CN101768067B - Method for preparing p-bromophenylacetone by biomimetic catalytic oxidation of p-bromoethylbenzene - Google Patents

Method for preparing p-bromophenylacetone by biomimetic catalytic oxidation of p-bromoethylbenzene Download PDF

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CN101768067B
CN101768067B CN 201010103449 CN201010103449A CN101768067B CN 101768067 B CN101768067 B CN 101768067B CN 201010103449 CN201010103449 CN 201010103449 CN 201010103449 A CN201010103449 A CN 201010103449A CN 101768067 B CN101768067 B CN 101768067B
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parabromoacetophenone
ethylbenzene
cobalt
bromine
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CN101768067A (en
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佘远斌
赵文伯
王磐
钟儒刚
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Beijing University of Technology
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Beijing University of Technology
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Abstract

The invention relates to a method for preparing p-bromophenylacetone by biomimetic catalytic oxidation of p-bromoethylbenzene, comprising the following steps of: taking p-bromoethylbenzene as raw material; selecting either of 1-30ppm mononuclear metal porphyrin and mu-oxo-dinuclear metal porphyrin or the both as a catalyst; introducing oxygen at the flow speed of 10 to 60mL/min under normal pressure without solvents; initiating reaction at 140 DEG C to 170 DEG C; and reacting for 6 to 16h at 80 DEG C to 120 DEG C to obtain the p-bromophenylacetone. The method uses the mode of high-temperature quick initiation and low-temperature reaction, greatly shortens the initiation time of the reaction and the reaction time, improves the reaction efficiency, reduces the energy consumption and operation costs and improves the reaction safety.

Description

Bionically catalyzing and oxidizing prepares the method for parabromoacetophenone to bromine ethylbenzene
Technical field
The present invention relates to a kind of preparation method of aromatic ketone, specifically, relate to a kind of bionically catalyzing and oxidizing prepares parabromoacetophenone to bromine ethylbenzene method.
Background technology
Parabromoacetophenone is important organic synthesis intermediate, is widely used in synthetic medicine, agricultural chemicals, dyestuff, essence and flavoring agent, perfume etc.At present the preparation method of parabromoacetophenone mainly contains friedel-crafts acylation method, 1-(4-bromophenyl) oxidation of ethanol method and to bromine ethylbenzene oxidation method etc.; Wherein bromine ethylbenzene oxidation method is divided into chemical oxidization method and molecular oxygen oxidation method again; Oxygen is as cheap and easy to get, cleanliness without any pollution and the good oxygenant of Atom economy; By oxygen to directly oxidize bromine ethylbenzene is prepared the method for parabromoacetophenone, have significant meliority with respect to other method.
Lee brace (Journal of Molecular Catalysis, 2008,22 (3): 209-213) wait the people to report that a kind of perfluor substituted metal porphyrin/high price salt system oxygen catalytic oxidation obtains the method for parabromoacetophenone to bromine ethylbenzene.This method is solvent-free, and 1.5MPa under 100 ℃ of conditions, reacts 24h, and under the condition that does not have high-valency metal salt to exist, the chromatogram yield of parabromoacetophenone is 22.5%; Add the serious K of environmental pollution 2Cr 2O 7After, the chromatogram yield of parabromoacetophenone can bring up to 37.4%.Its employed catalyzer is a perfluor substituted metal porphyrin, and consumption is 10 -3Mol/L (120ppm), high-valency metal salt is mainly Na 2MoO 4, K 2Cr 2O 7And KMnO 4, its consumption is 1/800 (1250ppm) of ethylbenzene mole number.
The main drawback of this method is:
(1) the perfluor substituted metal porphyrin catalytic activity of this method employing is lower, and under the situation that does not add the high price metal-salt, after the reaction 24, the yield of parabromoacetophenone is merely 22.5%.Reaction times is so long, and yield is so low, and this not only consumes a large amount of energy and resource, produce too high process cost, and productivity effect is extremely low.
(2) this method adopt consumption greatly (1250ppm), environmental pollution is serious and the high-valency metal salt of expensive as promotor.Therefore in the process of producing, produce poisonous in a large number, deleterious waste water, waste residue, the necessary Separation and Recovery of used high-valency metal salt, and Separation and Recovery need consume a large amount of energy, the high-valency metal salt of expensive has also increased production cost greatly simultaneously.
(3) this method is used the reaction conditions of high pressure (1.5MPa), causes facility investment and running cost to be multiplied, and energy consumption is high, particularly makes to produce to have potential danger, and security reduces greatly;
At present, the main method that adopts other ethylbenzene series compound of bionic catalysis system catalysis to prepare corresponding arone has following several kinds:
Valiollah Mirkhani (Applied Catalysis A:General; 2006; 303:221-229) with Majid Moghadam (Catalysis Communications; 2005,6:688-693) wait the people to report the loaded metal porphyrin in the solution of acetonitrile/water 1: 1 (volume ratio), use NaIO 4As oxygenant, but 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 this method is must use respectively to cost an arm and a leg and NaIO that environmental pollution is serious 4As chemical oxidizing agent, acetonitrile solution as solvent.
Shi-Jun Li (Tetrahedron Letters, 2005,46:8013-8015) wait the people to report chloramine-T/O 2/ metalloporphyrin system is in the acetonitrile equal solvent, and catalyzed oxidation ethylbenzene series compound obtains corresponding arone, catalyzer under the room temperature: raw material: chloramine-T=1: 20: 10 (mol ratio), the yield of methyl phenyl ketone can reach 67%.The main drawback of this method be must use respectively cost an arm and a leg and chloramine-T that environmental pollution is serious as chemical oxidizing agent, acetonitrile as solvent.
Rong-Min Wang (Journal of Applied Polymer Science; 1998,67:2027-2034) wait the people to report and gather porphyrin under 60～90 ℃ of conditions, oxygen catalytic oxidation ethylbenzene prepares 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 this method is that catalyst levels is big, and catalyst separating, recovery and purification power consumption are high.And because this reaction is an inhomogeneous reaction, although the highly selective of catalysis of metalloporphyrin agent has obtained fine embodiment, its high catalytic activity does not display fully, and 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 ethylbenzene prepares methyl phenyl ketone, and it is 60～85 ℃ that temperature is selected in reaction, and reaction selects benzene, chlorobenzene, butanone, pimelinketone as solvent or solvent-free.As use butanone or pimelinketone as solvent, then there is not induction time in this reaction, and uses benzene or chlorobenzene as solvent, then should reaction have 3 hours induction time.The main drawback of this method is that reaction induction time is long, and used solvent environment is unfriendly, and particularly benzene or chlorobenzene have limited use in industry.
In sum, the following main drawback of bionic catalysis method for oxidation existence for preparing other ethylbenzene compounds at present:
(1) use chemical oxidizing agent, not only in the process of producing, produce poisonous in a large number, deleterious waste water, waste residue, cause serious environmental to pollute, and raw material and production cost become very high accordingly;
(2) use solvent, even the benzene or the chlorobenzene that use industrial limit to use.Not only pollute, and cause increasing of energy consumption, increased process cost and production cost greatly because of the recovery of solvent because of its poisonous and harmful possibly cause serious environmental;
(3) working load or polymer/metallic porphyrin cause because of the preparation process is complicated that energy consumption is high, three waste discharge is many, complex process, cost increase.In addition because of catalyst levels big (480ppm), with after also must Separation and Recovery, and the cost of Separation and Recovery catalyzer is high, energy consumption is big, three waste discharge is many.Also have, because of the reaction of working load or polymer/metallic porphyrin is an inhomogeneous reaction, the high catalytic activity of metalloporphyrin can not get good embodiment.
(4) induction time oversize (reaching 3h) of reaction, thereby make the time lengthening of entire reaction causes 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 eco-friendly metalloporphyrin bionically catalyzing and oxidizing prepares the method for parabromoacetophenone to bromine ethylbenzene.
A kind of bionically catalyzing and oxidizing provided by the present invention prepares the method for parabromoacetophenone to bromine ethylbenzene; The steps include: being raw material bromine ethylbenzene; Under normal pressure, condition of no solvent; In the monokaryon metalloporphyrin of selecting have formula (I), formula (II) structure for use and the μ-oxygen-dinuclear metalloporphyrin with formula (III) structure any one or two kinds of combinations are as catalyzer, wherein, and central metallic ions M 1Be iron, manganese, cobalt, copper, zinc, nickel or chromium, central metallic ions M 2Be 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, not simultaneously, M 3Be iron, M 4Be manganese, M 3Be iron, M 4Be cobalt or M 3Be manganese, M 4Be cobalt, substituent R 11, R 12, R 13, R 21, R 22, R 23, R 31, R 32Or R 33Be hydrogen, halogen, nitro, hydroxyl, C 1-3Alkyl, C 1-3Alkoxyl group or carboxyl, dentate X are halogen, and said catalyzer also comprises middle substituting group of formula (I) and formula (I), formula (II) and formula (II), formula (III) and formula (III) and identical, the central metallic ions M in substituent position 1, M 2, M 3Or M 4Different combinations; Also comprise 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,
Figure GSA00000010532100041
Catalyst levels is 1～30ppm, with 10～60mL/min flow velocity aerating oxygen, earlier 140～170 ℃ of following high temperature initiation reactions; Then at 80～120 ℃ of following low-temp reaction 6～16h; Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone.
Preferred M 1, M 2, M 3Or M 4Be iron, manganese or cobalt, M 3And M 4Identical; Especially preferably when any two kinds of catalyst combination, wherein a kind of M 1, M 2, M 3Or M 4Be iron or manganese, another kind of M 1, M 2, M 3Or M 4Be 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 150～160 ℃; Preferred temperature of reaction is 100～110 ℃; The preferred reaction times is 8～12h.
The inventive method is compared with people's reported method such as Lee braces, has following beneficial effect:
(1) present method substitutes the lower perfluor substituted metal porphyrin of the catalytic activity of people's reports such as Lee brace as catalyzer with the higher metal porphyrins of catalytic activity; The preferred reaction time is 8～12h; 24h far below people such as Lee brace report; And the chromatogram yield is up to 89.3%, and separation yield also reaches 86.4%, far above 22.5% chromatogram yield in the documents.Significantly reducing of reaction times, the very big raising of yield can be saved the energy and resource significantly, reduces process cost, improves productivity effect;
(2) present method is not used any promotor, has no the problem of promotor;
(3) present method is only carried out under condition of normal pressure, with respect to the reaction under high pressure in the documents, facility investment, energy consumption and running cost is all significantly reduced, and the security of whole process of production 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 uses cleaning, cheap oxygen to replace serious, the expensive chemical oxidizing agent of environmental pollution as oxygenant.Not only significantly 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 possibly cause serious environmental to pollute, and because there is not the recovery problem of solvent, and the energy consumption of generation and cost are reduced greatly;
(3) present method with the metal porphyrins of minute quantity directly as catalyzer; And do not use very complicated load of preparation process or polymer/metallic porphyrin as catalyzer; Simplify the Preparation of catalysts process, can significantly reduce the environmental pollution that required energy consumption of Preparation of Catalyst and preparation process are produced.And, since the catalysis of metalloporphyrin agent to get consumption few, do not need after the reaction to separate, reclaim, avoided the generation of separation, recovery, purification process energy consumption.Simultaneously, but because 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 the contact probability and the reaction efficiency of metalloporphyrin and substrate, makes the high catalytic activity of metalloporphyrin obtain good embodiment;
(4) present method adopts high temperature to cause fast, and the mode of low-temp reaction makes reaction induction time become extremely short, has shortened the time of reaction greatly, has improved reaction efficiency, has reduced process cost and energy consumption.Low-temp reaction then helps to improve product selectivity, has reduced production of by-products, and the separation of product is become be more prone to, reaction and all reductions greatly of isolating energy consumption, and the security of production is improved.
Embodiment
Embodiment 1
In the 100mL there-necked flask, add 18.531g to bromine ethylbenzene, 1ppm (0.07mg) tetraphenyl iron porphyrin (is R in the formula (I) 11Be H, R 12Be H, R 13Be H, M 1Be Fe), 10ppm (0.86mg) four-(rubigan) cobalt porphyrin (is R in the formula (I) 11Be H, R 12Be H, R 13Be Cl, M 1Be Co), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 8h down at 100 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 79.8% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 72.4%, and purity is 99.5%.
Embodiment 2
In the 100mL there-necked flask, add 18.491g to bromine ethylbenzene, 5ppm (0.38mg) chlorination four-phenyl manganoporphyrin (is R in the formula (II) 21Be H, R 22Be H, R 23Be H, M 2Be Mn, X is Cl), 5ppm (0.44mg) chlorination four-(o-methoxyphenyl) cobalt porphyrins (are R in the formula (II) 21Be OCH 3, R 22Be H, R 23Be H, M 2Be Co, X is Cl), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 10h down at 100 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 83.8% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 76.5%, and purity is 99.3%.
Embodiment 3
In the 100mL there-necked flask, add 18.502g to bromine ethylbenzene, 1ppm (0.15mg) μ-oxygen-double-core four-phenyl iron porphyrin (is R in the formula (III) 31Be H, R 32Be H, R 33Be H, M 3, M 4Be Fe), 5ppm (0.88mg) μ-oxygen-double-core four-(rubigan) cobalt porphyrin (is R in the formula (III) 31Be H, R 32Be H, R 33Be Cl, M 3, M 4Be Co), aerating oxygen under the 50mL/min flow velocity 150 ℃ of following initiation reactions, reacts 10h down at 90 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 71.2% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 64.3%, and purity is 99.5%.
Embodiment 4
In the 100mL there-necked flask, add 18.487g to bromine ethylbenzene, 5ppm (0.45mg) chlorination four-(p-methoxyphenyl) iron porphyrins (are R in the formula (II) 21Be H, R 22Be H, R 23Be OCH 3, M 2Be Fe, X is Cl), 10ppm (1.78mg) μ-oxygen-double-core four-(rubigan) cobalt porphyrin (is R in the formula (III) 31Be H, R 32Be H, R 33Be Cl, M 3, M 4Be Co), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 95.6% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 86.4%, and purity is 99.1%.
Embodiment 5
In the 100mL there-necked flask, add 18.531g to bromine ethylbenzene, 1ppm (0.08mg) four-(o-methoxyphenyl) copper porphyrin (is R in the formula (I) 11Be OCH 3, R 12Be H, R 13Be H, M 1Be Cu), 10ppm (0.88mg) chlorination four-(o-methoxyphenyl) cobalt porphyrins (are R in the formula (II) 21Be OCH 3, R 22Be H, R 23Be H, M 2Be Co, X is Cl), aerating oxygen under the 50mL/min flow velocity 150 ℃ of following initiation reactions, reacts 16h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 96.7% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 81.2%, and purity is 99.2%.
Embodiment 6
In the 100mL there-necked flask, add 18.513g to bromine ethylbenzene, 1ppm (0.07mg) chlorination four-phenyl manganoporphyrin (is R in the formula (II) 21Be H, R 22Be H, R 23Be H, M 2Be Mn, X is Cl), 10ppm (0.92mg) four-(ortho-nitrophenyl base) cobalt porphyrin (is R in the formula (I) 11Be NO 2, R 12Be H, R 13Be H, M 1Be Co), aerating oxygen under the 30mL/min flow velocity 150 ℃ of following initiation reactions, reacts 10h down at 100 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 90.3% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 81.2%, and purity is 99.5%.
Embodiment 7
In the 100mL there-necked flask, add 18.512g to bromine ethylbenzene, 5ppm (0.75mg) μ-oxygen-double-core four-phenyl iron porphyrin (is R in the formula (III) 31Be H, R 32Be H, R 33Be H, M 3, M 4Be Fe), 10ppm (0.89mg) four-(rubigan) cobalt porphyrin (is R in the formula (I) 11Be H, R 12Be H, R 13Be Cl, M 1Be Co), aerating oxygen under the 20mL/min flow velocity 150 ℃ of following initiation reactions, reacts 8h down at 100 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 73.1% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 66.2%, and purity is 99.8%.
Embodiment 8
In the 100mL there-necked flask, add 18.515g to bromine ethylbenzene, 5ppm (0.47mg) four-(p-nitrophenyl) zinc protoporphyrin (is R in the formula (I) 11Be H, R 12Be H, R 13Be NO 2, M 1Be Zn), 10ppm (0.77mg) chlorination four-phenyl manganoporphyrin (is R in the formula (II) 21Be H, R 22Be H, R 23Be H, M 2Be Mn, X is Cl), aerating oxygen under the 50mL/min flow velocity 150 ℃ of following initiation reactions, reacts 10h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 83.5% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 73.1%, and purity is 99.4%.
Embodiment 9
In the 100mL there-necked flask, add 18.504g to bromine ethylbenzene, 20ppm (1.47mg) four-phenyl iron porphyrin (is R in the formula (I) 11Be H, R 12Be H, R 13Be H, M 1Be Fe), aerating oxygen under the 30mL/min flow velocity 150 ℃ of following initiation reactions, reacts 6h down at 80 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 39.2% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 31.7%, and purity is 99.5%.
Embodiment 10
In the 100mL there-necked flask, add 18.513g to bromine ethylbenzene, 10ppm (0.86mg) four-(rubigan) cobalt porphyrin (is R in the formula (I) 11Be H, R 12Be H, R 13Be Cl, M 1Be Co), aerating oxygen under the 20mL/min flow velocity 160 ℃ of following initiation reactions, reacts 12h down at 90 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 45.3% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 36.8%, and purity is 99.2%.
Embodiment 11
In the 100mL there-necked flask, add 18.514g to bromine ethylbenzene, 15ppm (1.30mg) four-(m-nitro base) manganoporphyrin (is R in the formula (I) 11Be H, R 12Be NO 2, R 13Be H, M 1Be Mn), aerating oxygen under the 30mL/min flow velocity 160 ℃ of following initiation reactions, reacts 10h down at 100 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 59.4% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 49.7%, and purity is 99.1%.
Embodiment 12
In the 100mL there-necked flask, add 18.502g to bromine ethylbenzene, 30ppm (2.43mg) four-(p-hydroxybenzene) nickel-porphyrin (is R in the formula (I) 11Be H, R 12Be H, R 13Be OH, M 1Be Ni), aerating oxygen under the 20mL/min flow velocity 170 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 60.5% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 51.3%, and purity is 99.8%.
Embodiment 13
In the 100mL there-necked flask, add 18.523g to bromine ethylbenzene, 20ppm (1.83mg) four-(p-nitrophenyl) zinc protoporphyrin (is R in the formula (I) 11Be H, R 12Be H, R 13Be NO 2, M 1Be Zn), aerating oxygen under the 30mL/min flow velocity 140 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 43.6% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 36.4%, and purity is 99.2%.
Embodiment 14
In the 100mL there-necked flask, add 18.524g to bromine ethylbenzene, 20ppm (1.73mg) four-(Chloro-O-Phenyl) chromium porphyrin (is R in the formula (I) 11Be Cl, R 12Be H, R 13Be H, M 1Be Cr), aerating oxygen under the 20mL/min flow velocity 170 ℃ of following initiation reactions, reacts 10h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 37.8% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 28.4%, and purity is 99.4%.
Embodiment 15
In the 100mL there-necked flask, add 18.511g to bromine ethylbenzene, 20ppm (1.74mg) four-(o-methoxyphenyl) copper porphyrin (is R in the formula (I) 11Be OCH 3, R 12Be H, R 13Be H, M 1Be Cu), aerating oxygen under the 30mL/min flow velocity 150 ℃ of following initiation reactions, reacts 8h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 49.9% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 41.5%, and purity is 99.3%.
Embodiment 16
In the 100mL there-necked flask, add 18.526g to bromine ethylbenzene, 15ppm (1.21mg) four-(carboxyl phenyl) manganoporphyrin (is R in the formula (I) 11Be H, R 12Be COOH, R 13Be H, M 1Be Mn), aerating oxygen under the 30mL/min flow velocity 160 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 72.4% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 62.3%, and purity is 99.8%.
Embodiment 17
In the 100mL there-necked flask, add 18.521g to bromine ethylbenzene, 10ppm (0.92mg) four-(ortho-nitrophenyl base) cobalt porphyrin (is R in the formula (I) 11Be NO 2, R 12Be H, R 13Be H, M 1Be Co), aerating oxygen under the 30mL/min flow velocity 170 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 80.6% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 72.3%, and purity is 99.4%.
Embodiment 18
In the 100mL there-necked flask, add 18.531g to bromine ethylbenzene, 10ppm (0.78mg) chlorination four-phenyl manganoporphyrin (is R in the formula (II) 21Be H, R 22Be H, R 23Be H, M 2Be Mn, X is Cl), aerating oxygen under the 40mL/min flow velocity 160 ℃ of following initiation reactions, reacts 12h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 81.3% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 69.2%, and purity is 99.3%.
Embodiment 19
In the 100mL there-necked flask, add 18.514g to bromine ethylbenzene, 5ppm (0.45mg) chlorination four-(rubigan) cobalt porphyrins (are R in the formula (II) 21Be H, R 22Be H, R 23Be Cl, M 2Be Co, X is Cl), aerating oxygen under the 20mL/min flow velocity 170 ℃ of following initiation reactions, reacts 16h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 90.1% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 82.4%, and purity is 99.3%.
Embodiment 20
In the 100mL there-necked flask, add 18.522g to bromine ethylbenzene, 15ppm (1.32mg) chlorination four-(p-methoxyphenyl) iron porphyrins (are R in the formula (II) 21Be H, R 22Be H, R 23Be OCH 3, M 2Be Fe, X is Cl), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 75.8% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 67.2%, and purity is 99.6%.
Embodiment 21
In the 100mL there-necked flask, add 18.502g to bromine ethylbenzene, 10ppm (0.75mg) bromination-tetraphenyl molybdenum porphyrin (is R in the formula (II) 21Be H, R 22Be H, R 23Be H, M 2Be Mo, X is Br), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 41.5% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 34.3%, and purity is 99.3%.
Embodiment 22
In the 100mL there-necked flask, add 18.506g to bromine ethylbenzene, 20ppm (1.93mg) chlorination four-(p-nitrophenyl) chromium porphyrins (are R in the formula (II) 21Be H, R 22Be H, R 23Be NO 2, M 2Be Cr, X is Cl), aerating oxygen under the 40mL/min flow velocity 170 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 48.5% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 40.1%, and purity is 99.6%.
Embodiment 23
In the 100mL there-necked flask, add 18.498g to bromine ethylbenzene, 20ppm (1.84mg) chlorination four-(Chloro-O-Phenyl) manganoporphyrins (are R in the formula (II) 21Be Cl, R 22Be H, R 23Be H, M 2Be Mn, X is Cl), aerating oxygen under the 50mL/min flow velocity 160 ℃ of following initiation reactions, reacts 14h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 84.3% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 75.2%, and purity is 99.3%.
Embodiment 24
In the 100mL there-necked flask, add 18.524g to bromine ethylbenzene, 5ppm (0.45mg) chlorination four-(o-methoxyphenyl) cobalt porphyrins (are R in the formula (II) 21Be OCH 3, R 22Be H, R 23Be H, M 2Be Co, X is Cl), aerating oxygen under the 50mL/min flow velocity 170 ℃ of following initiation reactions, reacts 14h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 90.3% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 81.3%, and purity is 99.1%.
Embodiment 25
In the 100mL there-necked flask, add 18.496g to bromine ethylbenzene, 15ppm (1.36mg) chlorination four-(ortho-nitrophenyl base) nickel-porphyrin (is R in the formula (II) 21Be NO 2, R 22Be H, R 23Be H, M 2Be Ni, X is Cl), aerating oxygen under the 50mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 48.6% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 40.3%, and purity is 99.1%.
Embodiment 26
In the 100mL there-necked flask, add 18.491g to bromine ethylbenzene, 10ppm (0.81mg) fluoridizes-and tetraphenyl ruthenium porphyrin (is R in the formula (II) 21Be H, R 22Be H, R 23Be H, M 2Be Ru, X is F), aerating oxygen under the 50mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 56.2% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 47.3%, and purity is 99.6%.
Embodiment 27
In the 100mL there-necked flask, add 18.511g to bromine ethylbenzene, 10ppm (1.48mg) μ-oxygen-double-core four-phenyl iron porphyrin (is R in the formula (III) 31Be H, R 32Be H, R 33Be H, M 3, M 4Be Fe), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 10h down at 100 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 48.4% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 36.1%, and purity is 99.3%.
Embodiment 28
In the 100mL there-necked flask, add 18.524g to bromine ethylbenzene, 1ppm (0.19mg) μ-oxygen-double-core four-(p-nitrophenyl) manganoporphyrin (is R in the formula (III) 31Be H, R 32Be H, R 33Be NO 2, M 3, M 4Be Mn), aerating oxygen under the 40mL/min flow velocity 160 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 52.3% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 44.2%, and purity is 99.7%.
Embodiment 29
In the 100mL there-necked flask, add 18.503g to bromine ethylbenzene, 5ppm (0.89mg) μ-oxygen-double-core four-(rubigan) cobalt porphyrin (is R in the formula (III) 31Be H, R 32Be H, R 33Be Cl, M 3, M 4Be Co), aerating oxygen under the 40mL/min flow velocity 170 ℃ of following initiation reactions, reacts 12h down at 100 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 85.4% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 77.8%, and purity is 99.5%.
Embodiment 30
In the 100mL there-necked flask, add 18.511g to bromine ethylbenzene, 5ppm (0.89mg) μ-oxygen-double-core four-(p-methoxyphenyl) iron-cobalt porphyrin (is R in the formula (III) 31Be H, R 32Be H, R 33Be OCH 3, M 3Be Fe, M 4Be Co), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 83.6% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 75.1%, and purity is 99.3%.
Embodiment 31
In the 100mL there-necked flask, add 18.514g to bromine ethylbenzene, 10ppm (1.63mg) μ-oxygen-double-core four-(p-hydroxybenzene) manganese-cobalt porphyrin (is R in the formula (III) 31Be H, R 32Be H, R 33Be OH, M 3Be Mn, M 4Be Co), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 100 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 92.1% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 83.2%, and purity is 99.4%.
Embodiment 32
In the 100mL there-necked flask, add 18.492g to bromine ethylbenzene, 10ppm (1.83mg) μ-oxygen-double-core four-(ortho-nitrophenyl base) cobalt porphyrin (is R in the formula (III) 31Be NO 2, R 32Be H, R 33Be H, M 3, M 4Be Co), aerating oxygen under the 40mL/min flow velocity 170 ℃ of following initiation reactions, reacts 10h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 90.3% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 81.1%, and purity is 99.2%.
Embodiment 33
In the 100mL there-necked flask, add 18.519g to bromine ethylbenzene, 10ppm (1.75mg) μ-oxygen-double-core four-(Chloro-O-Phenyl) manganoporphyrin (is R in the formula (III) 31Be Cl, R 32Be H, R 33Be H, M 3, M 4Be Mn), aerating oxygen under the 40mL/min flow velocity 160 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 88.5% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 77.9%, and purity is 99.8%.
Embodiment 34
In the 100mL there-necked flask, add 18.523g to bromine ethylbenzene, 10ppm (1.77mg) μ-oxygen-double-core four-(o-methoxyphenyl) manganese-cobalt porphyrin (is R in the formula (III) 31Be OCH 3, R 32Be H, R 33Be H, M 3Be Mn, M 4Be Co), aerating oxygen under the 30mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 90.2% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 81.3%, and purity is 99.3%.
Embodiment 35
In the 100mL there-necked flask, add 18.507g to bromine ethylbenzene, 10ppm (1.87mg) μ-oxygen-double-core four-(m-nitro base) iron-cobalt porphyrin (is R in the formula (III) 31Be H, R 32Be NO 2, R 33Be H, M 3Be Fe, M 4Be Co), aerating oxygen under the 30mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 100 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 91.1% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 82.2%, and purity is 99.1%.
Embodiment 36
In the 100mL there-necked flask, add 18.496g to bromine ethylbenzene, 1ppm (0.18mg) μ-oxygen-double-core four-(Chloro-O-Phenyl) iron porphyrin (is R in the formula (III) 31Be Cl, R 32Be H, R 33Be H, M 3, M 4Be Fe), 10ppm (1.78mg) μ-oxygen-double-core four-(Chloro-O-Phenyl) cobalt porphyrin (is R in the formula (III) 31Be Cl, R 32Be H, R 33Be H, M 3, M 4Be Co), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 93.2% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 83.1%, and purity is 99.2%.
Embodiment 37
In the 100mL there-necked flask, add 18.512g to bromine ethylbenzene, 5ppm (0.90mg) four-(p-methylphenyl) zinc protoporphyrin (is R in the formula (I) 11Be H, R 12Be H, R 13Be CH 3, M 1Be Zn), 10ppm (0.92mg) four-(p-nitrophenyl) zinc protoporphyrin (is R in the formula (I) 11Be H, R 12Be H, R 13Be NO 2, M 1Be Zn), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 65.6% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 51.4%, and purity is 99.2%.
Embodiment 38
In the 100mL there-necked flask, add 18.502g to bromine ethylbenzene, 5ppm (0.91mg) four-(2, the 4-3,5-dimethylphenyl) zinc protoporphyrin (is R in the formula (I) 11Be CH 3, R 12Be H, R 13Be CH 3, M 1Be Zn), 10ppm (0.92mg) four-(2, the 4-dinitrophenyl) zinc protoporphyrin (is R in the formula (I) 11Be NO 2, R 12Be H, R 13Be NO 2, M 1Be Zn), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 76.3% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 67.4%, and purity is 99.2%.
Embodiment 39
In the 100mL there-necked flask, add 18.518g to bromine ethylbenzene, 5ppm (0.44mg) bromination four-(ortho-nitrophenyl base) iron porphyrin (is R in the formula (II) 21Be NO 2, R 22Be H, R 23Be H, M 2Be Fe, X is Br), 10ppm (0.88mg) chlorination four-(p-methoxyphenyl) iron porphyrins (are R in the formula (II) 21Be H, R 22Be H, R 23Be OCH 3, M 2Be Fe, X is Cl), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 85.6% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 79.2%, and purity is 99.1%.
Embodiment 40
In the 100mL there-necked flask, add 18.507g to bromine ethylbenzene, 5ppm (0.82mg) μ-oxygen-double-core four-(p-hydroxybenzene) manganoporphyrin (is R in the formula (III) 31Be H, R 32Be H, R 33Be OH, M 3, M 4Be Mn), 10ppm (1.75mg) μ-oxygen-double-core four-(Chloro-O-Phenyl) manganoporphyrin (is R in the formula (III) 31Be Cl, R 32Be H, R 33Be H, M 3, M 4Be Mn), aerating oxygen under the 40mL/min flow velocity 150 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone, is 92.1% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 83.2%, and purity is 99.3%.

Claims (10)

1. a bionically catalyzing and oxidizing prepares the method for parabromoacetophenone to bromine ethylbenzene; The steps include: being raw material bromine ethylbenzene; Under normal pressure, condition of no solvent; In the monokaryon metalloporphyrin of selecting have formula (I), formula (II) structure for use and the μ-oxygen-dinuclear metalloporphyrin with formula (III) structure any one or two kinds of combinations are as catalyzer, or select middle substituting group of formula (I) and formula (I), formula (II) and formula (II), formula (III) and formula (III) and identical, the central metallic ions M in substituent position for use 1, M 2, M 3Or M 4Different combinations is as catalyzer, or selects for use substituting group in formula (I) and formula (I), formula (II) and formula (II), formula (III) and the formula (III) and substituent position is different, central metallic ions is identical or different combination as catalyzer, wherein, and central metallic ions M 1Be iron, manganese, cobalt, copper, zinc, nickel or chromium, central metallic ions M 2Be 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, not simultaneously, M 3Be iron, M 4Be manganese, M 3Be iron, M 4Be cobalt or M 3Be manganese, M 4Be cobalt, substituent R 11, R 12, R 13, R 21, R 22, R 23, R 31, R 32Or R 33Be hydrogen, halogen, nitro, hydroxyl, C 1-3Alkyl, C 1-3Alkoxyl group or carboxyl, dentate X are halogen,
Figure DEST_PATH_FSB00000822599500011
Figure FSA00000010532000021
Catalyst levels is 1～30ppm, with 10～60mL/min flow velocity aerating oxygen, earlier 140～170 ℃ of following high temperature initiation reactions; Then at 80～120 ℃ of following low-temp reaction 6～16h; Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains parabromoacetophenone.
2. according to the method for claim 1, it is characterized in that M 1, M 2, M 3Or M 4Be 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 the M in wherein a kind of catalyzer 1, M 2, M 3Or M 4Be iron or manganese, the M in the another kind of catalyzer 1, M 2, M 3Or M 4Be 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 a 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 150～160 ℃.
9. according to the method for claim 1, it is characterized in that temperature of reaction is 100～110 ℃.
10. according to the method for claim 1, it is characterized in that the reaction times is 8～12h.
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