CN103183594A - Method for preparing p-cresol into p-hydroxy benzaldehyde by catalytic oxidation of metalloporphyrin-metal salt composite catalyst - Google Patents
Method for preparing p-cresol into p-hydroxy benzaldehyde by catalytic oxidation of metalloporphyrin-metal salt composite catalyst Download PDFInfo
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Abstract
The invention relates to a method for preparing p-cresol into p-hydroxy benzaldehyde by the catalytic oxidation of a metalloporphyrin-metal salt composite catalyst. The method comprises the following steps: taking the p-cresol as a raw material, taking methanol or methanol water solution as a solvent, taking a combination of metalloporphyrin and metal salt as a catalyst or taking a combination of any two or three in a formula (1), a formula (II) or a formula (III) as a catalyst or taking a combination of the formula (1) and the formula (I), a combination of the formula (II) and the formula (II) and a combination of the formula (III) and the formula (III) as a catalyst, wherein the concentration of metalloporphyrin is 5-100 ppm, the concentration of the metal salt is 5-200 ppm, and the dosage of sodium hydroxide is 1-2.5 times of the molar dosage of the p-cresol; introducing oxygen of 0.1-1.0 MPa; and reacting for 1-12 hours at a temperature of 50-90 DEG C to obtain the p-hydroxy benzaldehyde. The method has the advantage that while a target product with high yield is obtained, the dosage of the catalyst is extremely less, and the alkali dosage is also remarkably reduced, so that not only can resources be effectively saved, and can the environment pollution be reduced, but also the purpose of reducing energy consumption can be achieved, and further, the effects of energy conservation and emission reduction can be completely realized.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic aldehyde, specifically, relate to a kind of metalloporphyrin-metal-salt composite catalyst catalyzed oxidation p-cresol and prepare the method for p-Hydroxybenzaldehyde.
Background technology
P-Hydroxybenzaldehyde is important organic synthesis intermediate, is widely used in fields such as medicine, agricultural chemicals, dyestuff.Though the method that with the p-cresol is the synthetic p-Hydroxybenzaldehyde of raw material at present is a lot, metalloporphyrin bionic catalysis oxidation style is comparatively superior.Open day of European patent EP 330036A1(: on August 30th, 1989) disclose the method that a kind of bionically catalyzing and oxidizing p-cresol prepares p-Hydroxybenzaldehyde, this method is to be catalyzer with metalloporphyrin or metalloporphyrin-metal-salt, solved traditional method (EP0012939A1, open day: the problem of environmental pollution that the use of a large amount of cobalt-chloride catalysts causes on July 9th, 1980), but still there is the big problem of catalyst levels in this method.On June 30th, 2010) and document (Chinese Journal of Chemical Engineering open day of Chinese patent CN101759536A(:, 2012,20:262～266.) reported that a kind of catalysis of metalloporphyrin oxidation p-cresol prepares the method for p-Hydroxybenzaldehyde, this method is that employing little metal porphyrin is catalyzer, further solved the big problem of catalyst levels in the aforesaid method, but still there is the not high problem of yield in this method.
Although the synthetic method of above-mentioned p-Hydroxybenzaldehyde has progressively obtained very big progress, adopt the synthetic method of above-mentioned catalysis of metalloporphyrin agent system still to have following problem:
(1) yield is all not high, has only 50.2%～81.0%;
(2) wish to get higher yields (55%～81.0%), then catalyst consumption is very big, 3900ppm～6400ppm;
When (3) wishing to get higher yields (55%～81.0%), then the consumption of alkali is very big, the mol ratio of alkali and p-cresol is 3～6:1, and high alkali number need neutralize with a large amount of acid will cause the later stage to be separated the time, and the salt that the neutralization back generates causes the wastewater treatment difficulty, and the energy consumption of later stage separation is increased, process cost significantly rises.
Summary of the invention
The objective of the invention is to overcome the problem that above-mentioned prior art exists.Provide a kind of yield height but catalyst levels is little, the alkali consumption is low metalloporphyrin-metal-salt composite catalyst catalyzed oxidation p-cresol prepares the method for p-Hydroxybenzaldehyde.
A kind of metalloporphyrin provided by the present invention-metal-salt composite catalyst catalyzed oxidation p-cresol prepares the method for p-Hydroxybenzaldehyde, the steps include: with the p-cresol to be raw material, be solvent with methyl alcohol or methanol aqueous solution, with the combination of metalloporphyrin and metal-salt as catalyzer, or with the combination of any two or three in formula (I), formula (II) and the formula (III) as catalyzer, or with substituting group and identical, the central metallic ions M in substituent position in formula (I) and formula (I), formula (II) and formula (II), formula (III) and the formula (III)
1, M
2, M
3Or M
4Different combinations are as catalyzer, or with 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, concentration 5～the 100ppm of metalloporphyrin, concentration 5～the 200ppm of metal-salt, the mol ratio of sodium hydroxide and p-cresol is 1～2.5:1, feeds 0.1～1.0MPa oxygen, reacts 1～12h down at 50～90 ℃, obtain p-Hydroxybenzaldehyde
Formula III
Wherein said metalloporphyrin is selected from any one or two kinds in the monokaryon metalloporphyrin of formula (I), formula (II) expression and the μ-oxygen-dinuclear metalloporphyrin that formula III is represented, in acetate, hydrochloride, nitrate and the sulphite of described metal-salt chosen from Fe, manganese, cobalt, copper, zinc, chromium or nickel any one or two kinds, M
1Be iron, manganese, cobalt, copper or zinc, M
2Be iron, manganese or cobalt, M
3And 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, methyl, methoxyl group or carboxyl, dentate X is halogen.
Preferably with the combination of metalloporphyrin and metal-salt as catalyzer.Especially preferably with the combination of metalloporphyrin and metal-salt as catalyzer, wherein said metalloporphyrin is formula (I) or formula (II).More preferably with the combination of metalloporphyrin and metal-salt as catalyzer, wherein said metalloporphyrin is formula (I) or formula (II), described metal-salt is acetate or the hydrochloride of iron, cobalt or manganese.
Preferred M
1, M
2, M
3Or M
4Be iron, manganese or cobalt, M
3And M
4Identical.Preferred X is chlorine.
The concentration of preferable alloy porphyrin is 10～50ppm, the concentration of preferable alloy salt is 10～100ppm, and the mol ratio of preferred sodium hydroxide and p-cresol is 1.5～2:1, and the preferred oxygen atmospheric pressure is 0.2～0.5MPa, preferable reaction temperature is 60～80 ℃, and the preferred reaction time is 3～7h.
The starting point concentration of p-cresol is 0.5～5mol/L.
The inventive method compared with prior art has following beneficial effect:
(1) present method is with the catalyzer that is combined as of a kind of metalloporphyrin-a kind of metal-salt or two kinds of metalloporphyrin-a kind of metal-salts or two kinds of metalloporphyrin-two kind of metal-salts or a kind of metalloporphyrin-two kind of metal-salt, utilize the redox potential that exists in the multiple composite catalyst combination of identical or different metal ion and part (acid group) and inhale power supply property difference, promote between the metal ion the mutual activation to substrate, realized between catalyst component the concerted catalysis oxygenizement to p-cresol effectively, the transformation efficiency of p-cresol and the selectivity of p-Hydroxybenzaldehyde are significantly improved simultaneously, and then improved the yield of p-Hydroxybenzaldehyde significantly, its yield can bring up to 87% by 50.2%～81.0%, this has obviously not only effectively utilized resource, and because the selectivity height makes by product few, energy-saving and emission-reduction have been embodied effectively.
(2) because the concerted catalysis effect between metalloporphyrin and the metal-salt, reduced the activation energy of reactant significantly, but the combination of a spot of metalloporphyrin-metal-salt or two kinds of metalloporphyrins is as the synergy fast reaction speed of catalyzer, thereby make the reacting middle catalyst consumption be reduced to 50ppm significantly by preferred 3900ppm～6400ppm in the prior art, and then significantly reduced resource consumption and the process cost in the reaction process, when reducing environmental pollution, also reached the purpose of energy-saving and emission-reduction.
(3) because the concerted catalysis effect between metalloporphyrin and the metal-salt has substantially exceeded the promoting catalysis of alkali in the prior art, the result makes the consumption of alkali be reduced to 2 times by 3～6 times of the preferred p-cresol mole dosage of prior art, acid amount used when the later stage is separated also obviously reduces, the brine waste that causes thus also significantly reduces thereupon, has reduced environmental pollution significantly.
(4) present method operational safety, technology are simple, can either economize on resources effectively, can reduce environmental pollution again, also can reach the purpose that cuts down the consumption of energy, and then realize energy-saving and emission-reduction truly.
Embodiment
Embodiment 1
Get 6.4 * 10
-3G chlorination four-(right-p-methoxy-phenyl) cobalt porphyrin (is namely led to R in the formula II
21=R
22=H, R
23=OCH
3, X=Cl, M
2=Co), 3.2 * 10
-2The g Iron diacetate, 12.0g p-cresol and 12.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.2MPa, and temperature control reacts 10h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 99.2%, and the selectivity of p-Hydroxybenzaldehyde is 80.0%, and the yield of p-Hydroxybenzaldehyde is 79.4%.
Embodiment 2
Get 8.6 * 10
-4G chlorination four-(right-nitrophenyl) iron porphyrin (is namely led to R in the formula II
21=R
22=H, R
23=NO
2, X=Cl, M
2=Fe), 3.8 * 10
-4The g zinc chloride, 16.0g p-cresol and 8.9g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.6MPa, and temperature control reacts 5h down for 70 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 83.0%, and the selectivity of p-Hydroxybenzaldehyde is 67.4%, and the yield of p-Hydroxybenzaldehyde is 55.9%.
Embodiment 3
Get 6.4 * 10
-3G chlorination four-(right-p-methoxy-phenyl) iron porphyrin (is namely led to R in the formula II
11=R
12=H, R
13=OCH
3, X=Cl, M
2=Fe), 1.8 * 10
-3The g Cobaltous diacetate, 16.0g p-cresol and 14.5g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.2MPa, and temperature control reacts 10h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 99.9%, and the selectivity of p-Hydroxybenzaldehyde is 87.1%, and the yield of p-Hydroxybenzaldehyde is 87.0%.
Embodiment 4
Get 9.3 * 10
-4G chlorination four-(right-p-methoxy-phenyl) iron porphyrin (is namely led to R in the formula II
21=R
22=H, R
23=OCH
3, X=Cl, M
2=Fe), 1.86 * 10
-3G four-(right-carboxyl phenyl) cobalt porphyrin (namely leads to R in the formula I
11=R
12=H, R
13=COOH, M
1=Co), 3.6 * 10
-4The g Cobaltous diacetate, 16.0g p-cresol and 14.5g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.7MPa, and temperature control reacts 4h down for 60 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 77.6%, and the selectivity of p-Hydroxybenzaldehyde is 72.3%, and the yield of p-Hydroxybenzaldehyde is 56.1%.
Embodiment 5
Get 8.3 * 10
-4G four-(right-hydroxy phenyl) copper porphyrin (namely leads to R in the formula I
11=R
12=H, R
13=OH, M
1=Cu), 1.0 * 10
-3The g iron protochloride, 3.6 * 10
-4The g zinc chloride, 16.0g p-cresol and 12.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 9h down for 70 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 86.9%, and the selectivity of p-Hydroxybenzaldehyde is 65.3%, and the yield of p-Hydroxybenzaldehyde is 56.7%.
Embodiment 6
Get 4.3 * 10
-3G four-(right-p-methoxy-phenyl) copper porphyrin (is R in the formula I
11=R
12=H, R
13=OCH
3, M
1=Cu), 3.8 * 10
-3The g iron protochloride, 16.0g p-cresol and 14.5g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 6h down for 55 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 87.1%, and the selectivity of p-Hydroxybenzaldehyde is 73.8%, and the yield of p-Hydroxybenzaldehyde is 64.3%.
Embodiment 7
Get 5.6 * 10
-4G four-(right-chloro-phenyl-) zinc protoporphyrin (is R in the formula I
11=R
12=H, R
13=Cl, M
1=Zn), 1.9 * 10
-3The g cobalt chloride, 17.5g p-cresol and 12.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.6MPa, and temperature control reacts 8h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 76.5%, and the selectivity of p-Hydroxybenzaldehyde is 82.1%, and the yield of p-Hydroxybenzaldehyde is 62.8%.
Embodiment 8
Get 7.5 * 10
-3G μ-oxygen-double-core four-(neighbour-aminomethyl phenyl) iron-manganoporphyrin (is R in the formula III
31=CH
3, R
32=R
33=H, M
3=Fe, M
4=Mn), 8.0 * 10
-3The g Cobaltous diacetate, 16.0g p-cresol and 12.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 10h down for 60 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 92.0%, and the selectivity of p-Hydroxybenzaldehyde is 75.3%, and the yield of p-Hydroxybenzaldehyde is 69.3%.
Embodiment 9
Get 6.6 * 10
-3G μ-oxygen-double-core four-(neighbour-hydroxy phenyl) cobalt-manganoporphyrin (is R in the formula III
31=OH, R
32=R
33=H, M
3=Co, M
4=Mn), 1.0 * 10
-3The g iron protochloride, 1.0 * 10
-3The g Cobaltous diacetate, 16.0g p-cresol and 8.9g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 9h down for 55 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 79.5%, and the selectivity of p-Hydroxybenzaldehyde is 68.3%, and the yield of p-Hydroxybenzaldehyde is 54.3%.
Embodiment 10
Get 1.1 * 10
-2G four-(neighbour-p-methoxy-phenyl) cobalt porphyrin (is R in the formula I
11=OCH
3, R
12=R
13=H, M
1=Co), 2.2 * 10
-2G chlorination four-(right-chloro-phenyl-) manganoporphyrin (is R in the formula II
21=R
22=H, R
23=Cl, X=Cl, M
2=Mn), 3.8 * 10
-4The g ferrous sulfate, 3.8 * 10
-4The g zinc acetate, 16.0g p-cresol and 14.5g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 7h down for 70 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 95.0%, and the selectivity of p-Hydroxybenzaldehyde is 82.0%, and the yield of p-Hydroxybenzaldehyde is 77.9%.
Embodiment 11
Get 1.2 * 10
-2G four-(neighbour-chloro phenyl) cobalt porphyrin (is R in the formula I
11=Cl, R
12=R
13=H, M
1=Co), 3.5 * 10
-2G chlorination four-(right-nitrophenyl) iron porphyrin (is R in the formula II
21=R
22=H, R
23=NO
2, X=Cl, M
2=Fe), 3.8 * 10
-4The g rose vitriol, 3.8 * 10
-4The g Iron nitrate, 16.0g p-cresol and 6.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.6MPa, and temperature control reacts 8h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 75.4%, and the selectivity of p-Hydroxybenzaldehyde is 76.0%, and the yield of p-Hydroxybenzaldehyde is 57.3%.
Embodiment 12
Get 4.4 * 10
-3G μ-oxygen-double-core four-(right-p-methoxy-phenyl) iron-iron porphyrin (is R in the formula III
31=R
32=H, R
33=OCH
3, M
3=M
4=Fe), 1.0 * 10
-3The g iron protochloride, 16.0g p-cresol and 12.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 6h down for 55 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 81.0%, and the selectivity of p-Hydroxybenzaldehyde is 81.2%, and the yield of p-Hydroxybenzaldehyde is 65.8%.
Embodiment 13
Get 1.2 * 10
-3G chlorination four-(right-nitrophenyl) cobalt porphyrin (is R in the formula II
21=R
22=H, R
23=NO
2, X=Cl, M
2=Co), 1.0 * 10
-3The g iron acetate, 16.0g p-cresol and 12.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.4MPa, and temperature control reacts 7h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 79.6%, and the selectivity of p-Hydroxybenzaldehyde is 82.4%, and the yield of p-Hydroxybenzaldehyde is 65.6%.
Embodiment 14
Get 7.0 * 10
-3G four-(neighbour-hydroxy phenyl) zinc protoporphyrin (is R in the formula I
11=OH, R
12=R
13=H, M
1=Zn, 1.0 * 10
-3The g Cobaltous diacetate, 16.0g p-cresol and 12.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.3MPa, and temperature control reacts 6h down for 80 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 86.5%, and the selectivity of p-Hydroxybenzaldehyde is 77.3%, and the yield of p-Hydroxybenzaldehyde is 66.9%.
Embodiment 15
Get 3.5 * 10
-3G four-(neighbour-hydroxy phenyl) zinc protoporphyrin (is R in the formula I
11=OH, R
12=R
13=H, M
1=Zn, 1.0 * 10
-3The g cobalt chloride, 16.0g p-cresol and 14.5g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 6h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 90.5%, and the selectivity of p-Hydroxybenzaldehyde is 79.0%, and the yield of p-Hydroxybenzaldehyde is 71.5%.
Embodiment 16
Get 5.4 * 10
-3G chlorination four-(right-chloro-phenyl-) cobalt porphyrin (is namely led to R in the formula II
21=R
22=H, R
23=Cl, X=Cl, M
2=Co), 1.8 * 10
-3The g zinc nitrate, 16.0g p-cresol and 12.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.6MPa, and temperature control reacts 4h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 74.0%, and the selectivity of p-Hydroxybenzaldehyde is 77.4%, and the yield of p-Hydroxybenzaldehyde is 57.3%.
Embodiment 17
Get 1.5 * 10
-3G chlorination four-(o-nitrophenyl) manganoporphyrin (is namely led to R in the formula II
21=NO
2, R
22=R
23=H, X=Cl, M
2=Mn), 3.8 * 10
-3G zinc sulfate, 16.0g p-cresol and 8.9g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 8h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 84.2%, and the selectivity of p-Hydroxybenzaldehyde is 76.2%, and the yield of p-Hydroxybenzaldehyde is 64.2%.
Embodiment 18
Get 1.7 * 10
-3G four-(right-p-methoxy-phenyl) manganoporphyrin (namely leads to R in the formula I
11=R
12=H, R
13=OCH
3, M
1=Mn), 9.5 * 10
-3The g zinc chloride, 16.0g p-cresol and 14.5g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 5h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 89.3%, and the selectivity of p-Hydroxybenzaldehyde is 78.1%, and the yield of p-Hydroxybenzaldehyde is 69.7%.
Embodiment 19
Get 4.3 * 10
-3G chlorination four-(right-p-methoxy-phenyl) iron porphyrin (is namely led to R in the formula II
21=R
22=H, R
23=OCH
3, X=Cl, M
2=Fe), 8.6 * 10
-3G four-(right-carboxyl phenyl) zinc protoporphyrin (namely leads to R in the formula I
11=R
12=H, R
13=COOH, M
1=Zn), 3.6 * 10
-4The g Iron diacetate, 8.0g p-cresol and 6.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.6MPa, and temperature control reacts 6h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 79.5%, and the selectivity of p-Hydroxybenzaldehyde is 71.0%, and the yield of p-Hydroxybenzaldehyde is 56.4%.
Embodiment 20
Get 4.3 * 10
-3G four-(right-hydroxy phenyl) copper porphyrin (namely leads to R in the formula I
11=R
12=H, R
13=OH, M
1=Cu), 2.0 * 10
-2The g Cobaltous diacetate, 3.6 * 10
-3The g ferrous sulfate, 16.0g p-cresol and 14.0g sodium hydroxide add in the 100mL autoclave, add 60mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 10h down for 60 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 76.9%, and the selectivity of p-Hydroxybenzaldehyde is 85.3%, and the yield of p-Hydroxybenzaldehyde is 65.6%.
Embodiment 21
Get 3.2 * 10
-3G chlorination four-(right-chloro-phenyl-) cobalt porphyrin (is namely led to R in the formula II
21=R
22=H, R
23=Cl, X=Cl, M
2=Co), 3.2 * 10
-3G four-(right-hydroxy phenyl) copper porphyrin (namely leads to R in the formula I
11=R
12=H, R
13=OH, M
1=Cu), 16.0g p-cresol and 8.9g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.3MPa, and temperature control reacts 9h down for 70 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 85.0%, and the selectivity of p-Hydroxybenzaldehyde is 77.1%, and the yield of p-Hydroxybenzaldehyde is 65.5%.
Embodiment 22
Get 3.6 * 10
-3G chlorination four-(right-p-methoxy-phenyl) manganoporphyrin (is namely led to R in the formula II
21=R
22=H, R
23=OCH
3, X=Cl, M
2=Mn), 8.6 * 10
-4G chlorination four-(right-hydroxy phenyl) iron porphyrin (is namely led to R in the formula II
21=R
22=H, R
23=OH, X=Cl, M
2=Fe), 16.0g p-cresol and 14.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.6MPa, and temperature control reacts 8h down for 55 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 86.2%, and the selectivity of p-Hydroxybenzaldehyde is 76.5%, and the yield of p-Hydroxybenzaldehyde is 65.9%.
Embodiment 23
Get 4.3 * 10
-3G μ-oxygen-double-core four-(right-p-methoxy-phenyl) iron-cobalt porphyrin (is R in the formula III
31=R
32=H, R
33=OCH
3, M
3=Fe, M
4=Co), 4.3 * 10
-3G μ-oxygen-double-core four-(right-p-methoxy-phenyl) manganese-manganoporphyrin (is R in the formula III
31=R
32=H, R
33=Cl, M
3=Mn), 16.0g p-cresol and 8.9g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.6MPa, and temperature control reacts 8h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 88.0%, and the selectivity of p-Hydroxybenzaldehyde is 75.7%, and the yield of p-Hydroxybenzaldehyde is 66.6%.
Embodiment 24
Get 3.2 * 10
-3G four-(right-hydroxy phenyl) manganoporphyrin (namely leads to R in the formula I
11=R
12=H, R
13=OH, M
1=Mn), 4.3 * 10
-3G μ-oxygen-double-core four-(right-chloro-phenyl-) manganese-manganoporphyrin (is R in the formula III
31=R
32=H, R
33=Cl, M
3=Mn), 16.0g p-cresol and 14.0g sodium hydroxide add in the 100mL autoclave, add 60mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 10h down for 65 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 91.2%, and the selectivity of p-Hydroxybenzaldehyde is 84.1%, and the yield of p-Hydroxybenzaldehyde is 76.7%.
Embodiment 25
Get 3.2 * 10
-3G chlorination four-(right-hydroxy phenyl) iron porphyrin (is namely led to R in the formula II
21=R
22=H, R
23=OH, X=Cl, M
2=Fe), 4.3 * 10
-3G μ-oxygen-double-core four-(right-p-methoxy-phenyl) cobalt-manganoporphyrin (is R in the formula III
31=R
32=H, R
33=Cl, M
3=Mn), 16.0g p-cresol and 8.9g sodium hydroxide add in the 100mL autoclave, add the methanol aqueous solution 40mL that contains methyl alcohol 70% (V:V), and feeding pressure is the oxygen of 0.6MPa, and temperature control reacts 5h down for 55 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 73.6%, and the selectivity of p-Hydroxybenzaldehyde is 75.3%, and the yield of p-Hydroxybenzaldehyde is 55.4%.
Embodiment 26
Get 3.2 * 10
-3G four-(right-chloro-phenyl-) cobalt porphyrin (namely leads to R in the formula I
11=R
12=H, R
13=Cl, M
1=Co), 2.5 * 10
-3G four-(right-hydroxy phenyl) copper porphyrin (namely leads to R in the formula I
11=R
12=H, R
13=OH, M
1=Cu), 16.0g p-cresol and 6.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.3MPa, and temperature control reacts 9h down for 55 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 93.0%, and the selectivity of p-Hydroxybenzaldehyde is 75.1%, and the yield of p-Hydroxybenzaldehyde is 69.8%.
Embodiment 27
Get 3.5 * 10
-3G four-(neighbour-p-methoxy-phenyl) cobalt porphyrin (is R in the formula I
11=OCH
3, R
12=R
13=H, M
1=Co), 1.4 * 10
-3The g cobalt chloride, 1.2 * 10
-3The g zinc acetate, 16.0g p-cresol and 6.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 8h down for 75 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 83.6%, and the selectivity of p-Hydroxybenzaldehyde is 74.5%, and the yield of p-Hydroxybenzaldehyde is 62.3%.
Embodiment 28
Get 3.5 * 10
-3G four-(o-nitrophenyl) cobalt porphyrin (is R in the formula I
11=NO
2, R
12=R
13=H, M
1=Co), 3.8 * 10
-3The g Cobaltous diacetate, 17.5g p-cresol and 8.9g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.7MPa, and temperature control reacts 7h down for 55 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 95.0%, and the selectivity of p-Hydroxybenzaldehyde is 80.0%, and the yield of p-Hydroxybenzaldehyde is 76.0%.
Embodiment 29
Get 7.3 * 10
-3G μ-oxygen-double-core four-(right-p-methoxy-phenyl) iron-iron porphyrin (is R in the formula III
31=R
32=H, R
33=OCH
3, M
3=M
4=Fe), 1.0 * 10
-2The g zinc acetate, 16.0g p-cresol and 14.5g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 6h down for 55 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 85.2%, and the selectivity of p-Hydroxybenzaldehyde is 82.1%, and the yield of p-Hydroxybenzaldehyde is 69.9%.
Embodiment 30
Get 3.5 * 10
-3G chlorination four-(right-nitrophenyl) cobalt porphyrin (is R in the formula II
21=R
22=H, R
23=NO
2, X=Cl, M
2=Co), 1.0 * 10
-3The g iron protochloride, 16.0g p-cresol and 14.5g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 3h down for 70 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of p-cresol is 88.2%, and the selectivity of p-Hydroxybenzaldehyde is 77.5%, and the yield of p-Hydroxybenzaldehyde is 68.4%.
Claims (10)
1. metalloporphyrin-metal-salt composite catalyst catalyzed oxidation p-cresol prepares the method for p-Hydroxybenzaldehyde, the steps include: with the p-cresol to be raw material, be solvent with methyl alcohol or methanol aqueous solution, with the combination of metalloporphyrin and metal-salt as catalyzer, or with the combination of any two or three in formula (I), formula (II) and the formula (III) as catalyzer, or with substituting group and identical, the central metallic ions M in substituent position in formula (I) and formula (I), formula (II) and formula (II), formula (III) and the formula (III)
1, M
2, M
3Or M
4Different combinations are as catalyzer, or with 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, concentration 5～the 100ppm of metalloporphyrin, concentration 5～the 200ppm of metal-salt, the mol ratio of sodium hydroxide and p-cresol is 1～2.5:1, feeds 0.1～1.0MPa oxygen, reacts 1～12h down at 50～90 ℃, obtain p-Hydroxybenzaldehyde
The formula I formula II
Formula III
Wherein said metalloporphyrin is selected from any one or two kinds in the μ-oxygen-dinuclear metalloporphyrin of the monokaryon metalloporphyrin of formula (I), formula (II) expression and formula (III) expression, in acetate, hydrochloride, nitrate and the sulphite of described metal-salt chosen from Fe, cobalt, manganese, copper, zinc, chromium or nickel any one or two kinds, M
1Be iron, manganese, cobalt, copper or zinc, M
2Be iron, manganese or cobalt, M
3And 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, methyl, methoxyl group or carboxyl, dentate X is halogen.
2. according to the method for claim 1, it is characterized in that combination with metalloporphyrin and metal-salt is as catalyzer.
3. according to the method for claim 2, it is characterized in that described metalloporphyrin is formula (I) or formula (II).
4. according to the method for claim 3, it is characterized in that described metal-salt is acetate or the hydrochloride of iron, cobalt or manganese.
5. 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.
6. according to the method for claim 1, the concentration that it is characterized in that metalloporphyrin is 10～50ppm, and the concentration of metal-salt is 10～100ppm.
7. according to the method for claim 1, the mol ratio that it is characterized in that sodium hydroxide and p-cresol is 1.5～2:1.
8. according to the method for claim 1, it is characterized in that oxygen pressure is 0.2～0.5MPa.
9. according to the method for claim 1, it is characterized in that temperature of reaction is 60～80 ℃.
10. according to the method for claim 1, it is characterized in that the reaction times is 3～5h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554398A (en) * | 2013-10-30 | 2014-02-05 | 华东师范大学 | Preparation method of metal porphyrin-phenolic aldehyde resin |
| CN114887619A (en) * | 2022-03-29 | 2022-08-12 | 齐鲁工业大学 | Catalytic system for catalytic oxidation of p-cresol under alkali-free condition and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929766A (en) * | 1988-02-24 | 1990-05-29 | Bayer Aktiengesellschaft | Process are the preparation of p-hydroxy-benzaldehydes |
| CN101759536A (en) * | 2009-12-25 | 2010-06-30 | 北京工业大学 | Method for preparing parahydroxybenzaldehyde by catalytic oxidation of paracresol with metalloporphyrin |
-
2013
- 2013-03-15 CN CN2013100843116A patent/CN103183594A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929766A (en) * | 1988-02-24 | 1990-05-29 | Bayer Aktiengesellschaft | Process are the preparation of p-hydroxy-benzaldehydes |
| CN101759536A (en) * | 2009-12-25 | 2010-06-30 | 北京工业大学 | Method for preparing parahydroxybenzaldehyde by catalytic oxidation of paracresol with metalloporphyrin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554398A (en) * | 2013-10-30 | 2014-02-05 | 华东师范大学 | Preparation method of metal porphyrin-phenolic aldehyde resin |
| CN103554398B (en) * | 2013-10-30 | 2015-07-08 | 华东师范大学 | Preparation method of metal porphyrin-phenolic aldehyde resin |
| CN114887619A (en) * | 2022-03-29 | 2022-08-12 | 齐鲁工业大学 | Catalytic system for catalytic oxidation of p-cresol under alkali-free condition and application |
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