Reaction method capable of utilizing oxygen to oxidize organic sulfur compounds

Abstract

The invention relates to a reaction method capable of utilizing oxygen to oxidize organic sulfur compounds. The reaction method is technically characterized in that crosslinked polystyrene immobilized metalloporphyrin complexes are adopted as catalytic agents, and the organic sulfur compounds are oxidized to generate sulfoxide compounds through oxygen. The reaction method solves the problems that the catalytic agents which are adopted in the conventional organic sulfur compound oxidization method have not high stability, are easy to decompose and inactivate, and are difficult to recycle. The reaction method comprises the steps as follows: oxygen is used as oxidizing agents and is pumped in continuously under normal temperature and normal pressure, the concentration of the catalytic agents is selected to range from 0.5 to 2.2 micromole / ml, reaction time ranges from 4 to 8 hours, and the productivity of the sulfoxide compounds ranges from 80 to 97 percent along with the changes of the amount of the catalytic agents, the reaction time and the reaction temperature. The reaction temperature is lower, so that the deep oxidation of sulfoxide can be controlled effectively. The catalytic agents adopted in the reaction method cannot be leaked, are easy to separate, and can be recycled for eight times; and the reaction yield remains unchanged approximately.

Description

technical field

[0001] The invention relates to a reaction method for oxidizing organic sulfides with oxygen, in particular to a method for using an immobilized metal complex as a catalyst to oxidize organic sulfides with oxygen to generate sulfoxide compounds. Background technique

[0002] Sulfoxide compounds are important synthetic intermediates and are widely used in industries such as medicine, pesticides, synthetic fibers, printing and dyeing, and rare metal extractants. The thioether oxidation method is the most direct and common method for the synthesis of sulfoxide, but sulfoxide can be further oxidized to sulfone, so how to control the oxidation to sulfoxide stage is the key issue of synthesis. Among many known synthetic methods, Gasparrini et al. (Tetrahedron 1983, 39, 3182) disclose a method of oxidizing dithiobenzylmethane with nitric acid to form sulfoxide. Raga et al. (J.Heterocycl.Chem.1992,29,1557) disclose a kind of NaIO 4 Oxidation method to obtain a sulf...

Examples

Embodiment 1

[0014] (1) 0.25g of cross-linked polystyrene immobilized metal porphyrin complex catalyst (R=Cl, M=Fe, X=Cl) with the structure of general formula (I) is added to 15ml of dibenzylsulfide Mix in ether and 50ml tetrahydrofuran;

[0015] (2) At room temperature, continuously feed pure oxygen, start stirring, and react for about 4 hours;

[0016] (3) After the reaction is finished, filter with suction, wash with tetrahydrofuran several times, and then recover the catalyst for next use. Filtrate with NaHCO 3 washed with aqueous solution, followed by anhydrous MgSO 4 Drying, concentration, and recrystallization from ethanol afforded dibenzyl sulfoxide in 85% yield. The catalyst was reused 8 times, and the reaction yield was basically unchanged.

Embodiment 2

[0018] (1) the metal porphyrin complex catalyst (R=NO) of cross-linked polystyrene immobilization with 0.24g general formula (I) structure 3 , M=Co, X=Ac) was added to 15ml of phenyl allyl sulfide and 50ml of dichloroethane and mixed;

[0019] (2) At room temperature, continuously feed pure oxygen, start stirring, and react for about 6 hours;

[0020] (3) After the reaction is finished, filter with suction, wash with ethylene dichloride several times, then recover the catalyst for next use. Filtrate with NaHCO 3 washed with aqueous solution, followed by anhydrous MgSO 4 Drying, concentration, and recrystallization from ethanol afforded phenylallyl sulfoxide in 91% yield. The catalyst was reused 8 times, and the reaction yield was basically unchanged.

Embodiment 3

[0022] (1) 0.25g has the cross-linked polystyrene solid-supported metal porphyrin complex catalyst (R=NO 3 , M=Mn, X=Cl) was added to 15ml dimethyl sulfide and 50ml acetonitrile and mixed;

[0023] (2) At room temperature, continuously feed pure oxygen, start stirring, and react for about 5 hours;

[0024] (3) After the reaction is finished, filter with suction, wash with acetonitrile for several times, then recover the catalyst for next use. Filtrate with NaHCO 3 washed with aqueous solution, followed by anhydrous MgSO 4 Drying, concentration, and distillation afforded dimethyl sulfoxide in 93% yield. The catalyst was reused 8 times, and the reaction yield was basically unchanged.

technical field

[0001] The invention relates to a reaction method for oxidizing organic sulfides with oxygen, in particular to a method for using an immobilized metal complex as a catalyst to oxidize organic sulfides with oxygen to generate sulfoxide compounds. Background technique

[0002] Sulfoxide compounds are important synthetic intermediates and are widely used in industries such as medicine, pesticides, synthetic fibers, printing and dyeing, and rare metal extractants. The thioether oxidation method is the most direct and common method for the synthesis of sulfoxide, but sulfoxide can be further oxidized to sulfone, so how to control the oxidation to sulfoxide stage is the key issue of synthesis. Among many known synthetic methods, Gasparrini et al. (Tetrahedron 1983, 39, 3182) disclose a method of oxidizing dithiobenzylmethane with nitric acid to form sulfoxide. Raga et al. (J.Heterocycl.Chem.1992,29,1557) disclose a kind of NaIO 4 Oxidation method to obtain a sulf...

Examples

Embodiment 1

[0014] (1) 0.25g of cross-linked polystyrene immobilized metal porphyrin complex catalyst (R=Cl, M=Fe, X=Cl) with the structure of general formula (I) is added to 15ml of dibenzylsulfide Mix in ether and 50ml tetrahydrofuran;

[0015] (2) At room temperature, continuously feed pure oxygen, start stirring, and react for about 4 hours;

[0016] (3) After the reaction is finished, filter with suction, wash with tetrahydrofuran several times, and then recover the catalyst for next use. Filtrate with NaHCO 3 washed with aqueous solution, followed by anhydrous MgSO 4 Drying, concentration, and recrystallization from ethanol afforded dibenzyl sulfoxide in 85% yield. The catalyst was reused 8 times, and the reaction yield was basically unchanged.

Embodiment 2

[0018] (1) the metal porphyrin complex catalyst (R=NO) of cross-linked polystyrene immobilization with 0.24g general formula (I) structure 3 , M=Co, X=Ac) was added to 15ml of phenyl allyl sulfide and 50ml of dichloroethane and mixed;

[0019] (2) At room temperature, continuously feed pure oxygen, start stirring, and react for about 6 hours;

[0020] (3) After the reaction is finished, filter with suction, wash with ethylene dichloride several times, then recover the catalyst for next use. Filtrate with NaHCO 3 washed with aqueous solution, followed by anhydrous MgSO 4 Drying, concentration, and recrystallization from ethanol afforded phenylallyl sulfoxide in 91% yield. The catalyst was reused 8 times, and the reaction yield was basically unchanged.

Embodiment 3

[0022] (1) 0.25g has the cross-linked polystyrene solid-supported metal porphyrin complex catalyst (R=NO 3 , M=Mn, X=Cl) was added to 15ml dimethyl sulfide and 50ml acetonitrile and mixed;

[0023] (2) At room temperature, continuously feed pure oxygen, start stirring, and react for about 5 hours;

[0024] (3) After the reaction is finished, filter with suction, wash with acetonitrile for several times, then recover the catalyst for next use. Filtrate with NaHCO 3 washed with aqueous solution, followed by anhydrous MgSO 4 Drying, concentration, and distillation afforded dimethyl sulfoxide in 93% yield. The catalyst was reused 8 times, and the reaction yield was basically unchanged.

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