CN101759541A - Method for preparing p-diacetylbenzene by biomimetic catalytic oxidation of p-diethylbenzene with oxygen - Google Patents
Method for preparing p-diacetylbenzene by biomimetic catalytic oxidation of p-diethylbenzene with oxygen Download PDFInfo
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Abstract
The invention relates to a method for preparing p-diacetylbenzene by biomimetic catalytic oxidation of p-diethylbenzene with oxygen, comprising the following steps: taking p-diethylbenzene 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 80-130 DEG C for 10-20h, thus obtaining the p-diacetylbenzene. 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 a kind of bionically catalyzing and oxidizing p-Diethylbenzene preparation diacetyl benzene.
Background technology
To diacetyl benzene is important organic synthesis intermediate, is widely used in synthetic medicine, agricultural chemicals, dyestuff, essence and flavoring agent, perfume etc.At present to main friedel-crafts acylation method of the preparation method of diacetyl benzene and p-Diethylbenzene oxidation style etc.; wherein the p-Diethylbenzene oxidation style 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 the method for oxygen to directly oxidize p-Diethylbenzene preparation, has significant superiority with respect to other method to diacetyl benzene.
JP 2001226307 (open day: on February 16th, 2000) disclose a kind of co-catalyst of forming by at least a material at least a metallic compound and ammoniacal liquor, organic bases or the halide salt; halogen compounds is made promotor; containing under solvent or the solvent-free condition; the oxidation of catalytic molecular oxygen contains the alkylaromatic hydrocarbon of two or more methylene radical; preparation contains the method for the aromatic compound of two or more acyl groups, needs to be isolated and excluded at any time the water that generates in the reaction in the reaction.Metallic compound preferable alloy salt wherein, the preferred cobalt of positively charged ion, manganese and cerium; The preferred chlorine of negatively charged ion, bromine and acetate, its consumption are 0.001～0.5% of raw material weight.Organic bases preferred amines compounds most preferably is tertiary amine compounds, and the total mole number of ammoniacal liquor, organic bases or halide salt is 0.1～30 times of metallic compound mole number.The preferred bromated compound of halogen compounds, its mole number are 0.5～30 times of metallic compound mole number.The preferred solvent-free or high boiling solvent of solvent, its consumption are half of raw material weight or still less.Preferred 0.05～the 10MPa of reaction pressure.Preferred 80～250 ℃ of temperature of reaction.Typical embodiment is as follows:
In there-necked flask, add p-Diethylbenzene 80g, CoCL2 0.0142g, pyridine 0.0189g and 47% hydrobromic acid aqueous solution 0.041g, use the Dean-Stark water trap to dewater, bubbling air under the 150mL/min flow velocity, at 120 ℃ of reaction 40h, the transformation efficiency of p-Diethylbenzene is 87.4%, and only is respectively 25.2% and 22% to the selectivity and the chromatogram yield of diacetyl benzene; Do not have pyridine and hydrobromic in the presence of, the transformation efficiency of p-Diethylbenzene is 27.4%, and only is respectively 17.4% and 4.78% to the selectivity and the chromatogram yield of diacetyl benzene.
The main drawback of this method is:
(1) because the catalyzer that this method is preferably used is metal-salt, ammoniacal liquor, organic bases and halide salt.The use meeting of metal-salt causes a large amount of brine wastes after reaction, and brine waste is one of the most difficult waste water that carries out biochemical treatment in the wastewater treatment process, and its result not only causes serious environmental to pollute, and can consume a large amount of energy and resource.And ammoniacal liquor, organic bases, the halide salt that especially contains chlorine or bromine at high temperature can cause very serious corrosion to equipment.In case be used for suitability for industrialized production, will increase the investment and the process cost of equipment significantly;
(2) the preferred bromine-containing compound of this method is as promotor.The use of promotor has not only increased production cost, and can cause very serious corrosion to equipment, and must increase the investment and the process cost of equipment significantly, also can increase a large amount of brine wastes after the reaction in addition, environment is caused bigger pollution, consume the more energy and resource;
(3) though this method has been used multiple catalyzer; and added promotor; but it is active and selectivity is still extremely low; as p-Diethylbenzene the reaction 40h after; just can reach 87.4% transformation efficiency, especially selectivity and the chromatogram yield to diacetyl benzene only is respectively 25.2% and 22%, if do not have pyridine and hydrobromic in the presence of; the transformation efficiency of p-Diethylbenzene only is 27.4%, and only is respectively 17.4% and 4.78% to the selectivity and the chromatogram yield of diacetyl benzene.Low selectivity like this, not only waste a large amount of raw materials, increased production cost, and the existence of a large amount of by products brings very big difficulty to last handling process, need to consume a large amount of energy and resource, cause very serious environmental pollution simultaneously, so this method may not be used for suitability for industrialized production;
(4) air velocity (150mL/min) of this method use is excessive, and too high gas flow rate, not only can cause the waste of the energy and resource, even and use reflux exchanger also can take more reaction raw materials and product out of in the tail gas exit in the actual production process, help its recovery and have to consume more heat-eliminating medium, the result can make production cost be multiplied.
(5) this method need be isolated and excluded the water that generates in the reaction at any time.Not only need to increase the investment of equipment and in actual production process, dewater at any time, and need to consume a large amount of energy, and can cause the waste of raw material.
The bionic catalysis system has the incomparable advantage of conventional metals salt catalyst system, catalyst levels is few, but natural degradation, do not produce secondary pollution, the reaction conditions gentleness, solvent-free, neutrality or basic solvent replace the serious acid solvent of equipment corrosion, and the selectivity of product height separates simple.
At present, adopt bionic catalysis system catalysis p-Diethylbenzene oxidation preparation that the method for diacetyl benzene 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:
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 the condition of high voltage that reaction needed adopts energy consumption height, 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 that poly-porphyrin is 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 industrial.
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 produce poisonous in a large number, deleterious waste water, waste residue in process of production, 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 restriction 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 may 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 preparation process is complicated that energy consumption height, three waste discharge are many, complex process, cost increase.In addition because of catalyst levels big (480ppm), with after also must Separation and Recovery, and cost height, the energy consumption of Separation and Recovery catalyzer are 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) Fan Ying induction time oversize (reaching 3h), 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 the preparation of eco-friendly metalloporphyrin bionically catalyzing and oxidizing p-Diethylbenzene is to the method for diacetyl benzene.
A kind of bionically catalyzing and oxidizing p-Diethylbenzene preparation provided by the present invention is to the method for diacetyl benzene; the steps include: with the p-Diethylbenzene to be raw material; under normal pressure, condition of no solvent; select the monokaryon metalloporphyrin of have formula (I), formula (II) structure for use and have any one or two kinds of combinations in the μ-oxygen-dinuclear metalloporphyrin of formula (III) structure 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, and described 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 140～170 ℃ of following high temperature initiation reactions; then at 80～130 ℃ of following low-temp reaction 10～20h; post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains diacetyl benzene.
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.
The preferred catalyst consumption is 5～15ppm.The preferred oxygen gas velocity is 30～50mL/min.Preferred kick off temperature is 150～160 ℃.Preferable reaction temperature is 100～120 ℃.The preferred reaction time is 16～18h.
The inventive method is compared with JP 2001226307 disclosed methods, has following beneficial effect:
(1) present method substitutes environmental pollution that JP 2001226307 uses serious metallic compound, ammoniacal liquor, organic bases and halide salt directly as catalyzer with the environmental friendliness metal porphyrins, has eliminated the problem of brine waste and equipment corrosion fully.Because the amount of the used metalloporphyrin of present method is few, do not need after the reaction to separate, reclaim, avoided the generation of separation, recovery, purification process energy consumption.Simultaneously, but metalloporphyrin natural degradation in environment can not produce secondary pollution;
(2) present method is not used any promotor, does not have any problem that causes because of promotor.
(3) present method uses metalloporphyrin as bionic catalyst, has high reactivity, the highly selective characteristics of approximate enzyme.Present method is behind reaction 18h, the p-Diethylbenzene peak rate of conversion just can reach 90.4%, selectivity and chromatogram yield to diacetyl benzene reach 73.9% and 66.8% respectively, separation yield also can reach 62.3%, the selectivity of principal product and chromatogram yield are all far above JP 2001226307 disclosed 25.2% and 22%, and the minimizing in reaction times, have not only accelerated the production cycle, and reduced energy consumption, reduced process cost;
(4) the preferred oxygen gas flow rate of present method is 30～50mL/min, the 150mL/min gas flow rate that is adopted far below JP 2001226307.The energy and resource have not only been saved in the reduction of gas flow rate, have increased reaction safety, even and do not use reflux exchanger also can not take reaction raw materials and product out of in the tail gas exit in actual production process.
(5) this method does not need to be isolated and excluded the water that generates in the reaction, and the existence of little water can also slow down speed of reaction, increases reaction safety.
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 may 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 required environmental pollution that energy consumption and preparation process produced of Preparation of Catalyst.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, and reaction and isolating energy consumption be reduction greatly all, and the security of production is improved.
Embodiment
Embodiment 1
In the 100mL there-necked flask, add the 13.474g p-Diethylbenzene, 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 18h down at 110 ℃.Post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization through freezing, centrifuging again, and the p-Diethylbenzene transformation efficiency is 80.4%, is 59.8% to diacetyl benzene yield, and purity is 99.1%.
Embodiment 2
In the 100mL there-necked flask, add the 13.432g p-Diethylbenzene, 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 16h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 85.1%, is 62.2% to diacetyl benzene yield, and purity is 99.3%.
Embodiment 3
In the 100mL there-necked flask, add the 13.487g p-Diethylbenzene, 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 16h down at 100 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 75.3%, is 50.6% to diacetyl benzene yield, and purity is 99.4%.
Embodiment 4
In the 100mL there-necked flask, add the 13.432g p-Diethylbenzene, 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 18h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 90.4%, is 62.3% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 5
In the 100mL there-necked flask, add the 13.448g p-Diethylbenzene, 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 20h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 93.2%, is 59.8% to diacetyl benzene yield, and purity is 99.8%.
Embodiment 6
In the 100mL there-necked flask, add the 13.533g p-Diethylbenzene, 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 140 ℃ of following initiation reactions, reacts 16h down at 130 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 87.8%, is 55.4% to diacetyl benzene yield, and purity is 99.8%.
Embodiment 7
In the 100mL there-necked flask, add the 13.433g p-Diethylbenzene, 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 18h down at 100 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 70.8%, is 49.8% to diacetyl benzene yield, and purity is 99.4%.
Embodiment 8
In the 100mL there-necked flask, add the 13.422g p-Diethylbenzene, 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 20h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 78.6%, is 47.2% to diacetyl benzene yield, and purity is 99.9%.
Embodiment 9
In the 100mL there-necked flask, add the 13.432g p-Diethylbenzene, 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 20h down at 80 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 45.4%, is 26.8% to diacetyl benzene yield, and purity is 99.1%.
Embodiment 10
In the 100mL there-necked flask, add the 13.533g p-Diethylbenzene, 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 170 ℃ of following initiation reactions, reacts 18h down at 100 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 50.4%, is 31.2% to diacetyl benzene yield, and purity is 99.7%.
Embodiment 11
In the 100mL there-necked flask, add the 13.388g p-Diethylbenzene, 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 18h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 53.9%, is 32.8% to diacetyl benzene yield, and purity is 99.8%.
Embodiment 12
In the 100mL there-necked flask, add the 13.396g p-Diethylbenzene, 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 18h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 54.7%, is 33.6% to diacetyl benzene yield, and purity is 99.5%.
Embodiment 13
In the 100mL there-necked flask, add the 13.427g p-Diethylbenzene, 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 18h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 40.7%, is 20.4% to diacetyl benzene yield, and purity is 99.5%.
Embodiment 14
In the 100mL there-necked flask, add the 13.404g p-Diethylbenzene, 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 18h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 45.6%, is 24.3% to diacetyl benzene yield, and purity is 99.6%.
Embodiment 15
In the 100mL there-necked flask, add the 13.407g p-Diethylbenzene, 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 16h down at 125 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 40.9%, is 20.8% to diacetyl benzene yield, and purity is 99.6%.
Embodiment 16
In the 100mL there-necked flask, add the 13.432g p-Diethylbenzene, 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 150 ℃ of following initiation reactions, reacts 16h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 76.8%, is 49.2% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 17
In the 100mL there-necked flask, add the 13.402g p-Diethylbenzene, 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 16h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 78.6%, is 50.9% to diacetyl benzene yield, and purity is 99.3%.
Embodiment 18
In the 100mL there-necked flask, add the 13.401g p-Diethylbenzene, 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 150 ℃ of following initiation reactions, reacts 18h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 80.4%, is 55.4% to diacetyl benzene yield, and purity is 99.3%.
Embodiment 19
In the 100mL there-necked flask, add the 13.403g p-Diethylbenzene, 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 18h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 70.3%, is 46.2% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 20
In the 100mL there-necked flask, add the 13.421g p-Diethylbenzene, 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 16h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 65.2%, is 40.8% to diacetyl benzene yield, and purity is 99.4%.
Embodiment 21
In the 100mL there-necked flask, add the 13.424g p-Diethylbenzene, 10ppm (0.75mg) bromination four-phenyl 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 diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 40.4%, is 19.8% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 22
In the 100mL there-necked flask, add the 13.374g p-Diethylbenzene, 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 18h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 70.4%, is 42.1% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 23
In the 100mL there-necked flask, add the 13.484g p-Diethylbenzene, 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 150 ℃ of following initiation reactions, reacts 16h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 80.6%, is 53.7% to diacetyl benzene yield, and purity is 99.4%.
Embodiment 24
In the 100mL there-necked flask, add the 13.465g p-Diethylbenzene, 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 160 ℃ of following initiation reactions, reacts 18h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 76.3%, is 49.8% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 25
In the 100mL there-necked flask, add the 13.401g p-Diethylbenzene, 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 170 ℃ of following initiation reactions, reacts 16h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 60.1%, is 33.1% to diacetyl benzene yield, and purity is 99.5%.
Embodiment 26
In the 100mL there-necked flask, add the 13.402g p-Diethylbenzene, 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 14h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 45.3%, is 21.3% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 27
In the 100mL there-necked flask, add the 13.421g p-Diethylbenzene, 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 18h down at 100 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 56.8%, is 25.7% to diacetyl benzene yield, and purity is 99.1%.
Embodiment 28
In the 100mL there-necked flask, add the 13.423g p-Diethylbenzene, 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 150 ℃ of following initiation reactions, reacts 18h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 69.5%, is 43.2% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 29
In the 100mL there-necked flask, add the 13.424g p-Diethylbenzene, 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 16h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 72.4%, is 46.3% to diacetyl benzene yield, and purity is 99.5%.
Embodiment 30
In the 100mL there-necked flask, add the 13.426g p-Diethylbenzene, 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 18h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 85.7%, is 50.9% to diacetyl benzene yield, and purity is 99.1%.
Embodiment 31
In the 100mL there-necked flask, add the 13.424g p-Diethylbenzene, 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 16h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 85.6%, is 55.6% to diacetyl benzene yield, and purity is 99.3%.
Embodiment 32
In the 100mL there-necked flask, add the 13.432g p-Diethylbenzene, 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 18h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 82.1%, is 55.1% to diacetyl benzene yield, and purity is 99.1%.
Embodiment 33
In the 100mL there-necked flask, add the 13.425g p-Diethylbenzene, 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 18h down at 110 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 80.4%, is 51.4% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 34
In the 100mL there-necked flask, add the 13.464g p-Diethylbenzene, 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 18h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 80.6%, is 52.8% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 35
In the 100mL there-necked flask, add the 13.424g p-Diethylbenzene, 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 16h down at 120 ℃.Freezing, the centrifuging of post reaction mixture obtains diacetyl benzene with ethyl alcohol recrystallization again, and the p-Diethylbenzene transformation efficiency is 82.4%, is 51.2% to diacetyl benzene yield, and purity is 99.6%.
Embodiment 36
In the 100mL there-necked flask, add the 13.414g p-Diethylbenzene, 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 16h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains diacetyl benzene, and the p-Diethylbenzene transformation efficiency is 87.2%, is 54.9% to diacetyl benzene yield, and purity is 99.2%.
Embodiment 37
In the 100mL there-necked flask, add the 13.418g p-Diethylbenzene, 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 18h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains diacetyl benzene, and the p-Diethylbenzene transformation efficiency is 55.1%, is 32.4% to diacetyl benzene yield, and purity is 99.1%.
Embodiment 38
In the 100mL there-necked flask, add the 13.403g p-Diethylbenzene, 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 18h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains diacetyl benzene, and the p-Diethylbenzene transformation efficiency is 60.3%, is 38.7% to diacetyl benzene yield, and purity is 99.4%.
Embodiment 39
In the 100mL there-necked flask, add the 13.407g p-Diethylbenzene, 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 16h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains diacetyl benzene, and the p-Diethylbenzene transformation efficiency is 74.3%, is 47.2% to diacetyl benzene yield, and purity is 99.6%.
Embodiment 40
In the 100mL there-necked flask, add the 13.416g p-Diethylbenzene, 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 18h down at 120 ℃.Post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains diacetyl benzene, and the p-Diethylbenzene transformation efficiency is 82.4%, is 53.6% to diacetyl benzene yield, and purity is 99.3%.
Claims (10)
1. bionically catalyzing and oxidizing p-Diethylbenzene preparation is to the method for diacetyl benzene; the steps include: with the p-Diethylbenzene to be raw material; under normal pressure, condition of no solvent; select the monokaryon metalloporphyrin of have formula (I), formula (II) structure for use and have any one or two kinds of combinations in the μ-oxygen-dinuclear metalloporphyrin of formula (III) structure 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, and described 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 140～170 ℃ of following high temperature initiation reactions; then at 80～130 ℃ of following low-temp reaction 10～20h; post reaction mixture is used ethyl alcohol recrystallization again through freezing, centrifuging, obtains diacetyl benzene.
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 100～120 ℃.
10. according to the method for claim 1, it is characterized in that the reaction times is 16～18h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107286005A (en) * | 2016-04-11 | 2017-10-24 | 中国石化扬子石油化工有限公司 | A kind of p-diethylbenzene homogeneous oxidizing prepares the method to diacetyl benzene |
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2010
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107286005A (en) * | 2016-04-11 | 2017-10-24 | 中国石化扬子石油化工有限公司 | A kind of p-diethylbenzene homogeneous oxidizing prepares the method to diacetyl benzene |
| CN107286005B (en) * | 2016-04-11 | 2021-03-19 | 中国石化扬子石油化工有限公司 | Method for preparing p-diacetylbenzene by homogeneous oxidation of p-diethylbenzene |
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