CN103113175B - New method for generating methyl ketone by using palladium catalytic oxidized olefins - Google Patents
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Abstract
The invention discloses a new method for generating methyl ketone by using palladium catalytic oxidized olefins. The method comprises the following step that: through taking an olefin compound as a raw material, taking air or oxygen as an oxidant, taking palladium acetate as a catalyst, taking benzoquinone and sodium nitrite as cocatalysts, and taking an acid as an initiator, the components are completely reacted in a reaction solvent so as to obtain a methyl ketone compound shown in formula (IV), (V) or (VI), wherein the structure of the olefin compound is shown in formula (I), (II) or (III). The method disclosed by the invention is mild in reaction conditions, high in efficiency and selectivity, and environment-friendly.
Description
(1) technical field
The present invention relates to a kind of method that palladium chtalyst olefin oxide generates methyl ketone.
(2) background technology
The reaction that palladium catalyst catalyzed oxidation alkene generates carbonyl compound is commonly called Wacker oxidation reaction.In chemical industry history, Wacker oxidation reaction is applied to the industrial reaction of organic synthesis at palladium catalyst first time, has very important historic significance.Wacker oxidation has the advantages such as reaction conditions gentleness, substrate selective are good, applied widely, therefore can with the potential functional group of alkenes compounds as ketone compounds in organic synthetic route design.
Need in Wacker oxidation reaction to use and a certain amount ofly reoxidize agent and carry out palladium metal Pd (0) in oxidation reaction process and generate Pd (II), with this, reaction is proceeded, conventional oxygenant mainly contains CuCl
2, CuCl, FeCl
3, K
2cr
2o
7, benzoquinones (BQ), alkyl peroxide (TBHP), heteropolyacid (HPA), H
2o
2, [Li Huaming, Shu Huoming, Ye Xingkai, the Wu Yue such as phthalocyanine iron (FePc); Chemical progress, 2001,13,461].But these oxygenant usage quantitys are larger, the general stoichiometric oxidant that need add just can make reaction carry out smoothly, therefore this type of reaction often also exists that such as atom availability is low, cost is high, environmental pollution is serious with equipment corrosion, reaction preference is poor and the reduction by product of oxygenant is difficult to problems such as being separated from reaction system, which greatly limits the large-scale application of these methods on laboratory and industrial production.For this reason, Green Oxidant oxygen is adopted to be paid close attention to widely as the Wacker oxidation reaction method of final oxygenant.But oxygen is chemically inert at normal temperatures and pressures, be difficult to directly be applied to Wacker oxidation reaction as oxygenant, the Wacker oxidation that the employing oxygen of existing bibliographical information carries out as final oxygenant reacts, and the difference according to catalyst system can be summarized as:
One, makes catalyzer to use part palladium compound: as [PdCl
2(PhCN)
2] [Naik, A.; Liu, M.N.; Zabel, M.; Reiser, O.Chem.Eur. J.2010,16,1624.].
Its two, use special solvent: as NSC 11801 [Wang, J.L.; He, L.N.; Miao, C.X.; Li, Y.N.Green Chem.2009,11,1317.]
Its three, pressurization and raise temperature of reaction: as 1-10atm O
2, 25-80 ° of C[Bueno, A.C.; De Souza, A.O.; Gusevskaya, E.V. Adv.Synth.Catal.2009,351,2491.].
These methods all also exist different shortcomings, the palladium part such as used expensive preparation difficulty, severe reaction conditions and low conversion rate etc., laboratory preparation and industrial application more difficult.Therefore, exploration and developing green, gentleness, Wacker oxidation reaction method easy and simple to handle have important scientific meaning and practical value.
(3) summary of the invention
The object of this invention is to provide a kind of mild condition, novel method that efficient highly selective, environment amenable catalyzed oxidation alkene prepare corresponding methyl ketone.
For achieving the above object, the technical solution used in the present invention is:
A kind of palladium chtalyst olefin oxide generates the method for methyl ketone, described method comprises: take olefin(e) compound as raw material, the structure of described olefin(e) compound is as shown in (I), (II) or (III), take air or oxygen as oxygenant, palladium is catalyzer, and benzoquinones and Sodium Nitrite are promotor, and acid is initiator, fully react in reaction solvent, the obtained methyl ketone of corresponding structure as shown in (IV), (V) or (VI); Described reaction solvent is the mixed solvent of water or organic solvent and water; Reaction equation is as follows:
In formula (I), (IV): R
1, R
2, R
3, R
4, R
5independently be selected from as the alkoxyl group of the alkyl of hydrogen, C1 ~ C4, C1 ~ C4, fluorine, chlorine, bromine, acetoxyl group, trifluoromethyl or cyano group separately;
In formula (II), (V): m is 1 or 2;
In formula (III), (VI): n is selected from the integer between 3 ~ 13;
Described acid is one of following: hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, perchloric acid;
Described organic solvent is one of following: ethyl acetate, methylene dichloride, acetic acid, chloroform, acetonitrile, methyl alcohol, ethanol, Isosorbide-5-Nitrae-dioxane, DMF, methyl-sulphoxide.
Further, R
1, R
2, R
3, R
4, R
5in wherein five be hydrogen; Or R
1, R
2, R
3, R
4, R
5in wherein four be hydrogen; Or R
1, R
2, R
3, R
4, R
5in wherein two be hydrogen.
The whole reaction process of the present invention is carried out in an airtight air or oxygen atmosphere, and preferably, described oxygenant is oxygen.
In the present invention, the dosage of catalyst acetic acid palladium can change, general 0.01 equivalent ~ 0.1 equivalent, but when it is lower than 0.01 equivalent (mol ratio of catalyzer and raw material olefin), reaction times is long, do not had actual synthesis meaning, preferably, the mol ratio of described catalyzer and olefin(e) compound is 0.01:1 ~ 0.1:1.
In the present invention, benzoquinones and Sodium Nitrite are as promotor, and wherein the mol ratio of benzoquinones and olefin(e) compound is 0.05 ~ 0.3:1, and the mol ratio of Sodium Nitrite and olefin(e) compound is 0.1 ~ 0.3:1.
In the present invention, the mol ratio of described acid and olefin(e) compound is preferably 0.1 ~ 0.5:1.
In the present invention, in described mixed solvent, organic solvent is 5:1 ~ 10:1 with the ratio of volume of water.
Reaction of the present invention is preferably at room temperature carried out, and more preferably temperature of reaction is at 20 ~ 30 DEG C; Reaction times is preferably 2h ~ 24h.
Concrete, the method of the invention is carried out in accordance with the following steps: make reaction vessel be full of oxygen, then in system, olefin(e) compound, palladium, benzoquinones, Sodium Nitrite is added, add rapidly mixed solvent and acid, wherein the mol ratio of catalyzer, acid, Sodium Nitrite, benzoquinones and olefin(e) compound is 0.01 ~ 0.1:0.1 ~ 0.5:0.1 ~ 0.3:0.05 ~ 0.3:1, and in mixed solvent, organic solvent is 5 ~ 10:1 with the ratio of volume of water; Then immediately by airtight for whole system, react 2 ~ 24h under room temperature, after reaction terminates, separation and purification obtains target product methyl ketone.
Described separation and purification adopts routine operation, is specially: revolved by the reaction solution obtained and steam except after desolventizing, residue over silica gel column purification (eluent, sherwood oil: ethyl acetate=10:1) obtains target product.
Beneficial effect of the present invention is mainly reflected in:
1, fast, the mild condition of speed of response, easy to operate.The present invention all can react in described solvent, and at room temperature (20 ~ 30 DEG C) can complete conversion, mild condition well, and speed of response is fast, and usually can complete reaction at 2h-24h, reaction efficiency is high.
2, good reaction selectivity, substrate conversion efficiency and product yield high.Reaction of the present invention efficiently can generate target product by highly selective, and transformation efficiency is close to 100%, and do not have other by products, yield is higher.
3, whole process is environmentally friendly, pollution-free.Reaction makes oxygenant with oxygen, can not, to environment, be a kind of synthetic method of green.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1:
Pass through repeatedly to substitute oxygen being furnished with in the Schlenk pipe of magneton stirring of 100mL, make whole system be in full oxygen atmosphere, in system, then add the p-methylstyrene (R namely in structural formula (I)
3for methyl, R
1, R
2, R
4, R
5be hydrogen) 1mmol, palladium 0.02mmol, benzoquinones 0.1mmol, Sodium Nitrite 0.2mmol, add rapidly 5.0mL solvent (methyl alcohol: water=4:0.5 (v/v)) and perchloric acid 0.4mmol, then immediately whole system is enclosed in oxygen atmosphere, under room temperature, reacts 5h, after reaction terminates, after solution is revolved steaming, residue over silica gel column purification (eluent, sherwood oil: ethyl acetate=10:1) obtains target product p-methyl aceto phenone, and yield is 91%.
1H?NMR(500MHz,CDCl
3):δ2.62(s,3H),7.47(t,J=7.5Hz,2H),7.58(t,J=7.0Hz,1H),7.97(t,J=4.5Hz,2H).
13C?NMR(125MHz,CDCl
3):δ26.5,128.2,128.5,133.0,137.1,198.1.
Embodiment 2:
Reactant used is to the bromstyrol (R namely in structural formula (I)
3for bromine, R
1, R
2, R
4, R
5be hydrogen), experimental technique and step are with embodiment 1, add solvent 5.0mL (acetonitrile: water=5:0.5 (v/v)) and hydrochloric acid 0.3mmol, catalyst acetic acid palladium consumption is 0.05mmol, benzoquinones 0.1mmol, Sodium Nitrite 0.2mmol, temperature of reaction is 30 DEG C, reaction times is 24h, yield 85%.
1H?NMR(500MHz,CDCl
3):δ2.60(s,3H),7.61-7.63(q,2H),7.83-7.84(q,2H).
13C?NMR(125MHz,CDCl
3):δ26.5,128.4,129.8,131.9,135.8,197.1.
Embodiment 3:
Reactant used is the chloro styrene (R namely in structural formula (I)
1for chlorine, R
3, R
2, R
4, R
5be hydrogen), experimental technique and step are with embodiment 1, add solvent 5.0mL (methylene dichloride: water=5:0.5 (v/v)) and acetic acid 0.3mmol, catalyst acetic acid palladium consumption is 0.05mmol, benzoquinones 0.1mmol, Sodium Nitrite 0.2mmol, temperature of reaction is 25 DEG C, reaction times is 5h, yield 87%.
1H?NMR(500MHz,CDCl
3):δ2.64(s,3H),7.28-7.33(q,1H),7.36-7.42(q,2H),7.53-7.55(q,1H).
13C?NMR(125MHz,CDCl
3):δ30.7,126.9,129.4,130.6,131.3,132.0,139.1,200.4.
Embodiment 4:
Reactant used be between the vinyl toluene (R namely in structural formula (I)
2for methyl, R
1, R
3, R
4, R
5be hydrogen), experimental technique and step are with embodiment 1, add solvent 5.0mL (acetic acid: water=5:1 (v/v)) and trifluoroacetic acid 0.5mmol, catalyst acetic acid palladium consumption is 0.05mmol, benzoquinones consumption is 0.15mmol, and the consumption of Sodium Nitrite is 0.3mmol, and temperature of reaction is 20 DEG C, reaction times is 5h, yield 87%.
1H?NMR(500MHz,CDCl
3):δ2.42(s,3H),2.60(s,3H),7.34-7.39(q,2H)7.77(t,J=7.0Hz,2H).
13C?NMR(125MHz,CDCl
3):δ21.3,26.6,125.6,128.4,128.7,133.8,137.2,138.3,198.3.
Embodiment 5:
Reactant used is 3,4, the 5-trimethoxy vinylbenzene (R namely in structural formula (I)
2, R
3, R
4be methoxyl group, R
1, R
5for hydrogen), experimental technique and step are with embodiment 1, add solvent 5.0mL (dimethyl sulfoxide (DMSO): water=4:0.5 (v/v)) and sulfuric acid 0.25mmol, catalyst acetic acid palladium consumption is 0.05mmol, benzoquinones consumption is 0.05mmol, and the consumption of Sodium Nitrite is 0.2mmol, and temperature of reaction is 30 DEG C, reaction times is 2h, yield 82%.
1H?NMR(500MHz,CDCl
3):δ2.60(s,3H),3.93(d,J=2.5Hz,9H),7.22(s,2H).
13C?NMR(125MHz,CDCl
3):δ26.4,56.3,60.9,105.9,132.5,143.1,153.1,196.9.
Embodiment 6:
Reactant used is to the acetoxy-styrene (R namely in structural formula (I)
3for acetoxyl group, R
1, R
2, R
4, R
5be hydrogen), experimental technique and step are with embodiment 1, add solvent 5.0mL (N, dinethylformamide: water=4:0.5 (v/v)) and perchloric acid 0.5mmol, catalyst acetic acid palladium consumption is 0.01mmol, and benzoquinones consumption is 0.1mmol, the consumption of Sodium Nitrite is 0.2mmol, temperature of reaction is 25 DEG C, and the reaction times is 12h, yield 85%.
1H?NMR(500MHz,CDCl
3):δ2.34(s,3H),2.61(s,3H),7.20(d,J=9.0Hz,2H),8.01(d,J=8.5Hz,2H).
13C?NMR(125MHz,CDCl
3):δ21.1,26.5,121.8,129.9,134.7,154.4,168.8,196.9.
Embodiment 7:
Reactant used is the m-trifluoromethyl styrene (R namely in structural formula (I)
2for trifluoromethyl, R
1, R
3, R
4, R
5be hydrogen), experimental technique and step are with embodiment 1, add solvent 5.0mL (1,4-dioxane: water=4:0.5 (v/v)) and perchloric acid 0.10mmol, catalyst acetic acid palladium consumption is 0.05mmol, and benzoquinones consumption is 0.3mmol, the consumption of Sodium Nitrite is 0.3mmol, temperature of reaction is 30 DEG C, and the reaction times is 24h, yield 80%.
1H?NMR(500MHz,CDCl
3):δ2.64(s,3H),7.61(t,J=10.0Hz,1H),7.81(d,J=7.5Hz,1H),8.13(d,J=8.0Hz,1H),8.20(s,1H),.
13CNMR(125MHz,CDCl
3):δ26.5,122.6,124.8,125.1,129.3,129.5,131.1,131.4,137.6.
Embodiment 8:
Reactant used is the p-isopropyl vinylbenzene (R namely in structural formula (I)
3for sec.-propyl, R
1, R
2, R
4, R
5be hydrogen), experimental technique and step, with embodiment 1, add 5.0mL water and 0.10mmol perchloric acid, catalyst acetic acid palladium consumption is 0.02mmol, and benzoquinones consumption is 0.10mmol, and the consumption of Sodium Nitrite is 0.1mmol, temperature of reaction is 25 DEG C, and the reaction times is 3h, yield 89%.
1H?NMR(500MHz,CDCl
3):δ1.28(d,J=7.0Hz,6H),2.59(s,3H),2.98(s,1H),7.32(d,J=8.5Hz,2H),7.91(d,J=8.5Hz,2H).
13C?NMR(125MHz,CDCl
3):δ23.6,26.5,34.2,126.6,128.6,135.1,154.6,197.8.
Embodiment 9:
Reactant used is the vinylbenzene (R namely in structural formula (I)
1, R
3, R
2, R
4, R
5be hydrogen), experimental technique and step are with embodiment 1, add solvent 5.0mL (methyl alcohol: water=5:0.5 (v/v)) and perchloric acid 0.4mmol, catalyst acetic acid palladium consumption is 0.05mmol, benzoquinones 0.1mmol, Sodium Nitrite 0.2mmol, temperature of reaction is 25 DEG C, reaction times is 3h, yield 91%.
1H?NMR(500MHz,CDCl
3):δ2.62(s,3H),7.47(t,J=7.5Hz,2H),7.58(t,J=7.0Hz,1H),7.97(t,J=4.5Hz,2H).13C?NMR(125MHz,CDCl3):δ26.5,128.2,128.5,133.0,137.1,198.1.
Embodiment 10:
Reactant used is tetrahydrobenzene (m=2 namely in structural formula (II)), experimental technique and step are with embodiment 1, add solvent 5.0mL (1,4-dioxane: water=4:0.5 (v/v)) and perchloric acid 0.5mmol, catalyst acetic acid palladium consumption is 0.1mmol, and benzoquinones consumption is 0.05mmol, the consumption of Sodium Nitrite is 0.3mmol, temperature of reaction is 30 DEG C, and the reaction times is 12h, yield 87%.
1H?NMR(500MHz,CDCl
3):δ1.71-1.75(m,2H),1.84-1.89(m,4H),2.34(t,J=5.0Hz,4H).
13C?NMR(125MHz,CDCl
3):δ24.9,26.9,41.9,212.0.
Embodiment 11:
Reactant used is cyclopentenes (m=1 namely in structural formula (II)), experimental technique and step are with embodiment 1, add solvent 5.0mL (ethanol: water=4:0.5 (v/v)) and hydrochloric acid 0.50mmol, catalyst acetic acid palladium consumption is 0.1mmol, benzoquinones consumption is 0.3mmol, and the consumption of Sodium Nitrite is 0.3mmol, and temperature of reaction is 30 DEG C, reaction times is 24h, yield 82%.
1H?NMR(500MHz,CDCl
3):δ1.93-1.96(m,4H),2.13-2.16(q,4H).
13C?NMR(125MHz,CDCl
3):δ23.1,38.2,220.5.
Embodiment 12:
Reactant used is 1-hexene (n=3 namely in structural formula (III)), experimental technique and step are with embodiment 1, add solvent 5.0mL (ethyl acetate: water=4:0.5 (v/v)) and sulfuric acid 0.3mmol, catalyst acetic acid palladium consumption is 0.05mmol, benzoquinones consumption is 0.1mmol, and the consumption of Sodium Nitrite is 0.2mmol, and temperature of reaction is 30 DEG C, reaction times is 24h, yield 78%.
1H?NMR(500MHz,CDCl
3):δ0.887(t,J=7.5Hz,3H),1.18-1.45(m,2H),1.57(s,1H),2.13(t,J=10.0Hz,3H),.
13CNMR(125MHz,CDCl
3):δ13.9,22.4,26.3,30.2,43.8,208.9.
Embodiment 13:
Reactant used is 1-hexadecylene (n=13 namely in structural formula (III)), experimental technique and step are with embodiment 1, add solvent 5.0mL (acetonitrile: water=4:0.5 (v/v)) and perchloric acid 0.5mmol, catalyst acetic acid palladium consumption is 0.02mmol, benzoquinones consumption is 0.2mmol, and the consumption of Sodium Nitrite is 0.3mmol, and temperature of reaction is 30 DEG C, reaction times is 24h, yield 95%.
1H?NMR(500MHz,CDCl
3):δ0.865(t,J=8.0Hz,3H),1.275-1.509(m,24H),2.43(t,J=10.0Hz,3H),.
13C?NMR(125MHz,CDCl
3):δ13.0,23.2,24.3,30.7,35.8,46.3,213.9.
Shown by above-mentioned example, utilize oxygen as final oxygenant under normal pressure provided by the present invention, take palladium as catalyzer, with benzoquinones, Sodium Nitrite for promotor, can efficiently, the catalyzed oxidation alkenes compounds of highly selective generates methyl ketone compounds, transformation efficiency in Wacker reaction system of solving over is not high, the problems such as by product is more, and this reaction is without copper system, effectively can reduce the corrosion to container, be a system with wide application prospect.
Claims (16)
1. the method for a palladium chtalyst olefin oxide generation methyl ketone, described method comprises: take olefin(e) compound as raw material, the structure of described olefin(e) compound is as shown in (I) or (III), take air or oxygen as oxygenant, palladium is catalyzer, and benzoquinones and Sodium Nitrite are promotor, and acid is initiator, fully react in reaction solvent, the obtained methyl ketone of corresponding structure as shown in (IV) or (VI); Described reaction solvent is the mixed solvent of water or organic solvent and water; Reaction equation is as follows:
In formula (I), (IV): R
1, R
2, R
3, R
4, R
5independently be selected from hydrogen, the alkyl of C1 ~ C4, the alkoxyl group of C1 ~ C4, fluorine, chlorine, bromine, acetoxyl group, trifluoromethyl or cyano group separately;
In formula (III), (VI): n is the integer between 3 ~ 13;
Described acid is one of following: hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, perchloric acid;
Described organic solvent is one of following: ethyl acetate, methylene dichloride, acetic acid, chloroform, acetonitrile, methyl alcohol, ethanol, Isosorbide-5-Nitrae-dioxane, DMF, methyl-sulphoxide.
2. the method for claim 1, is characterized in that described oxygenant is oxygen.
3. the method for claim 1, is characterized in that in described mixed solvent, organic solvent is 5 ~ 10:1 with the ratio of volume of water.
4. the method as described in one of claims 1 to 3, it is characterized in that described catalyzer, acid, Sodium Nitrite, benzoquinones and olefin(e) compound mol ratio be 0.01 ~ 0.1:0.1 ~ 0.5:0.1 ~ 0.3:0.05 ~ 0.3:1.
5. the method for claim 1, is characterized in that described reaction is at room temperature carried out.
6. the method for claim 1, is characterized in that described reaction is carried out at 20-30 DEG C.
7. the method as described in claim 5 or 6, is characterized in that the reaction times is 2 ~ 24h.
8. the method for claim 1, it is characterized in that described method is carried out in accordance with the following steps: make reaction vessel be full of oxygen, then in system, olefin(e) compound, palladium, benzoquinones, Sodium Nitrite is added, add rapidly mixed solvent and acid, the mol ratio of wherein said catalyzer, acid, Sodium Nitrite, benzoquinones and olefin(e) compound is 0.01 ~ 0.1:0.1 ~ 0.5:0.1 ~ 0.3:0.05 ~ 0.3:1, and in mixed solvent, organic solvent is 5 ~ 10:1 with the ratio of volume of water; Then immediately by airtight for whole system, react 2 ~ 24h under room temperature, after reaction terminates, separation and purification obtains target product methyl ketone.
9. the method for a palladium chtalyst olefin oxide generation formula V compound, described method comprises: take olefin(e) compound as raw material, the structure of described olefin(e) compound is as shown in (II), take air or oxygen as oxygenant, palladium is catalyzer, and benzoquinones and Sodium Nitrite are promotor, and acid is initiator, fully react in reaction solvent, the obtained compound of corresponding structure as shown in (V); Described reaction solvent is the mixed solvent of water or organic solvent and water; Reaction equation is as follows:
In formula (II), (V): m is 1 or 2;
Described acid is one of following: hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, perchloric acid;
Described organic solvent is one of following: ethyl acetate, methylene dichloride, acetic acid, chloroform, acetonitrile, methyl alcohol, ethanol, Isosorbide-5-Nitrae-dioxane, DMF, methyl-sulphoxide.
10. method as claimed in claim 9, is characterized in that described oxygenant is oxygen.
11. methods as claimed in claim 9, is characterized in that in described mixed solvent, organic solvent is 5 ~ 10:1 with the ratio of volume of water.
12. methods as described in one of claim 9 ~ 11, it is characterized in that described catalyzer, acid, Sodium Nitrite, benzoquinones and olefin(e) compound mol ratio be 0.01 ~ 0.1:0.1 ~ 0.5:0.1 ~ 0.3:0.05 ~ 0.3:1.
13. methods as claimed in claim 9, is characterized in that described reaction is at room temperature carried out.
14. methods as claimed in claim 9, is characterized in that described reaction is carried out at 20-30 DEG C.
15. methods as described in claim 13 or 14, is characterized in that the reaction times is 2 ~ 24h.
16. methods as claimed in claim 9, it is characterized in that described method is carried out in accordance with the following steps: make reaction vessel be full of oxygen, then in system, olefin(e) compound, palladium, benzoquinones, Sodium Nitrite is added, add rapidly mixed solvent and acid, the mol ratio of wherein said catalyzer, acid, Sodium Nitrite, benzoquinones and olefin(e) compound is 0.01 ~ 0.1:0.1 ~ 0.5:0.1 ~ 0.3:0.05 ~ 0.3:1, and in mixed solvent, organic solvent is 5 ~ 10:1 with the ratio of volume of water; Then immediately by airtight for whole system, react 2 ~ 24h under room temperature, after reaction terminates, separation and purification obtains target product.
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CN107344904B (en) * | 2016-05-04 | 2020-09-11 | 南京理工大学 | Method for generating methyl ketone by catalytic oxidation of olefin with palladium |
CN107324980A (en) * | 2017-07-05 | 2017-11-07 | 中国石油化工股份有限公司 | A kind of method that alkene generates MIBK through catalysis oxidation |
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