CN107344904B - Method for generating methyl ketone by catalytic oxidation of olefin with palladium - Google Patents
Method for generating methyl ketone by catalytic oxidation of olefin with palladium Download PDFInfo
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- CN107344904B CN107344904B CN201610290953.5A CN201610290953A CN107344904B CN 107344904 B CN107344904 B CN 107344904B CN 201610290953 A CN201610290953 A CN 201610290953A CN 107344904 B CN107344904 B CN 107344904B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
Abstract
The invention discloses a method for generating methyl ketone by oxidizing olefin under the catalysis of palladium. The method comprises the steps of taking terminal olefin or internal olefin compounds as raw materials, taking hydrogen peroxide or tert-butyl hydroperoxide as an oxidant, taking palladium acetate as a catalyst and inorganic acid as a cocatalyst, fully reacting in an organic solvent, tracking the reaction by TLC, extracting with ethyl acetate after the reaction is finished, and performing suction filtration, concentration and purification to obtain corresponding methyl ketone compounds. The invention takes palladium acetate as the catalyst, thus avoiding the use of expensive palladium matched with the catalyst; hydrogen peroxide or tert-butyl alcohol peroxide is used as an oxidant, and the product after complete decomposition is environment-friendly; the used inorganic acid is in catalytic measurement, and has small influence on the environment and equipment; the method has the advantages of reducing treatment difficulty by using a low-boiling-point organic solvent, being green and environment-friendly in reaction process, simple in treatment after reaction, suitable for terminal olefin and internal olefin compounds, wide in application substrate range and capable of overcoming the defect of poor applicability of the traditional Wacker oxidation reaction.
Description
Technical Field
The invention relates to a method for generating methyl ketone by palladium-catalyzed olefin oxide, belonging to the field of organic chemical preparation.
Background
The Wacker oxidation reaction is used as a method for preparing corresponding carbonyl compounds by oxidizing olefin, and has important significance in organic synthesis and industrial production. The traditional Wacker oxidation reaction uses palladium chloride and copper chloride as catalysts, and has the defects that chloride ions and copper ions generated in the reaction process are extremely harmful to the environment, and the traditional Wacker oxidation method has low applicability and is only limited to the oxidation of terminal olefins.
In order to overcome the defects, a plurality of palladium complex catalysts are applied to the Wacker reaction, and the defects of the traditional Wacker oxidation reaction can be effectively avoided by matching proper oxidants and solvents. The palladium complex catalyst can effectively avoid the agglomeration and loss of palladium and improve the selectivity and yield of the reaction. However, palladium, a non-renewable noble metal catalyst, is associated with complex ligands to form new catalysts that are very expensive to produce and cannot be adapted to industrial production [ a.naik et al, chem.eur.j.,2010,16,1624 ]. Palladium chloride is used as a catalyst, oxygen is used as an oxidant, N, N-dimethylacetamide is used as a solvent, the use of copper-containing compounds in the traditional Wacker oxidation reaction can be avoided, the reaction is more green and environment-friendly, but in order to smoothly carry out the reaction, the reaction pressure reaches 6atm, the operation difficulty and potential safety hazard are increased, and the N, N-dimethylacetamide is a high boiling point solvent, and the recovery is difficult [ T.Mitsudome and the like, Angew.chem., Int. Ed.,2006,45,481 ].
Therefore, how to overcome the defects of the traditional Wacker oxidation reaction, and simultaneously, the reaction process is simple, green and mild, and is suitable for industrial production is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a method for preparing methyl ketone by palladium-catalyzed olefin oxide, which has high selectivity, wide substrate application range and environmental friendliness and is suitable for industrial production.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for generating methyl ketone by catalytic oxidation of olefin with palladium takes an olefin compound shown in formula (I) or (II) as a raw material, hydrogen peroxide or tert-butyl hydroperoxide as an oxidant, palladium acetate as a catalyst and inorganic acid as a cocatalyst, and fully reacts in an organic solvent to prepare a corresponding methyl ketone compound shown in formula (III) or (IV), wherein the reaction equation is as follows:
in the formulae (I), (III), R1、R2、R3、R4、R5Each independently selected from hydrogen and C1-C4Alkyl, methoxy, fluoro, chloro, bromo;
in the formulae (II), (IV), R6Selected from methyl, ethyl, phenyl or substituted phenyl.
The inorganic acid is selected from sulfuric acid, nitric acid or phosphoric acid.
The organic solvent is selected from ethyl acetate, acetonitrile or acetone.
In the present invention, a commercially available hydrogen peroxide solution having a mass concentration of 30% was used as it is.
In the present invention, commercial t-butyl hydroperoxide having a mass concentration of 70% was used as it is.
In the invention, the molar ratio of the oxidant, the palladium acetate, the inorganic acid, the organic solvent and the olefin compound is preferably 1-10: 0.01-0.1: 0.01-0.1: 50-300: 1.
Preferably, the mass concentration of the inorganic acid is 60-90%.
Further preferably, the mass concentration of the inorganic acid is 70%.
In the invention, the temperature of the reaction system directly influences the reaction effect when the inorganic acid is added, so the adding time of the acid is 35-50 ℃ when the temperature of the reaction system reaches 20-50 ℃.
In the invention, the reaction of palladium catalytic oxidation of olefin to generate methyl ketone is carried out at 50-80 ℃ for 3-12 h. Preferably, the reaction of generating the methyl ketone by catalyzing and oxidizing the olefin by the palladium is carried out at 65-75 ℃ for 6-8 h.
Specifically, the method for preparing methyl ketone by palladium-catalyzed oxidation of olefin comprises the following steps: heating a mixed solution of an olefin compound, palladium acetate and an organic solvent to 20-50 ℃, adding a cocatalyst inorganic acid, then adding an oxidant, continuously heating to 50-80 ℃, reacting for 3-12 h, and separating and purifying to obtain a target product, namely a methyl ketone compound.
In the invention, the separation and purification adopt conventional operations, specifically: extracting the reaction liquid after the reaction is finished by ethyl acetate, distilling under reduced pressure to obtain a crude product, and then using ethyl acetate: and (3) using a mixed organic solvent with the volume ratio of petroleum ether being 1:20 as an eluent, and purifying by using a silica gel column to obtain a pure methyl ketone compound serving as a target product.
Compared with the prior art, the invention has the following remarkable effects:
1. the method is suitable for terminal olefin and internal olefin compounds, and overcomes the defect of poor applicability of the traditional Wacker oxidation reaction;
2. the palladium acetate is used as the catalyst, so that the use of expensive palladium matched with the catalyst is avoided, a good reaction effect can be achieved at 50-80 ℃, the reaction condition is mild, the operation is simple and convenient, the method is suitable for industrial production, and the reaction yield can reach 87% to the maximum;
3. hydrogen peroxide or tert-butyl alcohol peroxide is used as an oxidant, and the product after complete decomposition is environment-friendly; the used inorganic acid is in catalytic measurement, and has small influence on the environment and equipment; the low-boiling-point organic solvent is utilized, the treatment difficulty is reduced, the reaction process is green and environment-friendly, and the treatment after the reaction is simple.
Detailed Description
The technical solutions of the present invention will be further described below with reference to examples to provide those skilled in the art with a more complete understanding of the present invention, but the present invention is not limited thereto.
Example 1
Adding 1mmol of styrene, 0.02mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.02mmol of sulfuric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, and then heating to 65 ℃; the reaction was monitored by TLC (V ethyl acetate: V petroleum ether ═ 1)20) reacting for 6 hours, extracting with ethyl acetate until the organic layer is free from fluorescence, combining the organic layers, washing with water (3 × 30mL), drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to obtain a crude product, purifying with a silica gel column by using a mixed organic solvent of ethyl acetate and petroleum ether at a ratio of 1:20 as an eluent to obtain a target product, and analyzing by gas chromatography to obtain the acetophenone yield of 82%.1H NMR(300MHz,CDCl3):(ppm)7.96(d,J＝7.0Hz,2H),7.57(t,J＝7.5Hz,1H),7.47(t,J＝7.0Hz,2H),2.61(s,3H)；13C NMR(75MHz,CDCl3):(ppm)198.1,136.9,133.0,128.5,128.2,26.6.
Example 2
Adding 1mmol of p-methylstyrene, 0.02mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.02mmol of sulfuric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, heating to 65 ℃, monitoring the reaction by TLC (V ethyl acetate: V petroleum ether is 1: 20), extracting the mixture by ethyl acetate after 5h of reaction until the organic layer is free from fluorescence, combining the organic layers, washing by water (3 × 30mL), drying by anhydrous sodium sulfate, carrying out suction filtration, carrying out reduced pressure distillation to obtain a crude product, and purifying by using a silica gel column to obtain the target product of p-methylacetophenone with the yield of 86% by using a mixed organic solvent of ethyl acetate and petroleum ether being 1:20 as an eluent.1H NMR(300MHz,CDCl3):(ppm)7.85(d,J＝8.0Hz,2H),7.25(d,J＝8.0Hz,2H),2.57(s,3H),2.40(s,3H)；13C NMR(75MHz,CDCl3):(ppm)197.4,143.8,134.6,129.2,128.4,26.4,21.5.
Example 3
Adding 1mmol of p-chlorostyrene, 0.02mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting the mixture until the temperature is raised to 35 ℃, adding 0.02mmol of sulfuric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, subsequently raising the temperature to 75 ℃, monitoring the reaction by TLC (V ethyl acetate: V petroleum ether is 1: 20), extracting the mixture by using ethyl acetate until the organic layer is free of fluorescence after the reaction is carried out for 8 hours, combining the organic layers, washing the organic layers by water (3 × 30mL), drying the anhydrous sodium sulfate, carrying out suction filtration, distilling the mixture under reduced pressure to obtain a crude product, using a mixed organic solvent of ethyl acetate and petroleum ether as an eluent and using silicon with the ratio of ethyl acetate to petroleumPurifying with a gel column to obtain the target product p-chloroacetophenone with a yield of 78%.1H NMR(300MHz,CDCl3):(ppm)7.89(d,J＝8.5Hz,2H),7.43(d,J＝8.5Hz,2H),2.58(s,3H)；13C NMR(75MHz,CDCl3):(ppm)196.8,139.5,135.3,129.6,128.8,26.5.
Example 4
Adding 1mmol of m-chlorostyrene, 0.02mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.02mmol of sulfuric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, heating to 75 ℃, monitoring the reaction by TLC (V ethyl acetate: V petroleum ether is 1: 20), extracting the mixture by using ethyl acetate after 8 hours of reaction until the organic layer is free of fluorescence, combining the organic layers, washing by water (3 × 30mL), drying by using anhydrous sodium sulfate, performing suction filtration, performing reduced pressure distillation to obtain a crude product, and purifying by using a silica gel column to obtain the target product, namely the m-chloroacetophenone, wherein the yield is 72%.1H NMR(300MHz,CDCl3):7.93-7.92(m,1H),7.85-7.83(m,1H),7.55-7.52(m,1H),7.43-7.39(m,1H),2.60(s,3H)；13C NMR(75MHz,CDCl3):(ppm)196.6,138.5,134.8,132.9,129.8,128.3,125.9,26.5.
Example 5
Adding 1mmol of o-chlorostyrene, 0.02mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.02mmol of sulfuric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, heating to 75 ℃, monitoring the reaction by TLC (V ethyl acetate: V petroleum ether is 1: 20), extracting by using ethyl acetate after 12h of reaction until the organic layer is free from fluorescence, combining the organic layers, washing by water (3 × 30mL), drying by using anhydrous sodium sulfate, performing suction filtration, performing reduced pressure distillation to obtain a crude product, and purifying by using a silica gel column by using a mixed organic solvent of ethyl acetate and petroleum ether which is 1:20 as an eluent to obtain the target product of o-chloroacetophenone with the yield of 65%.1H NMR(300MHz,CDCl3):7.55-7.53(m,1H),7.40-7.29(m,3H),2.65(s,3H)；13C NMR(75MHz,CDCl3):(ppm)200.4,139.1,132.0,131.2,130.6,129.3,126.8,30.6.
Example 6
Adding 1mmol of p-fluorostyrene, 0.02mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.02mmol of sulfuric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, heating to 65 ℃, monitoring the reaction by TLC (V ethyl acetate: V petroleum ether is 1: 20), extracting the mixture by using ethyl acetate after 6h of reaction until the organic layer is free from fluorescence, combining the organic layers, washing by water (3 × 30mL), drying by using anhydrous sodium sulfate, performing suction filtration, performing reduced pressure distillation to obtain a crude product, and purifying by using a silica gel column by using a mixed organic solvent of ethyl acetate and petroleum ether is 1:20 as an eluent to obtain the target product of p-fluoroacetophenone, wherein the yield is 87%.1H NMR(300MHz,CDCl3):(ppm)8.00-7.96(m,2H),7.15-7.10(m,2H),2.59(s,3H)；13C NMR(75MHz,CDCl3):(ppm)196.5,165.7(d,J＝254.0Hz),133.5(d,J＝3.0Hz),130.9(d,J＝9.0Hz),115.6(d,J＝22.0Hz),26.5.
Example 7
Adding 1mmol of trans-1, 2-diphenylethylene, 0.02mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting, heating to 35 ℃, adding 0.02mmol of sulfuric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, heating to 65 ℃, monitoring the reaction by TLC (V ethyl acetate: V petroleum ether is 1: 20), extracting by using ethyl acetate after 8 hours of reaction until the organic layer is free from fluorescence, combining the organic layers, washing by water (3 × 30mL), drying by using anhydrous sodium sulfate, carrying out suction filtration, and carrying out reduced pressure distillation to obtain a crude product, wherein the mixed organic solvent of ethyl acetate and petroleum ether is 1:20 is used as an eluent, and purifying by using a silica gel column to obtain the target product 1, 2-diphenylethanone, wherein the yield is 75%.1H NMR(300MHz,CDCl3):8.04-8.01(m,2H),7.67(tt,J＝8.5Hz,J＝1.4Hz,1H),7.50-7.44(m,2H),7.37-7.27(m,5H),4.30(s,2H)；13C NMR(75MHz,CDCl3):197.6,136.4,134.5,133.1,129.4,128.6,126.8,45.3.
Example 8
Adding 1mmol of trans-4-octene, 0.02mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.02mmol of sulfuric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, and then heating to 65 ℃; TLC monitoring of transReacting for 6 hours, extracting with ethyl acetate until the organic layer is free of fluorescence, combining the organic layers, washing with water (3 × 30mL), drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to obtain a crude product, and purifying with a silica gel column by using a mixed organic solvent of ethyl acetate and petroleum ether at a ratio of 1:20 as an eluent to obtain the target product 4-octanone with a yield of 75%.1H NMR(300MHz,CDCl3)2.38(t,J＝7.3Hz,2H),2.37(t,J＝7.3Hz,2H),1.50-1.67(m,4H),1.31(J＝7.6Hz,2H),0.91(t,J＝7.3Hz,3H),0.90ppm(t,J＝7.3Hz,3H)；13C NMR(75MHz,CDCl3)211.1,44.7,42.5,26.0,22.4,17.3,13.8,13.8ppm.
Example 9
Adding 1mmol of styrene, 0.02mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.02mmol of sulfuric acid with the mass fraction of 70% and 6mmol of tert-butyl hydroperoxide with the mass fraction of 70%, and then heating to 65 ℃; the reaction was monitored by TLC (V ethyl acetate: V petroleum ether: 1: 20); after 6h of reaction, the organic layer was extracted with ethyl acetate until the organic layer was non-fluorescent, the organic layers were combined, washed with water (3 × 30mL), dried over anhydrous sodium sulfate, filtered with suction, and distilled under reduced pressure to give the crude product using ethyl acetate: using a mixed organic solvent with the ratio of 1:20 of petroleum ether as an eluent, and purifying by using a silica gel column to obtain a target product; the acetophenone yield was 72% by gas chromatography.
Example 10
Adding 1mmol of styrene, 0.02mmol of palladium acetate and 200mmol of ethyl acetate into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath kettle, reacting and heating to 35 ℃, adding 0.02mmol of nitric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, and then heating to 65 ℃; the reaction was monitored by TLC (V ethyl acetate: V petroleum ether: 1: 20); after 6h of reaction, the organic layer was extracted with ethyl acetate until the organic layer was non-fluorescent, the organic layers were combined, washed with water (3 × 30mL), dried over anhydrous sodium sulfate, filtered with suction, and distilled under reduced pressure to give the crude product using ethyl acetate: using a mixed organic solvent with the ratio of 1:20 of petroleum ether as an eluent, and purifying by using a silica gel column to obtain a target product; the acetophenone yield was 53% by gas chromatography analysis.
Example 11
Adding 1mmol of styrene, 0.02mmol of palladium acetate and 200mmol of acetone into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.02mmol of phosphoric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, and then heating to the reflux temperature; the reaction was monitored by TLC (V ethyl acetate: V petroleum ether: 1: 20); after 6h of reaction, the organic layer was extracted with ethyl acetate until the organic layer was non-fluorescent, the organic layers were combined, washed with water (3 × 30mL), dried over anhydrous sodium sulfate, filtered with suction, and distilled under reduced pressure to give the crude product using ethyl acetate: using a mixed organic solvent with the ratio of 1:20 of petroleum ether as an eluent, and purifying by using a silica gel column to obtain a target product; the acetophenone yield was 68% by gas chromatography.
Example 12
Adding 1mmol of styrene, 0.01mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.01mmol of sulfuric acid with the mass fraction of 70% and 1mmol of hydrogen peroxide with the mass fraction of 30%, and then heating to 65 ℃; the reaction was monitored by TLC (V ethyl acetate: V petroleum ether: 1: 20); after 6h of reaction, the organic layer was extracted with ethyl acetate until the organic layer was non-fluorescent, the organic layers were combined, washed with water (3 × 30mL), dried over anhydrous sodium sulfate, filtered with suction, and distilled under reduced pressure to give the crude product using ethyl acetate: using a mixed organic solvent with the ratio of 1:20 of petroleum ether as an eluent, and purifying by using a silica gel column to obtain a target product; the acetophenone yield was 47% by gas chromatography.
Example 13
Adding 1mmol of styrene, 0.05mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.05mmol of sulfuric acid with the mass fraction of 70% and 10mmol of hydrogen peroxide with the mass fraction of 30%, and then heating to 65 ℃; the reaction was monitored by TLC (V ethyl acetate: V petroleum ether: 1: 20); after 6h of reaction, the organic layer was extracted with ethyl acetate until the organic layer was non-fluorescent, the organic layers were combined, washed with water (3 × 30mL), dried over anhydrous sodium sulfate, filtered with suction, and distilled under reduced pressure to give the crude product using ethyl acetate: using a mixed organic solvent with the ratio of 1:20 of petroleum ether as an eluent, and purifying by using a silica gel column to obtain a target product; the acetophenone yield was 85% by gas chromatography.
Example 14
Adding 1mmol of styrene, 0.1mmol of palladium acetate and 50mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 35 ℃, adding 0.1mmol of sulfuric acid with the mass fraction of 70% and 6mmol of hydrogen peroxide with the mass fraction of 30%, and then heating to 65 ℃; the reaction was monitored by TLC (V ethyl acetate: V petroleum ether: 1: 20); after reacting for 3h, extracting with ethyl acetate until the organic layer is non-fluorescent, combining the organic layers, washing with water (3 × 30mL), drying with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to obtain a crude product using ethyl acetate: using a mixed organic solvent with the ratio of 1:20 of petroleum ether as an eluent, and purifying by using a silica gel column to obtain a target product; the acetophenone yield was 76% by gas chromatography analysis.
Example 15
Adding 1mmol of styrene, 0.02mmol of palladium acetate and 300mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 20 ℃, adding 0.02mmol of sulfuric acid with the mass fraction of 60% and 6mmol of hydrogen peroxide with the mass fraction of 30%, and then heating to 80 ℃; the reaction was monitored by TLC (V ethyl acetate: V petroleum ether: 1: 20); after 6h of reaction, the organic layer was extracted with ethyl acetate until the organic layer was non-fluorescent, the organic layers were combined, washed with water (3 × 30mL), dried over anhydrous sodium sulfate, filtered with suction, and distilled under reduced pressure to give the crude product using ethyl acetate: using a mixed organic solvent with the ratio of 1:20 of petroleum ether as an eluent, and purifying by using a silica gel column to obtain a target product; the acetophenone yield was 72% by gas chromatography.
Example 16
Adding 1mmol of styrene, 0.02mmol of palladium acetate and 200mmol of acetonitrile into a 50.0mL three-neck flask, placing the three-neck flask in an oil bath pot, reacting and heating to 50 ℃, and adding 0.02mmol of sulfuric acid with the mass fraction of 90% and 6mmol of hydrogen peroxide with the mass fraction of 30%; the reaction was monitored by TLC (V ethyl acetate: V petroleum ether: 1: 20); after 6h of reaction, the organic layer was extracted with ethyl acetate until the organic layer was non-fluorescent, the organic layers were combined, washed with water (3 × 30mL), dried over anhydrous sodium sulfate, filtered with suction, and distilled under reduced pressure to give the crude product using ethyl acetate: using a mixed organic solvent with the ratio of 1:20 of petroleum ether as an eluent, and purifying by using a silica gel column to obtain a target product; the acetophenone yield was 76% by gas chromatography analysis.
Claims (10)
1. A method for generating methyl ketone by catalytic oxidation of olefin with palladium is characterized in that olefin compounds shown in formula (I) or (II) are used as raw materials, hydrogen peroxide or tert-butyl hydroperoxide is used as an oxidant, palladium acetate is used as a catalyst, inorganic acid is used as a cocatalyst, and the raw materials are fully reacted in an organic solvent to prepare corresponding methyl ketone compounds shown in formula (III) or (IV),
in the formulae (I), (III), R1、R2、R3、R4、R5Each independently selected from hydrogen and C1-C4Alkyl, methoxy, fluoro, chloro, bromo;
in the formulae (II), (IV), R6Selected from methyl, ethyl, phenyl or substituted phenyl.
2. The process of claim 1 wherein the inorganic acid is selected from the group consisting of sulfuric acid, nitric acid and phosphoric acid.
3. The process of claim 1 wherein the organic solvent is selected from the group consisting of ethyl acetate, acetonitrile and acetone.
4. The method for palladium-catalyzed oxidation of olefin to methyl ketone as claimed in claim 1, wherein the molar ratio of the oxidant, palladium acetate, inorganic acid, organic solvent and olefin compound is 1-10: 0.01-0.1: 0.01-0.1: 50-300: 1.
5. The method of claim 1, wherein the inorganic acid is present at a concentration of 60 to 90 wt.% based on the total weight of the composition.
6. The method for producing methyl ketone by palladium-catalyzed oxidation of olefin as claimed in claim 1, wherein the inorganic acid is added at a time when the temperature of the reaction system reaches 20 to 50 ℃.
7. The method of claim 1, wherein the palladium-catalyzed oxidation of an olefin to methyl ketone is carried out at 50 to 80 ℃.
8. The method of claim 1, wherein the reaction time for palladium-catalyzed oxidation of an olefin to methyl ketone is 3 to 12 hours.
9. The process of any one of claims 1 to 8, wherein the process comprises the following steps: heating a mixed solution of an olefin compound, palladium acetate and an organic solvent to 20-50 ℃, adding a cocatalyst inorganic acid, then adding an oxidant, continuously heating to 50-80 ℃, reacting for 3-12 h, and separating and purifying to obtain a target product, namely a methyl ketone compound.
10. The method of claim 9, wherein the steps of separating and purifying are as follows: extracting the reaction liquid after the reaction is finished by ethyl acetate, distilling under reduced pressure to obtain a crude product, and then using ethyl acetate: and (3) using a mixed organic solvent with the volume ratio of petroleum ether being 1:20 as an eluent, and purifying by using a silica gel column to obtain the target product methyl ketone compound.
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| 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 |
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| CN101293799A (en) * | 2008-05-20 | 2008-10-29 | 大连理工大学 | Method for preparing aldehyde or ketone compounds with catalytic oxidation of alcohol compounds |
| 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 |
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| Title |
|---|
| Palladium-catalyzed allylic acetoxylation of olefins using hydrogen peroxide as oxidant;Chengguo Jia等;《Journal of Molecular Catalysis A: Chemical》;19951231;第101卷;第127-136页 * |
| Palladium-Catalyzed Oxidation of Terminal Olefins to Methyl Ketones by Hydrogen Peroxide;Michel Roussel等;《J.Org.Chem.》;19801231;第45卷;第5387-5390页 * |
| Wacker-Type Oxidation and Dehydrogenation of Terminal Olefins Using Molecular Oxygen as the Sole Oxidant without Adding Ligand;Yu-Fei Wang等;《Org. Lett.》;20140307;第16卷;第1610-1613页 * |
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| CN107344904A (en) | 2017-11-14 |
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