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Synthetic method for thioetherification and thiocarbonylation of halogenated alkane

A technology of halogenated alkane thiocarbonyl group and halogenated alkane sulfide, which is applied in the field of organic synthesis, can solve the problems of complicated substrate preparation, low yield, unpleasant odor and high toxicity of mercaptan, and achieves a simple, economical and practical method. strong effect

Active Publication Date: 2021-10-19
ANHUI AGRICULTURAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The purpose of the present invention is to solve the low yield of the traditional synthesis method of alkyl sulfides, complicated preparation of substrates, narrow scope of application of substrates, unpleasant smell and high toxicity of mercaptans, and the starting substrates of halogenated alkane thiocarbonylation mainly Focus on Csp 2 Problems at the -X bond, providing a synthetic method for the thioetherification and thiocarbonylation of haloalkanes

Method used

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  • Synthetic method for thioetherification and thiocarbonylation of halogenated alkane
  • Synthetic method for thioetherification and thiocarbonylation of halogenated alkane
  • Synthetic method for thioetherification and thiocarbonylation of halogenated alkane

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] To prepare 2-methylthio-4-p-methylphenylbutane, the reaction scheme is as follows:

[0042]

[0043] Add IPrCuCl (4.87mg, 0.01mol), NaO t Bu (76.8mg, 4equiv.) and dried stir bar. charging N 21-(3-Iodobutyl)-4-methylbenzene (0.2 mmol, 1 equiv.), methyl 3-(methylthio)propionate (0.6 mmol, 3 equiv.) and xylene (2 mL) were added under the same conditions. The resulting solution was heated to 140°C and the reaction was stirred at this temperature for 24 hours. Then, cool to room temperature. The solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography, eluting with petroleum ether, and a colorless liquid (31 mg, 80%) was isolated.

[0044] The proton nuclear magnetic resonance spectrum analysis result is as follows:

[0045] 1 H NMR (600MHz, Chloroform-d) δ7.10(d, J=4.9Hz, 4H), 2.75–2.69(m, 2H), 2.66(p, J=6.8Hz, 1H), 2.33(d, J= 4.8Hz, 3H), 2.07(d, J=4.9Hz, 3H), 1.87(m, 1H), 1.77(m, 1H), 1.31(d, J=6.7Hz, 3H)....

Embodiment 2

[0053] To prepare 4-methylthiophenvalyl ether, the reaction scheme is as follows:

[0054]

[0055] Add IPrCuCl (4.87mg, 0.01mmol), NaO t Bu (76.8mg, 4equiv.) and dried stir bar. charging N 2 (4-Iodopentyloxy)benzene (0.2 mmol, 1 equiv.), methyl 3-(methylthio)propionate (0.6 mmol, 3 equiv.) and xylene (2 mL) were added under the same conditions. The resulting solution was heated to 140°C and the reaction was stirred at this temperature for 24 hours. Then, cool to room temperature. The solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography, eluting with petroleum ether, and a colorless liquid (35 mg, 83%) was isolated.

[0056] The proton nuclear magnetic resonance spectrum analysis result is as follows:

[0057] 1 H NMR (600MHz, Chloroform-d) δ7.27(m,2H),7.01–6.80(m,3H),3.97(m,2H),2.73(h,J=6.8Hz,1H),2.08(s, 3H), 1.96–1.84 (m, 2H), 1.78–1.62 (m, 2H), 1.31 (d, J=6.7Hz, 3H).

[0058] The carbon NMR analysis re...

Embodiment 3

[0065] To prepare 2-methylthio-4-ethoxyphenylbutane, the reaction scheme is as follows:

[0066]

[0067] Add IPrCuCl (4.87mg, 0.01mmol), NaO t Bu (76.8mg, 4equiv.) and dried stir bar. charging N 2 Add 1-ethoxy-4-(3-iodobutyl)benzene (0.2mmol, 1equiv.), methyl 3-(methylthio)propanoate (0.6mmol, 3equiv.) and xylene (2mL) . Methyl 3-(methylthio)propionate (0.6 mmol, 3 equiv.) and xylene (2 mL). The resulting solution was heated to 140°C and the reaction was stirred at this temperature for 24 hours. Then, cool to room temperature. The solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography, eluting with petroleum ether, and a colorless liquid (33 mg, 74%) was isolated.

[0068] The proton nuclear magnetic resonance spectrum analysis result is as follows:

[0069] 1 H NMR (600MHz, Chloroform-d) δ7.15–7.05(m,2H),6.85–6.76(m,2H),4.01(q,J=7.0Hz,2H),2.77–2.55(m,3H), 2.06(s, 3H), 1.85(m, 1H), 1.74(m, 1H), 1.39(t, J=...

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Abstract

The invention relates to the technical field of organic synthesis, in particular to a synthetic method for thioetherification and thiocarbonylation of halogenated alkane. According to the method, a 3-methylthiopropionic acid methyl ester derivative is used as a vulcanizing reagent to realize thioetherification and thiocarbonylation of halogenated alkane; IPrCuCl is used as a catalyst to realize thioetherification; in the presence of carbon monoxide, IPrCuCl and bis-salicylamide ethyl cobalt are used for co-catalysis to obtain thioester; and the vulcanizing reagent is easy to synthesize, mild in reaction condition and high in practicability. According to the invention, thiol with strong smell, high toxicity and environmental pollution is not used, good functional group tolerance and excellent yield and purity are achieved, harsh reaction conditions are not needed, and the method is suitable for industrial production.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a synthesis method for thioetherification and thiocarbonylation of halogenated alkanes. Background technique [0002] Alkyl sulfide is a class of sulfur atoms, the general formula is R-S-R 1 Alkyl thioesters are a class of ester compounds containing a sulfur atom and an acyl group (a covalent bond formed by an alkane and a carbon-oxygen double bond molecule), which are the structural units of various drugs. Many thioethers and thioesters have significant biological activities and have important medical value in antitumor, anticancer, antiviral, bactericidal, anti-inflammatory and antiparasitic aspects. For example, clindamycin, the third-generation product of lincomycin, contains a thioether structure and is an effective Gram semi-synthetic antibiotic drug (Chen Y, Wang J.K. Journal of Chemical & Engineering Data 2007:52:1908.). Fluticasone propionate is a thioester-c...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C319/20C07C321/20C07C323/16C07C323/07C07C321/28C07C321/04C07D317/72C07C327/14C07C327/12
CPCC07C319/20C07D317/72C07C327/14C07C327/12C07C321/20C07C323/16C07C323/07C07C321/28C07C321/04Y02P20/584C07C327/22C07C327/24C07C321/14
Inventor 李亚辉裴博群孙荣静田青强王丽丽吴瑕
Owner ANHUI AGRICULTURAL UNIVERSITY
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