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Method for synthesizing difluoroalkyl or difluoromethyl sulfur-containing or selenium-containing compounds

A technology of difluoromethyl and difluoroalkyl, applied in the preparation of sulfide, organic chemistry, etc., can solve the problem of no difluoroalkyl or difluoromethyl, etc.

Active Publication Date: 2019-08-23
TAIZHOU UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] At present, there is no report on the related methods for the convenient introduction of difluoroalkyl or difluoromethyl groups into sulfur- or selenium-containing compounds

Method used

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  • Method for synthesizing difluoroalkyl or difluoromethyl sulfur-containing or selenium-containing compounds
  • Method for synthesizing difluoroalkyl or difluoromethyl sulfur-containing or selenium-containing compounds
  • Method for synthesizing difluoroalkyl or difluoromethyl sulfur-containing or selenium-containing compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0051] In a 50 mL dry reaction tube, add diphenyl sulfoxide (202.3 mg, 1.0 mmol), phenyl difluoroenol silyl ether (342.5 mg, 1.5 mmol), ethyl acetate 10.0 mL, and then dropwise add acetic anhydride ( 153.1mg, 1.5mmol), magnetically stirred at -40°C for 24 hours, detected by TLC, the raw material disappeared, concentrated directly, and further purified by column chromatography to obtain the product with a yield of 99%;

[0052] 2,2-Difluoro-1-phenyl-2-(2-(phenylthio)phenyl)ethanone (3a)

[0053] 1 H NMR (400MHz, CDCl 3 )δ7.98(d, J=7.4Hz, 2H), 7.86(dd, J=7.6, 1.7Hz, 1H), 7.63–7.53(m, 1H), 7.48–7.36(m, 4H), 7.32(d ,J=7.4Hz,1H),7.25–7.17(m,3H),7.11–7.03(m,2H); 19 F NMR (376MHz, CDCl 3 )δ–93.63(s,2F); 13 C NMR (100MHz, CDCl 3 ): δ189.0(t, J=31.0Hz), 135.7, 135.6(t, J=23.0Hz), 134.6(t, J=4.0Hz), 134.5, 133.5, 133.3(t, J=2.1Hz), 131.3, 130.4, 129.8 (t, J = 2.6Hz), 129.0, 128.4, 127.6, 127.2, 126.5 (t, J = 8.6Hz), 116.4 (t, J = 254.4Hz); HRMS (ESI) calcd for [C 20 h 14 f 2 O...

Embodiment 2

[0055] In a 50mL dry reaction tube, add 4,4'-xylene sulfoxide (230.3mg, 1.0mmol), phenyl difluoroenol silyl ether (342.5mg, 1.5mmol), dichloromethane 10.0mL, then drop Add trifluoromethanesulfonic anhydride (423.2mg, 1.5mmol), stir magnetically at -30°C for 24 hours, detect by TLC, the raw material disappears, concentrate directly, and then further purify by column chromatography to obtain the product with a yield of 93%;

[0056] 2,2-Difluoro-2-(5-methyl-2-(p-tolylthio)phenyl)-1-acetophenone (3b)

[0057] 1 H NMR (400MHz, CDCl 3 )δ7.98(dd,J=8.3,0.9Hz,2H),7.67–7.65(m,1H),7.61–7.53(m,1H),7.46–7.38(m,2H),7.20(d,J= 1.1Hz, 2H), 7.01(d, J=8.0Hz, 2H), 6.99–6.91(m, 2H), 2.43(s, 3H), 2.29(s, 3H); 19 FNMR (376MHz, CDCl 3 )δ–93.54(s,2F); 13 C NMR (100MHz, CDCl 3 )δ189.2(t, J=31.1Hz), 137.8, 137.1, 135.4(t, J=22.8Hz), 134.5, 133.4, 132.5, 132.1, 131.3(t, J=4.0Hz), 130.3, 129.7, 129.7 ,128.3,126.9(t,J=8.3Hz),116.4(t,J=254.2Hz),21.2,21.0; HRMS(ESI)calcd for[C 20 h 18 f 2 OSNa (M+...

Embodiment 3

[0059] In a 50 mL dry reaction tube, add 4,4'-dibromodiphenyl sulfoxide (360.1 mg, 1.0 mmol), phenyl difluoroenol silyl ether (342.5 mg, 1.5 mmol), dichloromethane 10.0 mL , then dropwise added trifluoroacetic anhydride (315.0mg, 1.5mmol), stirred magnetically at -10°C for 12 hours, detected by TLC, the raw material disappeared, concentrated directly, and further purified by column chromatography to obtain the product, with a yield of 86%;

[0060] 2-(5-Bromo-2-((4-bromophenyl)thio)phenyl)-2,2-difluoro-1-acetophenone (3d)

[0061] 1 H NMR (400MHz, CDCl 3 )δ8.02–7.94(m,3H),7.66–7.57(m,1H),7.54(dd,J=8.4,2.2Hz,1H),7.51–7.43(m,2H),7.40–7.33(m, 2H), 7.17(d, J=8.4Hz, 1H), 7.00–6.90(m, 2H); 19 F NMR (376MHz, CDCl 3 )δ–93.64(s,2F); 13 C NMR (100MHz, CDCl 3)δ188.4(t, J=31.1Hz), 137.4(t, J=23.2Hz), 136.0, 134.5, 133.9, 133.2(t, J=3.8Hz), 132.8(t, J=2.5Hz), 132.3 , 131.7, 130.3–129.4(m), 128.6, 115.9(t, J=256.5Hz); HRMS(ESI)calcdfor[C 20 h 12 Br 2 f 2 OSNa (M+Na + )]:518.8836...

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Abstract

The invention discloses a method for preparing difluoroalkyl or difluoromethyl substituted sulfur-containing or selenium-containing compounds. According to the method provided by the invention, one aryl or heteroaryl sulfoxide and selenoxide and one aryl or heteroaryl difluorosilyl enol ether are used as raw materials, and under the action of an activator, [3,3]-sigma rearrangement is performed tosynthesize one corresponding difluoroalkyl substituted sulfur-containing or selenium-containing compound; and the difluoroalkyl substituted sulfur-containing or selenium-containing compounds are prepared by the [3,3]-sigma rearrangement and a Haller-Bauer reaction in one pot, the synthetic method is simple, and has a high yield and mild conditions, thereby having good application prospects.

Description

technical field [0001] The invention relates to a new method for synthesizing difluoroalkyl and difluoromethyl sulfur-containing (selenium) compounds, belonging to the technical category of organic chemistry. Background technique [0002] The fluorine atom has various characteristics such as small atomic radius, strong electronegativity and low polarizability, and selectively introduces fluorine atoms or fluorine-containing groups into the compound. The physical, chemical and physiological properties of the corresponding compound Properties (such as electronegativity, chemical and metabolic stability, binding ability to target protein, bioavailability, lipid solubility, membrane permeability, and antioxidant activity) are usually significantly improved compared to their parent molecules. Since the number of naturally occurring fluorine-containing organic compounds is extremely rare in nature, the artificial synthesis of fluorine-containing organic compounds has been widely c...

Claims

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Application Information

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IPC IPC(8): C07C319/14C07C391/02C07D213/70C07D333/34C07C323/22
CPCC07C319/14C07C391/02C07D213/70C07D333/34C07C323/22
Inventor 王治明丁寒锋李金山张永刚
Owner TAIZHOU UNIV
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