CN101747168B - Method for preparing o-bromoacetophenone by biomimetic catalytic oxidation of o-bromoethylbenzene with oxygen - Google Patents
Method for preparing o-bromoacetophenone by biomimetic catalytic oxidation of o-bromoethylbenzene with oxygen Download PDFInfo
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Abstract
The invention relates to a method for preparing o-bromoacetophenone by biomimetic catalytic oxidation of o-bromoethylbenzene with oxygen, comprising the following steps: taking o-bromoethylbenzene as the raw material, selecting any one of 1-30ppm of mononuclear metalloporphyrin and mu-oxo-dinuclear metalloporphyrin or the composition of the two substances as the catalyst under normal pressure and in the absence of solvents, introducing oxygen at the flow rate of 10-60mL/min, initiating reaction at 140-170 DEG C and then carrying out reaction at 80-120 DEG C for 6-16h, thus obtaining the o-bromoacetophenone. In the method, the way of high temperature quick initiation and low temperature reaction is adopted, thus minimizing the reaction initiation time, greatly shortening the reaction time, improving the reaction efficiency, reducing the energy consumption, lowering the operation cost and improving the reaction safety.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic ketone, specifically, relate to the method for the adjacent bromoacetophenone of the adjacent bromine Preparation of ethylbenzene of a kind of bionically catalyzing and oxidizing.
Background technology
Adjacent bromoacetophenone is important organic synthesis intermediate, is widely used in synthetic medicine, agricultural chemicals, dyestuff, essence and flavoring agent, perfume etc.The preparation method of present adjacent bromoacetophenone mainly contains friedel-crafts acylation method, 1-(2-bromophenyl) oxidation of ethanol method and adjacent bromine ethylbenzene oxidation method etc.; wherein adjacent bromine ethylbenzene oxidation method 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; method by the adjacent bromoacetophenone of the adjacent bromine Preparation of ethylbenzene of oxygen to directly oxidize has significant superiority with respect to other method.
US 20030144554 (open day: on January 15th, 2002) disclose a kind of method that catalytic molecular oxygen ethyl oxide aromatic hydrocarbons prepares aromatic ketone.Its preferred Co (PPA)
3, Cu (PPA)
2, Ni (HPPA) (PPA)
2, Mn (HPPA)
2Cl
2And (PPA) Cl of Ru (HPPA)
2As catalyzer, the preferred catalytic agent concentration is 10
-5～10
-2Mol/L, preferable reaction temperature is 100～150 ℃, and preferred reaction pressure is normal pressure～3MPa, most preferably is 1.5MPa, and the preferred reaction time is 2～12h.Unique embodiment is as follows:
The preparation method of adjacent bromoacetophenone wherein: in the autoclave of 100mL, add the adjacent bromine ethylbenzene of 10mL, 14.5mg Co (PBHA)
2(400ppm), be under 0.8MPa at oxygen pressure, at 140 ℃ of reaction 8h, by gas chromatographic analysis, the transformation efficiency of adjacent bromine ethylbenzene is 35%, the selectivity of adjacent bromoacetophenone and chromatogram yield are respectively 70.4% and 24.64%.
The main drawback of the method is:
(1) the method catalyst levels large (400ppm), catalyzer needs to recycle, and the recovery of catalyzer need to consume a large amount of energy;
(2) activity and selectivity due to catalyzer that the method is used is lower, even the consumption of catalyzer more (400ppm), reaction pressure (0.8MPa) and temperature of reaction (140 ℃) are higher, but after reaction 8h, the transformation efficiency of adjacent bromine ethylbenzene is only 35%, and the selectivity of adjacent bromoacetophenone and chromatogram yield are only respectively 70.4% and 24.64%;
(3) the preferred temperature of reaction of the method (100～150 ℃) is higher, particularly adjacent bromine ethylbenzene need to react under 140 ℃, and not only energy consumption is very high under too high temperature of reaction, and the danger of using a large amount of oxygen can make the security of production greatly reduce, operate at high like this temperature increases;
(4) higher (normal pressure～3MPa) of the preferred reaction pressure of the method, particularly adjacent bromine ethylbenzene need to react under 0.8MPa, use the reaction conditions of high pressure, cause facility investment and running cost to be multiplied, energy consumption is high, particularly make to produce to have potential danger, security reduces greatly.
The bionic catalysis system has the incomparable advantage of traditional metal salt catalyst system, catalyst levels is few, but natural degradation, do not produce secondary pollution, reaction conditions is gentle, 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 adjacent bromine ethylbenzene oxidation of bionic catalysis system catalysis to prepare adjacent bromoacetophenone 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 the loaded metal porphyrin 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
4The 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, 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 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 produce poisonous, harmful in a large number waste water, waste residue in the process of producing, 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), use afterwards also necessary Separation and Recovery, and the cost of Separation and Recovery catalyzer is high, energy consumption is large, 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 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 the method for the adjacent bromoacetophenone of the adjacent bromine Preparation of ethylbenzene of eco-friendly metalloporphyrin bionically catalyzing and oxidizing.
The method of the adjacent bromoacetophenone of the adjacent bromine Preparation of ethylbenzene of a kind of bionically catalyzing and oxidizing provided by the present invention, the steps include: take adjacent bromine ethylbenzene as raw material, under normal pressure, condition of no solvent, select the monokaryon metalloporphyrin of have formula (I), formula (II) structure and have any one or two kinds of combinations in the μ-oxygen of formula (III) structure-dinuclear metalloporphyrin as catalyzer, wherein, 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 is halogen, and described catalyzer also comprises the middle substituting group of formula (I) and 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, passes into oxygen with 10～60mL/min flow velocity, and first 140～170 ℃ of lower high temperature initiation reactions, then at 80～120 ℃ of lower low-temp reaction 6～16h, reacted mixture obtains adjacent bromoacetophenone through underpressure distillation.
Preferred M
1, M
2, M
3Or M
4Be 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
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 the disclosed method of US 20030144554, has following beneficial effect:
(1) (1～30ppm) eco-friendly metal porphyrins substitutes the disclosed a large amount of metal complexes catalyst system of US 20030144554 (amount of Co in the preparation process of adjacent bromoacetophenone (PBHA) is as 400ppm) directly as catalyzer to present method take minute quantity, 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.；
(2) present method uses metalloporphyrin as bionic catalyst, has the high reactivity of approximate enzyme, the characteristics of highly selective.Adjacent bromine conversion of ethylbenzene is up to 95.2%, far above the transformation efficiency of US 20030144554 disclosed 35%; Adjacent bromoacetophenone selectivity and chromatogram yield are respectively 91.5% and 87.1%, even separation yield is also up to 83.4%, far above the selectivity of US 20030144554 disclosed 70.4% and 24.64% chromatogram yield;
(3) the preferred temperature of reaction of present method is only 100～110 ℃, the temperature (temperature of reaction in the preparation process of adjacent bromoacetophenone is 140 ℃) that adopts lower than US 20030144554.The reduction of temperature of reaction has not only greatly reduced energy consumption and the process cost in the reaction, and makes production process become safer;
(4) present method is only carried out under condition of normal pressure, with respect to the reaction under high pressure that US 20030144554 adopts, facility investment, energy consumption and running cost is all significantly reduced, and the security of whole production process 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 that environmental pollution is serious, expensive NaIO
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, facility investment, energy consumption and running cost is all significantly reduced, and the security of whole production process is greatly improved;
(4) present method with the metal porphyrins of minute quantity directly as catalyzer, and do not use the very complicated load of preparation process 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 makes 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 helps 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 production is improved.
Embodiment
Embodiment 1
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.562g, 1ppm (0.07mg) tetraphenyl iron porphyrin (is R in formula (I)
11Be H, R
12Be H, R
13Be H, M
1Be Fe), 10ppm (0.86mg) four-(rubigan) cobalt porphyrin (is R in formula (I)
11Be H, R
12Be H, R
13Be Cl, M
1Be Co), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 8h under 100 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 80.2%, and adjacent bromoacetophenone yield is 73.4%, and purity is 99.3%.
Embodiment 2
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.495g, 5ppm (0.38mg) chlorination four-phenyl manganoporphyrin (is R in 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 formula (II)
21Be OCH
3, R
22Be H, R
23Be H, M
2Be Co, X is Cl), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 10h under 100 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 83.4%, and adjacent bromoacetophenone yield is 76.8%, and purity is 99.1%.
Embodiment 3
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.512g, 1ppm (0.15mg) μ-oxygen-double-core four-phenyl iron porphyrin (is R in 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 formula (III)
31Be H, R
32Be H, R
33Be Cl, M
3, M
4Be Co), pass into oxygen under the 50mL/min flow velocity, 150 ℃ of lower initiation reactions, react 10h under 90 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 70.3%, and adjacent bromoacetophenone yield is 64.3%, and purity is 99.5%.
Embodiment 4
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.489g, 5ppm (0.45mg) chlorination four-(p-methoxyphenyl) iron porphyrins (are R in formula (II)
21Be H, R
22Be H, R
23Be 0CH
3, M
2Be Fe, X is Cl), 10ppm (1.78mg) μ-oxygen-double-core four-(rubigan) cobalt porphyrin (is R in formula (III)
31Be H, R
32Be H, R
33Be Cl, M
3, M
4Be Co), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 95.2%, and adjacent bromoacetophenone yield is 83.4%, and purity is 99.4%.
Embodiment 5
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.521g, 1ppm (0.08mg) four-(o-methoxyphenyl) copper porphyrin (is R in 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 formula (II)
21Be OCH
3, R
22Be H, R
23Be H, M
2Be Co, X is Cl), pass into oxygen under the 50mL/min flow velocity, 150 ℃ of lower initiation reactions, react 16h under 120 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 95.6%, and adjacent bromoacetophenone yield is 80.6%, and purity is 99.3%.
Embodiment 6
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.514g, 1ppm (0.07mg) chlorination four-phenyl manganoporphyrin (is R in formula (II)
21Be H, R
22Be H, R
23Be H, M
2Be Mn, X is Cl), 10ppm (0.92mg) four-(O-Nitrophenylfluorone) cobalt porphyrin (is R in formula (I)
11Be NO
2, R
12Be H, R
13Be H, M
1Be Co), pass into oxygen under the 30mL/min flow velocity, 150 ℃ of lower initiation reactions, react 10h under 100 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 89.4%, and adjacent bromoacetophenone yield is 80.2%, and purity is 99.6%.
Embodiment 7
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.503g, 5ppm (0.75mg) μ-oxygen-double-core four-phenyl iron porphyrin (is R in 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 formula (I)
11Be H, R
12Be H, R
13Be Cl, M
1Be Co), pass into oxygen under the 20mL/min flow velocity, 150 ℃ of lower initiation reactions, react 8h under 100 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 72.3%, and adjacent bromoacetophenone yield is 65.4%, and purity is 99.3%.
Embodiment 8
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.505g, 5ppm (0.47mg) four-(p-nitrophenyl) zinc protoporphyrin (is R in formula (I)
11Be H, R
12Be H, R
13Be NO
2, M
1Be Zn), 10ppm (0.77mg) chlorination four-phenyl manganoporphyrin (is R in formula (II)
21Be H, R
22Be H, R
23Be H, M
2Be Mn, X is Cl), pass into oxygen under the 50mL/min flow velocity, 150 ℃ of lower initiation reactions, react 10h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 82.3%, and adjacent bromoacetophenone yield is 72.3%, and purity is 99.4%.
Embodiment 9
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.513g, 20ppm (1.47mg) four-phenyl iron porphyrin (is R in formula (I)
11Be H, R
12Be H, R
13Be H, M
1Be Fe), pass into oxygen under the 30mL/min flow velocity, 150 ℃ of lower initiation reactions, react 6h under 80 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 40.2%, and adjacent bromoacetophenone yield is 32.7%, and purity is 99.3%.
Embodiment 10
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.512g, 10ppm (0.86mg) four-(rubigan) cobalt porphyrin (is R in formula (I)
11Be H, R
12Be H, R
13Be Cl, M
1Be Co), pass into oxygen under the 20mL/min flow velocity, 160 ℃ of lower initiation reactions, react 12h under 90 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 46.3%, and adjacent bromoacetophenone yield is 37.8%, and purity is 99.5%.
Embodiment 11
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.554g, 15ppm (1.30mg) four-(m-nitro base) manganoporphyrin (is R in formula (I)
11Be H, R
12Be NO
2, R
13Be H, M
1Be Mn), pass into oxygen under the 30mL/min flow velocity, 160 ℃ of lower initiation reactions, react 10h under 100 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 57.8%, and adjacent bromoacetophenone yield is 48.3%, and purity is 99.1%.
Embodiment 12
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.512g, 30ppm (2.43mg) four-(p-hydroxybenzene) nickel-porphyrin (is R in formula (I)
11Be H, R
12Be H, R
13Be OH, M
1Be Ni), pass into oxygen under the 20mL/min flow velocity, 170 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 59.6%, and adjacent bromoacetophenone yield is 50.4%, and purity is 99.4%.
Embodiment 13
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.531g, 20ppm (1.83mg) four-(p-nitrophenyl) zinc protoporphyrin (is R in formula (I)
11Be H, R
12Be H, R
13Be NO
2, M
1Be Zn), pass into oxygen under the 30mL/min flow velocity, 140 ℃ of lower initiation reactions, react 10h under 120 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 42.3%, and adjacent bromoacetophenone yield is 35.2%, and purity is 99.1%.
Embodiment 14
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.513g, 20ppm (1.73mg) four-(Chloro-O-Phenyl) chromium porphyrin (is R in formula (I)
11Be Cl, R
12Be H, R
13Be H, M
1Be Cr), pass into oxygen under the 20mL/min flow velocity, 170 ℃ of lower initiation reactions, react 10h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 36.5%, and adjacent bromoacetophenone yield is 27.1%, and purity is 99.4%.
Embodiment 15
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.512g, 20ppm (1.74mg) four-(o-methoxyphenyl) copper porphyrin (is R in formula (I)
11Be OCH
3, R
12Be H, R
13Be H, M
1Be Cu), pass into oxygen under the 30mL/min flow velocity, 150 ℃ of lower initiation reactions, react 8h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 49.8%, and adjacent bromoacetophenone yield is 42.3%, and purity is 99.4%.
Embodiment 16
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.516g, 15ppm (1.21mg) four-(carboxyl phenyl) manganoporphyrin (is R in formula (I)
11Be H, R
12Be COOH, R
13Be H, M
1Be Mn), pass into oxygen under the 30mL/min flow velocity, 160 ℃ of lower initiation reactions, react 10h under 120 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 70.2%, and adjacent bromoacetophenone yield is 61.6%, and purity is 99.8%.
Embodiment 17
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.512g, 10ppm (0.92mg) four-(O-Nitrophenylfluorone) cobalt porphyrin (is R in formula (I)
11Be NO
2, R
12Be H, R
13Be H, M
1Be Co), pass into oxygen under the 30mL/min flow velocity, 170 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 79.8%, and adjacent bromoacetophenone yield is 70.3%, and purity is 99.4%.
Embodiment 18
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.541g, 10ppm (0.78mg) chlorination four-phenyl manganoporphyrin (is R in formula (II)
21Be H, R
22Be H, R
23Be H, M
2Be Mn, X is Cl), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, react 12h under 120 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 80.1%, and adjacent bromoacetophenone yield is 68.7%, and purity is 99.2%.
Embodiment 19
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.513g, 5ppm (0.45mg) chlorination four-(rubigan) cobalt porphyrins (are R in formula (II)
21Be H, R
22Be H, R
23Be Cl, M
2Be Co, X is Cl), pass into oxygen under the 20mL/min flow velocity, 170 ℃ of lower initiation reactions, react 16h under 120 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 89.3%, and adjacent bromoacetophenone yield is 80.2%, and purity is 99.1%.
Embodiment 20
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.524g, 15ppm (1.32mg) chlorination four-(p-methoxyphenyl) iron porphyrins (are R in formula (II)
21Be H, R
22Be H, R
23Be OCH
3, M
2Be Fe, X is Cl), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 120 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 75.8%, and adjacent bromoacetophenone yield is 66.9%, and purity is 99.6%.
Embodiment 21
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.532g, 10ppm (0.75mg) bromination-tetraphenyl molybdenum porphyrin (is R in formula (II)
21Be H, R
22Be H, R
23Be H, M
2Be Mo, X is Br), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 120 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 42.5%, and adjacent bromoacetophenone yield is 34.2%, and purity is 99.3%.
Embodiment 22
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.496g, 20ppm (1.93mg) chlorination four-(p-nitrophenyl) chromium porphyrins (are R in formula (II)
21Be H, R
22Be H, R
23Be NO
2, M
2Be Cr, X is Cl), pass into oxygen under the 40mL/min flow velocity, 170 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 47.8%, and adjacent bromoacetophenone yield is 39.6%, and purity is 99.6%.
Embodiment 23
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.488g, 20ppm (1.84mg) chlorination four-(Chloro-O-Phenyl) manganoporphyrins (are R in formula (II)
21Be Cl, R
22Be H, R
23Be H, M
2Be Mn, X is Cl), pass into oxygen under the 50mL/min flow velocity, 160 ℃ of lower initiation reactions, react 14h under 120 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 85.3%, and adjacent bromoacetophenone yield is 75.2%, and purity is 99.2%.
Embodiment 24
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.504g, 5ppm (0.45mg) chlorination four-(o-methoxyphenyl) cobalt porphyrins (are R in formula (II)
21Be OCH
3, R
22Be H, R
23Be H, M
2Be Co, X is Cl), pass into oxygen under the 50mL/min flow velocity, 170 ℃ of lower initiation reactions, react 14h under 120 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 89.0%, and adjacent bromoacetophenone yield is 80.4%, and purity is 99.1%.
Embodiment 25
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.498g, 15ppm (1.36mg) chlorination four-(O-Nitrophenylfluorone) nickel-porphyrins (are R in formula (II)
21Be NO
2, R
22Be H, R
23Be H, M
2Be Ni, X is Cl), pass into oxygen under the 50mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 49.8%, and adjacent bromoacetophenone yield is 40.3%, and purity is 99.1%.
Embodiment 26
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.486g, 10ppm (0.81mg) fluoridizes-and tetraphenyl ruthenium porphyrin (is R in formula (II)
21Be H, R
22Be H, R
23Be H, M
2Be Ru, X is F), pass into oxygen under the 50mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 55.8%, and adjacent bromoacetophenone yield is 47.6%, and purity is 99.6%.
Embodiment 27
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.515g, 10ppm (1.48mg) μ-oxygen-double-core four-phenyl iron porphyrin (is R in formula (III)
31Be H, R
32Be H, R
33Be H, M
3, M
4Be Fe), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 10h under 100 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 48.6%, and adjacent bromoacetophenone yield is 35.3%, and purity is 99.2%.
Embodiment 28
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.514g, 1ppm (0.19mg) μ-oxygen-double-core four-(p-nitrophenyl) manganoporphyrin (is R in formula (III)
31Be H, R
32Be H, R
33Be NO
2, M
3, M
4Be Mn), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 52.6%, and adjacent bromoacetophenone yield is 45.8%, and purity is 99.7%.
Embodiment 29
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.513g, 5ppm (0.89mg) μ-oxygen-double-core four-(rubigan) cobalt porphyrin (is R in formula (III)
31Be H, R
32Be H, R
33Be Cl, M
3, M
4Be Co), pass into oxygen under the 40mL/min flow velocity, 170 ℃ of lower initiation reactions, react 12h under 100 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 86.2%, and adjacent bromoacetophenone yield is 78.4%, and purity is 99.5%.
Embodiment 30
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.514g, 5ppm (0.89mg) μ-oxygen-double-core four-(p-methoxyphenyl) iron-cobalt porphyrin (is R in formula (III)
31Be H, R
32Be H, R
33Be OCH
3, M
3Be Fe, M
4Be Co), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 81.1%, and adjacent bromoacetophenone yield is 74.1%, and purity is 99.3%.
Embodiment 31
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.512g, 10ppm (1.63mg) μ-oxygen-double-core four-(p-hydroxybenzene) manganese-cobalt porphyrin (is R in formula (III)
31Be H, R
32Be H, R
33Be OH, M
3Be Mn, M
4Be Co), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 100 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 90.5%, and adjacent bromoacetophenone yield is 80.5%, and purity is 99.4%.
Embodiment 32
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.510g, 10ppm (1.83mg) μ-oxygen-double-core four-(O-Nitrophenylfluorone) cobalt porphyrin (is R in formula (III)
31Be NO
2, R
32Be H, R
33Be H, M
3, M
4Be Co), pass into oxygen under the 40mL/min flow velocity, 170 ℃ of lower initiation reactions, react 10h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 88.6%, and adjacent bromoacetophenone yield is 77.9%, and purity is 99.3%.
Embodiment 33
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.509g, 10ppm (1.75mg) μ-oxygen-double-core four-(Chloro-O-Phenyl) manganoporphyrin (is R in formula (III)
31Be Cl, R
32Be H, R
33Be H, M
3, M
4Be Mn), pass into oxygen under the 40mL/min flow velocity, 160 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 86.5%, and adjacent bromoacetophenone yield is 76.2%, and purity is 99.1%.
Embodiment 34
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.503g, 10ppm (1.77mg) μ-oxygen-double-core four-(o-methoxyphenyl) manganese-cobalt porphyrin (is R in formula (III)
31Be OCH
3, R
32Be H, R
33Be H, M
3Be Mn, M
4Be Co), pass into oxygen under the 30mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 94.3%, and adjacent bromoacetophenone yield is 81.8%, and purity is 99.2%.
Embodiment 35
In the 100mL there-necked flask, add the adjacent bromine ethylbenzene of 18.517g, 10ppm (1.87mg) μ-oxygen-double-core four-(m-nitro base) iron-cobalt porphyrin (is R in formula (III)
31Be H, R
32Be NO
2, R
33Be H, M
3Be Fe, M
4Be Co), pass into oxygen under the 30mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 100 ℃.Reacted mixture obtains adjacent bromoacetophenone through underpressure distillation, and adjacent bromine conversion of ethylbenzene is 93.1%, and adjacent bromoacetophenone yield is 80.2%, and purity is 99.4%.
Embodiment 36
In the 100mL there-necked flask, add 18.516g to bromine ethylbenzene, 1ppm (0.18mg) μ-oxygen-double-core four-(Chloro-O-Phenyl) iron porphyrin (is R in 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 formula (III)
31Be Cl, R
32Be H, R
33Be H, M
3, M
4Be Co), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains parabromoacetophenone through underpressure distillation, is 90.6% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 80.3%, and purity is 99.2%.
Embodiment 37
In the 100mL there-necked flask, add 18.502g to bromine ethylbenzene, 5ppm (0.90mg) four-(p-methylphenyl) zinc protoporphyrin (is R in 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 formula (I)
11Be H, R
12Be H, R
13Be NO
2, M
1Be Zn), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains parabromoacetophenone through underpressure distillation, is 61.4% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 48.5%, and purity is 99.2%.
Embodiment 38
In the 100mL there-necked flask, add 18.508g to bromine ethylbenzene, 5ppm (0.91mg) four-(2,4-3,5-dimethylphenyl) zinc protoporphyrin (is R in formula (I)
11Be CH
3, R
12Be H, R
13Be CH
3, M
1Be Zn), 10ppm (0.92mg) four-(2,4-dinitrophenyl) zinc protoporphyrin (is R in formula (I)
11Be NO
2, R
12Be H, R
13Be NO
2, M
1Be Zn), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains parabromoacetophenone through underpressure distillation, is 74.2% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 65.1%, and purity is 99.2%.
Embodiment 39
In the 100mL there-necked flask, add 18.517g to bromine ethylbenzene, 5ppm (0.44mg) bromination four-(O-Nitrophenylfluorone) iron porphyrins (are R in 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 formula (II)
21Be H, R
22Be H, R
23Be OCH
3, M
2Be Fe, X is Cl), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains parabromoacetophenone through underpressure distillation, is 83.7% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 76.4%, and purity is 99.3%.
Embodiment 40
In the 100mL there-necked flask, add 18.509g to bromine ethylbenzene, 5ppm (0.82mg) μ-oxygen-double-core four-(p-hydroxybenzene) manganoporphyrin (is R in 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 formula (III)
31Be Cl, R
32Be H, R
33Be H, M
3, M
4Be Mn), pass into oxygen under the 40mL/min flow velocity, 150 ℃ of lower initiation reactions, react 12h under 110 ℃.Reacted mixture obtains parabromoacetophenone through underpressure distillation, is 91.1% to the bromine conversion of ethylbenzene, and the parabromoacetophenone yield is 80.4%, and purity is 99.0%.
Claims (10)
1. the method for the adjacent bromoacetophenone of the adjacent bromine Preparation of ethylbenzene of a bionically catalyzing and oxidizing, the steps include: take adjacent bromine ethylbenzene as raw material, under normal pressure, condition of no solvent, select the monokaryon metalloporphyrin of have formula (I), formula (II) structure and have 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 (I) 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
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,
Catalyst levels is 1～30ppm, passes into oxygen with 10～60mL/min flow velocity, and first 140～170 ℃ of lower high temperature initiation reactions, then at 80～120 ℃ of lower low-temp reaction 6～16h, reacted mixture obtains adjacent bromoacetophenone through underpressure distillation.
2. according to claim 1 method, is characterized in that M
1, M
2, M
3Or M
4Be iron, manganese or cobalt, M
3And M
4Identical.
3. according to claim 2 method, 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
4Be iron or manganese, the M in another kind of catalyzer
1, M
2, M
3Or M
4Be cobalt.
4. according to claim 3 method, the mol ratio that it is characterized in that iron porphyrin or manganoporphyrin and cobalt porphyrin is 1: 1～10.
5. according to claim 1 method, is characterized in that dentate X is chlorine.
6. according to claim 1 method, is characterized in that catalyst levels is 5～15ppm.
7. according to claim 1 method, is characterized in that oxygen gas flow rate is 30～50mL/min.
8. according to claim 1 method, is characterized in that kick off temperature is 150～160 ℃.
9. according to claim 1 method, is characterized in that temperature of reaction is 100～110 ℃.
10. according to claim 1 method, is characterized in that the reaction times is 8～12h.
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| CN104591990A (en) * | 2014-12-25 | 2015-05-06 | 北京工业大学 | Method for preparing p-hydroxyacetophenone by catalytically oxidizing paraethyl phenol with metalloporphyrin-metal salt composite catalyst |
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| 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 |
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| 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 et al.."Sheet Polymer and its Complexes. II. Preparation and Catalytic Activity of Polymeric Tetrakisphenylporphyrin Films Crosslinked by 4,4’-Biphenylene-Bisulfoate".《Journal of Applied Polymer Science》.1998,第67卷2027-2034页. * |
| RONG-MINWANGetal.."SheetPolymeranditsComplexes.II.PreparationandCatalyticActivityofPolymericTetrakisphenylporphyrinFilmsCrosslinkedby4 4’-Biphenylene-Bisulfoate".《Journal of Applied Polymer Science》.1998 |
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