CN100519499C - Method for preparing aromatic ketone or aromatic aldehyde by selectively oxidizing alkyl arene - Google Patents
Method for preparing aromatic ketone or aromatic aldehyde by selectively oxidizing alkyl arene Download PDFInfo
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- CN100519499C CN100519499C CNB2006100895892A CN200610089589A CN100519499C CN 100519499 C CN100519499 C CN 100519499C CN B2006100895892 A CNB2006100895892 A CN B2006100895892A CN 200610089589 A CN200610089589 A CN 200610089589A CN 100519499 C CN100519499 C CN 100519499C
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- aromatic
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- acridine
- hydroxyphthalimide
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- 150000008365 aromatic ketones Chemical class 0.000 title claims abstract description 11
- 150000003934 aromatic aldehydes Chemical class 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 21
- -1 alkyl arene Chemical class 0.000 title claims description 15
- 230000001590 oxidative effect Effects 0.000 title description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 40
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001251 acridines Chemical class 0.000 claims description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims 1
- 125000001743 benzylic group Chemical group 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 24
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 4
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 abstract 1
- 231100000086 high toxicity Toxicity 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- KKAJSJJFBSOMGS-UHFFFAOYSA-N 3,6-diamino-10-methylacridinium chloride Chemical compound [Cl-].C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 KKAJSJJFBSOMGS-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- RPCHNECSJGMRGP-UHFFFAOYSA-N 3-Ethylfuran Chemical compound CCC=1C=COC=1 RPCHNECSJGMRGP-UHFFFAOYSA-N 0.000 description 6
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 6
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- 206010037211 Psychomotor hyperactivity Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- DPKHZNPWBDQZCN-UHFFFAOYSA-N acridine orange free base Chemical compound C1=CC(N(C)C)=CC2=NC3=CC(N(C)C)=CC=C3C=C21 DPKHZNPWBDQZCN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种由吖啶类化合物、分子溴和N-羟基邻苯二甲酰亚胺三种有机小分子组成的非金属催化体系，可以催化分子氧作氧源的芳香烃选择氧化反应；使用该催化体系可以于温和条件下催化氧气氧化芳香烃生成芳香酮或芳香醛，避免了使用金属催化剂带来的毒性大、污染严重及费用高等缺点。A non-metallic catalytic system composed of acridine compounds, molecular bromine and N-hydroxyphthalimide three organic small molecules, which can catalyze the selective oxidation of aromatic hydrocarbons with molecular oxygen as the oxygen source; using the catalyst The system can catalyze the oxygen oxidation of aromatic hydrocarbons under mild conditions to generate aromatic ketones or aromatic aldehydes, avoiding the disadvantages of high toxicity, serious pollution and high cost caused by the use of metal catalysts.
Description
Technical field
The present invention relates to the catalyst system that is used for the various aromatic hydrocarbon benzyl of catalysis position selective oxidation reaction, specifically provided and a kind ofly can be used for the nonmetal catalyst system that organic molecule that aromatic hydrocarbon directly is oxidized to aromatic ketone or aromatic aldehyde is efficiently formed, this catalyst system can produce c h bond and the oxygen molecule that the organic free radical with overactivity function comes activated aromatics, thereby realizes the efficient oxidation process of aromatic hydrocarbon.
Background technology
The benzyl position selective oxidation of aromatic hydrocarbon is the great shift process in the organic chemistry, and its products obtained therefrom aromatic ketone, aromatic aldehyde etc. are the purposes intermediates of fine chemical product and synthesis of natural product very widely; Traditional method for oxidation mainly is to adopt oxidant stoichiometry Manganse Dioxide, dichromic acid etc. that aromatic hydrocarbon is carried out oxidation, and this process is seriously polluted, and Atom economy is poor; In recent years, begin to be subjected to people's attention with the green catalysis process of hydrogen peroxide and molecular oxygen as oxidant, wherein doing oxygen source with oxygen is a most competitive route.In this research field, mostly the catalyzer that adopts is transition metal-type compound (J.Mol.Catal.A:Chemical, 2003,201,9-22 at present; Adv.Synth.Catal.2005,347,703-705), there are shortcomings such as temperature of reaction height, selectivity of product difference in this type of system more.
In make the research that oxygen source carries out the organic substrates oxidizing reaction of molecular oxygen, Japanese's Hirai Naruhisa etc. has been reported the catalyst system (U.S. Pat 5 that a class is made up of 3-12 family metallic compound and N-hydroxyphthalimide, 981,420, European patent EP 858835, world patent WO9728897, Chinese patent CN 1185757A and Japanese Patent JP 11279112), this system can contain the aromatic hydroxy compound of methyl or methylene radical as catalyzed oxidation, generates oxygenatedchemicalss such as alcohol, ketone, acid down in mild conditions.
In Chinese patent CN1670130A, invented the nonmetal catalyst system that a kind of quinones and N-hydroxyphthalimide are combined into, also can be used for the catalytic oxidation of aromatic hydrocarbon.
Summary of the invention
The objective of the invention is to propose a kind of under mild conditions the alkylaromatic hydrocarbon selective oxidation become the method for aromatic ketone or aromatic aldehyde.
For achieving the above object, provided by the inventionly be used for the method that aromatic hydrocarbon selective is oxidized to aromatic ketone or aromatic aldehyde, in the presence of oxygen source, form catalyst system with acridine compound, halogenic molecule and three kinds of organic molecules of N-hydroxyphthalimide, aromatic hydrocarbon is prepared into aromatic ketone or aromatic aldehyde; Wherein: the molar percentage of catalyst system and reaction substrate is 0.01-30mol%; The molar percentage of halogenic molecule and reaction substrate is 0.01-5.0mol% in the catalyst system; The mol ratio of acridine compound and N-hydroxyphthalimide is 0.1-7 in the catalyst system; Temperature of reaction is 0-200 ℃; Reaction pressure is 0.001MPa-10MPa; Reaction times is 2-30 hour.
Acridine compound of the present invention is meant the acridine derivatives that does not contain or contain different substituents.
The nonmetal catalyst system that the present invention adopts shows the characteristics of sparing phase catalyst fully in reaction process, the catalytic activity height, and selectivity is higher; And catalyst levels can be optimized to trace, helps the separation and the purifying of reaction product.Reaction system is simple, and aftertreatment is easy; Production cost is low, and the no hidden danger of safety is also friendly to environment.
Specifically, the nonmetal catalyst system that is used for the oxidize aromatic hydrocarbon provided by the invention is made up of three kinds of organic molecules of the adjacent benzene dihydroxyl imines of acridine compound, molecular bromine and N-hydroxyl; Under mild conditions, the effect by each other can produce highly active free radical, and then the c h bond of activation aromatic hydrocarbons and the O-O key of molecular oxygen, to realize the clean oxidation process of aromatic hydrocarbon.
Acridine compound in the catalyst system component of the present invention can be that acridine, trypaflavine and acridine orange etc. contain various substituent acridine derivatives.
Molecular bromine in the catalyst system component of the present invention also can be by other halogen such as replacements such as iodine, chlorine.
Middle acridine compound concentrations in the catalyst system component of the present invention is 0.01-20mol%, and optimum concn is 1-10mol%; The mol ratio of acridine compound and N-hydroxyphthalimide is generally 0.1-7, and best proportioning coefficient is 1-5; The concentration of halogenic molecule is 0.01-5.0mol% (with the molar percentage of reaction substrate) in the catalyst system, and optimum concn is 1.0-3.0mol%.
Oxygen source used in the present invention is oxygen or air, and oxygen can consume by catalytic cycle in reaction process, and byproduct of reaction is a water, pollutes little.
Reaction of the present invention can also be carried out in organic solvent, and employed organic solvent comprises: nitrile solvents such as acetonitrile, cyanobenzene; Alcoholic solvent such as ethanol, methyl alcohol; Esters solvent such as ethyl acetate, methyl acetate, halogenated hydrocarbon solvents such as chloroform, monochloro methane; Aromatic hydrocarbon solvent such as benzene, chlorobenzene; Dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO) non-protonic solvents such as (DMSO).
The reaction conditions gentleness of the present invention in catalyzed reaction, temperature of reaction are between 0-200 ℃, and temperature of reaction is between 40-80 ℃ preferably.Pressure is at 0.01MPa-10MPa, and reaction pressure is 0.1-1.5MPa preferably.
The related substrate of this reaction is an aromatic hydrocarbon, can be to contain-CH
2,-CH
3Or-hydrocarbon compound such as the alkylaromatic hydrocarbon of CH group or fragrant alkene, wherein aromatic nucleus can be phenyl ring, naphthalene nucleus or anthracene nucleus etc., also can contain heteroatomic aromatic heterocycles such as N, S, O, as contains substituent pyridine, thiophene or furans etc.
Non-metallic catalyst is different organic molecule among the present invention, and raw material is cheap and easy to get, can high-level efficiency, highly selective catalysis aromatic oxidation prepares aromatic ketone etc., and environmental friendliness, product is handled well; Just alkyl aromatic hydrocarbon compound, oxygen that whole process consumed, with low cost, can satisfy the requirement of Technological Economy, good prospects for application is arranged, be a catalyst system that has wide application prospects.
Embodiment
Give further instruction below by example to the present invention.
Embodiment 1: the catalyzed oxidation of indane
1ml (8.1mmol) indane is dissolved in the 10ml acetonitrile, adds the 0.20mmol trypaflavine, 0.24mmol molecular bromine and 0.67mmol N-hydroxyphthalimide, at 75 ℃, the O of 0.3MPa
2Under the pressure, react after 5 hours, with gas chromatograph analytical reaction result; The transformation efficiency of indane can reach 92%, and the selectivity of indan-1-one can reach 79%; Can cool off this moment, and product is collected in distillation.
Embodiment 2: the catalyzed oxidation of indane
1ml (8.1mmol) indane is dissolved in the 10ml methyl alcohol, adds the 0.01mmol trypaflavine, 0.08mmol molecular bromine and 0.67mmol N-hydroxyphthalimide, at 50 ℃, the O of 0.3MPa
2Under the pressure, react after 25 hours, with gas chromatograph analytical reaction result; The transformation efficiency of indane can reach 73%, and the selectivity of indan-1-one can reach 54%; Can cool off this moment, and product is collected in distillation.
Embodiment 3: the catalyzed oxidation of indane
1ml (8.1mmol) indane is dissolved in the 10ml ethyl acetate, adds the 0.20mmol acridine, 0.24mmol molecular bromine and 0.08mmol N-hydroxyphthalimide, at 200 ℃, the O of 0.001MPa
2Under the pressure, react after 5 hours, with gas chromatograph analytical reaction result; The transformation efficiency of indane can reach 19%, and the selectivity of indan-1-one can reach 13%; Can cool off this moment, and product is collected in distillation.
Embodiment 4: the catalyzed oxidation of ethylbenzene:
1ml (8.3mmol) ethylbenzene is dissolved in the 10ml monochloro methane, adds the 0.21mmol trypaflavine, 0.25mmol molecular bromine and 1.47mmol N-hydroxyphthalimide, at 75 ℃, the O of 0.3MPa
2Under the pressure, react after 5 hours, with gas chromatograph analytical reaction result; The transformation efficiency of ethylbenzene can reach 67%, and the selectivity of methyl phenyl ketone is 94%; Can cool off this moment, and product is collected in distillation.
Embodiment 5: the catalyzed oxidation of naphthane:
1ml (7.4mmol) naphthane is dissolved in the 10ml chlorobenzene, adds the 0.19mmol trypaflavine, 0.22mmol molecular bromine and 0.56mmol N-hydroxyphthalimide, at 0 ℃, the O of 10MPa
2Under the pressure, react after 30 hours, with gas chromatograph analytical reaction result; The transformation efficiency of naphthane can reach 54%, and the selectivity of naphthane-1-ketone can reach 95%; Can cool off this moment, and product is collected in distillation.
Embodiment 6: the catalyzed oxidation of ditane
1ml (6.0mmol) ditane is dissolved among the 10mlDMF, adds the 0.15mmol trypaflavine, 0.18mmol molecular bromine and 0.45mmol N-hydroxyphthalimide, at 100 ℃, the O of 1.5MPa
2Under the pressure, react after 20 hours, with gas chromatograph analytical reaction result; The transformation efficiency of ditane can reach 65%, and the selectivity of benzophenone can reach 99%; Can cool off this moment, and product is collected in distillation.
Embodiment 7: the catalyzed oxidation of acenaphthene
0.77g (5.0mmol) acenaphthene is dissolved in the 10ml benzene, adds the 0.13mmol trypaflavine, 0.15mmol molecular bromine and 0.38mmol N-hydroxyphthalimide, at 40 ℃, the O of 1.0MPa
2Under the pressure, react after 24 hours, with gas chromatograph analytical reaction result; The transformation efficiency of acenaphthene can reach 70%, and the selectivity of acenaphthene-1-ketone can reach 88%; Can cool off this moment, and product is collected in distillation.
Embodiment 8: the catalyzed oxidation of parachlorotoluene:
1ml (9.3mmol) parachlorotoluene is dissolved in the 10ml dimethyl sulfoxide (DMSO), adds the 0.23mmol trypaflavine, 0.28mmol molecular bromine and 0.70mmol N-hydroxyphthalimide, at 100 ℃, the O of 0.3MPa
2Under the pressure, react after 3 hours, with gas chromatograph analytical reaction result; The transformation efficiency of parachlorotoluene can reach 13%, and the selectivity of 4-chloro-benzaldehyde is 45%, and can cool off this moment, and product is collected in distillation.
The catalyzed oxidation of embodiment 9:3-ethyl furan
1ml (8.1mmol) 3-ethyl furan is dissolved in the 10ml methyl acetate, adds the 0.21mmol trypaflavine, 0.45mmol molecular bromine and 0.61mmol N-hydroxyphthalimide, at 150 ℃, the O of 0.3MPa
2Under the pressure, react after 2 hours, with gas chromatograph analytical reaction result; The transformation efficiency of 3-ethyl furan can reach 51%, and the selectivity of 1-furans-3-ethyl ketone is 97%; Can cool off this moment, and product is collected in distillation.
Above-mentioned example shows, adopts novel metalloid catalyst system provided by the present invention, in suitable reaction medium, and according to the condition that provided of invention, can high-level efficiency, highly selective generates ketone or aldehyde material with the aromatic hydrocarbon catalyzed oxidation.Oxygen source can be oxygen or the air that directly feeds; Catalyst dissolution embodies the advantage and the effect of even phase catalyst fully in reaction system in reaction process, thereby the reaction conditions gentleness; After entire reaction, oxygen source all consumes, and catalyzer and substrate and product have than big difference, is easy to separate.In total reaction process, just organic substrates and the oxygen (air) that are consumed.Production cost, cheap, product mainly is an oxygenatedchemicals, and is relatively more friendly to environment.Reaction process is simple, can satisfy the requirement of Technological Economy, is the catalyst system with broad prospect of application.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100895892A CN100519499C (en) | 2006-07-05 | 2006-07-05 | Method for preparing aromatic ketone or aromatic aldehyde by selectively oxidizing alkyl arene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100895892A CN100519499C (en) | 2006-07-05 | 2006-07-05 | Method for preparing aromatic ketone or aromatic aldehyde by selectively oxidizing alkyl arene |
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| Publication Number | Publication Date |
|---|---|
| CN101100418A CN101100418A (en) | 2008-01-09 |
| CN100519499C true CN100519499C (en) | 2009-07-29 |
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| CNB2006100895892A Expired - Fee Related CN100519499C (en) | 2006-07-05 | 2006-07-05 | Method for preparing aromatic ketone or aromatic aldehyde by selectively oxidizing alkyl arene |
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| CN101830784A (en) * | 2010-05-18 | 2010-09-15 | 华东理工大学 | Method for preparing alpha-aryl ketones compounds |
| CN106032355B (en) * | 2015-03-10 | 2019-01-04 | 中国科学院大连化学物理研究所 | A kind of method that pyridine side chain c h bond is direct oxidation into ketone |
| CN112774662B (en) * | 2019-11-04 | 2023-08-15 | 北京氦舶科技有限责任公司 | Monoatomic catalyst and preparation method and application thereof |
| CN112159314B (en) * | 2020-09-08 | 2023-12-15 | 苏州陶逆科技有限公司 | Method for catalyzing oxidation of alpha-monosubstituted styrene to generate benzaldehyde by using N-hydroxyphthalimide |
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| CN1185757A (en) * | 1996-02-07 | 1998-06-24 | 大赛璐化学工业株式会社 | Oxidation catalyst system and process for oxidation with the same |
| CN1670130A (en) * | 2004-03-16 | 2005-09-21 | 中国科学院大连化学物理研究所 | A non-metallic composite catalytic system for catalytic selective oxidation of hydrocarbons |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1185757A (en) * | 1996-02-07 | 1998-06-24 | 大赛璐化学工业株式会社 | Oxidation catalyst system and process for oxidation with the same |
| CN1670130A (en) * | 2004-03-16 | 2005-09-21 | 中国科学院大连化学物理研究所 | A non-metallic composite catalytic system for catalytic selective oxidation of hydrocarbons |
Non-Patent Citations (1)
| Title |
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| 烷基芳香烃氧化反应的研究进展. 汪树清.石油化工高等学校学报，第11卷第2期. 1998 * |
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