CN101759540B - Method for preparing propiophenone by biomimetic catalytic oxidation of n-propylbenzene with oxygen - Google Patents
Method for preparing propiophenone by biomimetic catalytic oxidation of n-propylbenzene with oxygen Download PDFInfo
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Abstract
The invention relates to a method for preparing propiophenone by biomimetic catalytic oxidation of n-propylbenzene with oxygen, comprising the following steps: taking n-propylbenzene 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 140-160 DEG C and then carrying out reaction at 70-110 DEG C for 4-10h, thus obtaining the propiophenone. 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 method of preparing propiophenone by biomimetic catalytic oxidation of n-propylbenzene with oxygen.
Background technology
Propiophenone is important organic synthesis intermediate, is widely used in synthetic medicine, agricultural chemicals, dyestuff, essence and flavoring agent, perfume etc.The preparation method of Propiophenone mainly contains friedel-crafts acylation method, 1-phenylpropyl alcohol oxidation style and n-proplbenzene oxidation style etc. at present; wherein the n-proplbenzene oxidation style is divided into again chemical oxidization method and molecular oxygen oxidation method; oxygen is as cheap and easy to get, cleanliness without any pollution and the good oxygenant of Atom economy; the method that is prepared Propiophenone by the oxygen to directly oxidize n-proplbenzene has significant superiority with respect to other method.
The bionic catalysis system has the incomparable advantage of traditional metal salt catalyst system, catalyst levels is few, but natural degradation, do not produce secondary pollution, reaction conditions is gentle, solvent-free, neutrality or basic solvent replace the serious acid solvent of equipment corrosion, and selectivity of product is high, separates simple.
At present, the method main method that adopts the oxidation of metalloporphyrin bionic catalysis oxidation of n-propylbenzene to prepare Propiophenone has following several:
Valiollah Mirkhani (Applied Catalysis A:General, 2006,303:221-229) with Majid Moghadam (Catalysis Communications, 2005,6:688-693) etc. the people has reported the loaded metal porphyrin in the solution of acetonitrile/water 1: 1 (volume ratio), uses NaIO
4As oxygenant, but the oxidation of n-propylbenzene highly selective obtain Propiophenone, catalyzer: raw material: oxygenant=1: 80: 160 (mol ratio), the yield of reaction 6h Propiophenone can reach 60%.The main drawback of the method is to use respectively NaIO expensive and that environmental pollution is serious
4As chemical oxidizing agent, acetonitrile solution as solvent.
Shi-Jun Li (Tetrahedron Letters, 2005,46:8013-8015) etc. the people has reported chloramine-T/O
2/ complex of metalloporphyrin is in the acetonitrile equal solvent, and the catalyzed oxidation n-proplbenzene obtains Propiophenone under the room temperature, catalyzer: raw material: chloramine-T=1: 20: 10 (mol ratio), the yield of Propiophenone can reach 62%.The main drawback of the method be must use respectively expensive and chloramine-T that environmental pollution is serious as chemical oxidizing agent, acetonitrile as solvent.
Lee brace (Journal of Molecular Catalysis, 2008,22 (3): 209-213) etc. the people has reported that metalloporphyrin/high price salt system is solvent-free, 1.5MPa, under 100 ℃ of conditions, the oxygen catalytic oxidation n-proplbenzene obtains Propiophenone, under the condition that does not have high-valency metal salt to exist, the yield of Propiophenone is 20.1%, adds the serious K of environmental pollution
2Cr
2O
7After, yield can bring up to 27.9%.Its employed high-valency metal salt is mainly Na
2MoO
4, K
2Cr
2O
7, KMnO
4The main drawback of the method is that reaction needed employing energy consumption is high, the condition of high voltage of operational hazards, and must use the high-valency metal salt expensive, that environmental pollution is serious.
The main method that adopts in addition other metalloporphyrin bionic catalysis system oxidation ethylbenzene oxidation to prepare methyl phenyl ketone has following several:
Rong-Min Wang (Journal of Applied Polymer Science, 1998,67:2027-2034) etc. the people has reported that poly-porphyrin is under 60～90 ℃ of conditions, the oxygen catalytic oxidation n-proplbenzene prepares Propiophenone, the catalytic amount that every 15mmol raw material needs is 6mg (480ppm), reaction 8～9h, the Propiophenone yield is 13.7%, selectivity is 99%.The main drawback of the method is that catalyst levels is large, and catalyst separating, recovery and purification power consumption are high.And because this reaction is inhomogeneous reaction, although the highly selective of catalysis of metalloporphyrin agent has obtained fine embodiment, its high catalytic activity does not display fully, and the Propiophenone yield only reaches 13.7%.
Peng Qingjing (Acta PhySico-Chimica Sinica, 2001,17 (4): 292-294) reported [TPPMn]
2O catalytic air oxidation n-proplbenzene prepares Propiophenone, 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 the 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, there is following main drawback in the method that adopts at present metalloporphyrin bionic catalysis system to prepare arone:
(1) use chemical oxidizing agent, not only in the process of producing, produce poisonous, harmful in a large number waste water, waste residue, cause serious environmental pollution, and raw material and production cost become very high accordingly;
(2) use solvent, even the benzene or the chlorobenzene that use industrial restriction to use.Cause increasing of energy consumption not only because its poisonous and harmful may cause serious environmental pollution, and because of the recovery of solvent, greatly increased process cost and production cost;
(3) because use the reaction conditions of high pressure, cause facility investment and running cost to be multiplied, energy consumption is high, particularly makes to produce to have potential danger, and security reduces greatly;
(4) working load or polymer/metallic porphyrin cause because preparation process is complicated that energy consumption is high, three waste discharge is many, complex process, cost increase.Because of catalyst levels large (480ppm), use afterwards also necessary Separation and Recovery, and the cost of Separation and Recovery catalyzer is high, energy consumption is large in addition, three waste discharge is many.Also have, because the reaction of working load or polymer/metallic porphyrin is inhomogeneous reaction, the high catalytic activity of metalloporphyrin can not get good embodiment.
(5) induction time oversize (reaching 3h) of reaction, thereby make the time lengthening of whole reaction causes the increase of the serious and process cost of energy dissipation.
Summary of the invention
The object of the present invention is to provide a kind of yield higher, induction time is extremely short, and the method for eco-friendly metalloporphyrin preparing propiophenone by biomimetic catalytic oxidation of n-propylbenzene with oxygen.
The method of a kind of preparing propiophenone by biomimetic catalytic oxidation of n-propylbenzene with oxygen provided by the present invention, the steps include: take n-proplbenzene as raw material, under normal pressure, condition of no solvent, select the monokaryon metalloporphyrin of have formula (I), formula (II) structure and have any one or two kinds of combinations in the μ-oxygen of formula (III) structure-dinuclear metalloporphyrin as catalyzer, wherein, central metallic ions M
1Be iron, manganese, cobalt, copper, zinc, nickel or chromium, central metallic ions M
2Be iron, manganese, cobalt, nickel, chromium, molybdenum or ruthenium, central metallic ions M
3With central metallic ions M
4Identical or different, be iron, manganese or cobalt when identical, not simultaneously, M
3Be iron, M
4Be manganese, M
3Be iron, M
4Be cobalt or M
3Be manganese, M
4Be cobalt, substituent R
11, R
12, R
13, R
21, R
22, R
23, R
31, R
32Or R
33Be hydrogen, halogen, nitro, hydroxyl, C
1-3Alkyl, C
1-3Alkoxyl group or carboxyl, dentate X is halogen, and described catalyzer also comprises the middle substituting group of formula (I) and formula (I), formula (II) and formula (II), formula (III) and formula (III) and substituent position is identical, central metallic ions M
1, M
2, M
3Or M
4Different combinations; Also comprise the middle substituting group of formula (I) and formula (I), formula (II) and formula (II), formula (III) and formula (III) and the combination that substituent position is different, central metallic ions is identical or different,
Catalyst levels is 1～30ppm, passes into oxygen with 10～60mL/min flow velocity, and first 140～160 ℃ of lower high temperature initiation reactions, then at 70～110 ℃ of lower low-temp reaction 4～10h, reacted mixture obtains Propiophenone through underpressure distillation.
Preferred M
1, M
2, M
3Or M
4Be iron, manganese or cobalt, M
3And M
4Identical; Particularly preferably when any two kinds of catalyst combination, a kind of M wherein
1, M
2, M
3Or M
4Be iron or manganese, another kind of M
1, M
2, M
3Or M
4Be cobalt, the mol ratio of iron porphyrin or manganoporphyrin and cobalt porphyrin is 1: 1～10.
The preferred chlorine of dentate X.
Preferred catalyst levels is 5～15ppm; Preferred oxygen gas flow rate is 30～50mL/min; Preferred kick off temperature is 140～160 ℃; Preferred temperature of reaction is 90～100 ℃; The preferred reaction times is 6～8h.
The inventive method is compared with the method that aforesaid metalloporphyrin bionic catalysis system prepares arone, has following beneficial effect:
(1) present method uses cleaning, cheap oxygen to replace serious, the expensive NaIO of environmental pollution
4With the chemical oxidizing agents such as chloramine-T as oxygenant.Not only greatly reduce environmental pollution, and significantly reduced production cost;
(2) present method is not used solvent.Not only eliminate the poisonous and harmful solvent fully and may cause serious environmental pollution, and because there is not the recovery problem of solvent, and the energy consumption of production process and cost are reduced greatly;
(3) present method is only carried out under condition of normal pressure, with respect to the reaction under high pressure in the documents, facility investment, energy consumption and running cost is all significantly reduced, and the security of whole production process is greatly improved;
(4) present method with the metal porphyrins of minute quantity directly as catalyzer, and do not use the very complicated load of preparation process or polymer/metallic porphyrin as catalyzer, simplified the preparation process of catalyzer, can greatly reduce catalyzer and prepare the environmental pollution that required energy consumption and preparation process produce.And, because the consumption of catalysis of metalloporphyrin agent is few, do not need after the reaction to separate, reclaim, exempted from 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 contact probability and the reaction efficiency of metalloporphyrin and substrate, makes the high catalytic activity of metalloporphyrin obtain good embodiment;
(5) present method adopts high temperature to cause fast, and the mode of low-temp reaction makes reaction induction time become extremely short, has greatly shortened the time of reaction, has improved reaction efficiency, has reduced process cost and energy consumption.Low-temp reaction then helps to improve the selectivity of product, has reduced the generation of by product, and the separation of product is become be more prone to, and the energy consumption of reaction and separation processes all reduces greatly, and the security of production is improved.
Embodiment
Embodiment 1
In the 100mL there-necked flask, add the 12.172g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 6h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 79.6%, and the Propiophenone yield is 70.4%, and purity is 99.1%.
Embodiment 2
In the 100mL there-necked flask, add the 12.156g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 7h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 81.4%, and the Propiophenone yield is 71.6%, and purity is 99.8%.
Embodiment 3
In the 100mL there-necked flask, add the 12.132g n-proplbenzene, 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), under the 50mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 80 ℃ of lower reaction 7h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 68.3%, and the Propiophenone yield is 61.4%, and purity is 99.6%.
Embodiment 4
In the 100mL there-necked flask, add the 12.224g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 94.5%, and the Propiophenone yield is 85.8%, and purity is 99.2%.
Embodiment 5
In the 100mL there-necked flask, add the 12.078g n-proplbenzene, 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), under the 50mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 10h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 95.4%, and the Propiophenone yield is 80.4%, and purity is 99.1%.
Embodiment 6
In the 100mL there-necked flask, add the 12.168g n-proplbenzene, 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-(O-Nitrophenylfluorone) cobalt porphyrin (is R in the formula (I)
11Be NO
2, R
12Be H, R
13Be H, M
1Be Co), under the 30mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 88.7%, and the Propiophenone yield is 78.3%, and purity is 99.5%.
Embodiment 7
In the 100mL there-necked flask, add the 12.133g n-proplbenzene, 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), under the 20mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 80 ℃ of lower reaction 6h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 72.8%, and the Propiophenone yield is 62.8%, and purity is 99.3%.
Embodiment 8
In the 100mL there-necked flask, add the 12.122g n-proplbenzene, 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), under the 50mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 79.6%, and the Propiophenone yield is 71.5%, and purity is 99.0%.
Embodiment 9
In the 100mL there-necked flask, add the 12.142g n-proplbenzene, 20ppm (1.47mg) four-phenyl iron porphyrin (is R in the formula (I)
11Be H, R
12Be H, R
13Be H, M
1Be Fe), under the 30mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 70 ℃ of lower reaction 4h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 37.1%, and the Propiophenone yield is 28.4%, and purity is 99.3%.
Embodiment 10
In the 100mL there-necked flask, add the 12.143g n-proplbenzene, 10ppm (0.86mg) four-(rubigan) cobalt porphyrin (is R in the formula (I)
11Be H, R
12Be H, R
13Be Cl, M
1Be Co), under the 20mL/min flow velocity, pass into oxygen, 160 ℃ of lower initiation reactions, at 80 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 44.8%, and the Propiophenone yield is 35.9%, and purity is 99.3%.
Embodiment 11
In the 100mL there-necked flask, add the 12.165g n-proplbenzene, 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), under the 30mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 57.6%, and the Propiophenone yield is 48.7%, and purity is 99.2%.
Embodiment 12
In the 100mL there-necked flask, add the 12.153g n-proplbenzene, 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), under the 20mL/min flow velocity, pass into oxygen, 150 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 59.1%, and the Propiophenone yield is 50.1%, and purity is 99.3%.
Embodiment 13
In the 100mL there-necked flask, add the 12.164g n-proplbenzene, 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), under the 30mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 42.3%, and the Propiophenone yield is 34.2%, and purity is 99.2%.
Embodiment 14
In the 100mL there-necked flask, add the 12.142g n-proplbenzene, 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), under the 20mL/min flow velocity, pass into oxygen, 150 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 36.9%, and the Propiophenone yield is 27.6%, and purity is 99.5%.
Embodiment 15
In the 100mL there-necked flask, add the 12.132g n-proplbenzene, 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), under the 30mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 6h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 41.9%, and the Propiophenone yield is 33.5%, and purity is 99.4%.
Embodiment 16
In the 100mL there-necked flask, add the 12.165g n-proplbenzene, 15ppm (1.21mg) four-(carboxyl phenyl) manganoporphyrin (is R in the formula (I)
11Be H, R
12Be COOH, R
13Be H, M
1Be Mn), under the 30mL/min flow velocity, pass into oxygen, 150 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 77.8%, and the Propiophenone yield is 68.4%, and purity is 99.2%.
Embodiment 17
In the 100mL there-necked flask, add the 12.234g n-proplbenzene, 10ppm (0.92mg) four-(O-Nitrophenylfluorone) cobalt porphyrin (is R in the formula (I)
11Be NO
2, R
12Be H, R
13Be H, M
1Be Co), under the 30mL/min flow velocity, pass into oxygen, 160 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 78.4%, and the Propiophenone yield is 68.6%, and purity is 99.5%.
Embodiment 18
In the 100mL there-necked flask, add the 12.403g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 150 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 81.5%, and the Propiophenone yield is 72.3%, and purity is 99.3%.
Embodiment 19
In the 100mL there-necked flask, add the 12.034g n-proplbenzene, 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), under the 20mL/min flow velocity, pass into oxygen, 150 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 10h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 82.3%, and the Propiophenone yield is 71.8%, and purity is 99.3%.
Embodiment 20
In the 100mL there-necked flask, add the 12.045g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 73.9%, and the Propiophenone yield is 65.2%, and purity is 99.3%.
Embodiment 21
In the 100mL there-necked flask, add the 12.165g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 41.6%, and the Propiophenone yield is 35.1%, and purity is 99.2%.
Embodiment 22
In the 100mL there-necked flask, add the 12.232g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 150 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 50.4%, and the Propiophenone yield is 40.8%, and purity is 99.0%.
Embodiment 23
In the 100mL there-necked flask, add the 12.341g n-proplbenzene, 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), under the 50mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 9h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 85.9%, and the Propiophenone yield is 74.9%, and purity is 99.3%.
Embodiment 24
In the 100mL there-necked flask, add the 12.187g n-proplbenzene, 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), under the 50mL/min flow velocity, pass into oxygen, 150 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 9h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 83.2%, and the Propiophenone yield is 72.3%, and purity is 99.2%.
Embodiment 25
In the 100mL there-necked flask, add the 12.167g n-proplbenzene, 15ppm (1.36mg) chlorination four-(O-Nitrophenylfluorone) nickel-porphyrins (are R in the formula (II)
21Be NO
2, R
22Be H, R
23Be H, M
2Be Ni, X is Cl), under the 50mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 49.8%, and the Propiophenone yield is 40.5%, and purity is 99.4%.
Embodiment 26
In the 100mL there-necked flask, add the 12.153g n-proplbenzene, 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), under the 50mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 53.7%, and the Propiophenone yield is 42.5%, and purity is 99.2%.
Embodiment 27
In the 100mL there-necked flask, add the 12.143g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 6h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 48.2%, and the Propiophenone yield is 39.1%, and purity is 99.2%.
Embodiment 28
In the 100mL there-necked flask, add the 12.125g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 150 ℃ of lower initiation reactions, at 90 ℃ of lower reaction 6h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 54.8%, and the Propiophenone yield is 45.6%, and purity is 99.2%.
Embodiment 29
In the 100mL there-necked flask, add the 12.134g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 160 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 6h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 81.6%, and the Propiophenone yield is 72.3%, and purity is 99.5%.
Embodiment 30
In the 100mL there-necked flask, add the 12.121g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 81.9%, and the Propiophenone yield is 73.1%, and purity is 99.1%.
Embodiment 31
In the 100mL there-necked flask, add the 12.164g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 89.9%, and the Propiophenone yield is 80.7%, and purity is 99.3%.
Embodiment 32
In the 100mL there-necked flask, add the 12.134g n-proplbenzene, 10ppm (1.83mg) μ-oxygen-double-core four-(O-Nitrophenylfluorone) cobalt porphyrin (is R in the formula (III)
31Be NO
2, R
32Be H, R
33Be H, M
3, M
4Be Co), under the 40mL/min flow velocity, pass into oxygen, 160 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 6h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 83.2%, and the Propiophenone yield is 74.5%, and purity is 99.1%.
Embodiment 33
In the 100mL there-necked flask, add the 12.121g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 150 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 6h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 81.6%, and the Propiophenone yield is 70.9%, and purity is 99.2%.
Embodiment 34
In the 100mL there-necked flask, add the 12.130g n-proplbenzene, 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), under the 30mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 91.8%, and the Propiophenone yield is 81.5%, and purity is 99.3%.
Embodiment 35
In the 100mL there-necked flask, add the 12.145g n-proplbenzene, 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), under the 30mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 90.4%, and the Propiophenone yield is 80.7%, and purity is 99.6%.
Embodiment 36
In the 100mL there-necked flask, add the 12.146g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 91.7%, and the Propiophenone yield is 81.2%, and purity is 99.1%.
Embodiment 37
In the 100mL there-necked flask, add the 12.132g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 59.2%, and the Propiophenone yield is 48.7%, and purity is 99.3%.
Embodiment 38
In the 100mL there-necked flask, add the 12.108g n-proplbenzene, 5ppm (0.91mg) four-(2,4-3,5-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-(2,4-dinitrophenyl) zinc protoporphyrin (is R in the formula (I)
11Be NO
2, R
12Be H, R
13Be NO
2, M
1Be Zn), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 71.8%, and the Propiophenone yield is 62.4%, and purity is 99.5%.
Embodiment 39
In the 100mL there-necked flask, add the 12.137g n-proplbenzene, 5ppm (0.44mg) bromination four-(O-Nitrophenylfluorone) iron porphyrins (are 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 80.6%, and the Propiophenone yield is 73.3%, and purity is 99.6%.
Embodiment 40
In the 100mL there-necked flask, add the 12.117g n-proplbenzene, 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), under the 40mL/min flow velocity, pass into oxygen, 140 ℃ of lower initiation reactions, at 100 ℃ of lower reaction 8h.Reacted mixture obtains Propiophenone through underpressure distillation, and the n-proplbenzene transformation efficiency is 87.4%, and the Propiophenone yield is 78.7%, and purity is 99.6%.
Claims (10)
1. the method for a preparing propiophenone by biomimetic catalytic oxidation of n-propylbenzene with oxygen, the steps include: take n-proplbenzene as raw material, under normal pressure, condition of no solvent, select the monokaryon metalloporphyrin of have formula (I), formula (II) structure and have any one or two kinds of combinations in the μ-oxygen of formula (III) structure-dinuclear metalloporphyrin as catalyzer, or select formula (I) and the middle substituting group of formula (I), formula (II) and formula (II), formula (III) and formula (III) and substituent position is identical, central metallic ions M
1, M
2, M
3Or M
4Different combinations are as catalyzer, or select substituting group in formula (I) and formula (I), formula (II) and formula (II), formula (III) and the formula (III) and substituent position is different, central metallic ions is identical or different combination as catalyzer, wherein, central metallic ions M
1Be iron, manganese, cobalt, copper, zinc, nickel or chromium, central metallic ions M
2Be iron, manganese, cobalt, nickel, chromium, molybdenum or ruthenium, central metallic ions M
3With central metallic ions M
4Identical or different, be iron, manganese or cobalt when identical, not simultaneously, M
3Be iron, M
4Be manganese, M
3Be iron, M
4Be cobalt or M
3Be manganese, M
4Be cobalt, substituent R
11, R
12, R
13, R
21, R
22, R
23, R
31, R
32Or R
33Be hydrogen, halogen, nitro, hydroxyl, C
1-3Alkyl, C
1-3Alkoxyl group or carboxyl, dentate X are halogen,
Catalyst levels is 1～30ppm, passes into oxygen with 10～60mL/min flow velocity, and first 140～160 ℃ of lower high temperature initiation reactions, then at 70～110 ℃ of lower low-temp reaction 4～10h, reacted mixture obtains Propiophenone through underpressure distillation.
2. according to claim 1 method is characterized in that M
1, M
2, M
3Or M
4Be iron, manganese or cobalt, M
3And M
4Identical.
3. according to claim 2 method is characterized in that when any two kinds of catalyst combination, wherein the M in a kind of catalyzer
1, M
2, M
3Or M
4Be iron or manganese, the M in the another kind of catalyzer
1, M
2, M
3Or M
4Be cobalt.
4. according to claim 3 method, the mol ratio that it is characterized in that iron porphyrin or manganoporphyrin and cobalt porphyrin is 1: 1～10.
5. according to claim 1 method is characterized in that dentate X is chlorine.
6. according to claim 1 method is characterized in that catalyst levels is 5～15ppm.
7. according to claim 1 method is characterized in that oxygen gas flow rate is 30～50mL/min.
8. according to claim 1 method is characterized in that kick off temperature is 140～160 ℃.
9. according to claim 1 method is characterized in that temperature of reaction is 90～100 ℃.
10. according to claim 1 method is characterized in that the reaction times is 6～8h.
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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 |
| CN104478677B (en) * | 2014-11-20 | 2017-03-29 | 中山大学 | A kind of method that bionic catalysis diphenyl-methane dioxygen oxidation prepares benzophenone |
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Non-Patent Citations (4)
| Title |
|---|
| Cancheng Guo,et al..Selective oxidation of ethylbenzene with air catalyzed by simple μ-oxo dimeric metalloporphyrins under mild conditions in the absence of additives.《Journal of Molecular Catalysis A: Chemical》.2003,第192卷(第1-2期),295-302. * |
| Shi-Jun Li and Yan-Guang Wang.A novel and selective catalytic oxidation of hydrocarbons to ketones using chloramine-T/O2/Fe(TPP)Cl system.《Tetrahedron Letters》.2005,第46卷(第46期),8013–8015. * |
| 周贤太等.金属卟啉催化剂应用于均相氧化反应的研究进展.《有机化学》.2007,第27卷(第9期),1039-1049. * |
| 彭清静等.μ-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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