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A kind of synthetic method of α-acyl homoallyl sulfide compound

A technology of acyl homoallyl sulfide and thiol compounds, which is applied in the field of organic chemical synthesis, can solve the problems of restricting the practical application of known methods, environmental pollution caused by waste metal discharge, and increased reaction costs, achieving good application prospects and The effect of research value, no need for inert gas protection, and easy operation

Inactive Publication Date: 2019-05-28
WENZHOU UNIV
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Problems solved by technology

[0011] In 2015, Zhang’s research group found that in the presence of gold catalyst and ligand L1, the reaction of acetylene compounds and allyl sulfides can be realized to synthesize α-acyl substituted homoallyl sulfide compounds, and the required reaction conditions are mild. , the substrate has wide applicability and high yield, but requires the use of noble metal catalysts, which increases the reaction cost. The reaction formula is as follows:
[0019] As mentioned above and as can be seen, there are multiple methods for preparing homoallyl sulfide compounds in the prior art, but these reactions generally require the use of transition metals, especially noble metals, as catalysts, which increases the cost of the reaction. At the same time, waste The discharge of metals will also cause great pollution to the environment; secondly, diazo compounds are used as one of the raw materials for the reaction. This type of compound is active in nature, relatively complex in synthesis, and prone to occur under light or heating conditions. In addition, allyl sulfides are used as nucleophiles in almost all transition metal-catalyzed Doyle-Kirmse reactions. Synthesized under action, requiring additional steps for raw material synthesis
The existence of above-mentioned several problems has restricted the practical application of known method greatly

Method used

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  • A kind of synthetic method of α-acyl homoallyl sulfide compound
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  • A kind of synthetic method of α-acyl homoallyl sulfide compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0054] Embodiment 1: the synthesis of compound IV-1

[0055]

[0056] Add 2-bromoacetophenone (39.8 mg, 0.2 mmol), thiophenol (0.6 mmol, 3 equiv.), allyl bromide (1.4 mmol, 7 equiv.) and Dipotassium hydrogen phosphate (1.0 mmol, 5 equiv.) was added to 1 mL of DMF, and the temperature was raised to 130° C. for 24 h.

[0057] After the reaction was complete, the reaction was quenched with 15 mL of saturated ammonium chloride solution, extracted with ethyl acetate (15 mL×3), and 3 The mixed organic phase was washed, then washed with 15 mL of saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and the residue was purified by flash column chromatography (petroleum ether / ethyl acetate volume ratio of 100:1) to obtain The target product was obtained with an isolation yield of 90%, and the product was a colorless oily liquid.

[0058] NMR: 1 H NMR (500MHz, CDCl 3 )δ7.83(d, J=7.5Hz, 2H), 7.46(t, J=7.3Hz, 1H), 7.34(t, J=7.5Hz,...

Embodiment 2

[0060] Embodiment 2: the synthesis of compound IV-2

[0061]

[0062] Add 2-bromo-p-methoxyacetophenone (45.8 mg, 0.2 mmol), thiophenol (0.6 mmol, 3 equiv.), allyl bromide (1.4 mmol, 7equiv.) and dipotassium hydrogen phosphate (1.0mmol, 5equiv.), add 1mL DMF, and raise the temperature to 130°C for 24h.

[0063] After the reaction was complete, the reaction was quenched with 15 mL of saturated ammonium chloride solution, extracted with ethyl acetate (15 mL×3), and 3 The mixed organic phase was washed, then washed with 15 mL of saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and the residue was purified by flash column chromatography (petroleum ether / ethyl acetate volume ratio of 100:1) to obtain The target product was obtained with an isolation yield of 84%, and the product was a colorless oily liquid.

[0064] NMR: 1 H NMR (500MHz, CDCl 3 )δ8.05-7.76 (m, 2H), 7.51-7.12 (m, 5H), 6.91 (d, J=8.9Hz, 2H), 5.91-5.83 (m...

Embodiment 3

[0066] Embodiment 3: the synthesis of compound IV-3

[0067]

[0068] Add 2-bromo-m-methylacetophenone (42.6mg, 0.2mmol), thiophenol (0.6mmol, 3equiv.), allyl bromide (1.4mmol, 7equiv. .) and dipotassium hydrogen phosphate (1.0 mmol, 5 equiv.), add 1 mL of DMF, heat up to 130 ° C for 24 h.

[0069] After the reaction was complete, the reaction was quenched with 15 mL of saturated ammonium chloride solution, extracted with ethyl acetate (15 mL×3), and 3 The mixed organic phase was washed, then washed with 15 mL of saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and the residue was purified by flash column chromatography (petroleum ether / ethyl acetate volume ratio of 100:1) to obtain The target product was obtained with an isolation yield of 82%, and the product was a colorless oily liquid.

[0070] NMR: 1 H NMR (500MHz, CDCl 3 )δ7.79-7.63 (m, 2H), 7.40-7.20 (m, 7H), 5.99-5.78 (m, 1H), 5.21-5.01 (m, 2H), 4.48 (t, J...

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Abstract

The invention discloses a synthesis method of an alpha-acyl homoallyl thioether compound. A series of alpha-acyl homoallyl thioether compounds with application value are finally synthesized by adopting a three-component and one-pot method, taking an alpha-bromoacetophenone compound, a thiol compound and an allyl bromide compound as reactants, taking inorganic salt as an additive, taking an ultra-dry or anhydrous inorganic solvent as a solvent and reacting at the temperature of 60 DEG C to 130 DEG C. The synthesis method disclosed by the invention has the beneficial effects that a series of the homoallyl thioether compounds with the potential application value are synthesized in high yield, and the utilization of a transition metal catalyst and a diazo compound can also be avoided; meanwhile, additives including strong acid, strong alkali and the like are not needed in a reaction process, and the protection of inert gas is not needed; the after treatment of reaction is simple.

Description

technical field [0001] The invention relates to a method for synthesizing compounds, in particular to a method for synthesizing α-acyl homoallyl sulfide compounds by using a three-component one-pot method, and belongs to the field of organic chemical synthesis. Background technique [0002] Sulfur-containing organic compounds are widely used in chemical industry, medicine, and materials. Therefore, research and development of new carbon-sulfur bond construction methods without transition metal catalysis are of great importance to promote the development of organic and biomedical synthesis. significance. α-acyl homoallyl sulfide compounds are the key intermediates for the synthesis of a series of potentially physiologically active molecules. In traditional synthesis methods, noble metals such as Au, Ag, Rh, and Pd are usually used as catalysts, and diazo compounds Sulfur ylide formation [2,3]-rearrangement reaction (ie, Doyle-Kirmse reaction) in tandem with allyl sulfide ach...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C319/14C07C323/22C07C323/54C07C323/29C07D333/34C07D307/80
CPCC07C319/14C07D307/80C07D333/34C07C323/22C07C323/54C07C323/29
Inventor 夏远志王振荣林波
Owner WENZHOU UNIV
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