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Method for synthesis of p-carboxybenzene sulfonamide through catalytic oxidation

A technology for carboxylbenzenesulfonamide and methylbenzenesulfonamide, which is applied in the field of catalytic oxidation synthesis of p-carboxybenzenesulfonamide, can solve the problems of inability to catalyze the oxidation of methylbenzenesulfonamide, equipment corrosion, complicated preparation, etc., and achieves stable properties, Cost saving, simple post-processing effect

Active Publication Date: 2015-03-25
CHINA UNIV OF MINING & TECH
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  • Abstract
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Problems solved by technology

But this reaction needs to add acetic acid simultaneously as oxygen-absorbing medium (the mass ratio of acetic acid and toluene is 1.2:1), and equipment corrosion is serious; The preparation of azole complexes is relatively cumbersome and costly; in addition to oxidizing methyl to carboxyl, this reaction will also generate intermediate oxidation products such as methylol and aldehyde, and the selectivity of the product to generate carboxyl is 89.25%; the reaction conditions can convert Toluene is oxidized, but when a strong electron-withdrawing sulfonamide group is introduced into the methyl group, the methyl group cannot be oxidized to generate p-carboxybenzenesulfonamide. In fact, many new oxidation catalysts can catalyze the oxidation of toluene to benzoic acid, but they cannot catalyze the oxidation of toluene to benzoic acid. Oxidation of toluenesulfonamide

Method used

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  • Method for synthesis of p-carboxybenzene sulfonamide through catalytic oxidation
  • Method for synthesis of p-carboxybenzene sulfonamide through catalytic oxidation
  • Method for synthesis of p-carboxybenzene sulfonamide through catalytic oxidation

Examples

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Effect test

Embodiment 1

[0045] Example 1: Step 1: In a 1L three-necked flask equipped with a condenser, a stirrer and a thermometer, add 380mL of ammonia water, then grind and pulverize 1mol p-toluenesulfonic acid chlorine, dissolve it in 300mL of toluene, and quickly add it to the three-necked flask , fully stirred, the reaction solution was milky, stirred at room temperature for 1-1.5 hours, cooled to 0°C, white crystals precipitated, filtered, the filter cake was washed with water, drained, weighed about 140g after drying, melting point 136-137 ℃. Yield 81.87%.

[0046] Step 2: Weigh 0.1mol of p-carboxybenzenesulfonamide, CeO 2 Add 0.005mol and 0.2mol of tert-butyl hydroperoxide into a 100mL reaction flask, adjust the pH to 12 with hydrochloric acid and sodium hydroxide, and then react at 80°C for 10h. After the reaction is complete, cool to room temperature. The catalyst is removed by filtration, washed and dried with water, and recycled. 6 mol / L HCl was added dropwise to the filtrate to adjus...

Embodiment 2

[0047] Embodiment 2: Step 2: Weigh 0.1mol of p-carboxybenzenesulfonamide, 0.002mol of TiO 2 , 0.8mol of tert-butyl hydroperoxide was added to the glass reactor, hydrochloric acid and sodium hydroxide were used to adjust the pH to 10, and then reacted at 70°C for 8h. After the reaction was completed, it was cooled to room temperature. The catalyst is removed by filtration, washed and dried with water, and recycled. 6 mol / L HCl was added dropwise to the filtrate to adjust the pH=2 to 3, and white crystals of p-carboxybenzenesulfonamide were precipitated. Filtrate, wash until neutral, and dry to obtain p-carboxybenzenesulfonamide with a yield of 81.83%. The purity of the product is 92.54% after analysis by Agilent 1200 high performance liquid chromatography.

[0048] Others are the same as in Example 1.

Embodiment 3

[0049] Embodiment 3: Step 2: Weigh 0.1mol of p-carboxybenzenesulfonamide, 0.001mol of WO 3 , 0.6mol of tert-butyl hydroperoxide was added to a 100mL reaction flask, hydrochloric acid and sodium hydroxide were used to adjust the pH to 14, and then reacted at 100°C for 1 hour. After the reaction was completed, it was cooled to room temperature. The catalyst is removed by filtration, washed and dried with water, and recycled. 6mol / L HCl was added dropwise to the filtrate to adjust the pH=3-4, and white crystals of p-carboxybenzenesulfonamide were precipitated. Filter, wash until neutral, and dry to obtain p-carboxybenzenesulfonamide with a yield of 82.85%. The purity of the product is 95.47% after analysis and detection by an Agilent 1200 type high performance liquid chromatograph.

[0050] Others are the same as in Example 1.

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Abstract

The invention relates to a method for synthesis of p-carboxybenzene sulfonamide through catalytic oxidation, belonging to a method for preparing p-carboxybenzene sulfonamide. According to the method, p-carboxybenzene sulfonamide is prepared by two-step reaction by taking p-toluenesulfonyl chloride as raw material. The method comprises the following steps: firstly performing ammonolysis on p-toluenesulfonyl chloride to obtain p-toluenesulfonamide, oxidizing p-toluenesulfonamide to obtain a product, namely p-carboxybenzene sulfonamide by taking a hydroperoxide as an oxidant to replace traditional strong oxidants, namely sodium bichromate, potassium permanganate and the like under the catalytic action of a metal oxide and heteropoly acid in mild conditions in a water phase, wherein the yield is 81.83-87.88%, the purity of the product detected by analysis of an Agilent 1200 type high performance liquid chromatographic instrument is 92.54-95.47% and the selectivity of p-carboxybenzene sulfonamide can achieve 100%. According to the method, the catalysts and the oxidant are non-toxic and environment-friendly, a byproduct is water or alcohol which is environment-friendly, the reaction conditions are mild, the post-treatment is simple, the catalysts can be recycled, and the cost is saved, so that the method is an ideal green synthesis method of p-carboxybenzene sulfonamide.

Description

technical field [0001] The invention relates to a method for preparing p-carboxybenzenesulfonamide, in particular to a method for catalytically oxidizing and synthesizing p-carboxybenzenesulfonamide. technical background [0002] P-carboxybenzenesulfonamide (I) is an important pharmaceutical synthesis intermediate, used for the synthesis of probenecid, halazone, etc., and its sodium salt can also be used as an inhibitor of carbonic anhydrase, and its development and utilization are very promising , whose structure is as follows: [0003] [0004] The preparation of p-carboxybenzenesulfonamide takes p-toluenesulfonyl chloride (II) as a raw material, firstly aminolysis it into p-toluenesulfonamide (III), and then oxidizes it into p-carboxybenzenesulfonamide. The aromatic ring of p-toluenesulfonamide contains a strong electron-withdrawing group, which is a difficult substrate to oxidize, so its oxidation often uses more than stoichiometric traditional strong oxidant KMnO 4...

Claims

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Application Information

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IPC IPC(8): C07C311/16C07C303/40
Inventor 梁静杨会会魏贤勇宗志敏
Owner CHINA UNIV OF MINING & TECH
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