CN101747204B - Method for preparing p-nitroacetophenone by biomimetic catalytic oxidation of p-nitroethylbenzene with oxygen - Google Patents
Method for preparing p-nitroacetophenone by biomimetic catalytic oxidation of p-nitroethylbenzene with oxygen Download PDFInfo
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Abstract
The invention relates to a method for preparing p-nitroacetophenone by biomimetic catalytic oxidation of p-nitroethylbenzene with oxygen, comprising the following steps: taking p-nitroethylbenzene 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 150-200 DEG C and then carrying out reaction at 80-128 DEG C for 6-18h, thus obtaining the p-nitroacetophenone. 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 a kind of bionically catalyzing and oxidizing prepares p-nitroacetophenone to nitro ethylbenzene method.
Background technology
P-nitroacetophenone 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 p-nitroacetophenone mainly contains methyl phenyl ketone nitrofication process, 1-(4-nitrophenyl) oxidation of ethanol method and to nitro ethylbenzene oxidation method etc.; Wherein nitro 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 nitro ethylbenzene is prepared the method for p-nitroacetophenone, have significant meliority with respect to other method.
SU 1330128 (open day: on February 15th, 1985) disclose a kind of catalytic oxygen or atmospheric oxidation prepare p-nitroacetophenone to nitro ethylbenzene method; This method uses manganese acetate as catalyzer; Nickel acetate or tin acetate are as promotor, and catalytic oxygen or atmospheric oxidation prepare p-nitroacetophenone to nitro ethylbenzene.Its preferred manganese acetate consumption is 0.05～0.1% (90～900ppm) of a raw material weight; Nickel acetate or tin acetate consumption be the manganese acetate consumption 1～3% (0.9～27ppm), temperature of reaction is 130～170 ℃, and oxygen gas flow rate is 0.5L/min; Air velocity is 15L/h, and reaction pressure is 1～20atm.When 1atm, the manganese acetate consumption is 0.05% of a raw material weight, and the nickel acetate consumption is 3% of a manganese acetate consumption, 140 ℃ of temperature of reaction, and oxygen gas flow rate is 0.5L/min, reaction 4h, the yield of resulting p-nitroacetophenone is 58.6%.Special needs to be pointed out is, in order to reduce the explosion hazard of this reaction, need constantly speed make up water in reaction system with 0.2～0.4mL/mLh.
The main drawback of this method is:
(1) this method must use manganese acetate as catalyzer, nickel acetate or tin acetate as promotor, and its large usage quantity (Primary Catalysts consumption: 90～900ppm; Promotor consumption: 0.9～27ppm).And all acetate all can cause serious corrosion to equipment under high temperature (130～170 ℃) condition of high voltage;
(2) because employed catalyzer of this method and promotor all are metal-salts, and in reaction process, also need make up water constantly, the result can cause a large amount of brine wastes after reaction.And brine waste is the most difficult one of waste water of biochemical treatment that carries out in the wastewater treatment process.Its result not only causes serious environmental to pollute, and can consume a large amount of energy and resource;
(3) the preferred temperature of reaction of this method (130～170 ℃) is higher, and not only energy consumption is very high under too high temperature of reaction, and the danger of under high like this temperature, using a large amount of oxygen can make the security of production reduce greatly, operate heightens;
(4) oxygen gas flow rate (0.5L/min) of this method use is excessive; And high oxygen gas flow rate like this; Not only can cause production process to be in extreme danger, and can cause the waste of the energy and resource, even in actual production process, use reflux exchanger also can take more reaction raw materials and product out of in the tail gas exit; Help its recovery and have to consume more heat-eliminating medium, the result can make production cost be multiplied.
The bionic catalysis system has the incomparable advantage of traditional metal salt catalystsystem; Catalyst levels is few, but natural degradation does not produce secondary pollution; Reaction conditions is gentle; Solvent-free, neutral or basic solvent replaces the serious acid solvent of equipment corrosion, and selectivity of product is high, separates simple.
At present, adopt the catalysis of bionic catalysis system that the method that the nitro ethylbenzene oxidation prepares p-nitroacetophenone is not seen bibliographical information as yet, and have only the bibliographical information that uses other ethylbenzene series compound of bionic catalysis system catalysis to prepare corresponding arone.Main method 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.
Lee brace (Journal of Molecular Catalysis, 2008,22 (3): 209-213) wait the people to report 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 does not have high-valency metal salt to exist; 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%.Its employed high-valency metal salt is mainly Na
2MoO
4, K
2Cr
2O
7, KMnO
4The main drawback of this method is that reaction needed adopts that energy consumption is high, the condition of high voltage of operational hazards, and must use cost an arm and a leg, high-valency metal salt that environmental pollution is serious.
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, and then there is not induction time in this reaction, and uses benzene or chlorobenzene as solvent, and then there is the induction time of 3h in this reaction.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) because use the highly compressed reaction conditions, 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 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.
(5) 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 p-nitroacetophenone to nitro ethylbenzene.
A kind of bionically catalyzing and oxidizing provided by the present invention prepares the method for p-nitroacetophenone to nitro ethylbenzene; The steps include: being raw material nitro 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,
Catalyst levels is 1～30ppm, with 10～60mL/min flow velocity aerating oxygen, earlier 150～200 ℃ of following high temperature initiation reactions; Then at 80～128 ℃ of following low-temp reaction 6～18h; Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains p-nitroacetophenone.
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 160～170 ℃; Preferred temperature of reaction is 100～120 ℃; The preferred reaction times is 8～12h.
The inventive method is compared with SU 1330128 disclosed methods, has following beneficial effect:
(1) (1～30ppm) metal porphyrins substitutes SU 1330128 disclosed a large amount of metal-salt catalystsystem (Primary Catalysts consumptions: 90～900ppm to present method with minute quantity; The promotor consumption: 0.9～27ppm) directly as catalyzer, has eliminated catalyzer fully to the corrosion on Equipment problem;
(2) because the amount of the used metalloporphyrin of present method is few, do not need Separation and Recovery, but and metalloporphyrin natural degradation in environment, can not produce secondary pollution;
(3) the preferred temperature of reaction of present method is merely 100～120 ℃, is lower than 130～170 ℃ of the preferred temperature that SU 1330128 adopted.The reduction of temperature of reaction has not only significantly reduced energy consumption and the process cost in the reaction, and makes production process become safer;
(4) the preferred oxygen gas flow rate of present method is merely 30～50mL/min, the oxygen gas flow rate 500mL/min that is adopted far below SU 1330128.The energy and resource have not only been saved in the reduction of oxygen gas flow rate, have reduced production cost, and have further increased reaction safety.In addition, even in actual production process, do not use reflux exchanger can not take reaction raw materials and product out of in the tail gas exit yet.
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 NaIO of environmental pollution
4With chemical oxidizing agents such as chloramine-T 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 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 the documents, facility investment, energy consumption and running cost is all significantly reduced, and the security of whole process of production is greatly improved;
(4) 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, because the consumption of catalysis of metalloporphyrin agent is 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;
(5) 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 15.097g to nitro 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 160 ℃ of following initiation reactions, reacts 8h down at 120 ℃.Post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again through freezing, centrifuging, and its yield is 60.4%, and purity is 99.4%.
Embodiment 2
In the 100mL there-necked flask, add 15.145g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 64.2%, and purity is 99.2%.
Embodiment 3
In the 100mL there-necked flask, add 15.135g to nitro 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 160 ℃ of following initiation reactions, reacts 12h down at 100 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 65.3%, and purity is 99.6%.
Embodiment 4
In the 100mL there-necked flask, add 15.125g to nitro 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 160 ℃ of following initiation reactions, reacts 14h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 69.8%, and purity is 99.3%.
Embodiment 5
In the 100mL there-necked flask, add 15.132g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 65.5%, and purity is 99.0%.
Embodiment 6
In the 100mL there-necked flask, add 15.123g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 128 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 60.6%, and purity is 99.7%.
Embodiment 7
In the 100mL there-necked flask, add 15.139g to nitro 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 160 ℃ of following initiation reactions, reacts 6h down at 100 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 45.4%, and purity is 99.1%.
Embodiment 8
In the 100mL there-necked flask, add 15.143g to nitro 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 160 ℃ of following initiation reactions, reacts 18h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 55.4%, and purity is 99.7%.
Embodiment 9
In the 100mL there-necked flask, add 15.115g to nitro 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 160 ℃ of following initiation reactions, reacts 14h down at 80 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 20.2%, and purity is 99.1%.
Embodiment 10
In the 100mL there-necked flask, add 15.132g to nitro 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 200 ℃ of following initiation reactions, reacts 12h down at 90 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 35.1%, and purity is 99.3%.
Embodiment 11
In the 100mL there-necked flask, add 15.142g to nitro 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 170 ℃ of following initiation reactions, reacts 12h down at 100 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 45.3%, and purity is 99.2%.
Embodiment 12
In the 100mL there-necked flask, add 15.113g to nitro 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 190 ℃ of following initiation reactions, reacts 14h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 30.1%, and purity is 99.5%.
Embodiment 13
In the 100mL there-necked flask, add 15.107g to nitro 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 150 ℃ of following initiation reactions, reacts 14h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 15.4%, and purity is 99.5%.
Embodiment 14
In the 100mL there-necked flask, add 15.127g to nitro 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 190 ℃ of following initiation reactions, reacts 14h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 30.8%, and purity is 99.6%.
Embodiment 15
In the 100mL there-necked flask, add 15.117g to nitro 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 160 ℃ of following initiation reactions, reacts 14h down at 125 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 30.3%, and purity is 99.6%.
Embodiment 16
In the 100mL there-necked flask, add 15.126g to nitro 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 170 ℃ of following initiation reactions, reacts 12h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 50.7%, and purity is 99.2%.
Embodiment 17
In the 100mL there-necked flask, add 15.178g to nitro 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 190 ℃ of following initiation reactions, reacts 10h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 60.4%, and purity is 99.5%.
Embodiment 18
In the 100mL there-necked flask, add 15.087g to nitro 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 170 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 59.6%, and purity is 99.4%.
Embodiment 19
In the 100mL there-necked flask, add 15.099g to nitro 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 190 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 54.3%, and purity is 99.2%.
Embodiment 20
In the 100mL there-necked flask, add 15.094g to nitro 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 160 ℃ of following initiation reactions, reacts 12h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 45.7%, and purity is 99.0%.
Embodiment 21
In the 100mL there-necked flask, add 15.127g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 15.1%, and purity is 99.1%.
Embodiment 22
In the 100mL there-necked flask, add 15.120g to nitro 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 190 ℃ of following initiation reactions, reacts 12h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 30.5%, and purity is 99.2%.
Embodiment 23
In the 100mL there-necked flask, add 15.111g to nitro 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 170 ℃ of following initiation reactions, reacts 8h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 56.4%, and purity is 99.4%.
Embodiment 24
In the 100mL there-necked flask, add 15.142g to nitro 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 190 ℃ of following initiation reactions, reacts 12h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 55.4%, and purity is 99.2%.
Embodiment 25
In the 100mL there-necked flask, add 15.094g to nitro 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 160 ℃ of following initiation reactions, reacts 12h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 33.2%, and purity is 99.5%.
Embodiment 26
In the 100mL there-necked flask, add 15.092g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 19.2%, and purity is 99.3%.
Embodiment 27
In the 100mL there-necked flask, add 15.113g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 100 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 45.5%, and purity is 99.1%.
Embodiment 28
In the 100mL there-necked flask, add 15.089g to nitro 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 170 ℃ of following initiation reactions, reacts 10h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 25.3%, and purity is 99.2%.
Embodiment 29
In the 100mL there-necked flask, add 15.142g to nitro 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 190 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 55.2%, and purity is 99.5%.
Embodiment 30
In the 100mL there-necked flask, add 15.092g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 50.4%, and purity is 99.1%.
Embodiment 31
In the 100mL there-necked flask, add 15.132g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 58.8%, and purity is 99.3%.
Embodiment 32
In the 100mL there-necked flask, add 15.098g to nitro 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 190 ℃ of following initiation reactions, reacts 10h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 60.3%, and purity is 99.2%.
Embodiment 33
In the 100mL there-necked flask, add 15.125g to nitro 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 170 ℃ of following initiation reactions, reacts 10h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 49.4%, and purity is 99.2%.
Embodiment 34
In the 100mL there-necked flask, add 15.147g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 58.4%, and purity is 99.4%.
Embodiment 35
In the 100mL there-necked flask, add 15.138g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains p-nitroacetophenone with ethyl alcohol recrystallization again, and its yield is 57.2%, and purity is 99.7%.
Embodiment 36
In the 100mL there-necked flask, add 15.084g to nitro 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 160 ℃ of following initiation reactions, reacts 12h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains p-nitroacetophenone, and its yield is 60.9%, and purity is 99.5%.
Embodiment 37
In the 100mL there-necked flask, add 15.108g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains p-nitroacetophenone, and its yield is 33.6%, and purity is 99.6%.
Embodiment 38
In the 100mL there-necked flask, add 15.123g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains p-nitroacetophenone, and its yield is 48.7%, and purity is 99.4%.
Embodiment 39
In the 100mL there-necked flask, add 15.117g to nitro 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 160 ℃ of following initiation reactions, reacts 10h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains p-nitroacetophenone, and its yield is 55.2%, and purity is 99.2%.
Embodiment 40
In the 100mL there-necked flask, add 15.113g to nitro 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 160 ℃ of following initiation reactions, reacts 12h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains p-nitroacetophenone, and its yield is 56.6%, and purity is 99.1%.
Claims (10)
1. a bionically catalyzing and oxidizing prepares the method for p-nitroacetophenone to nitro ethylbenzene; The steps include: being raw material nitro 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,
Catalyst levels is 1～30ppm, with 10～60mL/min flow velocity aerating oxygen, earlier 150～200 ℃ of following high temperature initiation reactions; Then at 80～128 ℃ of following low-temp reaction 6～18h; Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains p-nitroacetophenone.
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 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 8～12h.
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| CN103694093A (en) * | 2013-12-23 | 2014-04-02 | 北京工业大学 | Method for preparing p-methoxybenzaldehyde perfume in presence of metalloporphyrin through catalytic oxidation of p-methoxytoluene |
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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 201010103450 patent/CN101747204B/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 (6)
| Title |
|---|
| canchen个 guo.selective oxidation of ethylbenzene with air catalyzed by simple u-oxo dimeric metalloporphyrins under mild conditions in the absence of additives.《journal of molecular catalysis A》.2003,第192卷295-302. |
| rong-min wang.sheet polymer and its complexes.《Journal of applied polymer science》.1998,第67卷2027-2034. |
| selective oxidation of ethylbenzene with air catalyzed by simple u-oxo dimeric metalloporphyrins under mild conditions in the absence of additives;canchen个 guo;《journal of molecular catalysis A》;20031231;第192卷;295-302 * |
| 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. |
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