CN102267886A - Method for preparing p-ethyl acetophenone by selectively oxidizing p-diethylbenzene with oxygen or air under catalysis of metalloporphyrin - Google Patents
Method for preparing p-ethyl acetophenone by selectively oxidizing p-diethylbenzene with oxygen or air under catalysis of metalloporphyrin Download PDFInfo
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- CN102267886A CN102267886A CN2011101580744A CN201110158074A CN102267886A CN 102267886 A CN102267886 A CN 102267886A CN 2011101580744 A CN2011101580744 A CN 2011101580744A CN 201110158074 A CN201110158074 A CN 201110158074A CN 102267886 A CN102267886 A CN 102267886A
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Abstract
The invention relates to a method for preparing p-ethyl acetophenone by selectively oxidizing p-diethylbenzene with oxygen or air under catalysis of metalloporphyrin. In the method, p-diethylbenzene is used as a raw material, 1-100 ppm of metalloporphyrin is used as a catalyst (the catalyst has no need of separation and recovery), oxygen or air is introduced at a flow rate of 10-80 mL/min, reaction is carried out under normal pressure and solvent-free conditions at the temperature of 130-180 DEG C for 0.5-2 hours, and the obtained reaction mixture is subjected to reduced pressure distillation to obtain p-ethyl acetophenone. By using the method provided by the invention, p-ethyl acetophenone can be synthesized at high selectivity and high yield under environmentally-friendly conditions within shorter reaction time. In the method, because the solvent is not used and the catalyst has no need of separation and recovery, the solvent and catalyst recovery problem can be completely avoided, thus significantly reducing the energy consumption and effectively saving the synthesis cost; because a chemical oxidant, any additives and solvent are not used, the environmental pollution is minimized; and the method is simple in reaction operation and has broad application prospects in industry.
Description
Technical field
The present invention relates to the method for a kind of catalysis of metalloporphyrin oxygen or air selective oxidation p-Diethylbenzene preparation to the ethylbenzene ethyl ketone.
Background technology
Traditionally the ethylbenzene ethyl ketone is mainly obtained through the Friedel-Crafts acylation reaction by Lewis acid or strong protonic acid catalysis ethylbenzene and acetic anhydride or Acetyl Chloride 98Min., wherein the catalyzer of widespread usage is AlCl
3Patent PL159081B1 (open day: on November 30th, 1992) disclose a kind of synthetic method of Friedel-Crafts acylation reaction, acetic anhydride and AlCl of passing through to the ethylbenzene ethyl ketone
3Mol ratio be 1: 1.1～1.9,0～60 ℃ of temperature of reaction when temperature of reaction is 5～10 ℃, is 85% to ethylbenzene ethyl ketone yield.In this catalyst system, catalyst levels is very big on the one hand, not only can improve synthetic cost greatly, and can cause extremely serious environmental pollution problem; Produce a large amount of hydrogen chloride gas on the other hand in the reaction process, meeting is etching apparatus seriously, and needs very high facility investment and process cost.
Isabelle Kondolff (Tetrahedron, 2004,60 (17): 3813-3818) waiting the people to adopt the Suzuki linked reaction is solvent with toluene, consumption is 0.4% chlorination Allylpalladium (II) dipolymer/suitable, suitable, suitable-1 of substrate weight, 2,3,4-four-(diphenyl phosphine methyl) pentamethylene is a catalyzer, and consumption is substrate molar weight duple K
2CO
3, catalysis parabromoacetophenone and ethyl-boron dihydroxide are synthetic to the ethylbenzene ethyl ketone at 130 ℃ of reaction 20h under argon shield, and are 89% to the separation yield of ethylbenzene ethyl ketone.Although this method gained is higher to the yield of ethylbenzene ethyl ketone, raw materials used and catalyzer costliness and preparation complexity, severe reaction conditions, synthetic cost is higher; Use toluene as solvent, not only increased raw materials cost, and solvent need reclaim, and the energy consumption that reclaims is very big, running cost increases; Also owing to use a large amount of alkali, and also need neutralize with a large amount of acid in last handling process, with producing in a large number the brine waste that can not handle with biochemical process, cause aftertreatment extremely difficult, environmental pollution is serious.
S.Sudha (Journal of Porous Materials, 2009,16 (2): 215-226) waiting the people is that catalyzer has synthesized the ethylbenzene ethyl ketone at 250～400 ℃ of catalysis ethylbenzene and acetic acid ethyl reaction with Fe-Al-MCM-41 or Zn-Al-MCM-41, and selectivity is less than 45%.The shortcoming of this method is lower to ethylbenzene ethyl ketone selectivity, and by product is more, separation difficulty; And this method temperature of reaction is too high, causes big, the synthetic cost height of energy consumption, potential safety hazard to give prominence to.
(Journal ofthe Chemical Society-Perkin Transactions 1,2001, (6): 578-583) wait with the p-Diethylbenzene is raw material to Kenneth K.Laali, Ce (OTf)
4Be oxygenant, acetonitrile is a solvent, has at room temperature synthesized to the ethylbenzene ethyl ketone Ce (OTf)
4With the p-Diethylbenzene mol ratio be 2: 1 o'clock, the reaction 22h, can reach 45.6% to ethylbenzene ethyl ketone yield; When its mol ratio is 4: 1, reaction 25h, its yield can bring up to 61.3%.Ce (OTf)
4Preparation model and water content thereof its oxidation capacity is had a significant impact severe reaction conditions not only, and use expensive Ce (OTf)
4As oxygenant, cost an arm and a leg, poisonous and acetonitrile highly volatile is solvent, not only increased synthetic cost, and solvent recuperation causes greater energy consumption, solvent evaporates again can serious environment pollution.Simultaneously, this method long reaction time causes reaction efficiency low, and energy consumption is big and running cost is high.
In sum, mainly there is following problem in present synthetic method to the ethylbenzene ethyl ketone:
(1) catalyst levels is big, and with after need Separation and Recovery.And cost height, the energy consumption of Separation and Recovery catalyzer are big, and three waste discharge causes environmental pollution more;
(2) need to use a large amount of alkali, also need a large amount of acid to neutralize in subsequent separation process accordingly, the result produces the brine waste that is difficult to biochemical treatment in a large number, has both wasted resource, causes environmental pollution again;
(3) need with an organic solvent, even the bigger acetonitrile of toxicity is solvent, not only causes environmental pollution, increase raw materials cost, but also can cause the significantly increase of energy consumption and process cost because of the recovery of solvent;
(4) need to use chemical oxidizing agent, not only increased raw material and synthetic cost, and because of producing a large amount of poisonous and hazardous waste water, waste residue, and cause serious environmental to pollute;
(5) need very high temperature of reaction (250～400 ℃), cause the energy consumption height, synthetic cost height, and potential safety hazard is big;
(6) long reaction time (surpassing 20h) causes reaction efficiency low, and energy consumption is big and running cost is high;
(7) severe reaction conditions.Carry out under argon shield as need, not only increased synthetic cost, and complicated operation.
Up to the present, Shang Weijian has bionic catalysis system catalytic oxygen or the preparation of air selective oxidation p-Diethylbenzene that the method for ethylbenzene ethyl ketone is reported.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, provide a kind of catalyst levels few and need not reclaim, the reaction times is short, the preparation of solvent-free and eco-friendly metalloporphyrin biomimetic-catalysis oxygen or air selective oxidation p-Diethylbenzene is to the method for ethylbenzene ethyl ketone.
A kind of catalysis of metalloporphyrin selective oxidation p-Diethylbenzene preparation provided by the present invention is to the method for ethylbenzene ethyl ketone, the steps include: with the p-Diethylbenzene to be raw material, select for use and have formula (I), the monokaryon metalloporphyrin of formula (II) structure and have any one or two kinds in the dinuclear metalloporphyrin of formula (III) structure as catalyzer, catalyst levels is 1～100ppm, at normal pressure, under the condition of no solvent, flow velocity aerating oxygen or air with 10～80mL/min, react 0.5～2h down in 130～180 ℃, the gained reaction mixture obtains the ethylbenzene ethyl ketone through underpressure distillation
Wherein, M
1Be iron, cobalt, manganese, copper, zinc, nickel or chromium, M
2Be iron, cobalt, manganese, nickel or chromium, M
3And M
4Identical or different, be iron, cobalt or manganese when identical, not simultaneously, M
3Be iron, M
4Be manganese, M
3Be iron, M
4Be cobalt or M
3Be manganese, M
4Be cobalt; 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 a halogen.
Above-mentioned M
1, M
2, M
3Or M
4Preferred iron, cobalt or manganese, M
3And M
4Identical.
Above-mentioned R
11, R
12, R
13, R
21, R
22, R
23, R
31, R
32Or R
33Preferred nitro, chlorine or hydrogen.
The preferred chlorine of above-mentioned X.
Preferred 10～the 30ppm of above-mentioned catalyst levels.
Preferred 30～the 60mL/min of oxygen or air velocity.
Preferred 150～160 ℃ of temperature of reaction.
Preferred 1～2h of reaction times.
The inventive method is compared the existing method of ethylbenzene ethyl ketone with synthetic, has following beneficial effect:
(1) present method is that catalyzer is used for synthetic to the ethylbenzene ethyl ketone with eco-friendly metal porphyrins, and its advantage is the consumption few (ppm level) of catalysis of metalloporphyrin agent, and need not separate and reclaim after the reaction.Himself can after the use in environment natural degradation, can not produce secondary pollution;
(2) present method need not add alkali and other any auxiliary agents, not only greatly reduces synthetic cost, has simplified last handling process yet, has avoided the environmental pollution that consequent spent acid, salkali waste and brine waste caused;
(3) present method is not used any solvent, not only can eliminate the environmental pollution that the poisonous and harmful solvent may cause fully, and has avoided the problem of solvent recuperation fully, and synthetic energy consumption and cost are reduced greatly;
(4) present method uses cheap oxygen of cleaning or air to replace the serious and expensive chemical oxidizing agent of contaminate environment, has not only reduced environmental pollution significantly, and greatly reduces raw material and synthetic cost;
(5) present method temperature of reaction lower (130～180 ℃) has not only been saved energy consumption, has reduced cost, and has increased security;
(6) in present method reaction times short (less than 2h), not only improved reaction efficiency greatly, reduced energy consumption, and saved running cost;
(7) present method reaction conditions is gentle, easy and simple to handle relatively.
Embodiment
Embodiment 1
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 15ppm tetraphenylarsonium chloride base cobalt porphyrin (is R in the formula (II)
21Be H, R
22Be H, R
23Be H, M
2Be Co, X is Cl), with the flow velocity aerating oxygen of 60mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 55.5%, to ethylbenzene ethyl ketone selectivity be 70.4%, yield is 39.1%.
Embodiment 2
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 30ppm tetraphenylarsonium chloride base cobalt porphyrin (is R in the formula (II)
21Be H, R
22Be H, R
23Be H, M
2Be Co, X is Cl), with the flow velocity bubbling air of 60mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 34.8%, to ethylbenzene ethyl ketone selectivity be 70.1%, yield is 24.4%.
Embodiment 3
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 30ppm chlorination four-(right-carboxyl phenyl) iron porphyrin (is R in the formula (II)
21Be H, R
22Be H, R
23Be COOH, M
2Be Fe, X is Cl), with the flow velocity aerating oxygen of 30mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 73.8%, to ethylbenzene ethyl ketone selectivity be 53.8%, yield is 39.7%.
Embodiment 4
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 10ppm chlorination four-(right-nitrophenyl) cobalt porphyrin (is R in the formula (II)
21Be H, R
22Be H, R
23Be NO
2, M
2Be Co, X is Cl), with the flow velocity aerating oxygen of 60mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 62.0%, to ethylbenzene ethyl ketone selectivity be 69.8%, yield is 43.3%.
Embodiment 5
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 10ppm tetraphenyl cobalt porphyrin (is R in the formula (I)
11Be H, R
12Be H, R
13Be H, M
1Be Co), with the flow velocity aerating oxygen of 50mL/min, under normal pressure, at 150 ℃ of reaction 2h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 64.3%, to ethylbenzene ethyl ketone selectivity be 65.6%, yield is 42.2%.
Embodiment 6
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 15ppm chlorination four-(neighbour-chloro-phenyl-) manganoporphyrin (is R in the formula (II)
21Be Cl, R
22Be H, R
23Be H, M
2Be Mn, X is Cl), with the flow velocity aerating oxygen of 50mL/min, under normal pressure, at 150 ℃ of reaction 2h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 68.2%, to ethylbenzene ethyl ketone selectivity be 58.7%, yield is 40.0%.
Embodiment 7
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 10ppm four-(right-chloro-phenyl-) zinc protoporphyrin (is R in the formula (I)
11Be H, R
12Be H, R
13Be Cl, M
1Be Zn), with the flow velocity aerating oxygen of 60mL/min, under normal pressure, at 160 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 46.7%, to ethylbenzene ethyl ketone selectivity be 30.6%, yield is 14.3%.
Embodiment 8
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 10ppm chlorination four-(right-nitrophenyl) chromium porphyrin (is R in the formula (II)
21Be H, R
22Be H, R
23Be NO
2, M
2Be Cr, X is Cl), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 150 ℃ of reaction 2h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 50.1%, to ethylbenzene ethyl ketone selectivity be 36.8%, yield is 18.4%.
Embodiment 9
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 15ppm bromination four-(right-p-methoxy-phenyl) molybdenum porphyrin (is R in the formula (II)
21Be H, R
22Be H, R
23Be OCH
3, M
2Be Mo, X is Br), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 51.5%, to ethylbenzene ethyl ketone selectivity be 49.2%, yield is 25.3%.
Embodiment 10
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 15ppm four-(right-hydroxy phenyl) ruthenium porphyrin (is R in the formula (I)
11Be H, R
12Be H, R
13Be OH, M
1Be Ru), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 52.4%, to ethylbenzene ethyl ketone selectivity be 43.2%, yield is 22.6%.
Embodiment 11
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 100ppm four-(right-the n-propyl phenyl) iron porphyrin (is R in the formula (I)
11Be H, R
12Be H, R
13Be CH
3CH
2CH
2, M
1Be Fe), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 150 ℃ of reaction 0.5h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 41.8%, to ethylbenzene ethyl ketone selectivity be 30.8%, yield is 12.9%.
Embodiment 12
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 15ppm four-(right-ethoxyl phenenyl) cobalt porphyrin (is R in the formula (I)
11Be H, R
12Be H, R
13Be OC
2H
5, M
1Be Co), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 180 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 80.1%, to ethylbenzene ethyl ketone selectivity be 49.2%, yield is 39.4%.
Embodiment 13
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 15ppm chlorination four-(-chloro-phenyl-) nickel-porphyrin (is R in the formula (II)
21Be H, R
22Be Cl, R
23Be H, M
2Be Ni, X is Cl), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 50.6%, to ethylbenzene ethyl ketone selectivity be 42.6%, yield is 21.6%.
Embodiment 14
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 30ppm μ-oxygen-double-core tetraphenyl iron porphyrin (is R in the formula (III)
31Be H, R
32Be H, R
33Be H, M
3And M
4All be Fe), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 56.7%, to ethylbenzene ethyl ketone selectivity be 39.2%, yield is 22.2%.
Embodiment 15
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 30ppm μ-oxygen-double-core four-(rubigan) cobalt porphyrin (is R in the formula (III)
31Be H, R
32Be H, R
33Be Cl, M
3And M
4All be Co), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 150 ℃ of reaction 2h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 70.4%, to ethylbenzene ethyl ketone selectivity be 50.6%, yield is 35.6%.
Embodiment 16
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 30ppm μ-oxygen-double-core four-(p-nitrophenyl) manganoporphyrin (is R in the formula (III)
31Be H, R
32Be H, R
33Be NO
2, M
3And M
4All be Mn), with the flow velocity aerating oxygen of 20mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 68.5%, to ethylbenzene ethyl ketone selectivity be 48.2%, yield is 33.0%.
Embodiment 17
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 30ppm μ-oxygen-double-core four-(p-methylphenyl) iron-manganoporphyrin (is R in the formula (III)
31Be H, R
32Be H, R
33Be CH
3, M
3Be Fe, M
4Be Mn), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 160 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 60.5%, to ethylbenzene ethyl ketone selectivity be 41.3%, yield is 25.0%.
Embodiment 18
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 30ppm μ-oxygen-double-core four-(ortho-nitrophenyl base) iron-cobalt porphyrin (is R in the formula (III)
31Be NO
2, R
32Be H, R
33Be H, M
3Be Fe, M
4Be Co), with the flow velocity bubbling air of 60mL/min, under normal pressure, at 150 ℃ of reaction 2h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 72.6%, to ethylbenzene ethyl ketone selectivity be 49.1%, yield is 35.6%.
Embodiment 19
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 20ppm μ-oxygen-double-core four-(rubigan) manganese-cobalt porphyrin (is R in the formula (III)
31Be H, R
32Be H, R
33Be Cl, M
3Be Mn, M
4Be Co), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 74.3%, to ethylbenzene ethyl ketone selectivity be 51.8%, yield is 38.5%.
Embodiment 20
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 5ppm four-(Chloro-O-Phenyl) copper porphyrin (is R in the formula (I)
11Be Cl, R
12Be H, R
13Be H, M
1Be Cu), 10ppm chlorination four-(rubigan) iron porphyrin (is R in the formula (II)
21Be H, R
22Be H, R
23Be Cl, M
2Be Fe, X is Cl), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 78.2%, to ethylbenzene ethyl ketone selectivity be 56.5%, yield is 44.2%.
Embodiment 21
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 1ppm tetraphenylarsonium chloride base manganoporphyrin (is R in the formula (II)
21Be H, R
22Be H, R
23Be H, M
2Be Mn, X is Cl), 10ppm μ-oxygen-double-core tetraphenyl iron porphyrin (is R in the formula (III)
31Be H, R
32Be H, R
33Be H, M
3And M
4All be Fe), with the flow velocity aerating oxygen of 40mL/min, under normal pressure, at 150 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 75.3%, to ethylbenzene ethyl ketone selectivity be 52.6%, yield is 39.6%.
Embodiment 22
In the 100mL there-necked flask, add the 13.4g p-Diethylbenzene successively, 10ppm μ-oxygen-double-core four-(rubigan) cobalt porphyrin (is R in the formula (III)
31Be H, R
32Be H, R
33Be Cl, M
3And M
4All be Co), 5ppm μ-oxygen-double-core four-(p-methoxyphenyl) iron porphyrin (is R in the formula (III)
31Be H, R
32Be H, R
33Be OCH
3, M
3And M
4All be Fe), with the flow velocity bubbling air of 80mL/min, under normal pressure, at 140 ℃ of reaction 1h.The gained reaction mixture must be to the ethylbenzene ethyl ketone through underpressure distillation, and the p-Diethylbenzene transformation efficiency is 60.3%, to ethylbenzene ethyl ketone selectivity be 47.8%, yield is 28.8%.
Claims (8)
1. the preparation of catalysis of metalloporphyrin oxygen or air selective oxidation p-Diethylbenzene is to the method for ethylbenzene ethyl ketone, the steps include: with the p-Diethylbenzene to be raw material, select for use and have formula (I), the monokaryon metalloporphyrin of formula (II) structure and have any one or two kinds in the dinuclear metalloporphyrin of formula (III) structure as catalyzer, catalyst levels is 1～100ppm, at normal pressure, under the condition of no solvent, flow velocity aerating oxygen or air with 10～80mL/min, react 0.5～2h down in 130～180 ℃, the gained reaction mixture obtains the ethylbenzene ethyl ketone through underpressure distillation
Wherein, M
1Be iron, cobalt, manganese, copper, zinc, nickel or chromium, M
2Be iron, cobalt, manganese, nickel or chromium, M
3And M
4Identical or different, be iron, cobalt or manganese when identical, not simultaneously, M
3Be iron, M
4Be manganese, M
3Be iron, M
4Be cobalt or M
3Be manganese, M
4Be cobalt; 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 a halogen.
2. according to the method for claim 1, it is characterized in that M
1, M
2, M
3Or M
4Be iron, cobalt or manganese, M
3And M
4Identical.
3. according to the method for claim 1, it is characterized in that R
11, R
12, R
13, R
21, R
22, R
23, R
31, R
32Or R
33Be nitro, chlorine or hydrogen.
4. according to the method for claim 1, it is characterized in that X is a chlorine.
5. according to the method for claim 1, it is characterized in that catalyst levels is 10～30ppm.
6. according to the method for claim 1, it is characterized in that oxygen or air velocity are 30～60mL/min.
7. according to the method for claim 1, it is characterized in that temperature of reaction is 150～160 ℃.
8. according to the method for claim 1, it is characterized in that the reaction times is 1～2h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961632A (en) * | 2015-05-21 | 2015-10-07 | 南京工业大学 | Method for preparing p-ethyl acetophenone by catalytic oxidation of p-diethylbenzene with supported molecular sieve |
| CN109046458A (en) * | 2018-06-30 | 2018-12-21 | 浙江工业大学 | Preparation method of p-nitroacetophenone |
| CN112047821A (en) * | 2020-08-05 | 2020-12-08 | 中山大学 | Preparation method of methyl ethyl ketone |
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| CN101747166A (en) * | 2010-01-29 | 2010-06-23 | 北京工业大学 | Method for preparing m-ethylacetophenone by biomimetic catalytic oxidation of m-diethylbenzene with oxygen |
| CN101747204A (en) * | 2010-01-29 | 2010-06-23 | 北京工业大学 | Method for preparing p-nitroacetophenone by biomimetic catalytic oxidation of p-nitroethylbenzene with oxygen |
| CN101759542A (en) * | 2010-01-29 | 2010-06-30 | 北京工业大学 | Method for preparing acetophenone by biomimetic catalytic oxidation of ethylbenzene with oxygen |
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| CN104961632A (en) * | 2015-05-21 | 2015-10-07 | 南京工业大学 | Method for preparing p-ethyl acetophenone by catalytic oxidation of p-diethylbenzene with supported molecular sieve |
| CN109046458A (en) * | 2018-06-30 | 2018-12-21 | 浙江工业大学 | Preparation method of p-nitroacetophenone |
| CN109046458B (en) * | 2018-06-30 | 2021-07-27 | 浙江工业大学 | Preparation method of p-nitroacetophenone |
| CN112047821A (en) * | 2020-08-05 | 2020-12-08 | 中山大学 | Preparation method of methyl ethyl ketone |
| CN112047821B (en) * | 2020-08-05 | 2022-05-03 | 中山大学 | Preparation method of methyl ethyl ketone |
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