CN104591990A - Method for preparing p-hydroxyacetophenone by catalytically oxidizing paraethyl phenol with metalloporphyrin-metal salt composite catalyst - Google Patents

Method for preparing p-hydroxyacetophenone by catalytically oxidizing paraethyl phenol with metalloporphyrin-metal salt composite catalyst Download PDF

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CN104591990A
CN104591990A CN201410822256.0A CN201410822256A CN104591990A CN 104591990 A CN104591990 A CN 104591990A CN 201410822256 A CN201410822256 A CN 201410822256A CN 104591990 A CN104591990 A CN 104591990A
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formula
metalloporphyrin
cobalt
manganese
iron
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佘远斌
杜晓雅
宋旭锋
于艳敏
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Beijing University of Technology
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Abstract

The invention relates to a method for preparing p-hydroxyacetophenone by catalytically and selectively oxidizing paraethyl phenol with a metalloporphyrin-metal salt composite catalyst. The method is characterized in that paraethyl phenol is taken as a raw material, methanol is taken as a solvent, metalloporphyrin expressed by a formula (I) or a formula (II) and a metal salt is taken as a composite catalyst or metalloporphyrin expressed by a formula (I), a formula (II) or a formula (III) is taken as the catalyst, the concentration of metalloporphyrin is 5-100ppm, the concentration of the metal salt is 500-2000ppm, the molar ratio of sodium hydroxide to ethyl phenol is (1-2.5): 1, the oxygen pressure is 0.2-0.5MPa, the reaction temperature ranges from 60 to 90 DEG C, the reaction time is 3-7h, and p-hydroxyacetophenone is obtained under all the conditions. According to the invention, the dosage of the catalyst is extremely low and the reaction time is short; after reaction, the catalyst does not need to be separated and recovered; the consumption of resources and the operating cost are reduced in the reaction process, and the purposes of saving energy and reducing emission are achieved while the environmental pollution is reduced.

Description

Metalloporphyrin-metal-salt composite catalyst catalyzed oxidation p-ethyl phenol prepares the method for parahydroxyacet-ophenone
Technical field
The present invention relates to a kind of method preparing aromatic ketone, specifically, relate to the method that a kind of metalloporphyrin-metal-salt composite catalyst catalytic selective oxidation p-ethyl phenol prepares parahydroxyacet-ophenone.
Background technology
Parahydroxyacet-ophenone (its structural formula is as follows) is important Fine Organic Chemical product, be widely used in the every field such as medicine, agricultural chemicals, dyestuff, liquid crystal material, simultaneously it still synthesizes choleretic, antipyretic and analgesic, anti-premature labor medicine, the raw material of asthma inhibitor and important intermediate, has important using value.
The preparation method of current parahydroxyacet-ophenone mainly contains with phenol and the acetic anhydride Fries rearrangementization method that is raw material, with methyl-phenoxide and the Acetyl Chloride 98Min. friedel-crafts acylation method that is raw material with take p-ethyl phenol as the direct oxidation method of raw material.
The people (Catalysis Communications, 2011,510-513) such as Fatemeh Rajabi report with silicon dioxide carried Co (II) as catalyst choice oxidation p-ethyl phenol prepares the method for parahydroxyacet-ophenone.The method take p-ethyl phenol as raw material, acetic acid is solvent, with silicon dioxide carried Co (II) for catalyzer, HP is radical initiator, pass into 1atm oxygen, at 100 DEG C, react 12h, obtain parahydroxyacet-ophenone, wherein the mol ratio of reactant, catalyzer, radical initiator is 200:1:20.The selectivity of parahydroxyacet-ophenone is 90%, and yield is 78%.
The main drawback that the method exists is as follows:
(1) catalyst levels very large (up to 5000ppm), and need Separation and Recovery after reaction, and Separation and Recovery catalyzer can cause, and cost is high, energy consumption large, and three waste discharge is many, environmental pollution is serious;
(2) long reaction time (more than 10h), and reaction efficiency is low, energy consumption is large and running cost is high;
(3) the method must use HP as radical initiator, and large usage quantity (consumption is 10000ppm), the separation of post catalyst reaction and initiator is more difficult, add product preparation cost, also there is the problems such as environmental pollution is serious, energy consumption is high simultaneously.
Summary of the invention
The object of the invention is to overcome above-mentioned problems of the prior art, provide that a kind of catalyst levels is minimum, the reaction times is very short, cost is low and pollute the method that little metalloporphyrin-metal-salt composite catalyst catalytic selective oxidation p-ethyl phenol prepares parahydroxyacet-ophenone.
A kind of metalloporphyrin provided by the present invention-metal-salt composite catalyst catalytic selective oxidation p-ethyl phenol prepares the method for parahydroxyacet-ophenone, the steps include: to take p-ethyl phenol as raw material, methyl alcohol is solvent, the combination of the metalloporphyrin that formula (I) or formula (II) represent and metal-salt is as catalyzer, or formula (I), the metalloporphyrin that formula (II) or formula (III) represent is as catalyzer, the concentration of metalloporphyrin is 5 ~ 100ppm, the concentration of metal-salt is 500 ~ 2000ppm, the mol ratio of sodium hydroxide and p-ethyl phenol is 1 ~ 2.5:1, oxygen pressure 0.2 ~ 0.5MPa, temperature of reaction 60 ~ 90 DEG C, reaction times 3 ~ 7h, obtain parahydroxyacet-ophenone.
Wherein, M 1for cobalt, iron, manganese, copper or zinc, M 2for cobalt, manganese or iron, M 3and M 4identical or different, be cobalt, iron or manganese time identical, time different, M 3for iron, M 4for manganese or M 3for iron, M 4for cobalt or M 3for manganese, M 4for cobalt, substituent R 11, R 12, R 13, R 21, R 22, R 23, R 31, R 32or R 33for hydrogen, halogen, nitro, hydroxyl, methyl, methoxyl group or carboxyl, dentate X is halogen, the acetate of described metal-salt chosen from Fe, cobalt, manganese, copper, zinc or nickel, hydrochloride, nitrate or vitriol.
The metalloporphyrin preferably represented using formula (I) or formula (II) and the combination of metal-salt are as catalyzer.The metalloporphyrin particularly preferably represented using formula (I) or formula (II) and the combination of Cobaltous diacetate are as catalyzer.More preferably the metalloporphyrin represented using formula (II) and the combination of Cobaltous diacetate are as catalyzer.
Preferred M 1for cobalt, iron or manganese.
Preferred M 2for cobalt or manganese.
Preferred M 3, M 4for cobalt, iron or manganese, M 3and M 4identical.
Preferred X is chlorine.
The concentration of preferable alloy porphyrin is 50 ~ 100ppm.
The concentration of preferable alloy salt is 1000ppm.
The mol ratio of preferred sodium hydroxide and p-ethyl phenol is 2:1.
Preferred oxygen pressure is 0.3MPa.
Preferable reaction temperature is 85 DEG C.
The preferred reaction time is 3 ~ 5h.
The inventive method compared with prior art has following beneficial effect:
(1) present method with environmental friendliness and the metalloporphyrin-metal-salt of consumption few (5 ~ 100ppm) be combined as catalyzer, effectively achieve between catalyst component the concerted catalysis effect to hydroxyl ethylbenzene, and do not need after reaction to be separated, to reclaim catalyzer, the resource consumption in reaction process and process cost can be greatly reduced, and while minimizing environmental pollution, the object of energy-saving and emission-reduction can also be reached;
(2) present method preferred reaction times is 3 ~ 5h, and the reaction times shortens at least over half compared with prior art.This is due to the concerted catalysis effect between metalloporphyrin and metal-salt, utilize the redox potential and the electron-donating difference of suction that exist in the multiple composite catalyst combination of identical or different metal ion and part (acid group), promote the mutual activation to substrate between metal ion, accelerate speed of response, thus shorten the reaction times, not only substantially increase reaction efficiency, reduce energy consumption, and save running cost;
(3) present method does not use radical initiator, while reduction arone product preparation cost, can also overcome exist in reaction process environmental pollution, catalyst recovery and initiator loss, and the problem such as the energy consumption that produces therefrom is high, thus make its prospect in industrial applications in the future more wide.
Embodiment
Embodiment 1
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g tetraphenylarsonium chloride base Cob altporphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for H, M 2for Co, X are Cl), 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 31.42%, and yield is 10.52%.
Embodiment 2
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g tetraphenylarsonium chloride base iron porphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for H, M 2for Fe, X are Cl), 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 16.84%, and yield is 6.9%.
Embodiment 3
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g chlorination four-(p-p-methoxy-phenyl) manganoporphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for OCH 3, M 2for Mn, X are Cl), 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 60 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 15.67%, and yield is 2.99%.
Embodiment 4
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g tetra--(p-aminomethyl phenyl) copper porphyrin (i.e. R in logical formula I 11for H, R 12for H, R 13for CH 3, M 1for Cu), 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 15.12%, and yield is 5.0%.
Embodiment 5
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g tetra--(p-p-methoxy-phenyl) zinc protoporphyrin (i.e. R in logical formula I 11for H, R 12for H, R 13for OCH 3, M 1for Zn), 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 16.06%, and yield is 6.88%.
Embodiment 6
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g cobalt tetraphenylporphyrin (i.e. R in logical formula I 11for H, R 12for H, R 13for H, M 1for Co), 4g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 3h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 21.42%, and yield is 5.67%.
Embodiment 7
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 8 × 10 -3g chlorination four-(p-p-methoxy-phenyl) Cob altporphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for OCH 3, M 2for Co, X are Cl), 10g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 26.98%, and yield is 15.83%.
Embodiment 8
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g chlorination four-(p-hydroxy phenyl) Cob altporphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for OH, M 2for Co, X are Cl), 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 5h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 21.5%, and yield is 10.32%.
Embodiment 9
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g chlorination four-(p-carboxyl phenyl) Cob altporphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for COOH, M 2for Co, X are Cl), 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 7h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 19.46%, and yield is 7.66%.
Embodiment 10
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g chlorination four-(p-hydroxy phenyl) Cob altporphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for OH, M 2for Co, X are Cl), 0.0249g Cobaltous diacetate, 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.5MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 41.28%, and yield is 21.7%.
Embodiment 11
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g chlorination four-(p-chloro-phenyl-) Cob altporphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for Cl, M 2for Co, X are Cl), 0.02g ferric sulfate, 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 29.23%, and yield is 12.96%.
Embodiment 12
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g chlorination four-(p-nitrophenyl) iron porphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for NO 2, M 2for Fe, X are Cl), 0.0346g manganese acetate, 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 45.96%, and yield is 18.56%.
Embodiment 13
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g tetra--(p-p-methoxy-phenyl) manganoporphyrin (i.e. R in logical formula I 11for H, R 12for H, R 13for OCH 3, M 1for Mn), 0.0249g Cobaltous diacetate, 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 41.3%, and yield is 18.9%.
Embodiment 14
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g chlorination four-(p-carboxyl phenyl) Cob altporphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for COOH, M 2for Co, X are Cl), 0.0498g Cobaltous diacetate, 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.2MPa, at 75 DEG C, reacts 3h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 31.56%, and yield is 9.32%.
Embodiment 15
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g chlorination four-(p-hydroxy phenyl) manganoporphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for OH, M 2for Mn, X are Cl), 0.0187g cupric nitrate, 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 90 DEG C, reacts 7h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 32.12%, and yield is 13.45%.
Embodiment 16
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -4g chlorination four-(p-chloro-phenyl-) iron porphyrin (i.e. R in logical formula II 21for H, R 22for H, R 23for Cl, M 2for Fe, X are Cl), 0.0136g zinc chloride, 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.2MPa, at 85 DEG C, reacts 5h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 12.41%, and yield is 4.78%.
Embodiment 17
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 4 × 10 -3g tetra--(p-nitrophenyl) manganoporphyrin (i.e. R in logical formula I 11for H, R 12for H, R 13for NO 2, M 1for Mn), 0.04g ferric sulfate, 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.4MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 28.16%, and yield is 9.81%.
Embodiment 18
In 100mL autoclave, add 12.2g p-ethyl phenol successively, 1.5 × 10 -2g μ-oxygen-double-core four-(p-aminomethyl phenyl) manganoporphyrin (i.e. R in logical formula III 31for H, R 32for H, R 33for CH 3, M 3and M 4for Mn), 0.04g ferric sulfate, 8g sodium hydroxide, 30mL methyl alcohol, passes into the oxygen that pressure is 0.3MPa, at 85 DEG C, reacts 4h.Reacted mixture is through efficient liquid phase chromatographic analysis, and the selectivity of 4-hydroxyacetophenone is 27.56%, and yield is 12.05%.

Claims (10)

1. metalloporphyrin-metal-salt composite catalyst catalytic selective oxidation p-ethyl phenol prepares the method for parahydroxyacet-ophenone, the steps include: to take p-ethyl phenol as raw material, methyl alcohol is solvent, the combination of the metalloporphyrin that formula (I) or formula (II) represent and metal-salt is as catalyzer, or formula (I), the metalloporphyrin that formula (II) or formula (III) represent is as catalyzer, the concentration of metalloporphyrin is 5 ~ 100ppm, the concentration of metal-salt is 500 ~ 2000ppm, the mol ratio of sodium hydroxide and p-ethyl phenol is 1 ~ 2.5:1, oxygen pressure 0.2 ~ 0.5MPa, temperature of reaction 60 ~ 90 DEG C, reaction times 3 ~ 7h, obtain parahydroxyacet-ophenone.
Wherein, M 1for cobalt, iron, manganese, copper or zinc, M 2for cobalt, manganese or iron, M 3and M 4identical or different, be cobalt, iron or manganese time identical, time different, M 3for iron, M 4for manganese or M 3for iron, M 4for cobalt or M 3for manganese, M 4for cobalt, substituent R 11, R 12, R 13, R 21, R 22, R 23, R 31, R 32or R 33for hydrogen, halogen, nitro, hydroxyl, methyl, methoxyl group or carboxyl, dentate X is halogen, the acetate of described metal-salt chosen from Fe, cobalt, manganese, copper, zinc or nickel, hydrochloride, nitrate or vitriol.
2. method according to claim 1, is characterized in that the combination of metalloporphyrin and the metal-salt represented using formula (I) or formula (II) is as catalyzer.
3. method according to claim 2, is characterized in that the combination of metalloporphyrin and the Cobaltous diacetate represented using formula (I) or formula (II) is as catalyzer.
4. method according to claim 3, is characterized in that the combination of metalloporphyrin and the Cobaltous diacetate represented using formula (II) is as catalyzer.
5. method according to claim 1, is characterized in that M 1for cobalt, iron or manganese.
6. method according to claim 1, is characterized in that M 2for cobalt or manganese.
7. method according to claim 1, is characterized in that M 3, M 4for cobalt, iron or manganese, M 3and M 4identical.
8. method according to claim 1, is characterized in that the concentration of metalloporphyrin is 50 ~ 100ppm, and the concentration of metal-salt is 1000ppm.
9. method according to claim 1, is characterized in that the mol ratio of sodium hydroxide and p-ethyl phenol is 2:1.
10. method according to claim 1, is characterized in that the reaction times is 3 ~ 5h.
CN201410822256.0A 2014-12-25 2014-12-25 Method for preparing p-hydroxyacetophenone by catalytically oxidizing paraethyl phenol with metalloporphyrin-metal salt composite catalyst Pending CN104591990A (en)

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KR20230046796A (en) 2021-09-30 2023-04-06 노승호 Method for preparing p-Hydroxyacetophenone and cosmetic composition containing p-Hydroxyacetophenone

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Application publication date: 20150506