(m,3H),4.24(q,J=6.6Hz,1H),3.28(s,1H),1.50(d,J=6.6Hz,3H )ppm; 19 F NMR (376MHz, CDC 3 )δ-51.86(s,3F)ppm; 13 C NMR (126MHz, CDCl 3 )δ143.41,130.38(q,J=317.4Hz),128.67,127.85,126.70,60.61,22.54ppm.MS(EI):221.1;HRMS(EI):C 9 h 10 f 3 NS calculated value: 221.0486, experimental value: 221.0487. IR: υ3354, 30...

Embodiment 3

[0095]

[0096] Dissolve phenethylamine (37mg, 0.3mmol) and trifluoromethylthiolation reagent (100mg, 0.36mmol) in dichloromethane (6.0mL) under air conditions, stir at room temperature for 1 hour, add 100μl triethylamine, reduce The solvent was removed by rotary evaporation under high pressure, and the residue was purified by a flash silica gel column to obtain the corresponding nitrogen trifluoromethylthioated product a2 (63 mg, 94%). The purity is greater than 95% identified by hydrogen spectrum.

[0097] Nitrogen-trifluoromethylthio-2-phenyl-ethylamine (N-Phenethyl-S-(trifluoromethyl)thiohydroxylamine): 1 H NMR (400MHz, CDCl 3 )δ7.36-7.30(m,2H),7.28-7.23(m,1H),7.22-7.17(m,2H),3.36(td,J=6.8,6.0Hz,2H),2.89(br,NH, 1H),2.86(t,J=7.0Hz,2H)ppm; 19 F NMR (376MHz, CDCl 3 )δ-52.47(s,3F)ppm; 13 C NMR (126MHz, CDCl 3 )δ138.42,130.40(q,J=317.5Hz),128.76,128.65,126.54,54.62,36.60ppm.MS(EI):221.0;HRMS(EI):C 9 h 10 NF 3 S calculated value: 221.0486, experimental value: 221.048...

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Abstract

The invention discloses a trifluoromethylthio reagent as well as a synthetic method and application thereof and provides a compound I and a preparation method of the compound I. The preparation method comprises the step: reacting a compound 1a with trifluoromethylthio silver, so as to obtain the compound 1, wherein the reaction is as shown in the specification. The invention further provides application of the compound 1 as the trifluoromethylthio reagent. The compound 1 can react with amine compounds, thiol or phenolic compounds to generate the compound containing trifluoromethylthio. The trifluoromethylthio reagent 1 has the beneficial effects of high efficiency, conversion rate and yield, mild reaction conditions, low production cost and wide applicable range and is applicable to industrial production.

Description

technical field [0001] The invention relates to a trifluoromethylthiolation reagent, a synthesis method and an application thereof. Background technique [0002] Fluorine-containing functional groups are an important structural unit in drugs and pesticides. The introduction of fluorine functional groups can effectively increase metabolic stability, improve fat solubility, better penetrate cell membranes, and improve drug efficacy. Trifluoromethylthio is an important group in fluorine-containing functional groups. It has strong electronegativity and very good fat solubility (π=1.44), so trifluoromethylthio is introduced into small organic molecules can play a very important role. [0003] For the introduction of trifluoromethylthio (SCF) into the molecule 3 ) methods are mainly divided into: indirect introduction method and direct introduction method. The indirect introduction method is mainly trichloromethylthiobenzene and excess SbF 3 Under the condition of no solvent, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D275/06C07D213/76C07D239/38C07D263/58C07D277/78C07D217/08C07C313/20C07C319/24C07C321/28C07C323/09C07C323/07C07B45/00
Inventor 沈其龙徐春发
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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