A water-soluble transition metal complex catalyzed a method for synthesizing asymmetric sulfides in aqueous phase by molecular oxygen oxidation

A technology for the oxidation of water and transition metals with molecular oxygen, which is applied in the preparation of sulfides, organic chemistry, etc., can solve the problems of many reaction by-products, organic solvent pollution, etc., and achieves low by-products, mild oxidation characteristics, and high product selectivity. Effect

Active Publication Date: 2021-01-05
ZHENGZHOU UNIV
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Problems solved by technology

[0004] The present invention aims at the problems of organic solvent pollution and many reaction by-products in the preparation of asymmetric sulfides in the prior art, and provides a method for synthesizing asymmetric sulfides by oxidation of molecular oxygen in water phase. The present invention uses molecular oxygen as an oxidant, Using water as a solvent avoids the use of organic solvents, and the yield is high, and there is basically no problem of by-products

Method used

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  • A water-soluble transition metal complex catalyzed a method for synthesizing asymmetric sulfides in aqueous phase by molecular oxygen oxidation
  • A water-soluble transition metal complex catalyzed a method for synthesizing asymmetric sulfides in aqueous phase by molecular oxygen oxidation
  • A water-soluble transition metal complex catalyzed a method for synthesizing asymmetric sulfides in aqueous phase by molecular oxygen oxidation

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] The following structural formula has the preparation method of asymmetric sulfide:

[0051]

[0052] In the 50mL Shrek tube, add substrate phenylhydrazine 0.2mmol (22mg), p-methoxythiophenol 0.2mmol (28mg), copper acetate trihydrate 2.4mg (5mol%, the molar percentage is represented by the molar weight of metal ion The percentage of substrate molar weight is calculated, and the calculation method of other embodiments is the same), ligand L1, 5mg (5mol%), cesium carbonate 65mg (1eq.), water 2mL, add magneton, replace oxygen 0.1MPa, Stir the reaction in an oil bath at 100°C for 12h. After the reaction, the reaction tube was cooled to room temperature, 50 mL of saturated brine was added, extracted three times with dichloromethane (3*50 mL), dried by adding anhydrous sodium sulfate for 30 min, and then the low boiling point solvent was removed by a rotary evaporator. Then, the reaction mixture was separated and purified by column chromatography (silica gel column, 30*300...

Embodiment 2

[0054] The following structural formula has the preparation method of asymmetric sulfide:

[0055]

[0056] Add substrate 3,4-dimethylphenylhydrazine 0.2mmol (27mg), p-methoxythiophenol 0.2mmol (28mg), copper acetate trihydrate 4.8mg (10mol%), ligand L2, 10mg (10mol%), cesium carbonate 650mg (10eq.), water 2mL, add magneton, replace oxygen 0.3MPa, stir and react in 40°C oil bath for 5h. After the reaction, the reaction tube was cooled to room temperature, 50 mL of saturated brine was added, extracted three times with dichloromethane (3*50 mL), dried by adding anhydrous sodium sulfate for 30 min, and then the low boiling point solvent was removed by a rotary evaporator. Then, the reaction mixture was separated and purified by column chromatography (silica gel column, 30*300mm) (eluent: n-hexane:dichloromethane=2:1) ​​to obtain the target product with a yield of 92%. Target product characterization data: Yellow oil.(hexane:DCM=2:1as eluent). 1 H NMR (400MHz, CDCl 3 )δ=7.31...

Embodiment 3

[0058] The following structural formula has the preparation method of asymmetric sulfide:

[0059]

[0060] Add substrate 3-chlorophenylhydrazine 0.2mmol (28mg), p-methoxythiophenol 0.2mmol (28mg), copper chloride dihydrate 0.03mg (0.05mol%), ligand L2, 0.05mg (0.05mol%), potassium carbonate 84mg (3eq.), water 2mL, add magneton, replace oxygen 0.2MPa, stir and react in 80°C oil bath for 10h. After the reaction, the reaction tube was cooled to room temperature, 50 mL of saturated brine was added, extracted three times with dichloromethane (3*50 mL), dried by adding anhydrous sodium sulfate for 30 min, and then the low boiling point solvent was removed by a rotary evaporator. Then, the reaction mixture was separated and purified by column chromatography (silica gel column, 30*300mm) (eluent: n-hexane:dichloromethane=2:1) ​​to obtain the target product with a yield of 98%. Target product characterization data: Yellow solid.(hexane:DCM=2:1as eluent).50-53℃. 1 H NMR (400MHz, C...

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Abstract

Aiming at problems that in the prior art organic solvent pollution can be caused and a great number of reaction byproducts are generated when asymmetric sulfides are prepared, the invention disclosesa method for synthesizing an asymmetric sulfide from a molecular oxygen oxidation water phase under catalysis of a water-soluble transition metal compound. The method comprises the following steps: dispersing a sulfydryl compound and a hydrazine compound as substrates in a mole ratio of 1:1 into an alkali solution, and at 40-100 DEG C, in the presence of oxygen, and with a water-soluble transitionmetal compound as a catalyst, stirring to carry out reactions, thereby obtaining the asymmetric sulfide. By adopting the method, molecular oxygen is adopted as an oxidant, and water is adopted as a solvent, so that an organic solvent is avoided, a high yield can be achieved, and the problem of byproducts can be generally avoided.

Description

technical field [0001] The invention relates to the technical field of asymmetric sulfide synthesis, in particular to a method for synthesizing asymmetric sulfide by oxidation of molecular oxygen in water phase. Background technique [0002] Sulfur-containing compounds are important intermediates in organic synthesis and are widely used in medicinal chemistry and materials chemistry. The organic scaffold compound containing thiourea has remarkable curative effect on cancer, malaria, Alzheimer's disease, Parkinson's disease, AIDS and other diseases, and has important influence in the field of biology and pharmacy. Sulfur-containing compounds are also the building blocks of several natural products. For example, polysulfur aromatic alkaloids isolated from Ascidian ascidian can inhibit the growth of human colon, cervical, and breast cancer cells. Sulfur-containing compounds are also widely used in materials science, such as internal plasticization of PVC to achieve good plasti...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C323/20C07D213/70C07C323/37C07D277/74C07C321/28C07C319/14C07D333/34C07C323/21C07C323/09C07C321/30
CPCC07C321/28C07C321/30C07C323/09C07C323/20C07C323/21C07C323/37C07D213/70C07D277/74C07D333/34
Inventor 袁冰芯李恒任煊赫
Owner ZHENGZHOU UNIV
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