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Compound containing trifluoromethylthio group and preparation method thereof

A technology for trifluoromethylthio compounds, which is applied in the field of trifluoromethylthio compounds and their preparation, and can solve problems such as low yield, harsh reaction conditions, and unsuitability for industrial production

Active Publication Date: 2015-09-30
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

[0004] The technical problem to be solved by the present invention is to overcome the defects of harsh reaction conditions, low conversion rate, low yield, high production cost, limited applicable substrates and unsuitability for industrialized production in the method for introducing trifluoromethylthio in the prior art. , and provide compounds containing trifluoromethylthio and preparation methods thereof

Method used

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  • Compound containing trifluoromethylthio group and preparation method thereof
  • Compound containing trifluoromethylthio group and preparation method thereof
  • Compound containing trifluoromethylthio group and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0135] Example 1 Synthesis of trifluoromethylthiolation reagent 1.

[0136] 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.

[0137]

[0138] 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

[0140]

[0141] 2-Methyl-3-oxo-3-phenylpropanoic acid ethyl ester (61.8mg, 0.3mmol) and trifluoromethylthiolation reagent (100mg, 0.36mmol) and 4-dimethylaminopyridine (DMAP) (73mg, 0.60mmol) was dissolved in toluene (6.0ml) and reacted at room temperature for 8 hours. After the reaction, the solvent was removed by rotary evaporation under reduced pressure, and the residue was purified by flash silica gel column to obtain the corresponding product c1 (87 mg, 95%). The purity is greater than 95% identified by hydrogen spectrum.

[0142] 2-Methyl 2-trifluoromethylthio-3-oxo-3-phenylpropanoate (Ethyl2-methyl-3-oxo-3-phenyl-2-((trifluoromethyl)thio)propanoate): 1 H NMR (400MHz, CDCl 3 )δ7.98–7.91(m,2H),7.63–7.54(m,1H),7.44(t,J=7.8Hz,2H),4.24–4.13(m,2H),2.10(s,3H),1.07 (t,J=7.1Hz,3H)ppm; 19 F NMR (376MHz, CDCl 3 )δ-36.61(s,3F)ppm; 13 C NMR (101MHz, CDCl 3 )δ190.51,169.36,133.63,133.40,129.66(q,J=310.4Hz),129.02,128.62,63.68,63.24,24.23,13.41ppm.MS(ESI):307.0(M+H);HRMS(ESI...

Embodiment 3

[0144]

[0145] Diethyl 2-phenylmalonate (71mg, 0.30mmol) and trifluoromethylthiolation reagent (100mg, 0.36mmol) and 4-dimethylaminopyridine (DMAP) (73mg, 0.60mmol) were dissolved in toluene (6.0ml), react at room temperature for 8 hours. After the reaction, the solvent was removed by rotary evaporation under reduced pressure, and the residue was purified by flash silica gel column to obtain the corresponding product c2 (80 mg, 79%). The purity is greater than 95% identified by hydrogen spectrum.

[0146] Diethyl 2-phenyl 2-trifluoromethylthiomalonate (Dieth y l2-phenyl-2-((trifluoromethyl)thio)malonate): 1 H NMR (400MHz, CDCl 3 )δ7.79-7.57(m,2H),7.44-7.31(m,3H),4.46-4.08(m,4H),1.28(t,J=7.1Hz,6H)ppm; 19 F NMR (376MHz, CDCl 3 )δ-37.86(s,3F)ppm; 13 C NMR (126MHz, CDCl 3 )δ166.51,133.32,128.93,128.84(q,J=310.9Hz),128.60,128.30,67.11,63.33,13.68ppm.MS(EI):336.1;HRMS(EI):C 14 h 15 o 4 f 3 S calculated value: 336.0643, experimental value: 336.0641. IR: υ2985, 2940, 17...

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Abstract

The invention discloses a compound containing trifluoromethylthio group and a preparation method thereof. The invention discloses a compound 7, compound 9 or compound 11 containing trifluoromethylthio group. The invention provides a preparation method of the compound 7, 9 or 11, which comprises the following steps: in an organic solvent, carrying out substitution reaction on a compound 1 and a beta-eleostearate compound 6 in the presence of an alkali to obtain the compound 7; in an organic solvent, carrying out substitution reaction on the compound 1 and an aldehyde or ketone compound 8 in the presence of a catalyst and an additive to obtain the compound 9; and under the gas protection, carrying out substitution reaction on the compound 1, cuprous iodide and an alkyne compound 10 in an organic solvent in the presence of an alkali to obtain the compound 11. The preparation method of the compound 7, 9 or 11containing trifluoromethylthio group has the advantages of mild reaction conditions, high conversion rate, high yield and low production cost, and is suitable for industrial production.

Description

technical field [0001] The present invention relates to compounds containing trifluoromethylthio and their preparation methods. 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, fluo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C323/52C07C323/56C07C323/60C07C323/22C07C323/16C07C323/07C07C319/14C07D333/18
Inventor 沈其龙徐春发
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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