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

Application of novel persulfide reagent in synthesis of asymmetric persulfides

A persulfide, asymmetric technology, used in the application field of new persulfide reagents in the synthesis of asymmetric persulfides, can solve the unpleasant odor and high toxicity of thiols, poor homocoupling by-products, and suitable substrates. narrow range and other problems, to avoid homocoupling by-products, wide application range of substrates, and strong practicability

Active Publication Date: 2022-01-04
ANHUI AGRICULTURAL UNIVERSITY
View PDF4 Cites 1 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The purpose of the present invention is to solve the problem of unfavorable homo-coupling by-products, poor tolerance of functional groups and excessive oxidation of thiol precursors in the synthesis of existing persulfides, as well as the narrow scope of substrate application, the unpleasant smell of thiols and high To solve the problem of toxicity, the application of a new type of persulfide reagent in the synthesis of asymmetric persulfides is provided

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
  • Application of novel persulfide reagent in synthesis of asymmetric persulfides
  • Application of novel persulfide reagent in synthesis of asymmetric persulfides
  • Application of novel persulfide reagent in synthesis of asymmetric persulfides

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035]

[0036] Step 1: 1-Penten 3-one (2.5 g, 30 mmol, 1.0 equiv) and thioacetic acid (2.9 g, 39 mmol, 1.3 equiv) were added to EA (20 mL) at room temperature. And stir for 6h. Afterwards, the reaction was quenched with ice water and extracted into EA (3x20 mL). The combined organics were dried over sodium sulfate, filtered and concentrated in vacuo to give a clear colorless oil which was used without further purification. MeOH (10 mL) was added to the concentrated solution from the previous step. Then add H 2 SO 4 (2mol / L) solution to a pH range of 1-2, and the mixture was stirred at 85°C for 12h. Water (15 mL) was then added. After the organic layer was separated, the aqueous layer was extracted with 20 mL of ethyl acetate, the extract was combined with the organic layer, and washed successively with 5% aqueous sodium carbonate and saturated aqueous sodium chloride. The organic layer was dried over magnesium sulfate, filtered, and the organic solvent was distilled ...

Embodiment 2

[0047] Preparation of 1-(tert-butyldisulfanyl)pentan-3-one, the reaction scheme is as follows:

[0048]

[0049] 1-Mercapto-3-pentanone (5.9 g, 50 mmol, 1.0 equiv) was dissolved in 95% ethanol (40 mL), then tert-butylmercaptan (450 g, 500 mol, 10 equiv) was added. The mixture solution was cooled to 0° C., and an ethanol solution of iodine (10 g of iodine in 12 mL of ethanol) was added dropwise until the color of the reaction changed from colorless to red. After 12 h, saturated aqueous sodium bicarbonate solution was added until pH>7. The solution was concentrated in vacuo. The disulfide was extracted with ethyl acetate, and the organic layer was washed with 10% sodium bisulfite and brine. Finally, the organic layer was dried over sodium sulfate, filtered, concentrated and purified by flash chromatography (hexanes) to give the pure product as a brown liquid in 43% yield.

[0050] The proton nuclear magnetic resonance spectrum analysis result is as follows:

[0051] 1 H ...

Embodiment 3

[0059] To prepare 4-(tert-butyldisulfanyl)pentan-2-one, the reaction scheme is as follows:

[0060]

[0061] 4-Mercapto-2-pentanone (3.54 g, 30 mmol, 1.0 equiv) was dissolved in 95% ethanol (20 mL), then tert-butylmercaptan (27 g, 300 mmol, 10 equiv) was added. The mixture solution was cooled to 0° C., and an ethanol solution of iodine (10 g of iodine in 12 mL of ethanol) was added dropwise until the color of the reaction changed from colorless to red. After 12 h, saturated aqueous sodium bicarbonate solution was added until pH>7. The solution was concentrated in vacuo. The disulfide was extracted with ethyl acetate, and the organic layer was washed with 10% sodium bisulfite and brine. Finally, the organic layer was dried over sodium sulfate, filtered, concentrated and purified by flash chromatography (hexanes) to give the pure product as a brown liquid in 32% yield.

[0062] The proton nuclear magnetic resonance spectrum analysis result is as follows:

[0063] 1 H NMR...

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 relates to the technical field of organic synthesis, and in particular, relates to an application of a novel persulfide reagent in synthesis of asymmetric persulfides, wherein the novel persulfide reagent is easy to synthesize, mild in reaction condition and high in practicability, the persulfide reagent and (pseudo) haloalkane are adopted for nucleophilic substitution, and the novel persulfide reagent can be used for synthesizing various asymmetric persulfides; and the novel persulfide reagent is high in practicability, wide in substrate application range and suitable for industrial production, and the problems that in existing persulfide synthesis, undesirable co-coupling byproducts exist, functional group tolerance is poor, a thiol precursor is excessively oxidized, the substrate application range is narrow, and thiol is unpleasant in smell and high in toxicity are solved.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to the application of a novel persulfide reagent in the synthesis of asymmetric persulfides. Background technique [0002] Persulfide, also known as disulfide, represents a ubiquitous structural unit that is widely found in medicine, pesticides and polymer materials, and is the core pharmacophore of many drug molecules. The S-S bond has exceptionally flexible characteristics: the bond length is between 1.8 and The bond angles range from 90 to 180 degrees, and the dihedral angles range from 0 to 180 degrees, which makes persulfides rich in biological activity. In biology, S-S bonds play multiple roles in the regulation of various biochemical processes and in the stabilization of protein secondary and tertiary structures (Góngora-Benítez, M., Tulla-Puche, J., Albericio, F. Chem. Rev. 2014:114:901.). In addition to protein disulfides, many potent bioactive natural product...

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): C07C319/12C07C323/22C07C319/24C07D333/18C07C319/22C07C321/20C07C321/04C07C323/16C07C323/07C07C321/08C07D261/08
CPCC07C319/12C07C319/24C07D333/18C07C319/22C07D261/08C07C2601/14C07C2603/24C07C323/22C07C321/20C07C321/04C07C323/16C07C323/07C07C321/08
Inventor 李亚辉田青强王丽丽张翅鹰吴瑕
Owner ANHUI AGRICULTURAL 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