CN105801455A - Method for oxidatively synthesizing p-carboxybenzene sulfonamide through oxygen - Google Patents
Method for oxidatively synthesizing p-carboxybenzene sulfonamide through oxygen Download PDFInfo
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- CN105801455A CN105801455A CN201610324265.6A CN201610324265A CN105801455A CN 105801455 A CN105801455 A CN 105801455A CN 201610324265 A CN201610324265 A CN 201610324265A CN 105801455 A CN105801455 A CN 105801455A
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
- C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
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Abstract
The invention discloses a method for oxidatively synthesizing p-carboxybenzene sulfonamide through oxygen, and belongs to a method for preparing p-carboxybenzene sulfonamide.The method comprises the steps that oxygen is taken as an oxidizing agent, the oxygen pressure only needs to be maintained at 1 atm, and an oxidizing reaction is conducted in acetic acid by taking oxygen as the oxidizing agent under the action of a nitroxide free radical type catalyst and a metal salt or metallic oxide cocatalyst; p-methylphenyl sulphonylamine is catalytically oxidized to prepare p-carboxybenzene sulfonamide.The method comprises the processes that 5 mL of acetic acid, 1 mmol of p-methylphenyl sulphonylamine, the catalyst and the cocatalyst are sequentially added in a round-bottom flask with a magnetic stirring device, oxygen is introduced, and the pressure is maintained at 1 atm; the dosage mole ratio of the catalyst is 3%-8% of that of p-methylphenyl sulphonylamine, the dosage mole ratio of the cocatalyst is 0.5%-6% of that of p-methylphenyl sulphonylamine, reacting is finished after stirring is performed for 2-12 hours at the temperature of 40 DEG C-120 DEG C, cooling is performed, reduced pressure distillation is performed to remove acetic acid, residues are sequentially washed with water and acetone, and drying is performed to obtain p-carboxybenzene sulfonamide.The method has the advantages that the conditions are mild, and the yield is high.
Description
Technical field
The present invention relates to a kind of method preparing P-Carboxybenzenesulfonamide, particularly the method for a kind of dioxygen oxidation synthesis P-Carboxybenzenesulfonamide.
Background technology
P-Carboxybenzenesulfonamide (I) is important medical synthetic intermediate, is used for synthesizing probenecid, Harrar hydrazone etc., and its sodium salt can be additionally used in the inhibitor of carbonic anhydrase, and its structural formula is as follows:
The preparation of P-Carboxybenzenesulfonamide is with p-methylphenyl sulphonylamine for raw material, and using oxidant is carboxyl by methyl oxidation.But containing strong electron-withdrawing group group on p-methylphenyl sulphonylamine aromatic ring, being more dysoxidizable substrate, therefore its oxidation often uses more than stoichiometric tradition strong oxidizer KMnO4、Na2Cr2O7、CrO3、NaIO4Deng, it is present in reaction system with less valence state after these oxidant reactions, not only increases the difficulty of product separating-purifying, and the waste liquid discharged also brings ill effect to environment, there is also the drawbacks such as etching apparatus, efficiency is low simultaneously, do not meet the requirement of Green Chemistry.
Used oxygen to do oxidizing aromatic side chain to generally require and carry out when High Temperature High Pressure in the past, as Li Tao etc. reports employing cobalt-based pyrazole complexes as catalyst, aoxidize toluene with oxygen for oxidizer catalytic and prepare benzoic acid, reaction 140 minutes under 150 DEG C and 1.5Mpa (150atm), benzoic productivity is up to 75.96%, and benzoic selectivity reaches 89.25%.This reaction carries out at high temperature under high pressure, is the process of a serious power consumption, and equipment requirements is also higher；The required catalyst cobalt-based pyrazole complexes of reaction is prepared relatively complicated, relatively costly；This reaction, except being carboxyl by methyl oxidation, also can generate the intermediate oxidation product such as methylol, aldehyde radical, and the selectivity of product generating carboxyl is 89.25%；This reaction condition can by toluene oxidation, but after methyl para-position introduces strong electron-withdrawing group sulfoamido, methyl can not oxidized generation P-Carboxybenzenesulfonamide, in fact much novel oxidation catalyst can catalysis toluene oxidation be benzoic acid, but can not the oxidation of catalysis p-methylphenyl sulphonylamine.
Summary of the invention
The invention aims to provide a kind of cheap, environmental friendliness, the gentle method that dioxygen oxidation synthesizes P-Carboxybenzenesulfonamide efficiently.
The object of the present invention is achieved like this: the method is with oxygen for oxidant, oxygen pressure only needs to maintain 1atm, under the effect of NO free radical type catalyst and slaine or metal oxide promoters, with oxygen for oxidant, oxidation reaction carries out in acetic acid；Catalytic oxidation p-methylphenyl sulphonylamine prepares P-Carboxybenzenesulfonamide；
R1And R2Represent identical group or different group, R1And R2For hydrogen or C1-C6Alkyl；
Specific embodiment is as follows: equipped with, in the round-bottomed flask of magnetic stirring apparatus, being sequentially added into the acetic acid of 5mL, the p-methylphenyl sulphonylamine of 1mmol, catalyst and promoter, passes into oxygen, and to maintain pressure be 1atm；Consumption mol ratio is p-methylphenyl sulphonylamine consumption the 3%～8% of catalyst, consumption mol ratio is p-methylphenyl sulphonylamine consumption the 0.5%～6% of promoter, under 40～120 DEG C of conditions, stopped reaction after stirring 2～12 hours, cooling, decompression is distilled off acetic acid, and residue washes with water successively, washing with acetone, dries and obtains product P-Carboxybenzenesulfonamide.
The catalyst used is free radical type catalyst, for N-hydroxyl-2,2, the equal benzene tetramethyl imidodicarbonic diamide of 6,6-tetramethyl piperidines, HP, N-hydroxysaccharine, N, N-dihydroxy, 1,3,5-trihydroxy isocyanuric acid, N-hydroxy-N-methvl Benzoylamide, 3,5-dinitro-N-hydroxy-N-methvl Benzoylamide or 1-hydroxyl-2,2-diphenyl-3-indolone；It is only 3%～8% based on p-methylphenyl sulphonylamine mol ratio；The promoter used is cobalt acetate, manganese acetate, copper acetate, ferric acetate or manganese dioxide slaine, mol ratio based on p-methylphenyl sulphonylamine is only 0.5%～6%, the conversion ratio of p-methylphenyl sulphonylamine is 80.32～99.33%, the productivity of product P-Carboxybenzenesulfonamide is 70.83～94.05%, and selectivity is up to 97.65%；Catalyst and promoter all can pass through to wash to remove after completion of the reaction.
Beneficial effect; owing to have employed such scheme; using oxygen cheap, eco-friendly is oxidant; p-methylphenyl sulphonylamine is oxidized to product P-Carboxybenzenesulfonamide; productivity reaches as high as 94.05%; selectivity reaches as high as 97.65%; detecting purity by Agilent1200 type high performance liquid chromatograph analysis is 92.23～95.35%%; in oxidation product, P-Carboxybenzenesulfonamide is principal product; there is a small amount of 4-methylol benzsulfamide (II), formed without 4-formoxyl benzsulfamide (III).
By-product:
This method is compared with traditional p-methylphenyl sulphonylamine oxidizing process, the oxidant used is oxygen, not only reduce cost, and the by-product after aoxidizing is water, environmentally safe, acetic acid is distilled off through decompression after completion of the reaction, acetic acid recoverable, residue washes with water successively, washing with acetone, can realize product and catalyst and promoter, the separating of by-product, and post processing is simple and convenient.
This method reaction condition is gentle, carries out, and have high conversion and high selectivity in normal pressure (oxygen pressure maintains 1atm) under temperature (40～120 DEG C), and product purity is high, has good prospects for commercial application.
The present invention its substantial feature compared with traditional oxidizing process is: the method, with cheap oxygen for oxidant, greatly reduces cost, and by-product is water, environmentally safe；It can efficient oxidation p-methylphenyl sulphonylamine be just P-Carboxybenzenesulfonamide that this reaction only needs maintenance oxygen to be pressed in 1atm, mild condition, it is to avoid the use of high-temperature high-pressure apparatus, reduces energy consumption, it is the green synthesis method of a kind of desirable P-Carboxybenzenesulfonamide, there is prospects for commercial application.
Advantage:
1, reaction is a catalytic oxidation process, the consumption of catalyst and promoter is few, relative to raw material p-methylphenyl sulphonylamine, catalyst amount is only 3%～8%, promoter consumption is 0.5%～6%, the simple washing of process, a small amount of washing with acetone just can realize the separation of catalyst, promoter, by-product and product, easy and simple to handle.
2, not using traditional strong oxidizer, use oxygen is oxidant, not only greatly reduces cost, and by-product is water, and environment is safe from harm, and is an eco-friendly process；
3, reaction has at a relatively high selectivity and conversion ratio, and methyl oxidation is carboxyl by reaction, only has minute quantity p-methylphenyl sulphonylamine and is oxidized to 4-methylol benzsulfamide, without the generation of 4-formoxyl benzsulfamide.Under optimized condition, the conversion ratio of p-methylphenyl sulphonylamine is up to 99.33%, and the productivity of P-Carboxybenzenesulfonamide is up to 94.05%, and selectivity is up to 94.68%.
4, reaction condition is gentle, reaction carries out under normal pressure (1atm) and middle temperature (40～120 DEG C), and equipment requirements is simple, it is to avoid the drawback that must carry out at high temperature under high pressure when conventional use oxygen aoxidizes, reduce energy consumption, it is easy to industrial application.
Detailed description of the invention
The method is under the effect of NO free radical type catalyst and slaine or metal oxide promoters, and with oxygen for oxidant, catalytic oxidation p-methylphenyl sulphonylamine prepares P-Carboxybenzenesulfonamide:
R1And R2Represent identical group or different group, R1And R2For hydrogen or C1-C6Alkyl.
The catalyst used in this method is NO free radical type catalyst；Promoter is various slaine and metal-oxide, and oxidant is oxygen；Oxidation reaction carries out with acetic acid for solvent under normal pressure (1atm) and middle temperature (40～120 DEG C) condition；Catalytic oxidation p-methylphenyl sulphonylamine is oxidized to P-Carboxybenzenesulfonamide.
Described catalyst can be N-hydroxyl-2,2,6,6-tetramethyl piperidine, HP, N-hydroxysaccharine, N, the equal benzene tetramethyl imidodicarbonic diamide of N-dihydroxy, 1,3,5-trihydroxy isocyanuric acid, N-hydroxy-N-methvl Benzoylamide, 3,5-dinitro-N-hydroxy-N-methvl Benzoylamide or 1-hydroxyl-2,2-diphenyl-3-indolone；The structural formula of above-mentioned catalyst is as follows:
Described slaine or metal oxide promoters can be cobalt acetate, manganese acetate, copper acetate, ferric acetate or manganese dioxide；
The reactant used is p-methylphenyl sulphonylamine, containing the phenyl ring of electron-withdrawing substituent, itself is difficult to oxidation reaction；Therefore, when sulfoamido is replaced into the donor residues such as methoxyl group, acetamido, oxidation reaction is more easy to generation.
Specific embodiment is as follows:
Equipped with, in the round-bottomed flask of magnetic stirring apparatus, being sequentially added into acetic acid, p-methylphenyl sulphonylamine, catalyst, promoter；Consumption mol ratio is p-methylphenyl sulphonylamine consumption the 3%～8% of catalyst, the consumption mol ratio of promoter is 0.5%～6%, pass into oxygen, maintain oxygen pressure for 1atm, under 40～120 DEG C of conditions, stopped reaction after stirring 2～12 hours, decompression remove acetic acid, solvent acetic acid can Reusability, residue use water cyclic washing remove Residual acetic acid and promoter, residue removes catalyst and a small amount of by-product again with a small amount of washing with acetone, namely obtains product P-Carboxybenzenesulfonamide after filtration cakes torrefaction.
The productivity of product P-Carboxybenzenesulfonamide is 70.83～94.05%, and detecting purity by Agilent1200 type high performance liquid chromatograph analysis is 92.23～95.35%%.This oxidation reaction selectivity is high, only has a small amount of p-methylphenyl sulphonylamine and is oxidized to 4-methylol benzsulfamide (II), there is no the generation of 4-formoxyl benzsulfamide (III).
By-product:
R in 4-methylol benzsulfamide (II) and 4-formoxyl benzsulfamide (III)1And R2Represent identical group or different group, R1And R2For hydrogen or C1-C6Alkyl.
The reactant that this reaction uses contains electron withdraw group sulfoamido, is more difficult oxidized substrate, and therefore this reaction is equally applicable to the oxidation of other aromatic side chain containing electron withdraw group or electron donating group.
This reaction adopts oxygen to be oxidant, but when oxygen is used alone, oxidability is more weak, and therefore selecting the activity that suitable catalyst system and catalyzing improves oxygen is the key of the present invention.Catalyst used in the present invention is NO free radical type oxidant N-hydroxyl-2,2,6,6-tetramethyl piperidine, HP, N-hydroxysaccharine, N, the equal benzene tetramethyl imidodicarbonic diamide of N-dihydroxy, 1,3,5-trihydroxy isocyanuric acid, N-hydroxy-N-methvl Benzoylamide, 3,5-dinitro-N-hydroxy-N-methvl Benzoylamide, 1-hydroxyl-2,2-diphenyl-3-indolones etc., promoter is slaine or the metal-oxides such as cobalt acetate, manganese acetate, copper acetate, ferric acetate, manganese dioxide；This catalyst system and catalyzing consumption is few, catalytic efficiency is high, p-methylphenyl sulphonylamine: catalyst: during promoter=100:3～8:0.5～6, (oxygen pressure maintains 1atm) oxygen under normal pressure can be realized p-methylphenyl sulphonylamine is oxidized to P-Carboxybenzenesulfonamide, the conversion ratio of p-methylphenyl sulphonylamine reaches as high as 99.33%, and the productivity of product P-Carboxybenzenesulfonamide reaches as high as 94.05%；And after completion of the reaction by simple filtration, washing, the dry separation purification that can realize P-Carboxybenzenesulfonamide.
Embodiment 1: weigh the P-Carboxybenzenesulfonamide of 1mmol, N-hydroxysaccharine 0.06mmol, manganese dioxide 0.03mmol, adds in 25mL reaction bulb, add acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, it is warming up to 80 DEG C to react 6 hours, reacts complete, be cooled to room temperature.Filtration filters manganese dioxide, and filtrate decompression removes acetic acid, acetic acid recoverable.Washing residue removes the acetic acid of residual, N-hydroxysaccharine is removed and a small amount of to methylol benzsulfamide with a small amount of washing with acetone, filtration cakes torrefaction, P-Carboxybenzenesulfonamide can be obtained, productivity 81.86%, the conversion ratio of p-methylphenyl sulphonylamine is 86.32%, and the selectivity generating P-Carboxybenzenesulfonamide is 94.83%, and it is 94.20% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 2: weigh the P-Carboxybenzenesulfonamide of 1mmol, N, N-dihydroxy equal benzene tetramethyl imidodicarbonic diamide 0.03mmol, manganese acetate 0.06mmol, add in 25mL reaction bulb, add acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, be warming up to 120 DEG C and react 2 hours, react complete, be cooled to room temperature.Filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, remove acetic acid and the promoter manganese acetate of residual, a small amount of washing with acetone removes N, N-dihydroxy equal benzene tetramethyl imidodicarbonic diamide and a small amount of to methylol benzsulfamide, filtration cakes torrefaction, can obtain P-Carboxybenzenesulfonamide, productivity 70.83%, the conversion ratio of p-methylphenyl sulphonylamine is 80.32%, and the selectivity generating P-Carboxybenzenesulfonamide is 88.18%, and it is 92.23% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 3: weigh the P-Carboxybenzenesulfonamide of 1mmol, HP 0.08mmol, copper acetate 0.04mmol, adds in 25mL reaction bulb, add acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, it is warming up to 40 DEG C to react 12 hours, reacts complete, be cooled to room temperature.Filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, remove acetic acid and the promoter copper acetate of residual, a small amount of washing with acetone removes HP and a small amount of to methylol benzsulfamide, filtration cakes torrefaction, can obtaining P-Carboxybenzenesulfonamide, productivity 72.81%, the conversion ratio of p-methylphenyl sulphonylamine is 81.55%, the selectivity generating P-Carboxybenzenesulfonamide is 89.28%, and it is 94.42% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 4: weigh the P-Carboxybenzenesulfonamide of 1mmol, 3,5-dinitro-N-hydroxy-N-methvl Benzoylamide 0.05mmol, ferric acetate 0.05mmol, add in 25mL reaction bulb, add acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, be warming up to 100 DEG C and react 6 hours, react complete, be cooled to room temperature.Filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, remove acetic acid and the promoter ferric acetate of residual, a small amount of washing with acetone removes 3,5-dinitro-N-hydroxy-N-methvl Benzoylamide and a small amount of to methylol benzsulfamide, filtration cakes torrefaction, can obtain P-Carboxybenzenesulfonamide, productivity 74.25%, the conversion ratio of p-methylphenyl sulphonylamine is 82.43%, and the selectivity generating P-Carboxybenzenesulfonamide is 90.08%, and it is 93.12% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 5: weigh the P-Carboxybenzenesulfonamide of 1mmol, 1-hydroxyl-2,2-diphenyl-3-indolone 0.06mmol, cobalt acetate 0.005mmol, add in 25mL reaction bulb, add acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, be warming up to 100 DEG C and react 8 hours, react complete, be cooled to room temperature.Filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, remove acetic acid and the promoter cobalt acetate of residual, a small amount of washing with acetone removes 1-hydroxyl-2,2-diphenyl-3-indolones etc. and a small amount of to methylol benzsulfamide, filtration cakes torrefaction, can obtain P-Carboxybenzenesulfonamide, productivity 73.45%, the conversion ratio of p-methylphenyl sulphonylamine is 82.12%, and the selectivity generating P-Carboxybenzenesulfonamide is 89.44%, and it is 95.20% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 6: weigh the P-Carboxybenzenesulfonamide of 1mmol, 1,3,5-trihydroxy isocyanuric acid 0.06mmol, manganese dioxide 0.03mmol, adds in 25mL reaction bulb, adds acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, be warming up to 90 DEG C and react 12 hours, react complete, be cooled to room temperature.Filtering, remove manganese dioxide, filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, remove the acetic acid of residual, a small amount of washing with acetone removes 1,3,5-trihydroxy isocyanuric acid and a small amount of to methylol benzsulfamide, filtration cakes torrefaction, can obtaining P-Carboxybenzenesulfonamide, productivity 90.76%, the conversion ratio of p-methylphenyl sulphonylamine is 93.24%, the selectivity generating P-Carboxybenzenesulfonamide is 97.34%, and it is 95.15% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 7: weigh the P-Carboxybenzenesulfonamide of 1mmol, N-hydroxyl-2,2,6,6-tetramethyl piperidine 0.06mmol, manganese dioxide 0.03mmol, add in 25mL reaction bulb, add acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, be warming up to 100 DEG C and react 10 hours, react complete, be cooled to room temperature.Being filtered to remove manganese dioxide, filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, removing the acetic acid of residual, a small amount of washing with acetone removes N-hydroxyl-2, and 2,6,6-tetramethyl piperidine and a small amount of to methylol benzsulfamide, filtration cakes torrefaction, can obtain P-Carboxybenzenesulfonamide, productivity 72.87%, the conversion ratio of p-methylphenyl sulphonylamine is 80.88%, and the selectivity generating P-Carboxybenzenesulfonamide is 90.10%, and it is 95.35% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 8: weigh the P-Carboxybenzenesulfonamide of 1mmol, N-hydroxy-N-methvl Benzoylamide 0.06mmol, cobalt acetate 0.01mmol, adds in 25mL reaction bulb, add acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, it is warming up to 100 DEG C to react 12 hours, reacts complete, be cooled to room temperature.Filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, remove acetic acid and the promoter cobalt acetate of residual, a small amount of washing with acetone removes N-hydroxy-N-methvl Benzoylamide and a small amount of to methylol benzsulfamide, filtration cakes torrefaction, can obtaining P-Carboxybenzenesulfonamide, productivity 84.62%, the conversion ratio of p-methylphenyl sulphonylamine is 90.23%, the selectivity generating P-Carboxybenzenesulfonamide is 93.78%, and it is 93.42% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 9: weigh the P-Carboxybenzenesulfonamide of 1mmol, 1-hydroxyl-2,2-diphenyl-3-indolone 0.06mmol, cobalt acetate 0.02mmol, add in 25mL reaction bulb, add acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, be warming up to 100 DEG C and react 10 hours, react complete, be cooled to room temperature.Filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, remove acetic acid and the promoter cobalt acetate of residual, a small amount of washing with acetone removes 1-hydroxyl-2,2-diphenyl-3-indolone and a small amount of to methylol benzenesulfonimide, filtration cakes torrefaction, can obtain P-Carboxybenzenesulfonamide, productivity 84.14%, the conversion ratio of p-methylphenyl sulphonylamine is 89.12%, and the selectivity generating P-Carboxybenzenesulfonamide is 94.41%, and it is 95.32% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 10: weigh the P-Carboxybenzenesulfonamide of 1mmol, N-hydroxysaccharine 0.05mmol, cobalt acetate 0.02mmol, adds in 25mL reaction bulb, add acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, it is warming up to 80 DEG C to react 12 hours, reacts complete, be cooled to room temperature.Filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, remove acetic acid and the promoter cobalt acetate of residual, a small amount of washing with acetone removes N-hydroxysaccharine and a small amount of to methylol benzsulfamide, filtration cakes torrefaction, can obtaining P-Carboxybenzenesulfonamide, productivity 81.89%, the conversion ratio of p-methylphenyl sulphonylamine is 87.65%, the selectivity generating P-Carboxybenzenesulfonamide is 93.43%, and it is 94.20% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 11: weigh the P-Carboxybenzenesulfonamide of 1mmol, 3,5-dinitro-N-hydroxy-N-methvl Benzoylamide 0.05mmol, cobalt acetate 0.01mmol, add in 25mL reaction bulb, add acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, be warming up to 100 DEG C and react 10 hours, react complete, be cooled to room temperature.Filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, remove acetic acid and the promoter cobalt acetate of residual, a small amount of washing with acetone removes 3,5-dinitro-N-hydroxy-N-methvl Benzoylamide and a small amount of to methylol benzenesulfonimide, filtration cakes torrefaction, can obtain P-Carboxybenzenesulfonamide, productivity 94.05%, the conversion ratio of p-methylphenyl sulphonylamine is 99.33%, and the selectivity generating P-Carboxybenzenesulfonamide is 94.68%, and it is 95.14% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Embodiment 12: weigh the P-Carboxybenzenesulfonamide of 1mmol, 1,3,5-trihydroxy isocyanuric acid 0.06mmol, cobalt acetate 0.02mmol, adds in 25mL reaction bulb, adds acetic acid 5mL, pass into oxygen, maintain oxygen pressure for 1atm, be warming up to 100 DEG C and react 10 hours, react complete, be cooled to room temperature.Filtrate decompression removes acetic acid, acetic acid recoverable.Residue is washed repeatedly, remove acetic acid and the promoter cobalt acetate of residual, a small amount of washing with acetone removes 1,3,5-trihydroxy isocyanuric acid and a small amount of to methylol benzenesulfonimide, filtration cakes torrefaction, can obtaining P-Carboxybenzenesulfonamide, productivity 85.62%, the conversion ratio of p-methylphenyl sulphonylamine is 87.68%, the selectivity generating P-Carboxybenzenesulfonamide is 97.65%, and it is 93.44% that product detects purity through Agilent1200 type high performance liquid chromatograph analysis.
Claims (2)
1. the method for a dioxygen oxidation synthesis P-Carboxybenzenesulfonamide, it is characterized in that: the method is with oxygen for oxidant, oxygen pressure only needs to maintain 1atm, under the effect of NO free radical type catalyst and slaine or metal oxide promoters, with oxygen for oxidant, oxidation reaction carries out in acetic acid；Catalytic oxidation p-methylphenyl sulphonylamine prepares P-Carboxybenzenesulfonamide；
R1And R2Represent identical group or different group, R1And R2For hydrogen or C1-C6Alkyl；
Specific embodiment is as follows: equipped with, in the round-bottomed flask of magnetic stirring apparatus, being sequentially added into the acetic acid of 5mL, the p-methylphenyl sulphonylamine of 1mmol, catalyst and promoter, passes into oxygen, and to maintain pressure be 1atm；Consumption mol ratio is p-methylphenyl sulphonylamine consumption the 3%～8% of catalyst, consumption mol ratio is p-methylphenyl sulphonylamine consumption the 0.5%～6% of promoter, under 40～120 DEG C of conditions, stopped reaction after stirring 2～12 hours, cooling, decompression is distilled off acetic acid, and residue washes with water successively, washing with acetone, dries and obtains product P-Carboxybenzenesulfonamide.
2. the method for a kind of dioxygen oxidation according to claim 1 synthesis P-Carboxybenzenesulfonamide, it is characterized in that: the catalyst used is free radical type catalyst, for N-hydroxyl-2,2,6,6-tetramethyl piperidine, HP, N-hydroxysaccharine, N, the equal benzene tetramethyl imidodicarbonic diamide of N-dihydroxy, 1,3,5-trihydroxy isocyanuric acid, N-hydroxy-N-methvl Benzoylamide, 3,5-dinitro-N-hydroxy-N-methvl Benzoylamide or 1-hydroxyl-2,2-diphenyl-3-indolone；It is only 3%～8% based on p-methylphenyl sulphonylamine mol ratio；The promoter used is cobalt acetate, manganese acetate, copper acetate, ferric acetate or manganese dioxide slaine, mol ratio based on p-methylphenyl sulphonylamine is only 0.5%～6%, the conversion ratio of p-methylphenyl sulphonylamine is 80.32～99.33%, the productivity of product P-Carboxybenzenesulfonamide is 70.83～94.05%, and selectivity is up to 97.65%；Catalyst and promoter all can pass through to wash to remove after completion of the reaction.
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| PCT/CN2016/108404 WO2017197870A1 (en) | 2016-05-16 | 2016-12-02 | Method for oxidatively synthesizing p-carboxybenzene sulfonamide by means of oxygen |
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| FAN YANG ET AL.: "Oxidation of toluenes to benzoic acids by oxygen in non-acidic solvents", 《TETRAHEDRON》 * |
| NARUHISA HIRAI ET AL.: "Oxidation of Substituted Toluenes with Molecular Oxygen in the Presence of N,N’,N’-Trihydroxyisocyanuric Acid as a Key Catalyst", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| YASUSHI YOSHINO ET AL.: "Catalytic Oxidation of Alkylbenzenes with Molecular Oxygen under Normal Pressure and Temperature by N-Hydroxyphthalimide Combined with Co(OAc)2", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
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| CN114105773A (en) * | 2020-08-29 | 2022-03-01 | 营口昌成新材料科技有限公司 | Oxidation method of 3-nitro-o-xylene |
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