CN114478329B - Novel method for preparing sulfoxide and sulfone by catalytic oxidation of molecular oxygen under mild condition - Google Patents
Novel method for preparing sulfoxide and sulfone by catalytic oxidation of molecular oxygen under mild condition Download PDFInfo
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- CN114478329B CN114478329B CN202210037250.7A CN202210037250A CN114478329B CN 114478329 B CN114478329 B CN 114478329B CN 202210037250 A CN202210037250 A CN 202210037250A CN 114478329 B CN114478329 B CN 114478329B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates toAnd the technical field of catalytic molecular oxygen oxidation, and discloses a simple, green and practical method for converting thioether into sulfoxide or sulfoxide into sulfone based on catalytic molecular oxygen oxidation. In a synergistic action system of a catalyst of quaternary ammonium metavanadate, a free radical initiator of organic peroxide, alkyl mercaptan and an alkyl aromatic hydrocarbon solvent, catalytic oxidation of thioether molecular oxygen into sulfoxide or conversion of sulfoxide into sulfone is carried out under mild conditions, and the method can realize 100% selectivity of a product. And the method has wider applicability to sulfide or sulfoxide compounds as organic sulfide substrates. The catalytic oxidation method of the invention is 30-70 o The C can realize high-efficiency conversion under the mild reaction condition, has the advantages of energy conservation, low carbon and green environmental protection, and is a clean chemical production process conforming to the concept of green chemistry.
Description
Technical Field
The invention relates to a novel method for synthesizing sulfoxide by oxidizing thioether and sulfone by oxidizing sulfoxide, in particular to a novel method for synthesizing sulfoxide by oxidizing thioether by catalyzing molecular oxygen under mild conditions and synthesizing sulfone by oxidizing sulfoxide.
Background
The organic sulfide oxidation is an important organic reaction, and the product is widely applied to the synthesis of medicines, pesticides, functional materials and noble metal extractants and the oxidative desulfurization of fuel oil. Dimethyl sulfoxide (DMSO), for example, is known as a versatile solvent and is also a reactant widely used in pesticides, pharmaceuticals, synthetic fibers, synthetic resins, paints, dyes, electronics and antifreeze. Dimethyl sulfone (MSM) is used in industry as an organic synthetic high temperature solvent and raw material, gas chromatography fixative, analytical reagent, food additives, health foods and pharmaceuticals.
The production of sulfoxides and sulfones is generally accomplished by oxidizing the thioether and sulfoxide, respectively; but most often use conventional oxidants, such as HNO 3 And nitrogen dioxide (NO) 2 ) Both oxidizing agents have disadvantages, such as the use of nitric acidOr when nitrogen dioxide is oxidized, the generation process is dangerous, and unreacted oxidant pollutes the environment and corrodes equipment; hydrogen peroxide and ozone are green oxidants and in recent years efforts have been made to develop catalysts for the oxidation of hydrogen peroxide or ozone to dimethyl sulfoxide and dimethylsulfone, such as CN 103288691A, CN 103288692a and CN105017108A, respectively, which disclose titanium silicalite catalysts for the oxidation of ozone and peroxides to dimethyl sulfoxide and dimethylsulfone. However, when oxidized by hydrogen peroxide, the hydrogen peroxide has low effective utilization rate and high energy consumption, and the titanium-silicon molecular sieve catalyst is expensive.
Oxygen is a cheaper, more readily available, safer, more environmentally friendly green oxidant than hydrogen peroxideGreen Chem. 2019,21, 235-237.]. Therefore, the development of a new method using oxygen and air as oxidizing agents has no doubt important application value.
Molecular oxygen is difficult to activate and therefore requires severe reaction conditions such as high temperature, high pressure or high energy radiationJ. Am. Chem. Soc. 1980, 102, 1942-1948. ]. In order to achieve activation of molecular oxygen under mild reaction conditions, a catalyst is added to promote its activation.
The invention provides a simple, convenient and practical method for synthesizing sulfoxide or sulfoxide into sulfone by oxidizing thioether under mild conditions by adding a catalyst, a free radical initiator and a solvent to synergistically catalyze molecular oxygen. The method overcomes the defects of high energy consumption, high cost, serious pollution and corrosion and the like existing in the traditional production of sulfone, and realizes the production of sulfoxide and sulfone with low cost, high efficiency and environmental protection.
Disclosure of Invention
The invention aims to provide a novel method for catalyzing molecular oxygen to oxidize and synthesizing sulfoxide and sulfone in an environment-friendly way.
The novel method for synthesizing sulfoxide and sulfone by catalytic molecular oxygen oxidation is realized by the following technical scheme:
with a certain amount of a catalyst containing relatively active C (sp 3 ) H-bond hydrocarbon such as ethylbenzene, cumene, isobutylbenzene, cyclohexylbenzene, cyclohexylcyclohexane, tetrahydronaphthalene, decalin, etc. as solvent, quaternary ammonium metavanadate as catalyst, organic peroxyThe chemical compound and the alkyl mercaptan are free radical initiator, air or oxygen is provided by a steel bottle or an air bag, a certain amount of thioether or sulfoxide is taken as a reaction substrate, and the reaction is carried out under normal heating, normal pressure or high pressure, and the reaction conditions are as follows: temperature (30-70) o C) The conversion and the product selectivity are calculated by quantitative analysis of gas chromatography under the conditions of pressure (0.1-1.0 MPa) and time (2-48 h).
Compared with the traditional catalytic oxidation method, the novel method has the following advantages: the catalyst is cheap and easy to obtain, the reaction temperature is low, the operation is simple and convenient, and the catalyst is safe and environment-friendly.
Detailed Description
The following describes in detail a method for preparing sulfone by catalyzing molecular oxygen to oxidize sulfoxide or thioether under mild condition by using quaternary ammonium metavanadate in combination with specific examples, but these examples are not limited to the protection scope of the present invention, and are mainly described by taking oxidation of dimethyl sulfide and dimethyl sulfoxide as examples, and then extend to other thioether or sulfoxide compounds.
Example 1: into a 25 mL stainless steel autoclave, 10 mL ethylbenzene was added as a solvent, dimethyl sulfide 8 mmol was added, and 0.0192 mmol of tetrabutyl quaternary ammonium metavanadate (TBA) VO was added 3 The initiator cumene hydroperoxide and n-propanethiol were both 0.144 mmol, oxygen was supplied from a steel cylinder, and the reaction was carried out under pressure by conventional heating and magnetic stirring, the reaction conditions: temperature 30 o C. The pressure is 0.5 MPa, the time is 48 and h, the conversion rate is 77% and the dimethyl sulfoxide selectivity is 100% by quantitative analysis of gas chromatography.
Example 2: adding 10 mL cumene as solvent into 25 mL stainless steel autoclave, adding dimethyl sulfide 8 mmol,0.0128 mmol dodecyltrimethylammonium metavanadate (DTA) VO 3 The initiator cumene hydroperoxide and n-heptanethiol were both 0.096 mmol, oxygen was supplied from a steel cylinder, and the reaction was carried out under pressure by conventional heating and magnetic stirring, the reaction conditions: temperature 40 o C. The pressure is 0.3 MPa, the time is 36 and h, the conversion rate is 72% and the dimethyl sulfoxide selectivity is 100% by quantitative analysis of gas chromatography.
Example 3: stainless steel 25 to 25 mLInto the autoclave, 10 mL isobutylbenzene was added as a solvent, 8 mmol of dimethyl sulfide was added, and 0.0096 mmol of cetyltrimethylammonium metavanadate (CTAVO 3 ) The initiator tert-butyl alcohol hydrogen peroxide and benzyl mercaptan are 0.064 mmol, oxygen is provided by a steel bottle, and the reaction is carried out under the conditions of conventional heating and magnetic stirring and pressurization: temperature 50 o C. The pressure is 0.7 MPa, the time is 24 and h, the conversion rate is 66% by gas chromatography quantitative analysis, and the dimethyl sulfoxide selectivity is 100%.
Example 4: into a 25 mL stainless steel autoclave, 10 mL cyclohexylbenzene was added as a solvent, 8 mmol of dimethyl sulfide was added, and 0.0064 mmol of cetyltrimethylammonium metavanadate (CTAVO) 3 ) The initiator cyclohexanone peroxide and n-dodecyl mercaptan are 0.128 mmol, air is supplied by a steel cylinder, and the reaction is carried out under the conditions of conventional heating and magnetic stirring and pressurization: temperature 60 o C. The pressure is 1.0 MPa, the time is 12 and h, the conversion rate is 78% and the dimethyl sulfoxide selectivity is 100% by quantitative analysis of gas chromatography.
Example 5: into a 25 mL stainless steel autoclave, 10 mL cyclohexane was added as a solvent, 8 mmol of dimethyl sulfide was added, and 0.0096 mmol of didodecyl dimethyl ammonium metavanadate (DDAVO) 3 ) Initiator tert-butanol hydrogen peroxide and isopropyl mercaptan are both 0.096 mmol, air is supplied from a steel cylinder, and the reaction is carried out under pressure by conventional heating and magnetic stirring, the reaction conditions being: temperature 70 o C. The pressure is 0.9 MPa, the time is 2 h, the conversion rate is 65% by gas chromatography quantitative analysis, and the dimethyl sulfoxide selectivity is 100%.
Example 6: into a 25 mL three-necked round bottom flask, 10 mL tetrahydronaphthalene was added as a solvent, dimethyl sulfoxide 8 mmol was added, and 0.0128 mmol cetyltrimethylammonium metavanadate (CTAVO) 3 ) The initiator tert-butyl alcohol hydrogen peroxide and phenethyl mercaptan are 0.096 mmol, oxygen is provided by an air bag, and the reaction is carried out under normal pressure by conventional heating and magnetic stirring, wherein the reaction conditions are as follows: temperature 60 o C. Time 24 h, conversion was 87% and dimethylsulfone selectivity was 100% by gas chromatography.
Example 7: 25 to mL threeInto a round bottom flask, 10 mL decalin was added as a solvent, 8 mmol of dimethyl sulfoxide was added, and 0.0064 mmol of didodecyl dimethyl ammonium metavanadate (DDAVO) 3 ) The initiator cumene hydroperoxide and n-propanethiol are 0.096 mmol, oxygen is provided by an air bag, and the reaction is carried out under normal pressure by conventional heating and magnetic stirring, wherein the reaction conditions are as follows: temperature 70 o C. Time 18 h, conversion 92% and dimethylsulfone selectivity 100% were quantified by gas chromatography.
Example 8: into a 25 mL three-necked round bottom flask, 10 mL cumene was added as a solvent, dimethyl sulfoxide was 8 mmol, and cetyltrimethylammonium metavanadate (CTAVO) was added in an amount of 0.0128 mmol 3 ) The initiator cumene hydroperoxide and n-propanethiol are 0.112 mmol, air is provided by an air bag, and the reaction is carried out under normal pressure by conventional heating and magnetic stirring, wherein the reaction conditions are as follows: temperature 30 o C. Time 48 h, conversion 73% and dimethylsulfone selectivity 100% were quantified by gas chromatography.
Example 9: into a 25 mL three-neck round bottom flask, 10 mL tetrahydronaphthalene was added as a solvent, dimethyl sulfoxide 8 mmol,0.0096 mmol dodecyltrimethylammonium metavanadate (DTA) VO 3 The initiator ethylbenzene hydroperoxide and n-heptanethiol were 0.096 mmol, air was supplied by an air bag, and the reaction was carried out under normal pressure by conventional heating and magnetic stirring, and the reaction conditions were: temperature 70 o C. Time 8 h, conversion was 82% and dimethylsulfone selectivity was 100% by gas chromatography.
Example 10: into a 25 mL three-necked round bottom flask, 10 mL cumene as a solvent, 8 mmol of phenylsulfide and 0.0096 mmol of cetyltrimethylammonium metavanadate (CTAVO) were added 3 ) The initiator cumene hydroperoxide and n-heptanethiol were both 0.096 mmol, air was supplied with air bag, and the reaction was carried out under normal pressure by conventional heating and magnetic stirring, the reaction conditions: temperature 70 o C. Time 12 h, analyzed quantitatively by gas chromatography, the conversion of the benzyl sulfide was 81% and the selectivity to the benzyl sulfoxide was 100%.
Example 11: adding 10 mL cumene as solvent into 25 mL stainless steel autoclave, adding dimethyl sulfoxide 8 mmol, add 0.0160 mmol cetyltrimethylammonium metavanadate (CTAVO 3 ) Initiator tert-butanol hydrogen peroxide and n-propanethiol, both 0.096 mmol, were reacted by supplying air from a steel cylinder, heating conventionally and magnetically stirring, and pressurizing under the reaction conditions: temperature 60 o C. The pressure is 1.0 MPa, the time is 18 and h, the dimethyl sulfoxide conversion rate is 95% and the dimethyl sulfone selectivity is 100% by quantitative analysis of gas chromatography.
Example 12: into a 25 mL three-necked round bottom flask, 10 mL cumene as a solvent, 8 mmol of diphenyl sulfide and 0.0096 mmol of didodecyl dimethyl ammonium metavanadate (DDAVO) were added 3 ) The initiator cumene hydroperoxide and n-propanethiol are both 0.064 mmol, air is provided by an air bag, and the reaction is carried out under normal pressure by conventional heating and magnetic stirring, wherein the reaction conditions are as follows: temperature 70 o C. Time 24 h, quantitative analysis by gas chromatography, diphenyl sulfide conversion was 72% and diphenyl sulfoxide selectivity was 100%.
Example 13: into a 25 mL three-necked round bottom flask, 10 mL ethylbenzene was added as a solvent, 8 mmol of dibutyl sulfide, and 0.0128 mmol of cetyltrimethylammonium metavanadate (CTAVO) 3 ) The initiator ethylbenzene hydroperoxide and n-heptanethiol were each 0.096 mmol, oxygen was supplied by an air bag, and the reaction was carried out under normal pressure by conventional heating and magnetic stirring, and the reaction conditions were: temperature 50 o C. For 30 hours, the dibutyl ether conversion was 72% and the diphenyl sulfoxide selectivity was 100% by gas chromatography.
Example 14: into a 25 mL three-necked round bottom flask, 10 mL cumene as a solvent, 8 mmol of benzyl sulfoxide and 0.0064 mmol of cetyltrimethylammonium metavanadate (CTAVO) were added 3 ) The initiator cumene hydroperoxide and n-propanethiol are both 0.064 mmol, oxygen is provided by an air bag, and the reaction is carried out under normal pressure by conventional heating and magnetic stirring, wherein the reaction conditions are as follows: temperature 30 o C. Time 48 h, the conversion of the phenylsulfoxide was 98% and the phenylsulfone selectivity was 100% by quantitative analysis using gas chromatography.
Example 15: into a 25 mL three-necked round bottom flask, 10 mL tetrahydronaphthalene as a solvent, diphenyl sulfoxide 8 mmol, and 0.0192 mmol of bis (metavanadate) were addedDodecyl Dimethyl Ammonium (DDAVO) 3 ) The initiator cumene hydroperoxide and n-propanethiol are 0.144 mmol, oxygen is provided by an air bag, and the reaction is carried out under normal pressure by conventional heating and magnetic stirring, wherein the reaction conditions are as follows: temperature 40 o C. Time 36 h, diphenyl sulfoxide conversion was 93% and diphenyl sulfone selectivity was 100% by gas chromatography.
Claims (8)
1. Quaternary ammonium metavanadate under mild condition with free radical initiator and with relative active C (sp 3 ) -a method for the synergistic catalysis of the conversion of a molecular oxygen oxidizing thioether to a sulfoxide or of a sulfoxide to a sulfone by an H-bond hydrocarbon solvent, characterized in that it comprises the following steps: adding a catalyst, adding a catalytic amount of free radical initiator, a solvent and sulfoxide or thioether into a stainless steel autoclave or a three-neck flask reactor, and stirring and reacting for a certain time in an oxygen atmosphere at a lower temperature to synthesize a target product.
2. The method of claim 1, wherein the catalyst is a quaternary ammonium metavanadate.
3. The method of claim 1, wherein the free radical initiator is an organic peroxide and a hydrocarbyl thiol.
4. The process according to claim 1, wherein the solvent is a solvent containing relatively active C (sp 3 ) -H-bond hydrocarbons.
5. The method of claim 1, wherein the catalyst is used in an amount of 0.0064~0.0192 mmol.
6. The method of claim 1, wherein the initiator is used in an amount of 0.064 to 0.144 mmol.
7. The method according to claim 1, wherein the reaction temperature is 30-70 ℃ o C。
8. The method of claim 1, wherein the reaction time is 2-48 hours.
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