Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Method for breaking C-S bond of alpha-sulfo-arylethanone compound and ligand

A technology for thioaryl ethyl ketone and compound is applied in the field of cleaving C-S bonds, which can solve the problems of high cost and limited substrate, and achieve the effects of simple operation, wide tolerance and low reaction dosage.

Active Publication Date: 2021-01-05
WENZHOU UNIVERSITY
View PDF3 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] The purpose of the present invention is to provide a method and ligand for breaking the C-S bond of α-thioaryl ethyl ketone compound, which solves the problem of existing α-thioaryl The problem of high cost and limited substrates of the C-S bond breaking method of α-thioarylethanone compounds can efficiently break the C-S bond of α-thioarylethanone compounds, and is applicable to a wide range of substrates

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
  • Method for breaking C-S bond of alpha-sulfo-arylethanone compound and ligand
  • Method for breaking C-S bond of alpha-sulfo-arylethanone compound and ligand
  • Method for breaking C-S bond of alpha-sulfo-arylethanone compound and ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] A method for breaking the C-S bond of α-thioarylethanone compound, the synthesis route of the method is:

[0046]

[0047] The specific operation steps are as follows:

[0048] Add CoCl to a dry reaction tube at 25 °C 2 (0.05mmol), ADI Me (0.05mmol), α-phenylthioacetophenone (1a) (1mmol), biboronic acid pinacol ester (B 2 pin 2 , 1mmol), tetrahydrofuran (THF, 1mL) and methanol (2mmol), finally added sodium tert-butoxide (NaOtBu, 0.15mmol), then stirred at 65 ° C for 1h, separated by column chromatography to obtain acetophenone (1b) , colorless oil, yield 97%.

[0049] The NMR characterization data of acetophenone are:

[0050] 1 H NMR (CDCl 3 ,400MHz): δ8.00-7.94(m,2H),7.60-7.54(m,1H),7.51-7.44(m,2H),2.62(s,3H).

[0051] The NMR characterization data of thiophenol are:

[0052] 1 H NMR (CDCl 3 ,400MHz): δ6.91-7.40(m,5H),3.42(br,1H).

[0053] Among them, ligand ADI Me The preparation method is as follows:

[0054]

[0055] At room temperature, under n...

Embodiment 2-3

[0062] A method for breaking the C-S bond of α-thioarylethanone compound, which is basically the same as that of Example 1, the difference is that ADI is used respectively Et , ADI iPr Replace ADI Me , the yields of acetophenone were 81%, 53%, respectively.

[0063]

[0064]

[0065] ADI Et and ADI iPr ADI Me The preparation process is basically the same, ADI Et and ADI iPr They are also yellow solids, with melting points of 68-69°C and 73-74°C, and yields of 80% and 71%, respectively.

[0066] ADI Et The NMR characterization data of is:

[0067] 1 H NMR (CDCl 3 ,400MHz):δ12.12(br,1H),7.73(d,J=8.0Hz,2H),7.44-7.35(m,2H),7.33-7.25(m,2H),7.00-6.93(m,2H ),6.90-6.82(m,4H),6.79-6.73(m,2H),2.82(t,J=7.2Hz,8H),2.05(s,6H),1.22(d,J=7.2Hz,12H) .

[0068] ADI iPr The NMR characterization data of is:

[0069] 1 H NMR (CDCl 3 ,400MHz):δ12.01(br,1H),7.69(d,J=8.0Hz,2H),7.42-7.33(m,2H),7.30-7.24(m,2H),6.99-6.91(m,2H ),6.88-6.82(m,4H),6.77-6.70(m,2H),2.91-8.82(m,4H),2.02(...

Embodiment 4-5

[0071] A method for breaking the C-S bond of α-thioarylethanone compound, which is basically the same as that of Example 1, the difference is that NiCl is used in Examples 4-5 respectively 2 , FeCl 2 Replace CoCl 2 , the yields of acetophenone were 80%, 59%, respectively.

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 discloses a method for breaking a C-S bond of an alpha-sulfo-arylethanone compound, and a ligand. The method comprises the following steps: reacting the alpha-sulfo-arylethanone compound, bis(pinacolato)diboron, MX2, a ligand, alkali and methanol in an organic solvent at 25-65 DEG C to break the C-S bond in the alpha-sulfo-arylethanone compound. According to the method, chlorate of transition metal cobalt or nickel is used as a catalyst, ADI is used as a ligand, combination of bis(pinacolato)diboron and methanol is used as a reducing agent, C-S bonds are broken mildly under the alkaline condition, and the reducing agent is stable, cheap, easy to obtain, small in reaction dosage, mild in reaction condition, easy and convenient to operate, efficient and wide in substrate functional group tolerance.

Description

technical field [0001] The invention relates to a method for breaking a C-S bond, in particular to a method and a ligand for breaking a C-S bond of an α-thioarylethanone compound. Background technique [0002] With the advancement of human industrialization, the demand for fossil energy such as petroleum and coal continues to increase. The trace amount of sulfur contained in these fossil energy has brought about a series of serious air pollution problems, and acid rain is one of the manifestations. Therefore, the research on C-S bond breaking reaction is of great value to petrochemical industry, automobile industry and even the whole human society. [0003] The traditional desulfurization method generally adopts catalytic oxidation, but there are problems such as complex process, many by-products, low desulfurization rate, and large pollution in the desulfurization process. Transition metal-catalyzed C-S bond reductive cleavage reaction is one of the feasible alternatives, ...

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 Applications(China)
IPC IPC(8): C07C45/67C07C49/78B01J31/18C07C221/00C07C225/22C07C249/02C07C251/24C07C49/84C07C49/76C07C49/784C07C319/20C07C323/22C07C315/04C07C317/24C07C49/807C07C49/80C07C49/788C07D333/22
CPCC07C45/673B01J31/1805C07C221/00C07C225/22C07C249/02C07C251/24C07C319/20C07C315/04C07D333/22B01J2531/842B01J2531/845B01J2531/847B01J2531/0213C07C49/78C07C49/84C07C49/76C07C49/784C07C323/22C07C317/24C07C49/807C07C49/80C07C49/788Y02P20/584
Inventor 陈建辉蔡成丁洋浩刘波盛夏远志
Owner WENZHOU UNIVERSITY
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com