CN101774925B - Method for preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen - Google Patents
Method for preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen Download PDFInfo
- Publication number
- CN101774925B CN101774925B CN 201010103426 CN201010103426A CN101774925B CN 101774925 B CN101774925 B CN 101774925B CN 201010103426 CN201010103426 CN 201010103426 CN 201010103426 A CN201010103426 A CN 201010103426A CN 101774925 B CN101774925 B CN 101774925B
- Authority
- CN
- China
- Prior art keywords
- formula
- oxygen
- reaction
- cobalt
- nitroethylbenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen, comprising the following steps of: taking the o-nitroacetophenone as a raw material, selecting any or one combination of 1-30ppm of mononuclear metal porphyrin and mu-oxygen-binuclear metal porphyrin as catalysts, introducing oxygen at the flowing speed of 10-60mL/min; carrying out an initiating reaction at a temperature of 150-200DEG C; and then reacting at a temperature of 80-130DEG C for 10-18h to obtain the o-nitroacetophenone. By adopting a mode of rapid initiation at high temperature and reaction at low temperature, the method ensures that the initiating time for reaction is excessively short, greatly shortens the reaction time, improves the reaction efficiency, reduces energy source consumption, reduces the operation fees and enhances the reaction safety.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic ketone, specifically, relate to a kind of method of preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen.
Background technology
The ortho-nitrophenyl ethyl ketone is important organic synthesis intermediate, is widely used in synthetic medicine, agricultural chemicals, dyestuff, essence and flavoring agent, perfume etc.The preparation method of ortho-nitrophenyl ethyl ketone mainly contains methyl phenyl ketone nitrofication process, 1-(2-nitrophenyl) oxidation of ethanol method and o-nitroethylbenzene oxidation style etc. at present, wherein the o-nitroethylbenzene oxidation style is divided into again chemical oxidization method and molecular oxygen oxidation method, oxygen is as cheap and easy to get, cleanliness without any pollution and the good oxygenant of Atom economy, the method that is prepared the ortho-nitrophenyl ethyl ketone by the oxygen to directly oxidize o-nitroethylbenzene, have significant superiority with respect to other method.
William S.Emerson (Journal of the American Chemical Society, 1946,69:706) etc. the people has reported that a kind of chromium trioxide catalytic air oxidation o-nitroethylbenzene prepares the method for ortho-nitrophenyl ethyl ketone.The method is under the condition of 135～145 ℃, use chromium trioxide as catalyst atmospheric oxidation o-nitroethylbenzene, 2% (30200ppm) that wherein consumption of chromium trioxide is raw material weight, after reaction 28h, cooling, filter, with aqueous sodium carbonate, wash, under the condition of 112.5～113.5 ℃ (2mmHg), underpressure distillation obtains the ortho-nitrophenyl ethyl ketone, but yield is only 14%.
The main drawback of the method has:
(1) using hypertoxic chromium trioxide in the method is catalyzer, and consumption is (30200ppm) greatly, a large amount of like this waste water that contains chromium trioxide or waste sludge discharge, in environment, will cause very serious destruction to environment, even can jeopardize HUMAN HEALTH.Therefore, the necessary Separation and Recovery of chromium trioxide used, and Separation and Recovery need to consume a large amount of energy;
(2) the method is used the chromium trioxide catalyst activity extremely low, to such an extent as to yield is only 14% after reaction 28h, the reaction times is so long, yield is so low, this not only consumes a large amount of energy and resource, produces too high process cost, and productivity effect is extremely low.
(3) temperature of reaction (135～145 ℃) that the method adopts is higher.And too high temperature of reaction not only energy consumption is very high, and can make the security of producing significantly reduce;
(4) last handling process of the method adopts the aqueous sodium carbonate washing, and its result will produce a large amount of brine wastes, and brine waste is in wastewater treatment process, to be one of the most difficult waste water that carries out biochemical treatment, can cause serious environmental pollution;
(5) the method adopts the mode of the underpressure distillation ortho-nitrophenyl ethyl ketone of purifying, because of the boiling point (112.5～113.5 ℃ (2mmHg)) of ortho-nitrophenyl ethyl ketone very high, not only need very high temperature and vacuum tightness in the process of underpressure distillation, energy consumption is very high, and facility investment and process cost also can be multiplied, the security of production also can not be guaranteed;
The bionic catalysis system has the incomparable advantage of conventional metals salt catalyst system, catalyst levels is few, but natural degradation, do not produce secondary pollution, the reaction conditions gentleness, solvent-free, neutrality or basic solvent replace the serious acid solvent of equipment corrosion, and selectivity of product is high, separates simple.
At present, the method that adopts the oxidation of bionic catalysis system catalysis o-nitroethylbenzene to prepare the ortho-nitrophenyl ethyl ketone there is not yet bibliographical information, and only has the bibliographical information that uses other ethylbenzene series compound of bionic catalysis system catalysis to prepare corresponding arone.Main method has following several:
Valiollah Mirkhani (Applied Catalysis A:General, 2006,303:221-229) with Majid Moghadam (Catalysis Communications, 2005,6:688-693) etc. the people has reported that the loaded metal porphyrin is in the solution of acetonitrile/water 1: 1 (volume ratio), uses NaIO
4as oxygenant, but the highly selectivies such as oxidation ethylbenzene and n-proplbenzene obtain corresponding arone, catalyzer: raw material: oxygenant=1: 80: 160 (mol ratio), the yield of methyl phenyl ketone can reach 55%.The main drawback of the method is to use respectively NaIO expensive and that environmental pollution is serious
4as chemical oxidizing agent, acetonitrile solution as solvent.
Shi-Jun Li (Tetrahedron Letters, 2005,46:8013-8015) etc. the people has reported chloramine-T/O
2/ complex of metalloporphyrin is in the acetonitrile equal solvent, and under room temperature, the Oxidation Ethylbenzene series compound obtains corresponding arone, catalyzer: raw material: chloramine-T=1: 20: 10 (mol ratio), the yield of methyl phenyl ketone can reach 67%.The main drawback of the method be must use respectively expensive and chloramine-T that environmental pollution is serious as chemical oxidizing agent, acetonitrile as solvent.
Lee brace (Journal of Molecular Catalysis, 2008,22 (3): 209-213) etc. the people has reported that metalloporphyrin/high price salt system is solvent-free, 1.5MPa, under 100 ℃ of conditions, oxygen catalytic oxidation ethylbenzene series compound obtains corresponding arone, under the condition that there is no high-valency metal salt, the yield of methyl phenyl ketone is 36.3%, adds the serious K of environmental pollution
2cr
2o
7after, yield can bring up to 51.0%.The high-valency metal salt that it uses is mainly Na
2moO
4, K
2cr
2o
7, KMnO
4.The main drawback of the method is that reaction needed employing energy consumption is high, the condition of high voltage of operational hazards, and must use the high-valency metal salt expensive, that environmental pollution is serious.
Rong-Min Wang (Journal of Applied Polymer Science, 1998,67:2027-2034) etc. the people has reported that poly-porphyrin is under 60～90 ℃ of conditions, oxygen catalytic oxidation Preparation of ethylbenzene methyl phenyl ketone, the catalytic amount that every 15mmol raw material needs is 6mg (480ppm), reaction 8～9h, the methyl phenyl ketone yield is 13.7%, selectivity is 99%.The main drawback of the method is that catalyst levels is large, and catalyst separating, recovery and purification power consumption are high.And, because this reaction is inhomogeneous reaction, although the highly selective of catalysis of metalloporphyrin agent has obtained fine embodiment, its high catalytic activity does not display fully, the methyl phenyl ketone yield only reaches 13.7%.
Peng Qingjing (Acta PhySico-Chimica Sinica, 2001,17 (4): 292-294) reported [TPPMn]
2o catalytic air oxidation Preparation of ethylbenzene methyl phenyl ketone, it is 60～85 ℃ that temperature is selected in reaction, reaction selects benzene, chlorobenzene, butanone, pimelinketone as solvent or solvent-free.As use butanone or pimelinketone as solvent, and there is not induction time in this reaction, and uses benzene or chlorobenzene as solvent, and there is the induction time of 3h in this reaction.The main drawback of the method is that reaction induction time is long, and solvent environment used is unfriendly, and particularly benzene or chlorobenzene have limited use industrial.
In sum, the following main drawback of bionic catalysis method for oxidation existence for preparing at present other ethylbenzene compounds:
(1) use chemical oxidizing agent, not only in the process of producing, produce poisonous, poisonous in a large number waste water, waste residue, cause serious environmental pollution, and raw material and production cost become very high accordingly;
(2) use solvent, the benzene or the chlorobenzene that even use industrial restriction to use.Cause increasing of energy consumption not only because its poisonous and harmful may cause serious environmental pollution, and because of the recovery of solvent, greatly increased process cost and production cost;
(3) because use the reaction conditions of high pressure, cause facility investment and running cost to be multiplied, energy consumption is high, particularly makes to produce to have potential danger, and security reduces greatly;
(4) working load or polymer/metallic porphyrin, cause because preparation process is complicated that energy consumption is high, three waste discharge is many, complex process, cost increase.Separately, because of catalyst levels large (480ppm), by rear also necessary Separation and Recovery, and the cost of Separation and Recovery catalyzer is high, energy consumption is large, and three waste discharge is many.Also have, because the reaction of working load or polymer/metallic porphyrin is inhomogeneous reaction, the high catalytic activity of metalloporphyrin can not get good embodiment.
(5) induction time oversize (reaching 3h) of reaction, thereby make the time lengthening of whole reaction, cause the increase of the serious and process cost of energy dissipation.
Summary of the invention
The object of the present invention is to provide a kind of yield higher, induction time is extremely short, and the method for eco-friendly metalloporphyrin preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen.
The method of a kind of preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen provided by the present invention, the steps include: take that o-nitroethylbenzene is as raw material, under normal pressure, condition of no solvent, select the monokaryon metalloporphyrin of there is formula (I), formula (II) structure and there are any one or two kinds of combinations in the μ-oxygen of formula (III) structure-dinuclear metalloporphyrin as catalyzer, wherein, central metallic ions M
1for iron, manganese, cobalt, copper, zinc, nickel or chromium, central metallic ions M
2for iron, manganese, cobalt, nickel, chromium, molybdenum or ruthenium, central metallic ions M
3with central metallic ions M
4identical or different, be iron, manganese or cobalt when identical, when different, M
3for iron, M
4for manganese, M
3for iron, M
4for cobalt or M
3for manganese, M
4for cobalt, substituent R
11, R
12, R
13, R
21, R
22, R
23, R
31, R
32or R
33for hydrogen, halogen, nitro, hydroxyl, C
1-3alkyl, C
1-3alkoxyl group or carboxyl, dentate X is halogen, and described catalyzer also comprises formula (I) with substituting group in formula (I), formula (II) and formula (II), formula (III) and formula (III) and substituent position is identical, central metallic ions M
1, M
2, M
3or M
4different combinations; Also comprise the middle substituting group of formula (I) and formula (I), formula (II) and formula (II), formula (III) and formula (III) and the combination that substituent position is different, central metallic ions is identical or different,
Catalyst levels is 1～30ppm, with 10～60mL/min flow velocity, passes into oxygen, first 150～200 ℃ of lower high temperature initiation reactions, then at 80～130 ℃ of lower low-temp reaction 10～18h, reacted mixture is through freezing, centrifuging, then uses the ethanol frozen recrystallization, obtains the ortho-nitrophenyl ethyl ketone.
Preferred M
1, M
2, M
3or M
4for iron, manganese or cobalt, M
3and M
4identical; Particularly preferably when any two kinds of catalyst combination, a kind of M wherein
1, M
2, M
3or M
4for iron or manganese, another kind of M
1, M
2, M
3or M
4for cobalt, the mol ratio of iron porphyrin or manganoporphyrin and cobalt porphyrin is 1: 1～10.
The preferred chlorine of dentate X.
Preferred catalyst levels is 5～15ppm; Preferred oxygen gas flow rate is 30～50mL/min; Preferred kick off temperature is 160～170 ℃; Preferred temperature of reaction is 100～120 ℃; The preferred reaction times is 12～16h.
The method of the people such as the inventive method and William S.Emerson report is compared, and has following beneficial effect:
(1) present method is usingd the eco-friendly metal porphyrins of minute quantity (1～30ppm) and is substituted a large amount of (30200ppm) of people's report such as William S.Emerson and hypertoxic chromium trioxide directly as catalyzer, has eliminated the harm that highly toxic substance causes environment fully.And, because the consumption of catalysis of metalloporphyrin agent is few, do not need after reaction to separate, reclaim, avoided the generation of separation, recovery, purification process energy consumption.But and metalloporphyrin natural degradation in environment, can not produce secondary pollution;
(2) present method is used metalloporphyrin as bionic catalyst, has high reactivity, the highly selective characteristics of approximate enzyme.In present method, the highest yield of ortho-nitrophenyl ethyl ketone can reach 55.4%, far above 14% yield of the people such as William S.Emerson report;
(3) the preferred temperature of reaction of present method is only 100～120 ℃, lower than 135～145 ℃ of the people such as William S.Emerson report.The reduction of temperature of reaction has not only reduced energy consumption and the process cost in the reaction, also makes production process become safer, but also has reduced the generation of side reaction, has improved the selectivity of product;
(4) the product separation process of present method does not need to use the aqueous sodium carbonate washing, and only need use simply freezing, centrifugal filtering method separation, does not therefore have the aftertreatment problem of brine waste.
(5) present method adopts the method for ethanol frozen recrystallization to replace the vacuum distillation method of people's report such as the William S.Emerson ortho-nitrophenyl ethyl ketone of purifying, and the fusing point of ortho-nitrophenyl ethyl ketone higher (28.5 ℃), the frozen recrystallization process does not need to use too low temperature, therefore purification process reduces energy consumption greatly, reduce facility investment and process cost, and production security is greatly improved.
The inventive method is compared with the method for aforesaid other ethylbenzene series compound of bionic catalysis oxidation, has following beneficial effect:
(1) present method is used clean, cheap oxygen to replace serious, the expensive NaIO of environmental pollution
4with chemical oxidizing agents such as chloramine-Ts as oxygenant.Not only greatly reduce environmental pollution, and significantly reduced production cost;
(2) present method is not used solvent.Not only eliminate the poisonous and harmful solvent fully and may cause serious environmental pollution, and because there is not the recovery problem of solvent, and the energy consumption of production process and cost are reduced greatly;
(3) present method is only carried out under condition of normal pressure, with respect to the reaction under high pressure in documents, not only makes facility investment, energy consumption and running cost all significantly reduce, and the security of whole production process is greatly improved;
(4) present method is usingd the metal porphyrins of minute quantity directly as catalyzer, and do not use load that preparation process is very complicated or polymer/metallic porphyrin as catalyzer, simplified the preparation process of catalyzer, can greatly reduce catalyzer and prepare the environmental pollution that required energy consumption and preparation process produce.And, because the consumption of catalysis of metalloporphyrin agent is few, do not need after reaction to separate, reclaim, avoided the generation of separation, recovery, purification process energy consumption.Simultaneously, but due to metalloporphyrin natural degradation in environment, can not produce secondary pollution.Metalloporphyrin is directly as catalyzer, and reaction system is similar to homogeneous system, has increased contact probability and the reaction efficiency of metalloporphyrin and substrate, makes the high catalytic activity of metalloporphyrin obtain good embodiment;
(5) present method adopts high temperature to cause fast, and the mode of low-temp reaction, make reaction induction time become extremely short, has greatly shortened the time of reaction, has improved reaction efficiency, has reduced process cost and energy consumption.Low-temp reaction contributes to improve the selectivity of product, has reduced the generation of by product, and the separation of product is become be more prone to, and the energy consumption of reaction and separation processes all reduces greatly, and the security of producing is improved.
Embodiment
Embodiment 1
In the 100mL there-necked flask, add the 15.084g o-nitroethylbenzene, 1ppm (0.07mg) tetraphenyl iron porphyrin (is R in formula (I)
11for H, R
12for H, R
13for H, M
1for Fe), 10ppm (0.86mg) four-(rubigan) cobalt porphyrin (is R in formula (I)
11for H, R
12for H, R
13for Cl, M
1for Co), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 110 ℃, react 10h.Reacted mixture is through freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 45.4%, and purity is 99.2%.
Embodiment 2
In the 100mL there-necked flask, add the 15.132g o-nitroethylbenzene, 5ppm (0.38mg) chlorination four-phenyl manganoporphyrin (is R in formula (II)
21for H, R
22for H, R
23for H, M
2for Mn, X is Cl), 5ppm (0.44mg) chlorination four-(o-methoxyphenyl) cobalt porphyrins (are R in formula (II)
21for OCH
3, R
22for H, R
23for H, M
2for Co, X is Cl), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 49.2%, and purity is 99.4%.
Embodiment 3
In the 100mL there-necked flask, add the 15.167g o-nitroethylbenzene, 1ppm (0.15mg) μ-oxygen-double-core four-phenyl iron porphyrin (is R in formula (III)
31for H, R
32for H, R
33for H, M
3, M
4for Fe), 5ppm (0.88mg) μ-oxygen-double-core four-(rubigan) cobalt porphyrin (is R in formula (III)
31for H, R
32for H, R
33for Cl, M
3, M
4for Co), pass into oxygen under the 50mL/min flow velocity, 160 ℃ of lower initiation reactions, under 100 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 40.3%, and purity is 99.4%.
Embodiment 4
In the 100mL there-necked flask, add the 15.132g o-nitroethylbenzene, 5ppm (0.45mg) chlorination four-(p-methoxyphenyl) iron porphyrins (are R in formula (II)
21for H, R
22for H, R
23for OCH
3, M
2for Fe, X is Cl), 10ppm (1.78mg) μ-oxygen-double-core four-(rubigan) cobalt porphyrin (is R in formula (III)
31for H, R
32for H, R
33for Cl, M
3, M
4for Co), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 16h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 55.4%, and purity is 99.3%.
Embodiment 5
In the 100mL there-necked flask, add the 15.088g o-nitroethylbenzene, 1ppm (0.08mg) four-(o-methoxyphenyl) copper porphyrin (is R in formula (I)
11for OCH
3, R
12for H, R
13for H, M
1for Cu), 10ppm (0.88mg) chlorination four-(o-methoxyphenyl) cobalt porphyrins (are R in formula (II)
21for OCH
3, R
22for H, R
23for H, M
2for Co, X is Cl), pass into oxygen under the 50mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 51.5%, and purity is 99.0%.
Embodiment 6
In the 100mL there-necked flask, add the 15.093g o-nitroethylbenzene, 1ppm (0.07mg) chlorination four-phenyl manganoporphyrin (is R in formula (II)
21for H, R
22for H, R
23for H, M
2for Mn, X is Cl), 10ppm (0.92mg) four-(O-Nitrophenylfluorone) cobalt porphyrin (is R in formula (I)
11for NO
2, R
12for H, R
13for H, M
1for Co), pass into oxygen under the 30mL/min flow velocity, 160 ℃ of lower initiation reactions, under 130 ℃, react 10h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 53.6%, and purity is 99.8%.
Embodiment 7
In the 100mL there-necked flask, add the 15.103g o-nitroethylbenzene, 5ppm (0.75mg) μ-oxygen-double-core four-phenyl iron porphyrin (is R in formula (III)
31for H, R
32for H, R
33for H, M
3, M
4for Fe), 10ppm (0.89mg) four-(rubigan) cobalt porphyrin (is R in formula (I)
11for H, R
12for H, R
13for Cl, M
1for Co), pass into oxygen under the 20mL/min flow velocity, 160 ℃ of lower initiation reactions, under 100 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 39.8%, and purity is 99.4%.
Embodiment 8
In the 100mL there-necked flask, add the 15.122g o-nitroethylbenzene, 5ppm (0.47mg) four-(p-nitrophenyl) zinc protoporphyrin (is R in formula (I)
11for H, R
12for H, R
13for NO
2, M
1for Zn), 10ppm (0.77mg) chlorination four-phenyl manganoporphyrin (is R in formula (II)
21for H, R
22for H, R
23for H, M
2for Mn, X is Cl), pass into oxygen under the 50mL/min flow velocity, 160 ℃ of lower initiation reactions, under 110 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 42.4%, and purity is 99.0%.
Embodiment 9
In the 100mL there-necked flask, add the 15.132g o-nitroethylbenzene, 20ppm (1.47mg) four-phenyl iron porphyrin (is R in formula (I)
11for H, R
12for H, R
13for H, M
1for Fe), pass into oxygen under the 30mL/min flow velocity, 160 ℃ of lower initiation reactions, under 80 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 9.2%, and purity is 99.1%.
Embodiment 10
In the 100mL there-necked flask, add the 15.143g o-nitroethylbenzene, 10ppm (0.86mg) four-(rubigan) cobalt porphyrin (is R in formula (I)
11for H, R
12for H, R
13for Cl, M
1for Co), pass into oxygen under the 20mL/min flow velocity, 200 ℃ of lower initiation reactions, under 100 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 23.1%, and purity is 99.6%.
Embodiment 11
In the 100mL there-necked flask, add the 15.128g o-nitroethylbenzene, 15ppm (1.30mg) four-(m-nitro base) manganoporphyrin (is R in formula (I)
11for H, R
12for NO
2, R
13for H, M
1for Mn), pass into oxygen under the 30mL/min flow velocity, 170 ℃ of lower initiation reactions, under 110 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 34.3%, and purity is 99.2%.
Embodiment 12
In the 100mL there-necked flask, add the 15.136g o-nitroethylbenzene, 30ppm (2.43mg) four-(p-hydroxybenzene) nickel-porphyrin (is R in formula (I)
11for H, R
12for H, R
13for OH, M
1for Ni), pass into oxygen under the 20mL/min flow velocity, 190 ℃ of lower initiation reactions, under 110 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 23.1%, and purity is 99.5%.
Embodiment 13
In the 100mL there-necked flask, add the 15.127g o-nitroethylbenzene, 20ppm (1.83mg) four-(p-nitrophenyl) zinc protoporphyrin (is R in formula (I)
11for H, R
12for H, R
13for NO
2, M
1for Zn), pass into oxygen under the 30mL/min flow velocity, 150 ℃ of lower initiation reactions, under 120 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 10.4%, and purity is 99.5%.
Embodiment 14
In the 100mL there-necked flask, add the 15.104g o-nitroethylbenzene, 20ppm (1.73mg) four-(Chloro-O-Phenyl) chromium porphyrin (is R in formula (I)
11for Cl, R
12for H, R
13for H, M
1for Cr), pass into oxygen under the 20mL/min flow velocity, 190 ℃ of lower initiation reactions, under 110 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 19.8%, and purity is 99.6%.
Embodiment 15
In the 100mL there-necked flask, add the 15.107g o-nitroethylbenzene, 20ppm (1.74mg) four-(o-methoxyphenyl) copper porphyrin (is R in formula (I)
11for OCH
3, R
12for H, R
13for H, M
1for Cu), pass into oxygen under the 30mL/min flow velocity, 160 ℃ of lower initiation reactions, under 125 ℃, react 10h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 19.3%, and purity is 99.6%.
Embodiment 16
In the 100mL there-necked flask, add the 15.132g o-nitroethylbenzene, 15ppm (1.21mg) four-(carboxyl phenyl) manganoporphyrin (is R in formula (I)
11for H, R
12for COOH, R
13for H, M
1for Mn), pass into oxygen under the 30mL/min flow velocity, 170 ℃ of lower initiation reactions, under 120 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 45.7%, and purity is 99.2%.
Embodiment 17
In the 100mL there-necked flask, add the 15.102g o-nitroethylbenzene, 10ppm (0.92mg) four-(O-Nitrophenylfluorone) cobalt porphyrin (is R in formula (I)
11for NO
2, R
12for H, R
13for H, M
1for Co), pass into oxygen under the 30mL/min flow velocity, 190 ℃ of lower initiation reactions, under 110 ℃, react 16h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 48.4%, and purity is 99.3%.
Embodiment 18
In the 100mL there-necked flask, add the 15.101g o-nitroethylbenzene, 10ppm (0.78mg) chlorination four-phenyl manganoporphyrin (is R in formula (II)
21for H, R
22for H, R
23for H, M
2for Mn, X is Cl), pass into oxygen under the 40mL/min flow velocity, 170 ℃ of lower initiation reactions, under 120 ℃, react 15h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 49.6%, and purity is 99.3%.
Embodiment 19
In the 100mL there-necked flask, add the 15.103g o-nitroethylbenzene, 5ppm (0.45mg) chlorination four-(rubigan) cobalt porphyrins (are R in formula (II)
21for H, R
22for H, R
23for Cl, M
2for Co, X is Cl), pass into oxygen under the 20mL/min flow velocity, 190 ℃ of lower initiation reactions, under 120 ℃, react 18h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 55.1%, and purity is 99.2%.
Embodiment 20
In the 100mL there-necked flask, add the 15.121g o-nitroethylbenzene, 15ppm (1.32mg) chlorination four-(p-methoxyphenyl) iron porphyrins (are R in formula (II)
21for H, R
22for H, R
23for OCH
3, M
2for Fe, X is Cl), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 34.7%, and purity is 99.3%.
Embodiment 21
In the 100mL there-necked flask, add the 15.124g o-nitroethylbenzene, 10ppm (0.75mg) bromination four-phenyl molybdenum porphyrin (is R in formula (II)
21for H, R
22for H, R
23for H, M
2for Mo, X is Br), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 9.1%, and purity is 99.2%.
Embodiment 22
In the 100mL there-necked flask, add the 15.124g o-nitroethylbenzene, 20ppm (1.93mg) chlorination four-(p-nitrophenyl) chromium porphyrins (are R in formula (II)
21for H, R
22for H, R
23for NO
2, M
2for Cr, X is Cl), pass into oxygen under the 40mL/min flow velocity, 190 ℃ of lower initiation reactions, under 110 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 19.5%, and purity is 99.2%.
Embodiment 23
In the 100mL there-necked flask, add the 15.094g o-nitroethylbenzene, 20ppm (1.84mg) chlorination four-(Chloro-O-Phenyl) manganoporphyrins (are R in formula (II)
21for Cl, R
22for H, R
23for H, M
2for Mn, X is Cl), pass into oxygen under the 50mL/min flow velocity, 170 ℃ of lower initiation reactions, under 120 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 47.4%, and purity is 99.4%.
Embodiment 24
In the 100mL there-necked flask, add the 15.115g o-nitroethylbenzene, 5ppm (0.45mg) chlorination four-(o-methoxyphenyl) cobalt porphyrins (are R in formula (II)
21for OCH
3, R
22for H, R
23for H, M
2for Co, X is Cl), pass into oxygen under the 50mL/min flow velocity, 190 ℃ of lower initiation reactions, under 120 ℃, react 16h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 43.4%, and purity is 99.2%.
Embodiment 25
In the 100mL there-necked flask, add the 15.101g o-nitroethylbenzene, 15ppm (1.36mg) chlorination four-(O-Nitrophenylfluorone) nickel-porphyrins (are R in formula (II)
21for NO
2, R
22for H, R
23for H, M
2for Ni, X is Cl), pass into oxygen under the 50mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 16h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 21.2%, and purity is 99.5%.
Embodiment 26
In the 100mL there-necked flask, add the 15.102g o-nitroethylbenzene, fluoridize-tetraphenyl of 10ppm (0.81mg) ruthenium porphyrin (is R in formula (II)
21for H, R
22for H, R
23for H, M
2for Ru, X is F), pass into oxygen under the 50mL/min flow velocity, 160 ℃ of lower initiation reactions, under 110 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 9.1%, and purity is 99.2%.
Embodiment 27
In the 100mL there-necked flask, add the 15.101g o-nitroethylbenzene, 10ppm (1.48mg) μ-oxygen-double-core four-phenyl iron porphyrin (is R in formula (III)
31for H, R
32for H, R
33for H, M
3, M
4for Fe), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 100 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 31.5%, and purity is 99.1%.
Embodiment 28
In the 100mL there-necked flask, add the 15.123g o-nitroethylbenzene, 1ppm (0.19mg) μ-oxygen-double-core four-(p-nitrophenyl) manganoporphyrin (is R in formula (III)
31for H, R
32for H, R
33for NO
2, M
3, M
4for Mn), pass into oxygen under the 40mL/min flow velocity, 170 ℃ of lower initiation reactions, under 110 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 17.3%, and purity is 99.2%.
Embodiment 29
In the 100mL there-necked flask, add the 15.124g o-nitroethylbenzene, 5ppm (0.89mg) μ-oxygen-double-core four-(rubigan) cobalt porphyrin (is R in formula (III)
31for H, R
32for H, R
33for Cl, M
3, M
4for Co), pass into oxygen under the 40mL/min flow velocity, 190 ℃ of lower initiation reactions, under 120 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 46.2%, and purity is 99.5%.
Embodiment 30
In the 100mL there-necked flask, add the 15.126g o-nitroethylbenzene, 5ppm (0.89mg) μ-oxygen-double-core four-(p-methoxyphenyl) iron-cobalt porphyrin (is R in formula (III)
31for H, R
32for H, R
33for OCH
3, M
3for Fe, M
4for Co), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 46.4%, and purity is 99.1%.
Embodiment 31
In the 100mL there-necked flask, add the 15.114g o-nitroethylbenzene, 10ppm (1.63mg) μ-oxygen-double-core four-(p-hydroxybenzene) manganese-cobalt porphyrin (is R in formula (III)
31for H, R
32for H, R
33for OH, M
3for Mn, M
4for Co), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 46.8%, and purity is 99.3%.
Embodiment 32
In the 100mL there-necked flask, add the 15.112g o-nitroethylbenzene, 10ppm (1.83mg) μ-oxygen-double-core four-(O-Nitrophenylfluorone) cobalt porphyrin (is R in formula (III)
31for NO
2, R
32for H, R
33for H, M
3, M
4for Co), pass into oxygen under the 40mL/min flow velocity, 190 ℃ of lower initiation reactions, under 110 ℃, react 12h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 49.8%, and purity is 99.1%.
Embodiment 33
In the 100mL there-necked flask, add the 15.105g o-nitroethylbenzene, 10ppm (1.75mg) μ-oxygen-double-core four-(Chloro-O-Phenyl) manganoporphyrin (is R in formula (III)
31for Cl, R
32for H, R
33for H, M
3, M
4for Mn), pass into oxygen under the 40mL/min flow velocity, 170 ℃ of lower initiation reactions, under 110 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 37.3%, and purity is 99.2%.
Embodiment 34
In the 100mL there-necked flask, add the 15.104g o-nitroethylbenzene, 10ppm (1.77mg) μ-oxygen-double-core four-(o-methoxyphenyl) manganese-cobalt porphyrin (is R in formula (III)
31for OCH
3, R
32for H, R
33for H, M
3for Mn, M
4for Co), pass into oxygen under the 30mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 14h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 45.3%, and purity is 99.2%.
Embodiment 35
In the 100mL there-necked flask, add the 15.114g o-nitroethylbenzene, 10ppm (1.87mg) μ-oxygen-double-core four-(m-nitro base) iron-cobalt porphyrin (is R in formula (III)
31for H, R
32for NO
2, R
33for H, M
3for Fe, M
4for Co), pass into oxygen under the 30mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 13h.Reacted mixture is freezing, centrifuging, then obtains the ortho-nitrophenyl ethyl ketone with the ethanol frozen recrystallization, and its yield is 44.2%, and purity is 99.6%.
Embodiment 36
In the 100mL there-necked flask, add the 15.134g o-nitroethylbenzene, 1ppm (0.18mg) μ-oxygen-double-core four-(Chloro-O-Phenyl) iron porphyrin (is R in formula (III)
31for Cl, R
32for H, R
33for H, M
3, M
4for Fe), 10ppm (1.78mg) μ-oxygen-double-core four-(Chloro-O-Phenyl) cobalt porphyrin (is R in formula (III)
31for Cl, R
32for H, R
33for H, M
3, M
4for Co), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 12h.Reacted mixture is through freezing, centrifuging, then uses the frozen ethanol recrystallization, obtains the ortho-nitrophenyl ethyl ketone, and its yield is 58.3%, and purity is 99.2%.
Embodiment 37
In the 100mL there-necked flask, add the 15.112g o-nitroethylbenzene, 5ppm (0.90mg) four-(p-methylphenyl) zinc protoporphyrin (is R in formula (I)
11for H, R
12for H, R
13for CH
3, M
1for Zn), 10ppm (0.92mg) four-(p-nitrophenyl) zinc protoporphyrin (is R in formula (I)
11for H, R
12for H, R
13for NO
2, M
1for Zn), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 14h.Reacted mixture is through freezing, centrifuging, then uses the frozen ethanol recrystallization, obtains the ortho-nitrophenyl ethyl ketone, and its yield is 34.6%, and purity is 99.7%.
Embodiment 38
In the 100mL there-necked flask, add the 15.103g o-nitroethylbenzene, 5ppm (0.91mg) four-(2,4-3,5-dimethylphenyl) zinc protoporphyrin (is R in formula (I)
11for CH
3, R
12for H, R
13for CH
3, M
1for Zn), 10ppm (0.92mg) four-(2,4-dinitrophenyl) zinc protoporphyrin (is R in formula (I)
11for NO
2, R
12for H, R
13for NO
2, M
1for Zn), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 14h.Reacted mixture is through freezing, centrifuging, then uses the frozen ethanol recrystallization, obtains the ortho-nitrophenyl ethyl ketone, and its yield is 47.4%, and purity is 99.3%.
Embodiment 39
In the 100mL there-necked flask, add the 15.106g o-nitroethylbenzene, 5ppm (0.44mg) bromination four-(O-Nitrophenylfluorone) iron porphyrins (are R in formula (II)
21for NO
2, R
22for H, R
23for H, M
2for Fe, X is Br), 10ppm (0.88mg) chlorination four-(p-methoxyphenyl) iron porphyrins (are R in formula (II)
21for H, R
22for H, R
23for OCH
3, M
2for Fe, X is Cl), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 12h.Reacted mixture is through freezing, centrifuging, then uses the frozen ethanol recrystallization, obtains the ortho-nitrophenyl ethyl ketone, and its yield is 54.5%, and purity is 99.6%.
Embodiment 40
In the 100mL there-necked flask, add the 15.124g o-nitroethylbenzene, 5ppm (0.82mg) μ-oxygen-double-core four-(p-hydroxybenzene) manganoporphyrin (is R in formula (III)
31for H, R
32for H, R
33for OH, M
3, M
4for Mn), 10ppm (1.75mg) μ-oxygen-double-core four-(Chloro-O-Phenyl) manganoporphyrin (is R in formula (III)
31for Cl, R
32for H, R
33for H, M
3, M
4for Mn), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, under 120 ℃, react 13h.Reacted mixture is through freezing, centrifuging, then uses the frozen ethanol recrystallization, obtains the ortho-nitrophenyl ethyl ketone, and its yield is 57.6%, and purity is 99.4%.
Claims (10)
1. the method for a preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen, the steps include: take that o-nitroethylbenzene is as raw material, under normal pressure, condition of no solvent, select the monokaryon metalloporphyrin of there is formula (I), formula (II) structure and there are any one or two kinds of combinations in the μ-oxygen of formula (III) structure-dinuclear metalloporphyrin as catalyzer, or select formula (I) and the middle substituting group of formula (I), formula (II) and formula (II), formula (III) and formula (III) and substituent position is identical, central metallic ions M
1, M
2, M
3or M
4different combinations are as catalyzer, or select substituting group in formula (I) and formula (I), formula (II) and formula (II), formula (III) and formula (III) and substituent position is different, central metallic ions is identical or different combination as catalyzer, wherein, central metallic ions M
1for iron, manganese, cobalt, copper, zinc, nickel or chromium, central metallic ions M
2for iron, manganese, cobalt, nickel, chromium, molybdenum or ruthenium, central metallic ions M
3with central metallic ions M
4identical or different, be iron, manganese or cobalt when identical, when different, M
3for iron, M
4for manganese, M
3for iron, M
4for cobalt or M
3for manganese, M
4for cobalt, substituent R
11, R
12, R
13, R
21, R
22, R
23, R
31, R
32or R
33for hydrogen, halogen, nitro, hydroxyl, C
1-3alkyl, C
1-3alkoxyl group or carboxyl, dentate X is halogen,
Catalyst levels is 1～30ppm, with 10～60mL/min flow velocity, passes into oxygen, first 150～200 ℃ of lower high temperature initiation reactions, then at 80～130 ℃ of lower low-temp reaction 10～18h, reacted mixture is through freezing, centrifuging, then uses the ethanol frozen recrystallization, obtains the ortho-nitrophenyl ethyl ketone.
2. according to the method for claim 1, it is characterized in that M
1, M
2, M
3or M
4for iron, manganese or cobalt, M
3and M
4identical.
3. according to the method for claim 2, it is characterized in that when any two kinds of catalyst combination, wherein the M in a kind of catalyzer
1, M
2, M
3or M
4for iron or manganese, the M in another kind of catalyzer
1, M
2, M
3or M
4for cobalt.
4. according to the method for claim 3, the mol ratio that it is characterized in that iron porphyrin or manganoporphyrin and cobalt porphyrin is 1: 1～10.
5. according to the method for claim 1, it is characterized in that dentate X is chlorine.
6. according to the method for claim 1, it is characterized in that catalyst levels is 5～15ppm.
7. according to the method for claim 1, it is characterized in that oxygen gas flow rate is 30～50mL/min.
8. according to the method for claim 1, it is characterized in that kick off temperature is 160～170 ℃.
9. according to the method for claim 1, it is characterized in that temperature of reaction is 100～120 ℃.
10. according to the method for claim 1, it is characterized in that the reaction times is 12～16h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010103426 CN101774925B (en) | 2010-01-29 | 2010-01-29 | Method for preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010103426 CN101774925B (en) | 2010-01-29 | 2010-01-29 | Method for preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101774925A CN101774925A (en) | 2010-07-14 |
| CN101774925B true CN101774925B (en) | 2013-05-08 |
Family
ID=42511542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010103426 Expired - Fee Related CN101774925B (en) | 2010-01-29 | 2010-01-29 | Method for preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101774925B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985424B (en) * | 2010-09-21 | 2013-05-29 | 浙江工业大学 | Method for synthesizing o-nitroacetophenone compound |
| CN108947846B (en) * | 2018-06-30 | 2021-04-06 | 浙江工业大学 | Preparation method of p-nitroacetophenone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1521153A (en) * | 2003-02-08 | 2004-08-18 | 湖南大学 | Process for preparing aldehyde and alcohol by selective catalysis air oxidation of toluene and substituted toluene |
| CN1530357A (en) * | 2003-03-14 | 2004-09-22 | 湖南大学 | Method for catalytic conversion of alkyl cyclohexanol and alkyl cyclohexanone from air oxidized alkyl cyclohexane |
| CN101020144A (en) * | 2006-02-15 | 2007-08-22 | 中国科学院大连化学物理研究所 | Bionic composite catalyst system for selective oxidation of arene |
| CN101559384A (en) * | 2009-05-26 | 2009-10-21 | 中北大学 | Preparation of silica gel supported metalloporphyrin compound and application method thereof |
-
2010
- 2010-01-29 CN CN 201010103426 patent/CN101774925B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1521153A (en) * | 2003-02-08 | 2004-08-18 | 湖南大学 | Process for preparing aldehyde and alcohol by selective catalysis air oxidation of toluene and substituted toluene |
| CN1530357A (en) * | 2003-03-14 | 2004-09-22 | 湖南大学 | Method for catalytic conversion of alkyl cyclohexanol and alkyl cyclohexanone from air oxidized alkyl cyclohexane |
| CN101020144A (en) * | 2006-02-15 | 2007-08-22 | 中国科学院大连化学物理研究所 | Bionic composite catalyst system for selective oxidation of arene |
| CN101559384A (en) * | 2009-05-26 | 2009-10-21 | 中北大学 | Preparation of silica gel supported metalloporphyrin compound and application method thereof |
Non-Patent Citations (4)
| Title |
|---|
| rong-min wang.sheet polymer and its complexes.《Journal of applied polymer science》.1998,第67卷2027-2034. |
| sheet polymer and its complexes;rong-min wang;《Journal of applied polymer science》;19981231;第67卷;2027-2034 * |
| u-氧代双锰卟啉催化下空气高选择氧化乙苯;彭清静;《物理化学学报》;20010430;第17卷(第4期);292-294 * |
| 彭清静.u-氧代双锰卟啉催化下空气高选择氧化乙苯.《物理化学学报》.2001,第17卷(第4期),292-294. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101774925A (en) | 2010-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huber et al. | Historical landmarks of the application of molecular transition metal catalysts for olefin epoxidation | |
| Hirai et al. | Ruthenium‐Catalyzed Selective and Efficient Oxygenation of Hydrocarbons with Water as an Oxygen Source | |
| CN101759542B (en) | Method for preparing acetophenone by biomimetic catalytic oxidation of ethylbenzene with oxygen | |
| Wu et al. | Metal chlorides-catalyzed selective oxidation of cyclohexane by molecular oxygen under visible light irradiation | |
| CN105130821B (en) | It is a kind of to reduce the green synthesis method that ortho-nitraniline prepares o-phenylenediamine | |
| CN108097323A (en) | A kind of method that oxidative coupling of primary amine at room temperature prepares imines | |
| Chen et al. | Photocatalytic oxidation of alkenes and alcohols in water by a manganese (v) nitrido complex | |
| CN107954832A (en) | A kind of preparation method of hydrogenated bisphenol A | |
| CN101774925B (en) | Method for preparing o-nitroacetophenone by oxidizing o-nitroethylbenzene through biomimetic-catalysis oxygen | |
| CN103467434B (en) | Method for preparing eta-caprolactone by composite catalysis | |
| Han et al. | Direct synthesis of cyclic carbonates from olefins and CO2: Single-or multi-component catalytic systems via epoxide or halohydrin intermediate | |
| CN101747168B (en) | Method for preparing o-bromoacetophenone by biomimetic catalytic oxidation of o-bromoethylbenzene with oxygen | |
| CN101747204B (en) | Method for preparing p-nitroacetophenone by biomimetic catalytic oxidation of p-nitroethylbenzene with oxygen | |
| Lyons | Transition metal complexes as catalysts for the addition of oxygen to reactive organic substrates | |
| Larsson et al. | A catalytic system for allylic acetoxylation consisting of palladium (II) and nitrate and using oxygen as final oxidant | |
| CN111205238B (en) | Method for generating 2-aminophenol oxazine-3-ketone compound by catalyzing oxidation of molecular oxygen in aqueous phase | |
| CN101759541B (en) | Method for preparing p-diacetylbenzene by biomimetic catalytic oxidation of p-diethylbenzene with oxygen | |
| CN101759540B (en) | Method for preparing propiophenone by biomimetic catalytic oxidation of n-propylbenzene with oxygen | |
| CN101747166B (en) | Method for preparing m-ethylacetophenone by biomimetic catalytic oxidation of m-diethylbenzene with oxygen | |
| CN101768067B (en) | Method for preparing p-bromophenylacetone by biomimetic catalytic oxidation of p-bromoethylbenzene | |
| CN116217539A (en) | Method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation | |
| Karaman et al. | Asymmetric epoxidation of enones using cumyl hydroperoxide and in situ generated zinc complexes of chiral pyrrolidinyl alcohols | |
| CN110586180B (en) | Visible light catalysis N has2Preparation method of ruthenium hybrid deca-poly quaternary ammonium tungstate with O participating in selective oxidation | |
| CN102267886A (en) | Method for preparing p-ethyl acetophenone by selectively oxidizing p-diethylbenzene with oxygen or air under catalysis of metalloporphyrin | |
| Maldotti et al. | Novel reactivity of photoexcited iron porphyrins caged into a polyfluoro sulfonated membrane in catalytic hydrocarbon oxygenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130508 Termination date: 20160129 |
|
| EXPY | Termination of patent right or utility model |