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Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-nitrotoluene with metalloporphyrin and metal salt compound as catalyst

A technology of o-nitrobenzoic acid and composite catalyst, which is applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problems of methanol and benzene solvents with high toxicity, increased energy consumption, environmental pollution, and difficulty in wastewater treatment. problems, to achieve the effect of shortening the reaction time, reducing environmental pollution, and reducing the amount of acid.

Inactive Publication Date: 2013-07-10
BEIJING UNIV OF TECH
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Problems solved by technology

She Yuanbin and others have reported that in the alkaline medium of methanol (Fine Chemical Industry, 1998, 1(15): 45~47), methanol-benzene (Fine Chemical Industry, 2004, 21(6): 474~478), metal Phthalocyanine or metal porphyrin is a catalyst, and the method for preparing o-nitrobenzoic acid by catalytic oxygen oxidation o-nitrotoluene, this method mainly solves the traditional method (Tetrahedron Lett, 2003, 44: 2053~2056.) The problem of equipment corrosion caused by medium acidic medium, but this method still has the problem of high solvent toxicity
Chinese patent CN1944396A (disclosure date: April 11, 2007) discloses a method for preparing o-nitrobenzoic acid by biomimetic catalytic oxygen oxidation of o-nitrotoluene, which uses ethanol-water solution as a solvent to further solve the above-mentioned method The problem of high toxicity of methanol and benzene solvents
[0004] (1) The yields are not high, only 73.4% to 85.9%;
[0005] (2) The amount of alkali used is relatively large, ranging from 3.75mol / L to 6.0mol / L. A high amount of alkali will lead to a large amount of acid used for neutralization in the later separation, and the salt generated after neutralization will cause Wastewater treatment is difficult, which increases the energy consumption of the later separation, seriously pollutes the environment, and the cost is high;
[0006] (3) The reaction time is long, up to 12 hours, which makes the energy consumption of the reaction large and the operating cost high

Method used

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  • Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-nitrotoluene with metalloporphyrin and metal salt compound as catalyst
  • Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-nitrotoluene with metalloporphyrin and metal salt compound as catalyst
  • Method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-nitrotoluene with metalloporphyrin and metal salt compound as catalyst

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Take 8.6×10 -5 g chloride tetra-(p-chlorophenyl) cobalt porphyrin (i.e. R in the general formula (II) 21 =R 22 = H, R 23 =Cl,X=Cl,M 2 =Co), 1.8×10 -5 g manganese acetate, 1.4 g o-nitrotoluene and 2.0 g sodium hydroxide are added to a 100 mL autoclave, 20 mL of ethanol aqueous solution containing 80% (V:V) of ethanol is added, and oxygen at a pressure of 2.0 MPa is introduced, and in a water bath The temperature was controlled at 55°C for 6 hours. After the reaction was completed, the reaction liquid was detected by high performance liquid chromatography, and the conversion rate of o-nitrotoluene was 98.2%, the selectivity of o-nitrobenzoic acid was 97.9%, and the yield of o-nitrobenzoic acid was 96.1%.

Embodiment 2

[0023] Take 8.6×10 -5 g chloride tetra-(p-nitrophenyl)iron porphyrin (i.e. R in the general formula (II) 21 =R 22 = H, R 23 =NO 2 , X=Cl,M 2 =Fe), 3.8×10 -5 1g zinc chloride, 1.6g o-nitrotoluene and 1.8g sodium hydroxide are added to a 100mL autoclave, 20mL of ethanol aqueous solution containing 90% (V:V) of ethanol is added, and the pressure is 1.8MPa of oxygen, and the The reaction was carried out at a temperature of 50° C. for 5 hours. After the reaction was completed, the reaction liquid was detected by high performance liquid chromatography, and the conversion rate of o-nitrotoluene was 93.0%, the selectivity of o-nitrobenzoic acid was 96.2%, and the yield of o-nitrobenzoic acid was 89.5%.

Embodiment 3

[0025] Take 1.7×10 -4 g four-(p-chlorophenyl) manganese porphyrin (i.e. R in the general formula (I) 11 =R 12 = H, R 13 =Cl,M 1 =Mn), 9.5×10 -5 g cobalt acetate, 1.0 g o-nitrotoluene and 1.5 g sodium hydroxide are added to a 100 mL autoclave, 20 mL of ethanol aqueous solution containing 70% (V:V) of ethanol is added, and oxygen at a pressure of 1.5 MPa is introduced, and in a water bath The temperature was controlled at 45°C for 4 hours. After the reaction was completed, the reaction liquid was detected by high performance liquid chromatography, and the conversion rate of o-nitrotoluene was 76.2%, the selectivity of o-nitrobenzoic acid was 95.1%, and the yield of o-nitrobenzoic acid was 72.5%.

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Abstract

The invention relates to a method for preparing ortho-hydroxybenzoic acid by catalyzing and oxidizing ortho-nitrotoluene with a metalloporphyrin and metal salt compound as a catalyst. The method comprises the following steps of: introducing the oxygen of 0.5-2.5Mpa into the aqueous ethanol of 0.5-2.5mol / L sodium hydroxide by taking the aqueous ethanol comprising 50-95% by volume of ethanol as a solvent and taking the compound of a metalloporphyrin and a metal salt as a catalyst, or the compound of any two or three of a metalloporphyrin of formula I, a metalloporphyrin of formula II and a metalloporphyrin of formula III as a catalyst, or the compound of a metalloporphyrin of formula I and a metalloporphyrin of formula I or a metalloporphyrin of formula II and a metalloporphyrin of formula II or a metalloporphyrin of formula III and a metalloporphyrin of formula III as a catalyst, and carrying out reaction at the temperature of 35-55 DEG C for 1-6 hours to obtain the ortho-hydroxybenzoic acid, wherein the concatenation of the metalloporphyrin is 5-50ppm, and the concentration of the metal salt is 5-200ppm. The method provided by the invention has the advantages of high target product yield, short reaction time, small use amount of the alkali and low toxicity of the solvent. Due to the adoption of the method, the resource can be saved effectively, the pollution to the environment can be reduced, and the purposes of comprehensively saving energy and reducing emission can be achieved.

Description

technical field [0001] The invention relates to a preparation method of aromatic carboxylic acid, in particular to a method for preparing o-nitrobenzoic acid by catalyzing the oxidation of o-nitrotoluene with a metalloporphyrin-metal salt composite catalyst. Background technique [0002] O-nitrobenzoic acid is an important intermediate in organic synthesis, widely used in medicine, pesticides, dyes and other fields. Although there are many methods for synthesizing o-nitrobenzoic acid at present, the biomimetic catalytic oxidation of metalloporphyrins is relatively superior. She Yuanbin and others have reported that in the alkaline medium of methanol (Fine Chemical Industry, 1998, 1(15): 45~47), methanol-benzene (Fine Chemical Industry, 2004, 21(6): 474~478), metal Phthalocyanine or metal porphyrin is a catalyst, and the method for preparing o-nitrobenzoic acid by catalytic oxygen oxidation o-nitrotoluene, this method mainly solves the traditional method (Tetrahedron Lett, 2...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C205/57C07C201/12
Inventor 佘远斌尚晓芹王维冯瑛琪
Owner BEIJING UNIV OF TECH
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