Unlock instant, AI-driven research and patent intelligence for your innovation.

A kind of preparation method of α,α-difluoro-β-ketosulfone compound

A compound and fluoride technology, applied in the field of chemistry, can solve problems such as poor adaptability of functional groups, harsh reaction conditions, and low chemical selectivity, and achieve the effects of good yield, high purity, and simple synthetic route

Active Publication Date: 2022-05-13
SICHUAN UNIV
View PDF1 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This reaction requires the use of expensive reaction instruments and photocatalysts, and due to the limitations of the preparation of 2,2-difluoroenol silyl ether, the functional group adaptability is poor
[0010] In summary, the current methods for the preparation of α,α-difluoro-β-ketosulfones face problems such as low chemoselectivity, harsh reaction conditions, and poor adaptability of functional groups.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • A kind of preparation method of α,α-difluoro-β-ketosulfone compound
  • A kind of preparation method of α,α-difluoro-β-ketosulfone compound
  • A kind of preparation method of α,α-difluoro-β-ketosulfone compound

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0106] The preparation method mainly includes the following steps:

[0107] Under nitrogen or argon protection atmosphere, compound 1 (0.2mmol, 1equiv), fluoride initiator (0.1-0.2equiv) and organic solvent (0.5mL) were sequentially added to a screw-cap vial with a magnetic stirrer . The vial was stirred at 60-80°C for 20 h, cooled to room temperature after the reaction, concentrated the reaction solution, and directly subjected to silica gel column chromatography to obtain α,α-difluoro-β-ketosulfone compound (compound 2).

[0108] Among them, the fluoride initiators include metal fluorides such as silver fluoride, potassium fluoride, and cesium fluoride; the organic solvents include acetonitrile, acetone, N-methylpyrrolidone, N,N-dimethylformamide, N,N- Dimethylacetamide, dimethyl sulfoxide, etc.

Embodiment 1

[0109] Example 1, Ar 1 Universality of functional groups

[0110] 1. Preparation of Compound 2a of the present invention

[0111]

[0112] Under a nitrogen or argon protective atmosphere, compound 1a (0.2mmol, 1equiv), silver fluoride (2.5mg, 0.1equiv) and acetonitrile (0.5mL) were sequentially added to a screw cap vial with a magnetic stirrer. The vial was stirred at 60°C for 20 h. After the reaction was completed, it was cooled to room temperature, the reaction solution was concentrated, and directly subjected to silica gel column chromatography (petroleum ether / ethyl acetate=20 / 1, v / v) to obtain compound 2a as a white solid. Yield 97%, purity >95%.

[0113] 1 H NMR (400MHz, Chloroform-d) δ8.19-8.17 (m, 2H), 7.90 (d, J = 8.0Hz, 2H), 7.72-7.68 (m, 1H), 7.56-7.52 (m, 2H), 7.44(d, J=8.4Hz, 2H), 2.51(s, 3H). 19 F NMR (376MHz, Chloroform-d) δ-101.75. 13 C NMR (101MHz, Chloroform-d) δ184.0(t, J=23.2Hz), 147.8, 135.4, 132.1, 131.0, 130.8(t, J=3.1Hz), 130.3, 129.4, 128.9, 1...

Embodiment 2

[0190] Example 2, Ar 2 Universality of functional groups

[0191] 1. Preparation of compound 2u of the present invention

[0192]

[0193] Under nitrogen or argon protective atmosphere, compound 1u (0.2mmol, 1equiv), silver fluoride (2.5mg, 0.1equiv) and acetonitrile (0.5mL) were sequentially added into a screw cap vial with a magnetic stirrer. The vial was stirred at 60°C for 20 h. After the reaction was completed, it was cooled to room temperature, the reaction solution was concentrated, and directly subjected to silica gel column chromatography (petroleum ether / ethyl acetate=100 / 1, v / v) to obtain compound 2u as a white solid. The yield was 85%, and the purity was >95%.

[0194] 1 H NMR (400MHz, Chloroform-d) δ8.08(d, J=8.0Hz, 2H), 7.89(d, J=8.4Hz, 2H), 7.44(d, J=8.0Hz, 2H), 7.33(d ,J=8.4Hz,2H),2.50(s,3H),2.46(s,3H). 19 F NMR (376MHz, Chloroform-d) δ-101.69. 13 C NMR (101MHz, CDCl3) δ183.4(t, J=23.2Hz), 147.7, 147.0, 131.13(t, J=3.0Hz), 131.06, 130.3, 129.74, 129.71, ...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention provides a method for preparing α,α-difluoro-β-ketone sulfone compounds, which belongs to the field of chemical technology. At first a kind of composition of compound shown in the preparation formula I is provided, and it is made up of following components: compound 1, fluoride initiator and organic solvent; Wherein, Ar 1 and Ar 2 are independently selected from substituted or unsubstituted aryl groups, substituted or unsubstituted heteroatom aryl groups. Also provided is a method for preparing α,α-difluoro-β-ketone sulfone compounds from the composition. The invention uses metal fluorides as initiators, and can prepare a series of compounds under mild conditions. The preparation method has a simple synthetic route, good yield and high purity; it has the advantages of excellent functional group adaptability, etc., and can be used to prepare α,α-difluoro-β-ketone sulfone compounds with various functional groups, and has been successfully applied to Post-modification of natural product and drug molecules. In addition, the reaction scale of the present invention can be enlarged to gram level, can be used for industrial scale-up production, and has good application prospects.

Description

technical field [0001] The invention belongs to the technical field of chemistry, and in particular relates to a preparation method of α,α-difluoro-β-ketosulfone compounds. Background technique [0002] The fluorine atom has a large electronegativity and a small atomic radius, so introducing a single fluorine atom or multiple fluorine atoms into a compound can significantly change some characteristics and properties of the original compound, making the compound have many special physical and chemical properties. nature. Many fluorine-containing compounds have a wide range of applications in the fields of medicine, agriculture and materials. For example, in the field of materials, fluoropolymers have excellent properties such as good chemical stability and low surface energy, so they are widely used in the fields of rubber, resin, microelectronics industry and surfactants. Among the fluorine-containing compounds, α,α-difluoro-β-ketosulfone compounds are an important class o...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07C315/00C07D207/16C07D209/08C07D209/38C07D215/14C07D295/112C07D295/192C07D307/79C07D311/72C07D333/22C07D493/14C07J7/00C07C317/24C07C317/36C07C317/44C07B45/04
CPCC07C315/00C07D307/79C07D295/112C07D209/38C07D215/14C07D333/22C07D209/08C07D295/192C07D207/16C07D311/72C07D493/14C07J7/002C07B45/04C07C2601/14C07B2200/07C07C317/24C07C317/36C07C317/44
Inventor 练仲熊保健
Owner SICHUAN UNIV