CN104945288A - Method for preparing para toluene sulfonamide by directly amidating para-toluenesulfonic acid - Google Patents
Method for preparing para toluene sulfonamide by directly amidating para-toluenesulfonic acid Download PDFInfo
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Abstract
A method for preparing para toluene sulfonamide by directly amidating para-toluenesulfonic acid comprises the following steps: (1) anhydrous para-toluenesulfonic acid is dissolved in dichloromethane, a catalyst, namely organic boronic acid, and a 5A molecular sieve are added in a mixed solution, and the mixed solution is uniformly stirred for a certain time under the condition that the temperature is controlled to be -10 to 0 DEG C; (2) an ammonia gas is introduced at the -10 to 0 DEG C for reaction; (3) after the reaction is finished, suction filtration is conducted on the reaction liquid to remove the molecular sieve, and then washing is respectively performed once with an acid solution, an alkali solution and a salt solution; (4) an organic phase is dried through anhydrous sodium sulfate, then a drying agent is removed, a dichloromethane solvent is subjected to distillation recovery, and crude para toluene sulfonamide is obtained; (5) weighing is performed after washing with distilled water and drying, and the product purity is analyzed through liquid chromatography. The complexation is generated between organic boric acid energy and oxygen on a sulfonic acid molecule, the reaction activity of the para-toluenesulfonic acid is improved, ammonia molecules are easily combined with sulfur to generate amide, the whole reaction energy consumption is low, no waste acid is discharged, and the yield of para toluene sulfonamide is about 40%.
Description
Technical field
The present invention relates to the method that para toluene sulfonamide is prepared in the direct amidation of a kind of tosic acid, a kind of catalysis method sulfuryl amine reaction prepares the method for para toluene sulfonamide, belongs to organic chemistry filed.
Background technology
Para toluene sulfonamide is widely used in organic synthesis, is mainly used in synthesis chloramine-T and ammonia sulphur paraxin, also can be used for synthesis fluorescence dye, manufactures softening agent, synthetic resins, coating, sterilizing agent and wood working brightening agent etc., have sizable using value.Chinese patent literature " CN 102584647A " has reported para toluene sulfonamide industrialized preparing process, the method adopts multi-floating bodies reaction, Tosyl chloride and ammonia is carried out continuous amination reaction in counter-current absorption mode in dichloromethane solvent and generates acid amides.Although it achieve the qualified discharge of ammonia in tail gas; reduce environmental pollution; but the raw material Tosyl chloride in this method obtains with after tosic acid and chlorsulfonic acid reaction; this reaction can produce a large amount of spent acid; serious environment pollution; restrict by environment protection, therefore, find a kind of new catalysis process and prepare para toluene sulfonamide there is certain meaning.
Summary of the invention
The present invention proposes the method that para toluene sulfonamide is prepared in the direct amidation of a kind of tosic acid, utilizes catalyzer that tosic acid activity is improved, thus reaches direct amidate action.
The method that para toluene sulfonamide is prepared in the direct amidation of this tosic acid comprises the following steps:
(1) anhydrous tosic acid is dissolved in methylene dichloride, adds catalyzer organic boronic and molecular sieve 5A type, uniform stirring certain hour under control temperature-10 ~ 0 DEG C of condition; (2) pass into ammonia at the temperature disclosed above to react; (3), after reaction terminates, respectively wash carrying out acid, alkali, salts solution after reaction solution suction filtration removing molecular sieve once; (4) remove siccative after organic phase anhydrous sodium sulfate drying, through Distillation recovery dichloromethane solvent, and obtain para toluene sulfonamide crude product; (5) weigh after distilled water wash drying and use liquid-phase chromatographic analysis product purity.
The method of para toluene sulfonamide is prepared in the direct amidation of this tosic acid, catalyzer is organic boronic, organic boronic can produce complexing with the oxygen in the sulfur-to-oxygen double bond on sulfonic acid molecules, improve the positive polarity of sulphur atom in tosic acid molecule, thus improve the reactive behavior of tosic acid, amino molecule is easily combined with sulphur and generates acid amides, solvent uses hypotoxic methylene dichloride, and the temperature of reaction that can control anhydrous tosic acid and ammonia is carried out below 0 DEG C.Whole energy consumption of reaction is low, without spent acid discharge, achieves clean, quick, low toxicity production technique.The yield of para toluene sulfonamide is about 40%.
Embodiment
The method that para toluene sulfonamide is prepared in the direct amidation of this tosic acid comprises the following steps:
(1) anhydrous tosic acid is dissolved in methylene dichloride, adds organic boronic catalyzer and molecular sieve 5A type, uniform stirring certain hour under control temperature-10 ~ 0 DEG C of condition;
(2) heated by a certain amount of ammoniacal liquor, the ammonia of generation passes into reaction solution and reacts after gas drying treater, and reaction equation is:
(3) after reaction terminates, by reaction solution suction filtration removing molecular sieve;
(4) filtrate is carried out acid, alkali, salts solution and is respectively washed once, organic phase anhydrous sodium sulfate drying, is separated removing siccative, through Distillation recovery methylene dichloride, and obtains solid para toluene sulfonamide crude product;
(5) product is weighed after distilled water wash drying, and uses liquid-phase chromatographic analysis purity.
The direct amidation of this tosic acid is prepared in the method for para toluene sulfonamide, and ammonia adds thermogenesis by strong aqua, and ammonia passes in reaction flask more after drying, and therefore strong aqua is excessive; Catalyst levels is 5% ~ 10% of anhydrous tosic acid quality.
Catalyzer organic boronic refers to: 2-bromobenzeneboronic acid, 3-bromobenzeneboronic acid, 4-bromobenzeneboronic acid, 2-chlorophenylboronic acid, 3-chlorophenylboronic acid, 4-chlorophenylboronic acid.
Embodiment 1:
1, the anhydrous tosic acid of 3.444g (20mmol) and 0.172g 2-bromobenzeneboronic acid are dissolved in methylene dichloride, add 5g molecular sieve 5A type, uniform stirring 2h under 0 DEG C of condition.
2, heated by 20g 25% ammoniacal liquor, the ammonia of generation passes into reaction solution after gas drying treater.Every 4h adds 20g ammoniacal liquor, until 24h, adds altogether ammoniacal liquor 120g.
3, after suction filtration removing molecular sieve, filtrate is respectively with 10mL hydrochloric acid soln (concentration 0.5mol/L), and sodium hydroxide solution (concentration 0.5mol/L) and the saturated NaCl solution of 10mL of 10mL are respectively washed once.
4, organic phase is to remove siccative after anhydrous sodium sulfate drying, Distillation recovery methylene dichloride, obtains para toluene sulfonamide crude product, and dry after distilled water wash, obtain white crystal, weigh 1.456g.
5, through liquid-phase chromatographic analysis, effective constituent is 99.4%, and productive rate is 41.1%, records its melting range: 129.4-133.2 DEG C.
Embodiment 2:
1, the anhydrous tosic acid of 3.444g (20mmol) and 0.241g 4-bromine boric acid are dissolved in methylene dichloride, add 5g molecular sieve 5A type, uniform stirring 2h under 0 DEG C of condition.
2, heated by 20g 25% ammoniacal liquor, the ammonia of generation passes into reaction solution after gas drying treater.Every 4h adds 20g ammoniacal liquor, until 24h, adds altogether ammoniacal liquor 120g.
3, after suction filtration removing molecular sieve, filtrate is respectively washed once with the sodium hydroxide solution of the hydrochloric acid soln of 10mL concentration 0.5mol/L, concentration 0.5mol/L and saturated NaCl solution respectively.
4, organic phase is to remove siccative after anhydrous sodium sulfate drying, Distillation recovery methylene dichloride, obtains para toluene sulfonamide crude product, and dry after distilled water wash, obtain white crystal, weigh 0.53g
5, through liquid-phase chromatographic analysis, effective constituent is 98.8%, and productive rate is 15.3%, records its melting range: 130.1-133.7 DEG C.
Embodiment 3:
2,1, the anhydrous tosic acid of 3.444g (20mmol) and 0.31g 3-bromine boric acid are dissolved in methylene dichloride, add 5g molecular sieve 5A type, uniform stirring 2h under 0 DEG C of condition.
2, heated by 20g 25% ammoniacal liquor, the ammonia of generation passes into reaction solution after gas drying treater.Every 4h adds 20g ammoniacal liquor, until 24h, adds altogether ammoniacal liquor 120g.
3, after suction filtration removing molecular sieve, filtrate is respectively washed once with the sodium hydroxide solution of the hydrochloric acid soln of 10mL concentration 0.5mol/L, concentration 0.5mol/L and saturated NaCl solution respectively.
4, organic phase is to remove siccative after anhydrous sodium sulfate drying, Distillation recovery methylene dichloride, obtains para toluene sulfonamide crude product, and dry after distilled water wash, obtain white crystal, weigh 0.395g.
5, through liquid-phase chromatographic analysis, effective constituent is 98.9%, and productive rate is 11.4%, records its melting range: 130.7-134.1 DEG C.
Embodiment 4:
3,1, the anhydrous tosic acid of 3.444g (20mmol) and 0.344g 2-chlorophenylboronic acid are dissolved in methylene dichloride, add 5g molecular sieve 5A type, uniform stirring 2h under 0 DEG C of condition.
2, heated by 20g 25% ammoniacal liquor, the ammonia of generation passes into reaction solution after gas drying treater.Every 4h adds 20g ammoniacal liquor, until 24h, adds altogether ammoniacal liquor 120g.
3, after suction filtration removing molecular sieve, filtrate is respectively washed once with the sodium hydroxide solution of the hydrochloric acid soln of 10mL concentration 0.5mol/L, concentration 0.5mol/L and saturated NaCl solution respectively.
4, organic phase is to remove siccative after anhydrous sodium sulfate drying, Distillation recovery methylene dichloride, obtains para toluene sulfonamide crude product, and dry after distilled water wash, obtain white crystal, weigh 1.01g.
5, through liquid-phase chromatographic analysis, effective constituent is 97.3%, and productive rate is 28.7%, records its melting range: 129.3-134.2 DEG C.
Embodiment 5:
1,3.444g (20mmol) anhydrous tosic acid and 0.344g 3-chlorophenylboronic acid are dissolved in methylene dichloride, add 5g molecular sieve 5A type, uniform stirring 2h under 0 DEG C of condition.
2, heated by 20g 25% ammoniacal liquor, the ammonia of generation passes into reaction solution after gas drying treater.Every 4h adds 20g ammoniacal liquor, until 24h, adds altogether ammoniacal liquor 120g.
3, after suction filtration removing molecular sieve, filtrate is respectively washed once with the sodium hydroxide solution of the hydrochloric acid soln of 10mL concentration 0.5mol/L, concentration 0.5mol/L and saturated NaCl solution respectively.
4, organic phase is to remove siccative after anhydrous sodium sulfate drying, Distillation recovery methylene dichloride, obtains para toluene sulfonamide crude product, and dry after distilled water wash, obtain white crystal, weigh 0.379g.
5, through liquid-phase chromatographic analysis, effective constituent is 98.4%, and productive rate is 10.9%, records its melting range: 129.9-133.7 DEG C.
Embodiment 6:
1,3.444g (20mmol) anhydrous tosic acid and 0.172g 4-chloroboric acid are dissolved in methylene dichloride, add 5g molecular sieve 5A type, uniform stirring 2h under 0 DEG C of condition.
2, heated by 20g 25% ammoniacal liquor, the ammonia of generation passes into reaction solution after gas drying treater.Every 4h adds 20g ammoniacal liquor, until 24h, adds altogether ammoniacal liquor 120g.
3, after suction filtration removing molecular sieve, filtrate is respectively washed once with the sodium hydroxide solution of the hydrochloric acid soln of 10mL concentration 0.5mol/L, concentration 0.5mol/L and saturated NaCl solution respectively.
4, organic phase is to remove siccative after anhydrous sodium sulfate drying, Distillation recovery methylene dichloride, obtains para toluene sulfonamide crude product, and dry after distilled water wash, obtain white crystal, weigh 0.639g.
5, through liquid-phase chromatographic analysis, effective constituent is 97.7%, and productive rate is 18.2%, records its melting range: 128.4-133.3 DEG C.
Embodiment 7:
1,3.444g (20mmol) anhydrous tosic acid and 0.344g 2-bromobenzeneboronic acid are dissolved in methylene dichloride, add 5g molecular sieve 5A type, uniform stirring 2h under 0 DEG C of condition.
2, heated by 20g 25% ammoniacal liquor, the ammonia of generation passes into reaction solution after gas drying treater.Every 4h adds 20g ammoniacal liquor, until 24h, adds altogether ammoniacal liquor 120g.
3, after suction filtration removing molecular sieve, filtrate is respectively washed once with the sodium hydroxide solution of the hydrochloric acid soln of 10mL concentration 0.5mol/L, concentration 0.5mol/L and saturated NaCl solution respectively.
4, organic phase is to remove siccative after anhydrous sodium sulfate drying, Distillation recovery methylene dichloride, obtains para toluene sulfonamide crude product, and dry after distilled water wash, obtain white crystal, weigh 1.463g.
5, through liquid-phase chromatographic analysis, effective constituent is 99.5%, and productive rate is 42.5%, records its melting range: 130.5-133.6 DEG C.
Claims (1)
1. a method for para toluene sulfonamide is prepared in the direct amidation of tosic acid, it is characterized in that comprising the following steps:
(1) anhydrous tosic acid is dissolved in methylene dichloride, adds catalyzer organic boronic and molecular sieve 5A type, uniform stirring certain hour under control temperature-10 ~ 0 DEG C of condition;
(2) pass into ammonia at the temperature disclosed above to react;
(3), after reaction terminates, respectively wash carrying out acid, alkali, salts solution after reaction solution suction filtration removing molecular sieve once;
(4) remove siccative after organic phase anhydrous sodium sulfate drying, through Distillation recovery dichloromethane solvent, and obtain para toluene sulfonamide crude product;
(5) weigh after distilled water wash drying and use liquid-phase chromatographic analysis product purity.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565549A (en) * | 2016-11-08 | 2017-04-19 | 南安创友日化有限公司 | Method of synthesis of N-alkyl p-toluene sulfonamide |
| CN110028428A (en) * | 2019-05-13 | 2019-07-19 | 浙江嘉化新材料有限公司 | A kind of production method of para toluene sulfonamide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343244A (en) * | 2007-07-13 | 2009-01-14 | 上海药明康德新药开发有限公司 | Synthesis of sulfonylamines compounds |
| CN102584647A (en) * | 2012-01-11 | 2012-07-18 | 浙江嘉化能源化工股份有限公司 | Industrial production method for toluene sulfonamide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343244A (en) * | 2007-07-13 | 2009-01-14 | 上海药明康德新药开发有限公司 | Synthesis of sulfonylamines compounds |
| CN102584647A (en) * | 2012-01-11 | 2012-07-18 | 浙江嘉化能源化工股份有限公司 | Industrial production method for toluene sulfonamide |
Non-Patent Citations (1)
| Title |
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| 吴记勇等: "有机硼酸类催化剂在有机合成中的应用"", 《有机化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565549A (en) * | 2016-11-08 | 2017-04-19 | 南安创友日化有限公司 | Method of synthesis of N-alkyl p-toluene sulfonamide |
| CN110028428A (en) * | 2019-05-13 | 2019-07-19 | 浙江嘉化新材料有限公司 | A kind of production method of para toluene sulfonamide |
| CN110028428B (en) * | 2019-05-13 | 2021-11-02 | 浙江嘉化新材料有限公司 | Production method of p-toluenesulfonamide |
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Effective date of registration: 20191230 Address after: 314201 room 318, building 1, south side of Zhongshan Road and west side of Washan Road, Jiaxing Port Area, Jiaxing City, Zhejiang Province Patentee after: Zhejiang Jiafu New Material Technology Co., Ltd Address before: 314001 School of Biochemistry, Jiaxing University, 118 Jia Hang Road, Jiaxing, Zhejiang Co-patentee before: Zhejiang Jiahua Energy Chemical Co., Ltd. Patentee before: Jiaxing College |