CN103183595A - Method for preparing o-cresol into o-hydroxy benzaldehyde by catalytic oxidation of metalloporphyrin-metal salt composite catalyst - Google Patents

Method for preparing o-cresol into o-hydroxy benzaldehyde by catalytic oxidation of metalloporphyrin-metal salt composite catalyst Download PDF

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CN103183595A
CN103183595A CN2013100844373A CN201310084437A CN103183595A CN 103183595 A CN103183595 A CN 103183595A CN 2013100844373 A CN2013100844373 A CN 2013100844373A CN 201310084437 A CN201310084437 A CN 201310084437A CN 103183595 A CN103183595 A CN 103183595A
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metalloporphyrin
cresol
salicylaldhyde
ortho
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佘远斌
冯瑛琪
王维
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Beijing University of Technology
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Beijing University of Technology
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Abstract

The invention relates to a method for preparing o-cresol into o-hydroxy benzaldehyde by the catalytic oxidation of a metalloporphyrin-metal salt composite catalyst. The method comprises the following steps: taking a combination of metalloporphyrin and metal salt as a catalyst or taking a combination of any two or three in a formula (I), a formula (II) and a formula (III) as a catalyst or taking a combination of the formula (I) 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 in a methanol solvent, wherein the concentration of the metalloporphyrin is 5-50 ppm, and the concentration of the metal salt is 5-200 ppm; introducing oxygen of 0.1-0.5 MPa into methanol solution with 0.1 mol/L of sodium hydroxide solution; and reacting for 1-10 hours at a temperature of 50-90 DEG C to obtain the o-hydroxy benzaldehyde. The catalyst in the method has the advantages that the dosage is less, and the alkali dosage is less, 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

Metalloporphyrin-metal-salt composite catalyst catalyzed oxidation ortho-cresol prepares the method for salicylaldhyde
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 ortho-cresol and prepare the method for salicylaldhyde.
Background technology
Salicylaldhyde has another name called salicylic aldehyde, is a kind of colourless or light brown oily liquids, and the almond flavor is arranged, and is soluble in alcohol, ether, is slightly soluble in water.It is important fine chemical product, is widely used in the synthetic of intermediates such as agricultural chemicals, medicine, spices, dyestuff.Though the method that with the ortho-cresol is raw material synthesizing o-hydroxy formaldehyde at present is a lot, metalloporphyrin bionic catalysis oxidation style is comparatively superior.US5130493A (open day: on July 14th, 1992) disclose a kind of compound with metalloporphyrin or metal-salt or the two be the method that the catalyst oxidation ortho-cresol prepares salicylaldhyde.This method is to be raw material with the ortho-cresol, in the methanol solution of sodium hydroxide, has solved traditional method (Chinese patent 1475307, open day: the big problem of catalyst levels on February 18th, 2004).
Although the synthetic method of above-mentioned salicylaldhyde has obtained the yield of comparatively desirable salicylaldhyde, still there is following problem in aforesaid method:
(1) reaction catalyst system therefor amount is too big, is 1400ppm, and this has increased synthetic cost and process cost greatly;
(2) reaction institute alkali charge is 3 times of ortho-cresol mole dosage, and the separation after this makes reaction finish need neutralize with a large amount of acid, and a large amount of salt that neutralization produces make the intractability of waste water and expense significantly increase again;
(3) be reflected under the open condition of normal pressure and carry out, feed excess of oxygen and can take away the methanol steam that volatilizees under the hot conditions simultaneously, increased danger and the toxicity of operation greatly, and can cause reaction solution concentration to increase even solidify.
Summary of the invention
The objective of the invention is to overcome above-mentioned problems of the prior art.Provide a kind of reaction in encloses container, few, the alkali consumption of catalyst levels also few metalloporphyrin-metal-salt composite catalyst catalysis ortho-cresol produce the method for salicylaldhyde.
A kind of metalloporphyrin provided by the present invention-metal-salt composite catalyst catalyzed oxidation ortho-cresol prepares the method for salicylaldhyde, the steps include: in methanol solvate, 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 50ppm of metalloporphyrin, concentration 5～the 200ppm of metal-salt, in the methanol solution of 2.5～5mol/L sodium hydroxide, feed 0.1～0.5MPa oxygen, react 1～10h down at 50～90 ℃, obtain salicylaldhyde
Figure BDA00002925748700021
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, the acetate of described metal-salt chosen from Fe, cobalt, manganese, copper, zinc, chromium or nickel and any one or two kinds in the hydrochloride, 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.
The combination of preferable alloy porphyrin and metal-salt is as catalyzer.The combination of special preferable alloy porphyrin and metal-salt is as catalyzer, and wherein said metalloporphyrin is formula (I) or formula (II).More preferably the combination of metalloporphyrin and metal-salt is as catalyzer, and wherein said metalloporphyrin is formula (I) or formula (II), and described metal-salt is the acetate of iron, cobalt, manganese, copper, zinc, chromium or nickel.
Preferred M 1, M 2, M 3Or M 4Be iron, manganese or cobalt, M 3And M 4Identical.The preferred chlorine of X.
Preferable alloy porphyrin concentration is 10～40ppm, and the preferable alloy salt concn is 10～60ppm, and the preferred reaction time is 7～10h, and the preferred oxygen atmospheric pressure is 0.1～0.2MPa, and preferred naoh concentration is 3～5mol/L.
The starting point concentration of ortho-cresol is 1～3mol/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 Ortho Nitro Toluene effectively, catalyst consumption is reduced greatly, 1400ppm by prior art significantly reduces to 50ppm, and then greatly reduce resource consumption and process cost in the reaction process, this has obviously not only effectively utilized resource, and. make by product few because selectivity is high, embodied energy-saving and emission-reduction effectively.
(2) 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 2.5mol/L by the preferred 10mol/L of prior art, also obviously reduce in when the later stage is separated and with the acid amount, the brine waste that causes thus also significantly reduces thereupon, has reduced environmental pollution significantly.
(3) closed reactor is adopted in present method reaction, greatly reduces the danger and the toxicity that when methyl alcohol volatilizees with oxygen in the system of opening wide operation are caused, has increased stability and the security of reaction.
(4) few, the operational safety of present method catalyst system therefor and alkali number, 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 2.0 * 10 -3G 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 -5G 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 -5The g rose vitriol, 3.8 * 10 -5The g Iron nitrate, 5.4g ortho-cresol and 3.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.4MPa, 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 ortho-cresol is 54.0%, and the selectivity of salicylaldhyde is 25.1%, and the yield of salicylaldhyde is 13.5%.
Embodiment 2
Get 4.4 * 10 -4G 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, 5.4g ortho-cresol and 2.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 81.0%, and the selectivity of salicylaldhyde is 21.2%, and the yield of salicylaldhyde is 17.0%.
Embodiment 3
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, 2.2g ortho-cresol and 1.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 69.6%, and the selectivity of salicylaldhyde is 22.4%, and the yield of salicylaldhyde is 15.3%.
Embodiment 4
2.0 * 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, 6.2g ortho-cresol and 4.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.3MPa, and temperature control reacts 6h down for 75 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of ortho-cresol is 67.1%, and the selectivity of salicylaldhyde is 17.3%, and the yield of salicylaldhyde is 11.3%.
Embodiment 5
3.5 * 10 -4G 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, 10.8g ortho-cresol and 3.0g 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 60 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of ortho-cresol is 76.6%, and the selectivity of salicylaldhyde is 21.3%, and the yield of salicylaldhyde is 16.1%.
Embodiment 6
Get 5.4 * 10 -4G chlorination four-(right-chloro-phenyl-) cobalt porphyrin (is R in the general formula (II) 21=R 22=H, R 23=Cl, X=Cl, M 2=Co), 1.8 * 10 -3The g zinc nitrate, 5.4g ortho-cresol and 2.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 84.2%, and the selectivity of salicylaldhyde is 13.9%, and the yield of salicylaldhyde is 10.9%.
Embodiment 7
Get 1.5 * 10 -4G chlorination four-(o-nitrophenyl) manganoporphyrin (is R in the general formula (II) 21=NO 2, R 22=R 23=H, X=Cl, M 2=Mn), 3.8 * 10 -4G zinc sulfate, 5.4g ortho-cresol and 4.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 54.2%, and the selectivity of salicylaldhyde is 26.2%, and the yield of salicylaldhyde is 14.0%.
Embodiment 8
Get 1.7 * 10 -3G four-(right-p-methoxy-phenyl) manganoporphyrin (is R in the general formula (I) 11=R 12=H, R 13=Cl, M 1=Mn), 9.5 * 10 -5The g zinc chloride, 5.4g ortho-cresol and 4.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 5h down for 50 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of ortho-cresol is 69.3%, and the selectivity of salicylaldhyde is 18.1%, and the yield of salicylaldhyde is 12.4%.
Embodiment 9
Get 4.3 * 10 -4G chlorination four-(right-p-methoxy-phenyl) iron porphyrin (is R in the general formula (II) 21=R 22=H, R 23=Cl, X=Cl, M 2=Fe), 8.6 * 10 -3G four-(right-carboxyl phenyl) zinc protoporphyrin (is R in the general formula (I) 11=R 12=H, R 13=COOH, M 1=Zn), 8.6 * 10 -5The g Iron diacetate, 5.4g ortho-cresol and 3.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.3MPa, 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 ortho-cresol is 75.8%, and the selectivity of salicylaldhyde is 16.3%, and the yield of salicylaldhyde is 12.0%.
Embodiment 10
Get 4.3 * 10 -4G four-(right-hydroxy phenyl) copper porphyrin (is R in the general formula (I) 11=R 12=H, R 13=OH, M 1=Cu), 2.0 * 10 -2The g Cobaltous diacetate, 8.6 * 10 -5The g ferrous sulfate, 5.4g ortho-cresol and 4.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 10h down for 85 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of ortho-cresol is 76.9%, and the selectivity of salicylaldhyde is 15.3%, and the yield of salicylaldhyde is 11.4%.
Embodiment 11
Get 1.6 * 10 -3G chlorination four-(right-chloro-phenyl-) cobalt porphyrin (is R in the general formula (II) 21=R 22=H, R 23=Cl, X=Cl, M 2=Co), 3.3 * 10 -4G four-(right-hydroxy phenyl) copper porphyrin (is R in the general formula (I) 11=R 12=H, R 13=OH, M 1=Cu), 5.4g ortho-cresol and 1.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 52.6%, and the selectivity of salicylaldhyde is 27.1%, and the yield of salicylaldhyde is 14.0%.
Embodiment 12
Get 3.6 * 10 -4G chlorination four-(right-p-methoxy-phenyl) manganoporphyrin (is R in the general formula (II) 21=R 22=H, R 23=Cl, X=Cl, M 2=Mn), 8.6 * 10 -4G chlorination four-(right-hydroxy phenyl) iron porphyrin (is R in the general formula (II) 21=R 22=H, R 23=OH, X=Cl, M 2=Fe), 5.4g ortho-cresol and 1.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.2MPa, 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 ortho-cresol is 46.2%, and the selectivity of salicylaldhyde is 26.5%, and the yield of salicylaldhyde is 11.9%.
Embodiment 13
Get 4.3 * 10 -4G 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 -4G 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), 5.4g ortho-cresol and 2.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.4MPa, and temperature control reacts 6h down for 50 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of ortho-cresol is 72.3%, and the selectivity of salicylaldhyde is 25.7%, and the yield of salicylaldhyde is 17.9%.
Embodiment 14
Get 8.1 * 10 -5G four-(right-hydroxy phenyl) manganoporphyrin (is R in the general formula (I) 11=R 12=H, R 13=OH, M 1=Mn), 1.3 * 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), 5.4g ortho-cresol and 3.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, 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 ortho-cresol is 81.2%, and the selectivity of salicylaldhyde is 14.1%, and the yield of salicylaldhyde is 11.3%.
Embodiment 15
Get 1.8 * 10 -3G chlorination four-(right-hydroxy phenyl) iron porphyrin (is R in the general formula (II) 21=R 22=H, R 23=OH, X=Cl, M 2=Fe), 9.3 * 10 -5G 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), 5.4g ortho-cresol and 4.0g sodium hydroxide add in the 100mL autoclave, 20mL methyl alcohol, and feeding pressure is the oxygen of 0.3MPa, 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 ortho-cresol is 53.6%, and the selectivity of salicylaldhyde is 25.3%, and the yield of salicylaldhyde is 18.8%.
Embodiment 16
Get 1.6 * 10 -3G four-(right-chloro-phenyl-) cobalt porphyrin (is R in the general formula (I) 11=R 12=H, R 13=Cl, M 1=Co), 4.3 * 10 -34G four-(right-hydroxy phenyl) copper porphyrin (is R in the general formula (I) 11=R 12=H, R 13=OH, M 1=Cu), 5.4g ortho-cresol and 2.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 73.0%, and the selectivity of salicylaldhyde is 15.1%, and the yield of salicylaldhyde is 10.9%.
Embodiment 17
Get 3.5 * 10 -4G 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 -5The g cobalt chloride, 1.2 * 10 -5Zinc acetate, 5.4g ortho-cresol and 1.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 8h down for 50 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of ortho-cresol is 43.6%, and the selectivity of salicylaldhyde is 24.5%, and the yield of salicylaldhyde is 10.3%.
Embodiment 18
Get 2.5 * 10 -4G 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 -4The g Cobaltous diacetate, 5.4g ortho-cresol and 2.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.4MPa, and temperature control reacts 7h down for 85 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of ortho-cresol is 72.2%, and the selectivity of salicylaldhyde is 16.3%, and the yield of salicylaldhyde is 11.5%.
Embodiment 19
Get 7.3 * 10 -4G 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 -4The g zinc acetate, 5.4g ortho-cresol and 4.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 55.2%, and the selectivity of salicylaldhyde is 22.1%, and the yield of salicylaldhyde is 12.1%.
Embodiment 20
3.5 * 10 -4G 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, 5.4g ortho-cresol and 3.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 49.0%, and the selectivity of salicylaldhyde is 22.4%, and the yield of salicylaldhyde is 10.8%.
Embodiment 21
Get 6.4 * 10 -4G chlorination four-(right-p-methoxy-phenyl) cobalt porphyrin (is R in the general formula (II) 21=R 22=H, R 23=Cl, X=Cl, M 2=Co), 3.2 * 10 -4The g Iron diacetate, 5.4g ortho-cresol and 4.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 69.2%, and the selectivity of salicylaldhyde is 20.0%, and the yield of salicylaldhyde is 13.8%.
Embodiment 22
Get 8.6 * 10 -4G chlorination four-(right-nitrophenyl) iron porphyrin (is R in the general formula (II) 21=R 22=H, R 23=NO 2, X=Cl, M 2=Fe), 5.8 * 10 -4The g zinc chloride, 5.4g ortho-cresol and 1.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.4MPa, 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 ortho-cresol is 51.1%, and the selectivity of salicylaldhyde is 17.4%, and the yield of salicylaldhyde is 8.9%.
Embodiment 23
Get 1.4 * 10 -3G chlorination four-(right-p-methoxy-phenyl) iron porphyrin (is R in the general formula (II) 11=R 12=H, R 13=Cl, X=Cl, M 2=Fe), 1.8 * 10 -3The g Cobaltous diacetate, 5.4g ortho-cresol and 2.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 39.9%, and the selectivity of salicylaldhyde is 27.0%, and the yield of salicylaldhyde is 10.8%.
Embodiment 24
Get 9.3 * 10 -4G chlorination four-(right-p-methoxy-phenyl) iron porphyrin (is R in the general formula (II) 21=R 22=H, R 23=Cl, X=Cl, M 2=Fe), 1.86 * 10 -3G four-(right-carboxyl phenyl) cobalt porphyrin (is R in the general formula (I) 11=R 12=H, R 13=COOH, M 1=Co), 3.6 * 10 -3The g Cobaltous diacetate, 5.4g ortho-cresol and 2.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, 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 ortho-cresol is 45.8%, and the selectivity of salicylaldhyde is 22.3%, and the yield of salicylaldhyde is 10.2%.
Embodiment 25
Get 8.3 * 10 -4G four-(right-hydroxy phenyl) copper porphyrin (is R in the general formula (I) 11=R 12=H, R 13=OH, M 1=Cu), 1.0 * 10 -3The g iron protochloride, 6.0 * 10 -4The g zinc chloride, 5.4g ortho-cresol and 3.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 76.9%, and the selectivity of salicylaldhyde is 15.3%, and the yield of salicylaldhyde is 11.8%.
Embodiment 26
Get 9.0 * 10 -4G four-(right-p-methoxy-phenyl) copper porphyrin (is R in the formula (I) 11=R 12=H, R 13=Cl, M 1=Cu), 3.8 * 10 -4The g iron protochloride, 10.8g ortho-cresol and 5.0g sodium hydroxide add in the 100mL autoclave, add 40mL methyl alcohol, and feeding pressure is the oxygen of 0.1MPa, 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 ortho-cresol is 48.3%, and the selectivity of salicylaldhyde is 23.8%, and the yield of salicylaldhyde is 24.3%.
Embodiment 27
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, 5.4g ortho-cresol and 1.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.3MPa, and temperature control reacts 8h down for 80 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of ortho-cresol is 56.5%, and the selectivity of salicylaldhyde is 22.1%, and the yield of salicylaldhyde is 22.4%.
Embodiment 28
Get 7.5 * 10 -4G 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 -5The g Cobaltous diacetate, 5.4g ortho-cresol and 4.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 79.2%, and the selectivity of salicylaldhyde is 18.2%, and the yield of salicylaldhyde is 14.2%.
Embodiment 29
Get 6.6 * 10 -4G 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), 2.0 * 10 -4The g iron protochloride, 2.0 * 10 -4The g Cobaltous diacetate, 5.4g ortho-cresol and 4.0g sodium hydroxide add in the 100mL autoclave, add 20mL 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 ortho-cresol is 67.0%, and the selectivity of salicylaldhyde is 15.3%, and the yield of salicylaldhyde is 10.0%.
Embodiment 30
Get 1.1 * 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), 1.0 * 10 -3G 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, 5.4g ortho-cresol and 2.0g sodium hydroxide add in the 100mL autoclave, add 20mL methyl alcohol, and feeding pressure is the oxygen of 0.5MPa, and temperature control reacts 7h down for 90 ℃ in water-bath.After reaction was finished, reaction solution detected through high performance liquid chromatography, and the transformation efficiency of ortho-cresol is 64.0%, and the selectivity of salicylaldhyde is 25.1%, and the yield of salicylaldhyde is 16.0%.

Claims (10)

1. metalloporphyrin-metal-salt composite catalyst catalyzed oxidation ortho-cresol prepares the method for salicylaldhyde, the steps include: in methanol solvate, 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 50ppm of metalloporphyrin, concentration 5～the 200ppm of metal-salt, in the methanol solution of 2.5～5mol/L sodium hydroxide, feed 0.1～0.5MPa oxygen, react 1～10h down at 50～90 ℃, obtain salicylaldhyde
Figure FDA00002925748600011
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, the acetate of described metal-salt chosen from Fe, cobalt, manganese, copper, zinc, chromium or nickel and any one or two kinds in the hydrochloride, 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, wherein said metalloporphyrin is formula (I) or formula (II).
4. according to the method for claim 3, it is characterized in that described metal-salt is the acetate of iron, cobalt, manganese, copper, zinc, chromium or nickel.
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 10～40ppm, and the concentration of metal-salt is 10～60ppm.
7. according to the method for claim 1, it is characterized in that naoh concentration is 3～5mol/L.
8. according to the method for claim 1, it is characterized in that oxygen pressure is 0.1～0.2MPa.
9. according to the method for claim 1, it is characterized in that the reaction times is 7～10h.
10. according to the method for claim 1, it is characterized in that temperature of reaction is 60～70 ℃.
CN2013100844373A 2013-03-15 2013-03-15 Method for preparing o-cresol into o-hydroxy benzaldehyde by catalytic oxidation of metalloporphyrin-metal salt composite catalyst Pending CN103183595A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5130493A (en) * 1990-04-13 1992-07-14 Bayer Aktiengesellschaft Process for the preparation of o-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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5130493A (en) * 1990-04-13 1992-07-14 Bayer Aktiengesellschaft Process for the preparation of o-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

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