CN111675620A - Method for catalytic oxidation of toluene and derivatives thereof by metalloporphyrin - Google Patents

Method for catalytic oxidation of toluene and derivatives thereof by metalloporphyrin Download PDF

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CN111675620A
CN111675620A CN202010347658.5A CN202010347658A CN111675620A CN 111675620 A CN111675620 A CN 111675620A CN 202010347658 A CN202010347658 A CN 202010347658A CN 111675620 A CN111675620 A CN 111675620A
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toluene
reaction
derivatives
selectivity
metalloporphyrin
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佘远斌
齐备
沈海民
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract

A method for metalloporphyrin-catalyzed oxidation of toluene and its derivatives, the method comprising: dispersing metalloporphyrin and N-hydroxyphthalimide (NHPI) in toluene and derivatives thereof, sealing a reaction system, heating to 70-130 ℃ under stirring, introducing oxygen to 0.2-2.0 MPa, keeping the set temperature and oxygen pressure, stirring for reaction for 8 hours, and then carrying out aftertreatment on reaction liquid to obtain the aromatic acid product. The method has the advantages of no solvent, no additive, mild conditions, higher selectivity to aromatic acid and good tolerance to substrate. The work can not only effectively oxidize the hydrocarbon containing primary benzyl C-H bonds, but also provide important reference for constructing a more effective C-H bond oxidation system.

Description

Method for catalytic oxidation of toluene and derivatives thereof by metalloporphyrin
Technical Field
The invention relates to a novel method for preparing aromatic acid by selectively oxidizing toluene and derivatives thereof by using metalloporphyrin as a catalyst and molecular oxygen, belonging to the field of organic catalysis and fine organic synthesis.
Background
Toluene and its derivatives are converted to valuable benzyl hydroperoxide, benzyl alcohol, benzaldehyde, benzoic acid and its derivatives. These oxidation products have been widely used as food additives, flavoring agents, fragrances, pharmaceuticals and irreplaceable intermediates in the production of perfumes, pharmaceuticals, pesticides, dyes, resins and synthetic polymer fibers, with great market demand (CN 106977389; CN 106631761; Catalysis Science Technology,2019,9(16): 4441-. Benzoic acid, also known as benzoic acid, is an important organic synthesis intermediate, and the traditional production methods thereof include phthalic anhydride hydrolysis decarboxylation, toluene chlorination hydrolysis, toluene liquid phase oxidation, oxidant oxidation and catalytic oxidation, but these methods have the problems of low efficiency, high cost, environmental pollution, etc. (Catalysis Communications,2018,109: 76-79). Taking traditional high value-added benzoic acid as an example, cobalt carboxylate is used as a catalyst, bromide is used as an initiator, and acetic acid is used as a solvent to prepare the high value-added benzoic acid, which may cause serious pollution and corrosion of a reactor vessel. Industrially, with Co (OAc)2As a catalyst, liquid phase toluene was oxidized at 165 ℃ and 1.0MPa, which shows a toluene conversion of 14-15% and a benzoic acid selectivity of 92-93%, and contains only a small amount of by-products (Inorgnaica Chimica Acta,2017,467: 307-315; Catalysis Letters,2017,147(4): 856-864). Most of the methods reported in the existing documents use solvents and auxiliaries, the reaction temperature and pressure are high, the product selectivity is poor, and the requirements of environmental protection are not met. Therefore, it is urgently needed to develop a mild way to realize the oxidation of toluene and the derivatives thereof under the conditions of no solvent and no additive.
Metalloporphyrins are a useful and important class of transition metal complexes, which have been widely used as the general remedyA catalyst for the peroxidation of a hydrocarbon which functionalizes the C-H bond in the hydrocarbon. Because the metalloporphyrin has high O2Therefore, one tenth of the catalyst supported on the substrate is sufficient to achieve the oxidation functionalization of C-H bonds (Journal of Catalysis 2019, 369: 133-. Although metalloporphyrin as a catalyst has the advantages of small catalyst dosage, high catalytic efficiency, easy structure adjustment, good biocompatibility, environmental protection and the like, the metalloporphyrin is not excellent in toluene and a derivative system thereof.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing aromatic acid by selectively oxidizing toluene and derivatives thereof by using metalloporphyrin to catalyze molecular oxygen.
The technical scheme of the invention is as follows:
a method for metalloporphyrin-catalyzed oxidation of toluene and its derivatives, the method comprising:
dispersing metalloporphyrin and N-hydroxyphthalimide (NHPI) in toluene and derivatives thereof, sealing a reaction system, heating to 70-130 ℃ under stirring (preferably 80-120 ℃), introducing oxygen to 0.2-2.0 Mpa (preferably 0.4-1.2 Mpa), keeping the set temperature and oxygen pressure, stirring for reaction for 8 hours, and then carrying out aftertreatment on reaction liquid to obtain a product aromatic acid;
the mass ratio of the metalloporphyrin to the toluene and the toluene derivatives is 1: 100000-5000, preferably 1: 50000-10000;
the mass ratio of the NHPI to the toluene and the derivatives thereof is 1: 1000-5, preferably 1: 100-10 parts;
the post-treatment method comprises the following steps: after the reaction, triphenylphosphine (PPh) was added to the reaction solution3The amount of the toluene and the derivative thereof is 1.0-25%) and acetone (30-50 mL), the peroxide generated by reduction is stirred for 30min at room temperature (20-30 ℃), and the crude product is distilled, rectified under reduced pressure and recrystallized to obtain an oxidation product.
The method for analyzing the reaction result comprises the following steps: after the reaction is finished, peroxide generated by reduction of reaction liquid by triphenylphosphine is sampled and analyzed, acetone is used as a solvent for dilution, naphthalene is used as an internal standard for gas chromatography, the conversion rate of toluene and derivatives thereof and the selectivity of aromatic alcohol, aromatic aldehyde and peroxide are calculated, 2-naphthoic acid is used as an internal standard for liquid chromatography, and the selectivity of aromatic acid is calculated;
in the invention, the toluene and the derivatives thereof are: toluene, 4-nitrotoluene, 2-chlorotoluene, 3-chlorotoluene, 4-fluorotoluene, 4-methoxytoluene, 1-methylnaphthalene, 2-methylnaphthalene, 4-phenyltoluene, 3-methyltoluene, 4-methyltoluene and 2, 4-dichlorotoluene;
the metalloporphyrin is one of compounds shown in a formula (I): 5,10,15, 20-tetra (4-chlorophenyl) porphyrin cobalt (II), 5,10,15, 20-tetra (2-methoxyphenyl) porphyrin cobalt (II), 5,10,15, 20-tetra (2, 5-dichlorophenyl) porphyrin cobalt (II), 5,10,15, 20-tetra (2-methoxyphenyl) porphyrin manganese (II) or 5,10,15, 20-tetra (2-methoxyphenyl) porphyrin iron (II).
Figure BDA0002470752080000031
In the formula (I), R1、R2、R3、R4、R5、R6、R7Each independently is: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, benzyl, fluoro, chloro, bromo, or iodo;
m is Co2+、Mn2+、Ni2+、Fe2+、Cu2+Or Zn2+。
In order to improve the conversion rate of a substrate and the selectivity of aromatic acid, N-hydroxyphthalimide (NHPI) is introduced into a system to form a binary catalyst with metalloporphyrin for catalytic reaction, so that a good effect is achieved. Catalytic systems combining N-hydroxyphthalimide (NHPI) or its analogues with transition metal ions such as cobalt (II) and manganese (II) have been widely used for O2Oxidation of C-H bonds of various hydrocarbons (Catalysis Communications 2019, 123: 73-78; New Journal of Chemistry 2018, 42: 6343-. The method has the main advantages of no solvent, no additive, mild conditions and higher conversion rate and selectivity, so that the method has great potential in industrial application and has great reference value for the oxidation of other C-H bonds. This work is also a very convenient, practical and novel example of the efficient use of widely available and inexpensive hydrocarbons, and will be a significant reference for the more efficient use of hydrocarbons in both academic and industrial applications.
The invention has the following beneficial effects: the method for preparing the aromatic acid by selectively oxidizing the toluene and the derivative thereof by using the metalloporphyrin under the catalysis of molecular oxygen has the advantages of no solvent, no additive, mild condition, higher selectivity on the aromatic acid and good tolerance on a substrate. The work can not only effectively oxidize the hydrocarbon containing primary benzyl C-H bond, but also provide important reference for constructing a more effective C-H bond oxidation system; the invention is a new method for high-efficiency and feasible selective catalytic oxidation of toluene and toluene derivatives.
Detailed Description
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto.
The metalloporphyrins used in the present invention are synthesized by referring to Dyes and Pigments,2017,142 (116-.
Example 1
0.0024g (0.003mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI are dispersed in 6.8569g (50mmol) of p-nitrotoluene in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After the reaction is finished, iceWater was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 24.1%, the selectivity of p-nitrobenzyl hydroperoxide is 13.2%, the selectivity of p-nitrobenzyl alcohol is 17.9%, the selectivity of p-nitrobenzaldehyde is 6.9%, the selectivity of p-nitrobenzoic acid is 62.0%, and other obvious oxidation products are not detected.
Example 2
0.0032g (0.004mmol) of 5,10,15, 20-tetra (2-methoxyphenyl) porphyrin cobalt (II)0.82g (10%, mol/mol) NHPI is dispersed in 6.8569g (50mmol) of p-nitrotoluene in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 30.8%, the selectivity of p-nitrobenzyl hydroperoxide is 12.4%, the selectivity of p-nitrobenzyl alcohol is 17.9%, the selectivity of p-nitrobenzaldehyde is 6.1%, the selectivity of p-nitrobenzoic acid is 63.6%, and other obvious oxidation products are not detected.
Example 3
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0048g (0.006mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After the reaction is finished, the reaction kettle is used for reaction,ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 49.4%, the selectivity of p-nitrobenzyl hydroperoxide is 10.1%, the selectivity of p-nitrobenzyl alcohol is 21.5%, the selectivity of p-nitrobenzaldehyde is 3.9%, the selectivity of p-nitrobenzoic acid is 64.5%, and other obvious oxidation products are not detected.
Example 4
0.0048g (0.006mmol) of 5,10,15, 20-tetra (2-methoxyphenyl) porphyrin cobalt (II)0.82g (10%, mol/mol) of NHPI is dispersed in 6.8569g (50mmol) of p-nitrotoluene in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 0.4 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 0.4MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 22.3%, the selectivity of p-nitrobenzyl hydroperoxide is 19.1%, the selectivity of p-nitrobenzyl alcohol is 10.3%, the selectivity of p-nitrobenzaldehyde is 9.3%, the selectivity of p-nitrobenzoic acid is 61.3%, and other obvious oxidation products are not detected.
Example 5
0.0048g (0.006mmol) of 5,10,15, 20-tetra (2-methoxyphenyl) porphyrin cobalt (II)0.82g (10%, mol/mol) of NHPI is dispersed in 6.8569g (50mmol) of p-nitrotoluene in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 0.8 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 0.8MPa of oxygen pressure. After the reaction is finished, the reaction kettle is used for reaction,ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 37.7%, the selectivity of p-nitrobenzyl hydroperoxide is 14.6%, the selectivity of p-nitrobenzyl alcohol is 17.6%, the selectivity of p-nitrobenzaldehyde is 4.9%, the selectivity of p-nitrobenzoic acid is 62.9%, and other obvious oxidation products are not detected.
Example 6
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0048g (0.006mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.2 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.2MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 51.6%, the selectivity of p-nitrobenzyl hydroperoxide is 9.4%, the selectivity of p-nitrobenzyl alcohol is 21.6%, the selectivity of p-nitrobenzaldehyde is 3.3%, the selectivity of p-nitrobenzoic acid is 65.7%, and other obvious oxidation products are not detected.
Example 7
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0049g (0.006mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin cobalt (II) and 0.33g (4%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 80 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 80 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After the reaction is finished, ice waterCooled to room temperature, 1.3115g (5.00mmol) of triphenylphosphine (PPh) were added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 9.2%, the selectivity of p-nitrobenzyl hydroperoxide is 26.9%, the selectivity of p-nitrobenzaldehyde is 14.5%, the selectivity of p-nitrobenzoic acid is 58.6%, and other obvious oxidation products are not detected.
Example 8
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0049g (0.006mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin cobalt (II) and 0.49g (6%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 80 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 80 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 15.9%, the selectivity of p-nitrobenzyl hydroperoxide is 33.9%, the selectivity of p-nitrobenzyl alcohol is 9.1%, the selectivity of p-nitrobenzaldehyde is 11.9%, the selectivity of p-nitrobenzoic acid is 45.1%, and other obvious oxidation products are not detected.
Example 9
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0049g (0.006mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin cobalt (II) and 0.66g (8%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 80 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 80 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After the reaction was completed, ice water was cooled to room temperature, and 1.31 was added to the reaction mixture15g (5.00mmol) of triphenylphosphine (PPh)3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 16.6%, the selectivity of p-nitrobenzyl hydroperoxide is 29.7%, the selectivity of p-nitrobenzyl alcohol is 13.9%, the selectivity of p-nitrobenzaldehyde is 10.1%, the selectivity of p-nitrobenzoic acid is 46.3%, and other obvious oxidation products are not detected.
Example 10
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0049g (0.006mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 80 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 80 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 22.3%, the selectivity of p-nitrobenzyl hydroperoxide is 24.8%, the selectivity of p-nitrobenzyl alcohol is 18.5%, the selectivity of p-nitrobenzaldehyde is 7.5%, the selectivity of p-nitrobenzoic acid is 49.2%, and other obvious oxidation products are not detected.
Example 11
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0049g (0.006mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 90 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 90 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.0 g) was added to the reaction mixture0mmol) triphenylphosphine (PPh)3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 22.3%, the selectivity of p-nitrobenzyl hydroperoxide is 20.4%, the selectivity of p-nitrobenzyl alcohol is 21.9%, the selectivity of p-nitrobenzaldehyde is 6.7%, the selectivity of p-nitrobenzoic acid is 51.0%, and other obvious oxidation products are not detected.
Example 12
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0049g (0.006mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 100 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 100 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 30.9%, the selectivity of p-nitrobenzyl hydroperoxide is 18.7%, the selectivity of p-nitrobenzyl alcohol is 22.7%, the selectivity of p-nitrobenzaldehyde is 6.4%, the selectivity of p-nitrobenzoic acid is 52.2%, and other obvious oxidation products are not detected.
Example 13
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0049g (0.006mmol) of 5,10,15, 20-tetrakis (4-chlorophenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.00 mmo) was added to the reaction mixturel) triphenylphosphine (PPh)3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 40.4%, the selectivity of p-nitrobenzyl hydroperoxide is 15.2%, the selectivity of p-nitrobenzyl alcohol is 25.2%, the selectivity of p-nitrobenzaldehyde is 5.1%, the selectivity of p-nitrobenzoic acid is 54.5%, and other obvious oxidation products are not detected.
Example 14
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0044g (0.006mmol) of 5,10,15, 20-tetrakis (2-methylphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 41.5%, the selectivity of p-nitrobenzyl hydroperoxide is 11.5%, the selectivity of p-nitrobenzyl alcohol is 18.5%, the selectivity of p-nitrobenzaldehyde is 2.7%, the selectivity of p-nitrobenzoic acid is 67.3%, and other obvious oxidation products are not detected.
Example 15
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0045g (0.006mmol) of 5,10,15, 20-tetrakis (4-fluorophenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice-water, and 1.3115g (5.00mmol) of the mixture was added) Triphenylphosphine (PPh)3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 42.0 percent, the selectivity of p-nitrobenzyl hydroperoxide is 12.1 percent, the selectivity of p-nitrobenzyl alcohol is 23.9 percent, the selectivity of p-nitrobenzaldehyde is 3.0 percent, the p-nitrobenzoic acid is 61.0 percent, and other obvious oxidation products are not detected.
Example 16
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0049g (0.006mmol) of 5,10,15, 20-tetrakis (2-chlorophenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 43.0 percent, the selectivity of p-nitrobenzyl hydroperoxide is 10.5 percent, the selectivity of p-nitrobenzyl alcohol is 20.5 percent, the selectivity of p-nitrobenzaldehyde is 2.7 percent, the selectivity of p-nitrobenzoic acid is 66.3 percent, and other obvious oxidation products are not detected.
Example 17
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.0051g (0.006mmol) of 5,10,15, 20-tetrakis (4-carboxyphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of the mixture was addedTriphenylphosphine (PPh)3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 43.2 percent, the selectivity of p-nitrobenzyl hydroperoxide is 13.4 percent, the selectivity of p-nitrobenzyl alcohol is 18.7 percent, the selectivity of p-nitrobenzaldehyde is 2.3 percent, the selectivity of p-nitrobenzoic acid is 65.6 percent, and other obvious oxidation products are not detected.
Example 18
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0046g (0.006mmol) of 5,10,15, 20-tetrakis (3-cyanophenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 43.8%, the selectivity of p-nitrobenzyl hydroperoxide is 15.8%, the selectivity of p-nitrobenzyl alcohol is 17.3%, the selectivity of p-nitrobenzaldehyde is 2.5%, the selectivity of p-nitrobenzoic acid is 64.4%, and other obvious oxidation products are not detected.
Example 19
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0057g (0.006mmol) of 5,10,15, 20-tetrakis (2, 5-dichlorophenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 1.3115g (5.0 g) was added to the reaction mixture0mmol) triphenylphosphine (PPh)3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 42.8%, the selectivity of p-nitrobenzyl hydroperoxide is 11.8%, the selectivity of p-nitrobenzyl alcohol is 24.9%, the selectivity of p-nitrobenzaldehyde is 2.5%, the selectivity of p-nitrobenzoic acid is 60.8%, and other obvious oxidation products are not detected.
Example 20
In a 100mL stainless steel autoclave with a Teflon liner, 0.0047g (0.006mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin manganese (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 29.8%, the selectivity of p-nitrobenzyl hydroperoxide is 13.7%, the selectivity of p-nitrobenzyl alcohol is 12.2%, the selectivity of p-nitrobenzaldehyde is 7.7%, the selectivity of p-nitrobenzoic acid is 66.4%, and other obvious oxidation products are not detected.
Example 21
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0048g (0.006mmol) of nickel (II) 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After the reaction was completed, ice water was cooled to room temperature, and 1.3 parts of an organic solvent was added to the reaction mixture115g (5.00mmol) of triphenylphosphine (PPh)3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 18.8%, the selectivity of p-nitrobenzyl hydroperoxide is 16.0%, the selectivity of p-nitrobenzyl alcohol is 6.3%, the selectivity of p-nitrobenzaldehyde is 14.1%, the selectivity of p-nitrobenzoic acid is 63.6%, and other obvious oxidation products are not detected.
Example 22
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0047g (0.006mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin iron (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 18.6%, the selectivity of p-nitrobenzyl hydroperoxide is 16.0%, the selectivity of p-nitrobenzyl alcohol is 6.3%, the selectivity of p-nitrobenzaldehyde is 14.1%, the selectivity of p-nitrobenzoic acid is 63.6%, and other obvious oxidation products are not detected.
Example 23
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0048g (0.006mmol) of copper (II) 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After the reaction was completed, the reaction mixture was cooled to room temperature with ice water, and then added to the reaction mixture1.3115g (5.00mmol) of triphenylphosphine (PPh)3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 16.4%, the selectivity of p-nitrobenzyl hydroperoxide is 22.4%, the selectivity of p-nitrobenzyl alcohol is 14.3%, the selectivity of p-nitrobenzaldehyde is 15.3%, the selectivity of p-nitrobenzoic acid is 48.0%, and other obvious oxidation products are not detected.
Example 24
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0048g (0.006mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin zinc (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.8569g (50mmol) of p-nitrotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of p-nitrotoluene is 17.9%, the selectivity of p-nitrobenzyl hydroperoxide is 16.9%, the selectivity of p-nitrobenzyl alcohol is 12.7%, the selectivity of p-nitrobenzaldehyde is 23.3%, the selectivity of p-nitrobenzoic acid is 47.1%, and other obvious oxidation products are not detected.
Example 25
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0048g (0.006mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 4.6070g (50mmol) of toluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After the reaction was completed, the reaction mixture was cooled to room temperature with ice water, and then added to the reaction mixture1.3115g (5.00mmol) of triphenylphosphine (PPh)3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion of toluene was 35.1%, the selectivity to benzyl hydroperoxide was 3.7%, the selectivity to benzaldehyde was 4.0%, and benzoic acid was 92.3%, with no other significant oxidation products detected.
Example 26
0.0048g (0.006mmol) of 5,10,15, 20-tetra (2-methoxyphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI are dispersed in 7.1100g (50mmol) of 1-methylnaphthalene in a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, the autoclave is sealed, stirred and heated to 120 ℃, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion rate of 1-methylnaphthalene is 30.4%, the selectivity of 1-naphthylmethyl hydroperoxide is 14.8%, the selectivity of 1-naphthaldehyde is 6.3%, and the selectivity of 1-naphthoic acid is 78.9%, and other obvious oxidation products are not detected.
Example 27
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0048g (0.006mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 8.4907g (50mmol) of 4-phenyl toluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. Acetone is used as solventThe resulting reaction mixture was taken up to 100 mL. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. 4-phenyltoluene conversion was 73.5%, 4-phenylmethylhydroperoxide selectivity was 1.8%, 4-phenylbenzaldehyde selectivity was 6.6%, and 4-phenylbenzoic acid 91.6%, with no other significant oxidation products being detected.
Example 28
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0048g (0.006mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 5.3084g (50mmol) of 4-methyltoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion of 4-methyltoluene was 27.3%, the selectivity to benzhydryl hydroperoxide was 9.6%, p-dibenzoic acid was 81.3%, and no other products were calculated.
Example 29
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0048g (0.006mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 6.3290g (50mmol) of 4-chlorotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed,performing liquid chromatography analysis by using 2-naphthoic acid as an internal standard. The conversion rate of 4-chlorotoluene is 88.5%, the selectivity of 4-chlorobenzyl hydroperoxide is 1.0%, 4-chlorobenzyl alcohol is 1.6%, 4-chlorobenzaldehyde is 2.3%, and 4-chlorobenzoic acid is 95.1%, and other obvious oxidation products are not detected.
Example 30
In a 100mL stainless steel autoclave having a polytetrafluoroethylene liner, 0.0048g (0.006mmol) of 5,10,15, 20-tetrakis (2-methoxyphenyl) porphyrin cobalt (II) and 0.82g (10%, mol/mol) of NHPI were dispersed in 8.0515g (50mmol) of 2, 4-dichlorotoluene, the autoclave was sealed, stirred and warmed to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) And 50mL of acetone, and the resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography is carried out by taking naphthalene as an internal standard; 10mL of the resulting solution was removed, and liquid chromatography was performed using 2-naphthoic acid as an internal standard. The conversion of 2, 4-dichlorotoluene was 63.2%, the selectivity for 2, 4-dichlorobenzyl hydroperoxide was 2.1%, 2, 4-dichlorobenzaldehyde was 3.8%, and 2, 4-dichlorobenzoic acid was 94.1%, with no other significant oxidation products being detected.
Example 31 (amplification experiment)
0.0480g (0.06mmol) of 5,10,15, 20-tetra (2-methoxyphenyl) porphyrin cobalt (II) and 8.2g (10%, mol/mol) of NHPI are dispersed in 68.57g (0.5mol) of 4-nitrotoluene in a 1.0L stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, ice water was cooled to room temperature, and 13.11g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. Distilling, recovering 34.22g of 4-nitrotoluene, with a conversion rate of 49.9 percent, and performing reduced pressure rectification to obtain 8.22g of p-nitrobenzyl hydroperoxide, with a selectivity of 9.7 percent, 15.50g of p-nitrobenzyl alcohol, a selectivity of 20.2 percent, 3.26g of p-nitrobenzaldehyde, a selectivity of 4.3 percent and p-nitrotoluene55.10g of benzoic acid, and the selectivity is 65.8%.

Claims (6)

1. A method for catalytic oxidation of toluene and its derivatives by metalloporphyrin, which comprises:
dispersing metalloporphyrin and N-hydroxyphthalimide (NHPI) in toluene and derivatives thereof, sealing a reaction system, heating to 70-130 ℃ under stirring, introducing oxygen to 0.2-2.0 MPa, keeping the set temperature and oxygen pressure, stirring for reaction for 8 hours, and then carrying out aftertreatment on reaction liquid to obtain a product aromatic acid;
the mass ratio of the metalloporphyrin to the toluene and the toluene derivatives is 1: 100000-5000;
the mass ratio of the NHPI to the toluene and the derivatives thereof is 1: 1000-5;
the toluene and the derivatives thereof are: toluene, 4-nitrotoluene, 2-chlorotoluene, 3-chlorotoluene, 4-fluorotoluene, 4-methoxytoluene, 1-methylnaphthalene, 2-methylnaphthalene, 4-phenyltoluene, 3-methyltoluene, 4-methyltoluene and 2, 4-dichlorotoluene;
the metalloporphyrin is at least one of compounds shown in a formula (I):
Figure FDA0002470752070000011
in the formula (I), R1、R2、R3、R4、R5、R6、R7Each independently is: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, benzyl, fluoro, chloro, bromo, or iodo;
m is Co2+、Mn2+、Ni2+、Fe2+、Cu2+Or Zn2+。
2. The method for catalytic oxidation of toluene and its derivatives with metalloporphyrin as claimed in claim 1, wherein the ratio of the quantity of metalloporphyrin to toluene and its derivatives is 1: 50000-10000.
3. The metalloporphyrin-catalyzed oxidation method for toluene and its derivatives as claimed in claim 1 or 2, wherein the mass ratio of NHPI to toluene and its derivatives is 1: 100-10.
4. The method for catalytic oxidation of toluene and its derivatives with metalloporphyrin as claimed in claim 1, wherein the reaction temperature is 80-120 ℃.
5. The method for catalytic oxidation of toluene and its derivatives with metalloporphyrin as claimed in claim 1 or 2, wherein the reaction pressure is 0.4-1.2 MPa.
6. The metalloporphyrin-catalyzed oxidation method for toluene and its derivatives according to claim 1 or 2, wherein the post-treatment method comprises the following steps: after the reaction is finished, triphenylphosphine and acetone are added into the reaction solution, and triphenylphosphine PPh3The using amount of the acetone is 1.0-25% of the amount of the toluene and the derivatives thereof, the using amount of the acetone is 30-50 mL, the obtained product is stirred at room temperature (20-30 ℃) for 30min to reduce the generated peroxide, and the crude product is distilled, rectified under reduced pressure and recrystallized to obtain an oxidation product.
CN202010347658.5A 2020-04-28 2020-04-28 Method for catalytic oxidation of toluene and derivatives thereof by metalloporphyrin Pending CN111675620A (en)

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