A kind of synthetic method of thioetherification and thiocarbonylation of halogenated alkanes

A technology of halogenated alkane sulfide and synthesis method, which is applied in the synthesis field of halogenated alkane thioetherification and thiocarbonylation, can solve the problems of complicated preparation of substrates, low yield, unpleasant odor and high toxicity of mercaptan, and the like, The method is simple, economical and practical

Active Publication Date: 2022-05-20
ANHUI AGRICULTURAL UNIVERSITY
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  • Abstract
  • Description
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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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  • A kind of synthetic method of thioetherification and thiocarbonylation of halogenated alkanes
  • A kind of synthetic method of thioetherification and thiocarbonylation of halogenated alkanes
  • A kind of synthetic method of thioetherification and thiocarbonylation of halogenated alkanes

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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 present invention relates to the technical field of organic synthesis, in particular to a synthetic method for thioetherification and thiocarbonylation of halogenated alkanes; using methyl 3-methylthiopropionate derivatives as vulcanizing agents to realize the thioetherification and thiocarbonylation of halogenated alkanes Thiocarbonylation: Use IPrCuCl as a catalyst to realize thioetherification; in the presence of carbon monoxide, use IPrCuCl and bis-salicylamide ethyl cobalt to co-catalyze to obtain thioesters. The vulcanization reagent is easy to synthesize, the reaction conditions are relatively mild, and the practicability is strong. The invention avoids the use of mercaptans with strong odor, high toxicity and environmental pollution, has good functional group tolerance, excellent yield and purity, does not require harsh reaction conditions, and 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 Patents(China)
IPC IPC(8): C07C319/20C07C321/20C07C323/16C07C323/07C07C321/28C07C321/04C07D317/72C07C327/14C07C327/12
CPCC07C319/20C07D317/72C07C327/14C07C327/12C07C321/20C07C323/16C07C323/07C07C321/28C07C321/04Y02P20/584
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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