CN104888852A - Catalytic system for oxidation of olefins and application thereof - Google Patents
Catalytic system for oxidation of olefins and application thereof Download PDFInfo
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Abstract
The invention discloses a catalytic system for oxidation of olefins, belonging to the organocatalysis field. Palladium salt and non-oxidation reduction active metal salt are dissolved into a solvent to form a solution, wherein the solvent is a mixed solution of an organic solvent and water; the molar ratio of the palladium salt to the non-oxidation reduction active metal salt in the solution is 1:(2-10), and the concentration of the palladium salt is 1-10 mmol/L. The invention also provides a method for catalytic oxidation of olefins by use of the catalytic system. The catalytic system enables a reaction system to be simple and to be realized easily, the atom utilization rate is high, the pollution is low, the reaction efficiency is high and the cost is low.
Description
Technical field
The invention belongs to organic catalysis field, more specifically, relate to a kind of catalyst system and catalyzing for olefin hydrocarbon oxidation reaction and application.
Background technology
One of oxidation reaction important method becoming olefin functionalities of alkene.Palladium catalyst is the highest and most widely used a kind of transition-metal catalyst of catalytic activity in organic synthesis field.Alkene is in water-hydrochloric acid solution, and under the catalytic action of copper chloride and palladium bichloride, with oxygen to directly oxidize, the reaction generating aldehydes or ketones claims Wacker oxidation to react.
Wacker oxidation reaction response mechanism is the first palladium coordination of alkene, water is nucleophilic attack again, eliminate proton, then palladium is eliminated in reduction, be rearranged into carbonyls, Pd (II) is reduced to Pd (0), Cu (II) is oxidized to Pd (II) Pd (0) again, Pd (II) is made to continue the carrying out of catalytic reaction, Cu (II) is reduced into Cu (I), Cu (I) is being oxidized to Cu (II) in acid condition by oxygen, and whole catalytic reaction can be circulated down.
In the oxidation reaction of palladium chtalyst, an important problem is exactly how to stablize Pd (0) thus suppress catalysqt deactivation.Above-mentioned Wacker method mainly utilizes the copper ion with redox ability to be oxidized by Pd (0), realizes the regeneration of Pd (II).Also a kind of method is had to be in system, add equivalent oxidant such as silver iodide, benzoquinones, alkyl peroxide etc.; or utilize part carry out stable Pd (0) thus make catalyst regeneration; this usually can cause reaction system to become very complicated; Atom economy is not high yet, and a lot of conventional part can fast decoupled under oxidative conditions.So Wacker method has certain restriction on application.Therefore, need to develop and a kind ofly can make reaction system is simple, atom utilization is high, reaction efficiency is high low cost catalyst system and catalyzing or catalyst.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of catalyst system and catalyzing for olefin hydrocarbon oxidation reaction and application, its object is to, the metal ion of palladium salt and non-redox active is inserted a kind of new catalyst system and catalyzing of formation in solution, it is oxidized into aldehydes or ketones for homogeneous catalytic olefin, and the method has the advantage being easy to realize, atom utilization is high, reaction condition is gentle and efficiency is higher.Solve in existing olefin hydrocarbon oxidation reaction thus, due to copper ion, oxidant must be added or use part regenerated catalyst, thus make reaction complicated and the problem that cost is high.
For achieving the above object, according to one aspect of the present invention, provide a kind of catalyst system and catalyzing for olefin oxidation, it is palladium salt, non-redox active slaine is dissolved in the solution formed in solvent, described solvent is the mixed liquor that organic solvent and water are formed;
In described solution, the mol ratio of palladium salt and non-redox active slaine is 1 ︰ 2 ~ 10;
In described solution, the concentration of palladium salt is 1 mM/l ~ 10 mM/ls.
Further, in described solvent, the volume ratio of organic solvent and water is 5 ︰ 0.1 ~ 1.
Further, described palladium salt comprise in acid chloride, palladium bichloride and palladium nitrate one or more, be preferably acid chloride.
Further, described non-redox active slaine to comprise in trifluoromethane sulfonic acid scandium, scandium chloride, trifluoromethane sulfonic acid aluminium, trifluoromethane sulfonic acid magnesium, trifluoromethane sulfonic acid zinc, zinc chloride, trifluoromethane sulfonic acid calcium, calcium chloride, trifluoromethane sulfonic acid yttrium, trifluoromethane sulfonic acid ytterbium and trifluoromethyl sulfonate one or more.
Further, described organic solvent comprises one or more in acetonitrile, ethanol, DMF, DMA, dimethyl sulfoxide (DMSO), benzonitrile and toluene.
According to second aspect of the present invention, also provide a kind of method of catalytic olefin oxidations, it is characterized in that, it adopts catalyst system and catalyzing as above.
Further, described alkene comprises 1-hexene, 3-hexene, 1-octene, 4-octene, cyclohexene, cyclopentene, cyclo-octene and/or styrene.
Further, the mol ratio of the salt of palladium described in catalyst system and catalyzing and alkene is 1 ︰ 20 ~ 400.
Further, the oxygen pressure that reaction adopts is 0.1 MPa ~ 4 MPa, and the reaction time is 2 hours ~ 20 hours.
In general, the above technical scheme conceived by the present invention compared with prior art, can obtain following beneficial effect:
(1) catalyst system and catalyzing for olefin oxidation provided by the invention, be mainly used in catalytic olefin oxidations and generate aldehydes or ketones, this catalyst system and catalyzing non-redox active slaine replaces copper ion or other oxidants identical with copper ion effect, non-redox active slaine has increases the oxidability of palladium and the little feature of toxicity, owing to avoiding using copper ion or other oxidants, thus it is complicated to overcome reaction system in existing Wacker method, atom utilization is low, the problem that cost is high, accordingly, in the present invention's design, reaction system can make reaction system simple, be easy to realize, atom utilization is high, pollute little, reaction efficiency is high, with low cost.
(2) method of new catalytic olefin oxidations provided by the invention, its catalytic condition is gentle, can lower temperature, less pressure and under the short period catalyzed alkene be oxidized, thus cut down the Design and manufacture cost of consersion unit, test shows that its catalytic efficiency is high, reaction yield is high, and catalyst amount is few.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
In the present invention, the catalyst system and catalyzing for olefin oxidation is: palladium salt, non-redox active slaine are dissolved in the solution formed in solvent, and described solvent is the mixed liquor that organic solvent and water are formed; In described solution, the mol ratio of palladium salt and non-redox active slaine is 1 ︰ 2 ~ 10; In described solution, the concentration of palladium salt is 1/ liter ~ 10 mM/ls.
Non-redox active slaine can provide corresponding metal ion, when carrying out olefin oxidation, the metal ion of non-redox active take part in the process of living again of catalyst as lewis acid, its ginseng mM with the mechanism of reaction is: alkene elder generation and palladium coordination, water is nucleophilic attack again, eliminate proton, then alkene is oxidized, and palladium catalyst can be formed Pd-H key, before the reduction removal process of palladium, the metal ion of this non-redox active can stablize palladium hydrogen bond, thus oxygen is directly inserted between Pd-H key form Pd-OOH intermediate, further reaction generates corresponding palladium salt and hydrogen peroxide, thus achieve whole catalytic cycle.Test prove, the mol ratio of palladium salt and non-redox active slaine be 1 ︰ 2 ~ 10 and the concentration of palladium salt is 1 mM/l ~ 10 mM/ls time, above-mentioned reaction could be realized.
In an embodiment of the present invention, in described solvent, the volume ratio of organic solvent and water is 5 ︰ 0.1 ~ 1.Wherein, the effect of organic solvent is catalyst-solvent and reactant, and water participates in catalytic reaction as nucleopilic reagent.Test proves, when the volume ratio of organic solvent and water is 5 ︰ 0.1 ~ 1 in solvent, has the advantage avoiding Hydrolysis Reactions of Metal-ions, is conducive to the raising of productive rate.
In an embodiment of the present invention, described palladium salt comprises one or more in acid chloride, palladium bichloride and palladium nitrate.Olefin catalytic oxidation generally all makes catalyst with palladium, and above three kinds of palladium salt are comparatively conventional.
In an embodiment of the present invention, described non-redox active slaine to comprise in trifluoromethane sulfonic acid scandium, scandium chloride, trifluoromethane sulfonic acid aluminium, trifluoromethane sulfonic acid magnesium, trifluoromethane sulfonic acid zinc, zinc chloride, trifluoromethane sulfonic acid calcium, calcium chloride, trifluoromethane sulfonic acid yttrium, trifluoromethane sulfonic acid ytterbium and trifluoromethyl sulfonate one or more.
Preferably, described organic solvent comprises acetonitrile, ethanol, N, one or more in dinethylformamide (be called for short DMF), DMA (being called for short DMA), dimethyl sulfoxide (DMSO) (being called for short DMSO) and toluene.The effect of organic solvent is catalyst-solvent and reactant, and it is not limited to above several, in principle, as long as can catalyst-solvent and reactant all passable.
The present invention also provides a kind of method of catalytic olefin oxidations, and it adopts catalyst system and catalyzing as above, and preferably, described alkene is preferably 1-hexene, 3-hexene, 1-octene, 4-octene, cyclohexene, cyclopentene, cyclo-octene and/or styrene.
In an embodiment of the present invention, the mol ratio of the salt of palladium described in catalyst system and catalyzing and alkene is 1 ︰ 20 ~ 400.Catalyst system and catalyzing of the present invention has good catalytic capability.
Preferably, oxygen pressure is 0.1 MPa ~ 4 MPa, and the reaction time is 2 hours ~ 20 hours.
Embodiment 1
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid scandium, and the volume ratio of acetonitrile and water is acetonitrile: water=5:0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid scandium is 1:2, and the concentration of acid chloride is 4 mM/ls.Catalysis 1-hexene is oxidized, and the mol ratio of acid chloride and 1-hexene is 1:100, and oxygen pressure is 2 MPas, and 80 degrees celsius react 2 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 99%, and the productive rate of methyl-n-butyl ketone is the productive rate of 53%, 3-hexanone is 29%.
Embodiment 2
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid aluminium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid aluminium is 1:2, and the concentration of acid chloride is 4 mM/ls.Catalysis 1-hexene is oxidized, and the mol ratio of acid chloride and 1-hexene is 1:100, and oxygen pressure is 2 MPas, and 80 degrees celsius react 8 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 78%, and the productive rate of methyl-n-butyl ketone is the productive rate of 38%, 3-hexanone is 25%.
Embodiment 3
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of palladium bichloride and trifluoromethane sulfonic acid aluminium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of palladium bichloride and trifluoromethane sulfonic acid aluminium is 1:2, and the concentration of palladium bichloride is 4 mM/ls.Catalysis 1-hexene is oxidized, and the mol ratio of palladium bichloride and 1-hexene is 1:100, and oxygen pressure is 2 MPas, and 80 degrees celsius react 16 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 71%, and the productive rate of methyl-n-butyl ketone is the productive rate of 35%, 3-hexanone is 21%.
Embodiment 4
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of palladium nitrate and trifluoromethane sulfonic acid aluminium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.5, and the mol ratio of palladium nitrate and trifluoromethane sulfonic acid aluminium is 1:4, and the concentration of palladium nitrate is 1 mM/l.Catalysis 1-hexene is oxidized, and the mol ratio of palladium nitrate and 1-hexene is 1:20, and oxygen pressure is 2 MPas, and 80 degrees celsius react 20 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 80%, and the productive rate of methyl-n-butyl ketone is the productive rate of 48%, 3-hexanone is 23%.
Embodiment 5
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid ytterbium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid ytterbium is 1:2, and the concentration of acid chloride is 4 mM/ls.Catalysis 1-hexene is oxidized, and the mol ratio of acid chloride and 1-hexene is 1:100, and oxygen pressure is 2 MPas, and 80 degrees celsius react 10 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 58%, and the productive rate of methyl-n-butyl ketone is the productive rate of 31%, 3-hexanone is 18%.
Embodiment 6
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid yttrium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid yttrium is 1:2, and the concentration of acid chloride is 4 mM/ls.Catalysis 1-hexene is oxidized, and the mol ratio of acid chloride and 1-hexene is 1:100, and oxygen pressure is 2 MPas, and 80 degrees celsius react 12 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 53%, and the productive rate of methyl-n-butyl ketone is the productive rate of 28%, 3-hexanone is 16%.
Embodiment 7
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid scandium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid scandium is 1:2, and the concentration of acid chloride is 4 mM/ls.Catalysis cyclohexene oxide, the mol ratio of acid chloride and cyclohexene is 1:100, and oxygen pressure is 2 MPas, and 80 degrees celsius react 16 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 99%, and the productive rate of cyclohexanone is 86%.
Embodiment 8
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid scandium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid scandium is 1:2, and the concentration of acid chloride is 4 mM/ls.Catalysis oxidation of cyclopentene, the mol ratio of acid chloride and cyclopentene is 1:100, and oxygen pressure is 2 MPas, and 80 degrees celsius react 16 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 99%, and the productive rate of cyclopentanone is 80%.
Embodiment 9
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid scandium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid scandium is 1:2, and the concentration of acid chloride is 4 mM/ls.Catalysis cyclo-octene is oxidized, and the mol ratio of acid chloride and cyclo-octene is 1:50, and oxygen pressure is 2 MPas, and 80 degrees celsius react 20 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 90%, and the productive rate of cyclooctanone is 82%.
Embodiment 10
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid scandium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid scandium is 1:2, and the concentration of acid chloride is 1 mM/l.Styrene catalyzed oxidation, acid chloride and cinnamic mol ratio are 1:20, and oxygen pressure is 0.1 MPa, and 50 degrees celsius react 10 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 85%, and the productive rate of acetophenone is 64%, and the productive rate of benzaldehyde is 8%.
Embodiment 11
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid aluminium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.4, and the mol ratio of acid chloride and trifluoromethane sulfonic acid scandium is 1:2, and the concentration of acid chloride is 4 mM/ls.Styrene catalyzed oxidation, acid chloride and cinnamic mol ratio are 1:400, and oxygen pressure is 3 MPas, and 50 degrees celsius react 16 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 56%, and the productive rate of acetophenone is 42%, and the productive rate of benzaldehyde is 4%.
Embodiment 12
Catalyst system and catalyzing is the DMF solution (containing a small amount of water) of acid chloride and scandium chloride, and the volume ratio of DMF and water is DMF ︰ water=5 ︰ 1, and the mol ratio of acid chloride and scandium chloride is 1:10, and the concentration of acid chloride is 10 mM/ls.Catalysis 3-hexene is oxidized, and the mol ratio of acid chloride and 3-hexene is 1:20, and oxygen pressure is 2 MPas, and 100 degrees celsius react 20 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 70%, and the productive rate of methyl-n-butyl ketone is the productive rate of 41%, 3-hexanone is 18%.
Embodiment 13
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid aluminium, the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, the mol ratio of acid chloride and trifluoromethane sulfonic acid aluminium is 1:4, and the concentration of acid chloride is 6 mM/ls.Catalyzed 1-octylene is oxidized, and the mol ratio of acid chloride and 1-octene is 1:200, and oxygen pressure is 3 MPas, and 80 degrees celsius react 10 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 99%, and the productive rate of the productive rate of methyln-hexyl ketone to be the productive rate of 37%, 3-octanone be 27%, 4-octanone is 23%.
Embodiment 14
Catalyst system and catalyzing is the benzonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid aluminium, the volume ratio of benzonitrile and water is Ben Jia Jing ︰ water=5 ︰ 0.1, the mol ratio of acid chloride and trifluoromethane sulfonic acid aluminium is 1:4, and the concentration of acid chloride is 6 mM/ls.Catalysis 4-octene is oxidized, and the mol ratio of acid chloride and 4-octene is 1:20, and oxygen pressure is 3 MPas, and 80 degrees celsius react 8 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio 65%, the productive rate of the productive rate of methyln-hexyl ketone to be the productive rate of 20%, 3-octanone be 13%, 4-octanone is 15%.
Embodiment 15
Catalyst system and catalyzing is the ethanolic solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid aluminium, the volume ratio of second alcohol and water is benzene first nitrile ︰ water=5 ︰ 0.2, the mol ratio of acid chloride and trifluoromethane sulfonic acid aluminium is 1:6, and the concentration of acid chloride is 8 mM/ls.Catalysis 4-octene is oxidized, and the mol ratio of acid chloride and 4-octene is 1:50, and oxygen pressure is 3 MPas, and 80 degrees celsius react 12 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio 51%, the productive rate of the productive rate of methyln-hexyl ketone to be the productive rate of 19%, 3-octanone be 11%, 4-octanone is 12%.
Embodiment 16
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid magnesium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid magnesium is 1:8, and the concentration of acid chloride is 6 mM/ls.Styrene catalyzed oxidation, acid chloride and cinnamic mol ratio are 1:50, and oxygen pressure is 3 MPas, and 80 degrees celsius react 16 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 80%, and the productive rate of acetophenone is 71%.
Embodiment 17
Catalyst system and catalyzing is the DMSO solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid zinc, the volume ratio of DMSO and water is DMSO ︰ water=5 ︰ 0.4, the mol ratio of acid chloride and trifluoromethane sulfonic acid zinc is 1:10, and the concentration of acid chloride is 8 mM/ls.Catalysis 1-hexene is oxidized, and the mol ratio of acid chloride and 1-hexene is 1:50, and oxygen pressure is 4 MPas, and 80 degrees celsius react 16 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 64%, and the productive rate of methyl-n-butyl ketone is the productive rate of 34%, 3-hexanone is 18%.
Embodiment 18
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid calcium, the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.4, the mol ratio of acid chloride and trifluoromethane sulfonic acid calcium is 1:10, and the concentration of acid chloride is 8 mM/ls.Catalysis 1-hexene is oxidized, and the mol ratio of acid chloride and 1-hexene is 1:50, and oxygen pressure is 3 MPas, and 80 degrees celsius react 16 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 58%, and the productive rate of methyl-n-butyl ketone is the productive rate of 32%, 3-hexanone is 18%.
Embodiment 19
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethayl sulfonic acid yttrium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid yttrium is 1:4, and the concentration of acid chloride is 6 mM/ls.Styrene catalyzed oxidation, acid chloride and cinnamic mol ratio are 1:50, and oxygen pressure is 3 MPas, and 80 degrees celsius react 10 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 78%, and the productive rate of acetophenone is 68%.
Embodiment 20
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid ytterbium, and the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.2, and the mol ratio of acid chloride and trifluoromethane sulfonic acid ytterbium is 1:4, and the concentration of acid chloride is 6 mM/ls.Styrene catalyzed oxidation, acid chloride and cinnamic mol ratio are 1:50, and oxygen pressure is 3 MPas, and 80 degrees celsius react 10 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 81%, and the productive rate of acetophenone is 74%.
Embodiment 21
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and trifluoromethyl sulfonate, the volume ratio of acetonitrile and water is Yi Jing ︰ water=5 ︰ 0.5, the mol ratio of acid chloride and trifluoromethyl sulfonate is 1:10, and the concentration of acid chloride is 8 mM/ls.Styrene catalyzed oxidation, acid chloride and cinnamic mol ratio are 1:20, and oxygen pressure is 4 MPas, and 80 degrees celsius react 20 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 20%, and the productive rate of acetophenone is 15%.
Embodiment 22
Catalyst system and catalyzing is the DMA solution (containing a small amount of water) of acid chloride and zinc chloride, and the volume ratio of DMA and water is DMA ︰ water=5 ︰ 1, and the mol ratio of acid chloride and zinc chloride is 1:8, and the concentration of acid chloride is 10 mM/ls.Styrene catalyzed oxidation, acid chloride and cinnamic mol ratio are 1:20, and oxygen pressure is 3 MPas, and 100 degrees celsius react 20 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 25%, and the productive rate of acetophenone is 18%.
Embodiment 23
Catalyst system and catalyzing is the DMA solution (containing a small amount of water) of acid chloride and calcium chloride, and the volume ratio of DMA and water is DMA ︰ water=5 ︰ 1, and the mol ratio of acid chloride and calcium chloride is 1:8, and the concentration of acid chloride is 10 mM/ls.Styrene catalyzed oxidation, acid chloride and cinnamic mol ratio are 1:20, and oxygen pressure is 3 MPas, and 100 degrees celsius react 20 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 28%, and the productive rate of acetophenone is 20%.
Embodiment 24
Catalyst system and catalyzing is the toluene solution (containing a small amount of water) of acid chloride and trifluoromethane sulfonic acid scandium, the volume ratio of toluene and water is Jia Ben ︰ water=5 ︰ 0.2, the mol ratio of acid chloride and trifluoromethane sulfonic acid scandium is 1:1, and the concentration of acid chloride is 10 mM/ls.Styrene catalyzed oxidation, acid chloride and cinnamic mol ratio are 1:20, and oxygen pressure is 4 MPas, and 90 degrees celsius react 20 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 15%, and the productive rate of acetophenone is 10%.
Comparative example
This comparative example and embodiment 1 uniquely unlike, embodiment 1 adopts trifluoromethane sulfonic acid scandium to carry out catalytic reaction, and comparative example adopts copper triflate to carry out catalytic reaction, and other conditions are all identical.
Catalyst system and catalyzing is the acetonitrile solution (containing a small amount of water) of acid chloride and copper triflate, and the volume ratio of acetonitrile and water is acetonitrile: water=5:0.2, and the mol ratio of acid chloride and copper triflate is 1:2, and the concentration of acid chloride is 4 mM/ls.Catalysis 1-hexene is oxidized, and the mol ratio of acid chloride and 1-hexene is 1:100, and oxygen pressure is 2 MPas, and 80 degrees celsius react 2 hours.
After reaction terminates, adopt gas chromatographic analysis, its conversion ratio is 63%, and the productive rate of methyl-n-butyl ketone is the productive rate of 28%, 3-hexanone is 11%.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. for a catalyst system and catalyzing for olefin oxidation, it is characterized in that, it is palladium salt, non-redox active slaine is dissolved in the solution formed in solvent, wherein,
Palladium salt in described solution and the mol ratio of non-redox active slaine are 1 ︰ 2 ~ 10;
The concentration of the palladium salt in described solution is 1 mM/l ~ 10 mM/ls;
Described solvent is the mixed liquor that organic solvent and water are formed.
2. a kind of catalyst system and catalyzing for olefin oxidation as claimed in claim 1, it is characterized in that, in described solvent, the volume ratio of organic solvent and water is 5 ︰ 0.1 ~ 1.
3. a kind of catalyst system and catalyzing for olefin oxidation as claimed in claim 1 or 2, is characterized in that, described palladium salt comprise in acid chloride, palladium bichloride and palladium nitrate one or more, be preferably acid chloride.
4. a kind of catalyst system and catalyzing for olefin oxidation as claimed in claim 3, it is characterized in that, described non-redox active slaine to comprise in trifluoromethane sulfonic acid scandium, scandium chloride, trifluoromethane sulfonic acid aluminium, trifluoromethane sulfonic acid magnesium, trifluoromethane sulfonic acid zinc, zinc chloride, trifluoromethane sulfonic acid calcium, calcium chloride, trifluoromethane sulfonic acid yttrium, trifluoromethane sulfonic acid ytterbium and trifluoromethyl sulfonate one or more.
5. a kind of catalyst system and catalyzing for olefin oxidation as described in claim 1 or 3, it is characterized in that, described organic solvent comprise in acetonitrile, ethanol, DMF, DMA, dimethyl sulfoxide (DMSO), benzonitrile and toluene one or more.
6. a method for catalytic olefin oxidations, is characterized in that, it adopts the catalyst system and catalyzing as described in one of claim 1-5.
7. method as claimed in claim 6, it is characterized in that, described alkene comprises 1-hexene, 3-hexene, 1-octene, 4-octene, cyclohexene, cyclopentene, cyclo-octene and/or styrene.
8. method as claimed in claims 6 or 7, it is characterized in that, the mol ratio of the salt of palladium described in catalyst system and catalyzing and alkene is 1 ︰ 20 ~ 400.
9. method as claimed in claim 8, is characterized in that, the oxygen pressure that reaction adopts is 0.1 MPa ~ 4 MPa, and the reaction time is 2 hours ~ 20 hours, and reaction temperature is 50 DEG C ~ 100 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510287401.4A CN104888852B (en) | 2015-05-29 | 2015-05-29 | A kind of catalyst system and catalyzing and application for olefin oxidation |
Applications Claiming Priority (1)
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| CN201510287401.4A CN104888852B (en) | 2015-05-29 | 2015-05-29 | A kind of catalyst system and catalyzing and application for olefin oxidation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040305A (en) * | 2016-06-15 | 2016-10-26 | 华中科技大学 | Olefin isomerism catalyst system and application thereof |
| CN114276223A (en) * | 2021-12-24 | 2022-04-05 | 江南大学 | Synthetic method of alpha-iodine-alpha-trifluoromethyl arylethanone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113175A (en) * | 2013-02-04 | 2013-05-22 | 浙江工业大学 | New method for generating methyl ketone by using palladium catalytic oxidized olefins |
| CN104492484A (en) * | 2014-12-16 | 2015-04-08 | 华中科技大学 | Olefin isomerization catalyst and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113175A (en) * | 2013-02-04 | 2013-05-22 | 浙江工业大学 | New method for generating methyl ketone by using palladium catalytic oxidized olefins |
| CN104492484A (en) * | 2014-12-16 | 2015-04-08 | 华中科技大学 | Olefin isomerization catalyst and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| WILLIAM H. CLEMENT ET AL.: ""Improved Prodedures for Converting Higher α–Olefins to Methyl Ketones with Palladium Chloride"", 《J. ORG. CHEM.》 * |
| 李华明等: ""钯配合物催化烯烃氧化合成酮类物质的研究进展"", 《化学进展》 * |
| 王阿忠: ""分子氧参与的钯催化烯炔烃的氧化反应的研究"", 《中国博士学位论文全文数据库工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040305A (en) * | 2016-06-15 | 2016-10-26 | 华中科技大学 | Olefin isomerism catalyst system and application thereof |
| CN106040305B (en) * | 2016-06-15 | 2019-01-15 | 华中科技大学 | A kind of olefin isomerization catalyst system and its application |
| CN114276223A (en) * | 2021-12-24 | 2022-04-05 | 江南大学 | Synthetic method of alpha-iodine-alpha-trifluoromethyl arylethanone |
| CN114276223B (en) * | 2021-12-24 | 2022-12-20 | 江南大学 | Synthetic method of alpha-iodine-alpha-trifluoromethyl arylethanone |
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| CN104888852B (en) | 2017-08-25 |
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