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2-arylsulfonyl-2, 2-difluorodiazoethane compound, preparation method and application thereof

The technology of difluorodiazoethane and arylsulfone group is applied in the field of preparation of diazonium compounds, and can solve the problems of high risk factor and difficult operation, and achieve the effects of simple use, convenient preparation and mild reaction conditions.

Inactive Publication Date: 2018-08-10
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, both trifluorodiazoethane and difluorodiazoethane are gaseous compounds, which are difficult to operate and have a high risk factor, especially in large-scale production. Therefore, the design and development of new fluorine-containing diazo It is very necessary and urgent to apply it to the synthesis of drug and pesticide molecules

Method used

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  • 2-arylsulfonyl-2, 2-difluorodiazoethane compound, preparation method and application thereof
  • 2-arylsulfonyl-2, 2-difluorodiazoethane compound, preparation method and application thereof
  • 2-arylsulfonyl-2, 2-difluorodiazoethane compound, preparation method and application thereof

Examples

Experimental program
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Effect test

example 1

[0039] Example 1: Preparation of 2-phenylsulfone-2,2-difluorodiazoethane compound

[0040]

[0041] 1): Dissolve 16.9g of 2,2-difluoro-2-phenylthioethanol in a mixture of 60ml of water and 60ml of acetic acid, add 20mL of 30% hydrogen peroxide, heat and reflux for 3 hours, and the reaction is complete as detected by thin-layer chromatography Afterwards, after washing, extraction and separation, the organic phase was spin-dried to obtain 14 g of white solid 2,2-difluoro-2-phenylsulfone ethanol, with a yield of 85%. 1 H NMR (400MHz, CDCl 3 )δ: 7.99(d, J=7.8Hz, 2H), 7.78(t, J=7.5Hz, 1H), 7.63(t, J=7.8Hz, 2H), 4.29(td, J=12.9, 7.4Hz, 2H), 2.73(t, J=7.3Hz, 1H). 19 F NMR (377MHz, CDCl 3 )δ: -111.19(t,J=12.9Hz). 13 C NMR (101MHz, CDCl 3 )δ: 135.75, 132.34, 130.69, 129.50, 120.74(t, J=289.2Hz), 59.94(t, J=24.9Hz).

[0042] 2): Dissolve 13.5 grams of 2,2-difluoro-2-phenylsulfone ethanol in 100 mL of acetonitrile, add 7 ml of pyridine, add 10.5 mL of trifluoromethanesulfonic anhy...

example 2

[0045] Example 2: Preparation of 2-(4-chlorophenyl)sulfone-2,2-difluorodiazoethane compound

[0046]

[0047] 1): Dissolve 7.8g of 2,2-difluoro-2-(4-chlorophenyl)thioethanol in a mixture of 50ml of water and 50ml of acetic acid, add 14mL of 30% hydrogen peroxide, and heat to reflux for 3 hours. After the completion of the reaction as detected by thin-layer chromatography, washing, extraction, and separation, the organic phase was spin-dried to obtain 8.5 g of white solid 2,2-difluoro-2-(4-chlorophenyl)sulfone ethanol, with a yield of 94%. 1 HNMR (400MHz, CDCl 3 )δ: 7.92(d, J=7.8Hz, 2H), 7.66(d, J=7.8Hz, 2H), 4.4(td, J=11.9, 8.4Hz, 2H), 2.61(t, J=6.3Hz, 1H). 19 F NMR (377MHz, CDCl 3 )δ: -108.19(t,J=10.9Hz). 13 CNMR (101MHz, CDCl 3 )δ: 137.75, 134.34, 131.61, 128.22, 121.74(t, J=279.2Hz), 62.24(t, J=23.9Hz).

[0048] 2): Dissolve 8.5 grams of 2,2-difluoro-2-(4-chlorophenyl)sulfone ethanol in 80ml of acetonitrile, add 4.5ml of pyridine, and add 6.2ml of trifluoromethanes...

example 3

[0050] Example 3: Preparation of 2-(4-fluorophenyl)sulfone-2,2-difluorodiazoethane compound

[0051]

[0052] 1): Dissolve 10.4g of 2,2-difluoro-2-(4-fluorophenyl)thioethanol in a mixture of 60ml of water and 60ml of acetic acid, add 18ml of 30% hydrogen peroxide, and heat to reflux for 3 hours. After the completion of the reaction as detected by thin-layer chromatography, washing, extraction, and separation, the organic phase was spin-dried to obtain 11.5 g of white solid 2,2-difluoro-2-(4-fluorophenyl)sulfone ethanol, with a yield of 96%. 1 HNMR (400MHz, CDCl 3 )δ: 7.89(d, J=9.3Hz, 2H), 7.69(d, J=9.3Hz, 2H), 4.26(td, J=16.9, 7.4Hz, 2H), 2.67(t, J=7.4Hz, 1H). 19 F NMR (377MHz, CDCl 3 )δ: -112.19(t, J=12.9Hz), -101.28(m). 13 C NMR (101MHz, CDCl 3 )δ: 141.24, 137.75, 131.61, 128.22, 122.74 (t, J = 282.3Hz), 58.24 (t, J = 19.9Hz).

[0053] 2): Dissolve 11.5 grams of 2,2-difluoro-2-(4-fluorophenyl)sulfone ethanol in 100ml of acetonitrile, add 6.3ml of pyridine, and add 9...

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Abstract

The invention relates to a 2-arylsulfonyl-2, 2-difluorodiazoethane compound, a preparation method and application thereof. The preparation method of the 2-arylsulfonyl-2, 2-difluorodiazoethane compound includes: dissolving 2, 2-difluoro-2-aryl sulfonyl ethylamine hydrochloride in a mixed solvent of an organic solvent and water, adding nitrite, carrying out stirring at room temperature for completereaction, and then conducting washing, extraction, separation and column chromatography purification to obtain the yellow liquid 2-arylsulfonyl-2, 2-difluorodiazoethane. The obtained target compoundis a diazo compound containing sulfonyl difluoromethyl, can be subjected to [3+2] cycloaddition reaction with alkyne so as to synthesize a pyrazole compound containing difluoromethyl. The difluorodiazoethane compound provided by the invention has the characteristics of convenient preparation, simple use and mild reaction conditions, and the invention provides an effective method for synthesis of compounds containing difluoromethyl.

Description

technical field [0001] The invention provides a preparation method and application of a difluoromethyl-containing diazo compound, and specifically discloses a preparation method and application of a 2-arylsulfone-2,2-difluorodiazoethane compound. Its application in [3+2] cycloaddition reactions. Background technique [0002] Fluorine is the atom with the most electronegativity among known elements and has strong electron-attracting properties. When fluorine atoms are introduced into organic compounds, the electron cloud density distribution inside the compound molecule and the acidity and alkalinity of the internal structure will greatly change. Variation (J.-A. Ma, D. Cahard, Chem. Rev., 2008, 108, PR1-43). Due to its special electronic effect, simulation effect, hindering effect, and fat-soluble penetration effect, fluorine-containing compounds are widely used in the fields of pesticides, medicines, and materials (I. Ojima, Fluorine in Medicinal Chemistry and Chemical Bio...

Claims

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Application Information

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IPC IPC(8): C07C315/04C07C317/28C07D213/71C07D231/14C07D231/12
CPCC07C315/02C07C315/04C07C317/28C07D213/71C07D231/12C07D231/14C07C317/18C07C317/22
Inventor 马军安曾俊良张发光
Owner TIANJIN UNIV
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