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

A kind of preparation method of aromatic cyclo[b]thiophene-3(2h)-one-1,1-dioxide

A technology of dioxide and thiophene, which is applied in the field of preparation of aromatic cyclo[b]thiophene-3-one-1,1-dioxide, can solve the problem of affecting the overall yield, increasing reaction steps, and reducing yield, etc. problem, to achieve the effect of high reaction yield, fast reaction speed and low cost

Active Publication Date: 2021-11-16
JINAN SHAOYUAN MEDICAL TECH +1
View PDF2 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN104744429B discloses a simple synthesis method of cyclo[b]thiophene-3(2H)-one-1,1-dioxide, which utilizes an aromatic ring (or heterocyclic) cyano compound containing an ortho-halogen substitution and an alkane Sodium sulfinate is dissolved in a suitable solvent, and a suitable base is used as an acid-binding agent to obtain the intermediate cyclo[b]thiophene-3(2H)-imine-1,1-dioxide; the intermediate of imine The body is hydrolyzed in aqueous hydrochloric acid to obtain cyclo[b]thiophene-3(2H)-one-1,1-dioxide, but the process of preparing imine from cyano group in this method has a low yield, and the hydrolysis process increases Reaction steps, the yield is further reduced, affecting the overall yield

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 aromatic cyclo[b]thiophene-3(2h)-one-1,1-dioxide
  • A kind of preparation method of aromatic cyclo[b]thiophene-3(2h)-one-1,1-dioxide
  • A kind of preparation method of aromatic cyclo[b]thiophene-3(2h)-one-1,1-dioxide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0051] In this example, the aromatic ring [b]thiophen-3(2H)-one-1,1-dioxide represented by compound 2 was prepared via compound 1 through the following steps, wherein n in formula II is a benzene ring, X For F, R1 is hydrogen, and the reaction formula is as follows:

[0052]

[0053] 20.0g 2-fluorobenzaldehyde (0.161mol, 1.0eq), 33g sodium methylsulfinate (0.323mol, 2.0eq) were added to a 250mL round-bottomed flask filled with 130mL dimethyl sulfoxide, and replaced with nitrogen three times, Stir overnight at 100°C under nitrogen atmosphere. On the second day, there was almost no raw material and no unclosed ring by-products, and the heating was stopped, cooled to room temperature, and poured into about 800mL of ice water. Extracted 3 times with 200 mL of ethyl acetate, combined the organic phases, washed 3 times with 50 mL of saturated sodium chloride. The organic phase was dried with anhydrous sodium sulfate, passed through a silica gel pad, spin-dried the solvent, mixe...

Embodiment 2

[0060] In this example, the aromatic ring [b]thiophen-3(2H)-one-1,1-dioxide represented by compound 4 was prepared via compound 3 through the following steps, wherein n in formula II is bromobenzene, X for F, R 1 is hydrogen, the reaction formula is as follows:

[0061]

[0062] Add 2g (0.01mol, 1eq) of 5-bromo-2-fluorobenzaldehyde, 2.04g (0.02mol, 2eq) of sodium methanesulfinate into a 50mL single-necked bottle, then add 14mL of dimethyl sulfoxide, and then stir for 10min. Heating, external temperature 115°C, internal temperature 100°C, reaction for 16h, TLC detection of complete reaction, cooling down, pouring 80mL ice water, 100mL ethyl acetate extraction twice, combined organic phase, washing 3 times with saturated brine 50mL, drying, the crude product Silica gel column chromatography (petroleum ether: ethyl acetate = 3:1) yielded the product Compound 3 with a mass of about 2.0 g and a yield of about 76.4%.

[0063] [M-1] - =260.6;

[0064] 1 H NMR (400MHz, DMSO) δ...

Embodiment 3

[0069] In this example, the aromatic ring [b]thiophen-3(2H)-one-1,1-dioxide represented by compound 6 was prepared via compound 5 through the following steps, wherein n in formula II is trifluoromethyl Benzene, X is F, R 1 is hydrogen, the reaction formula is as follows:

[0070]

[0071] 50mL one-port bottle, add 1.92g (0.01mol, 1eq) of 5-trifluoromethyl-2-fluorobenzaldehyde, 2.04g (0.02mol 2eq) of sodium methanesulfinate, then add 14mL of dimethyl sulfoxide, and then Stir for 10 minutes, heat, react at an external temperature of 115 °C and an internal temperature of 100 °C for 16 h, TLC detects that the reaction is complete, cool down, pour 80 mL of ice water, extract twice with 100 mL of ethyl acetate, combine the organic phases, wash three times with 50 mL of saturated saline, and dry , silica gel column chromatography (petroleum ether: ethyl acetate = 3:1) to obtain about 1.7 g of compound 5 as a light yellow solid, with a yield of 67.5%.

[0072] [M-1] - =250.9;

...

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 aromatic ring[b]thiophene-3(2H)-one-1,1-dioxide, the method is: reacting the compound shown in formula I with an oxidizing agent to obtain the aromatic compound Cyclo[b]thiophene-3(2H)-ketone-1,1-dioxide; the present invention also provides the preparation method of the compound shown in formula I; the preparation method provided by the present invention has high reaction yield and fast reaction speed Fast, easy to obtain raw materials, low cost, mild reaction, easy to control, simple post-processing, very little waste generated, and low pollution. Large and low yield, the method provided by the invention provides a feasible synthetic route for green chemical industry, and has high production and application value.

Description

technical field [0001] The invention belongs to the field of synthesis of pharmaceutical intermediates, and relates to a preparation method of aromatic ring[b]thiophene-3(2H)-one-1,1-dioxide. Background technique [0002] Aromatic[b]thiophene-3(2H)-one-1,1-dioxide is an important intermediate in organic synthesis. This kind of compound has high reactivity and is widely used in drug synthesis. [0003] At present, the main synthesis method is prepared by oxidation or ring closure, and the oxidation method includes the oxidation of 1,3-dihydrothiophene rings and m-chloroperoxybenzoic acid or the oxidation of 1,3-dihydrothiophene rings and hydrogen peroxide Obtained, the cost of this method is high, and post-treatment is comparatively loaded down with trivial details difficulty, especially the processing of oxidizing agent; And the aromatic sulfonic acid of ortho-halogen substitution, the aromatic carboxylic acid ester of ortho-position substitution, aromatic ring and chlorosul...

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): C07D333/64C07D495/04
CPCC07D333/64C07D495/04
Inventor 王海波泮廷廷郑燕
Owner JINAN SHAOYUAN MEDICAL TECH
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