CN114105834A - Preparation method of N, N, N, N-tetraallyloxybisbenzenesulfonamide - Google Patents
Preparation method of N, N, N, N-tetraallyloxybisbenzenesulfonamide Download PDFInfo
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- CN114105834A CN114105834A CN202210089950.0A CN202210089950A CN114105834A CN 114105834 A CN114105834 A CN 114105834A CN 202210089950 A CN202210089950 A CN 202210089950A CN 114105834 A CN114105834 A CN 114105834A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C303/38—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 reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
The invention belongs to the technical field of chemical production, and particularly relates to a preparation method of N, N, N, N-tetraallyloxybis-benzenesulfonamide, which comprises the following steps: (1) amination reaction: mixing diallylamine and water, heating, adding 4, 4-oxo-bis-benzenesulfonyl chloride in portions, and simultaneously dropwise adding liquid alkali; (2) cooling and filtering: after the amination reaction is finished, cooling, adding hydrochloric acid for neutralization, and filtering to obtain a filter cake; (3) dissolving and recrystallizing: adding methanol into the filter cake, heating, stirring for dissolving, cooling for crystallizing, filtering, and oven drying. The invention has mild reaction condition, simple process, short reaction time, high yield up to more than 97 percent, high product content up to more than 98 percent and stable product quality, and can react in a water phase.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a preparation method of N, N, N, N-tetraallyloxybis-benzenesulfonamide.
Background
The N, N, N, N-tetraallyloxybis-benzenesulfonamide is a high-efficiency polyolefin cross-linking agent, can be added into high-molecular materials of polyvinyl chloride, polyethylene, polypropylene and polyacrylic resin, etc., and can be cross-linked with the materials to form a three-dimensional network structure, so that the strength, elasticity, plasticity and flexibility of the materials are greatly enhanced.
At present, no related production process is reported in China.
Disclosure of Invention
The invention aims to provide a preparation method of N, N, N, N-tetraallyloxybisbenzenesulfonamide, which has the advantages of mild reaction conditions, short reaction time, high yield and stable product quality, and aims to solve the problems in the background technology.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of N, N, N, N-tetraallyloxybis-benzenesulfonamide comprises the following steps:
(1) amination reaction: mixing diallylamine and water, heating to 60 ℃, adding 4, 4-oxo-bis-benzenesulfonyl chloride in portions, and simultaneously dropwise adding liquid alkali, wherein the reaction pH is controlled to be 8-10;
(2) cooling and filtering: after the amination reaction is finished, cooling to 30 ℃, adding hydrochloric acid for neutralization, and filtering to obtain a filter cake and a brine filtrate;
(3) dissolving and recrystallizing: and adding methanol into the filter cake, heating to 60 ℃, stirring for dissolving, cooling to 30 ℃, separating out crystals, performing suction filtration to obtain a solid and a methanol filtrate, and drying the solid to obtain the N, N, N, N-tetraallyloxybis-benzenesulfonamide.
Amination reaction:
as an improvement, in step (1), the molar ratio of the 4, 4-oxybis-benzenesulfonyl chloride, the diallylamine and the liquid base is 1: 2.0-2.1: 2.0 to 2.1.
As an improvement, in the step (1), the temperature of the dropwise addition of the liquid caustic soda is 60-75 ℃, and the reaction temperature is 60-75 ℃ after the dropwise addition.
As an improvement, in the step (1), the 4, 4-oxybis-benzenesulfonyl chloride is added in four times, wherein the first addition is 1/2 of the total addition of the 4, 4-oxybis-benzenesulfonyl chloride, and the last addition is 1/3 of the residual amount of the 4, 4-oxybis-benzenesulfonyl chloride.
As an improvement, in the step (1), the mass concentration of the liquid alkali is 30%.
As an improvement, in the step (2), the pH after neutralization is = 6-7.
As an improvement, in the step (3), the methanol filtrate is distilled and recovered.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the preparation method provided by the invention has mild reaction conditions, simple process, short reaction time, high yield, high product content of more than 98% and stable product quality, and can be used for carrying out reaction in a water phase.
Drawings
FIG. 1 is a process flow diagram provided by the present invention;
FIG. 2 is an HPLC chromatogram of the N, N, N, N-tetraallyloxybis-benzenesulfonamide as a standard in the detection of samples of examples 1, 4 and 5;
FIG. 3 is an HPLC chromatogram of the standard N, N, N, N-tetraallyloxybisbenzenesulfonamide in the sample detection in examples 2 and 3;
FIGS. 4 to 8 are HPLC chromatograms of N, N, N, N-tetraallyloxybisbenzenesulfonamide obtained in examples 1 to 5.
Detailed Description
The present invention will be further described with reference to the following detailed description and accompanying drawings.
Example 1
200g of water and 98.14g of diallylamine (content 99%, 1.0mol, molar ratio 2.0) are added into a 1000ml four-necked bottle, heated to 60 ℃ in a water bath, and 133.33g of liquid alkali (content 30%, 1.0mol, molar ratio 2.1) is added into a dropping funnel and is mounted on the four-necked bottle for standby.
Weighing 4 parts of 4, 4-oxybis benzene sulfonyl chloride, namely 92.75g, 30.92g, 30.92g and 30.91g respectively, weighing 185.5g (with the content of 99 percent and 0.5 mol) of the total amount of the materials for later use, adding the 4, 4-oxybis benzene sulfonyl chloride in four batches after the temperature is raised to 60 ℃, firstly adding 1/2 of the total amount, adding 1/3 of the residual amount every time for three times, slowly dropwise adding liquid alkali after adding the 4, 4-oxybis benzene sulfonyl chloride each time, controlling the pH value to be 8-10, detecting the pH value to be 8-10 after the materials are added, keeping the temperature to be 60 ℃ for reaction for 2 hours, sampling and detecting that the raw materials are completely reacted, cooling to 30 ℃, adding hydrochloric acid to adjust the pH to be 6-7, filtering, refining a filter cake, and removing the filtrate which is sodium chloride salt wastewater to treat the wastewater.
Adding the filter cake into a 1000ml four-mouth bottle, adding 365g of methanol (mass ratio of filter cake to methanol is about 1: 1.5), heating to 60 ℃, stirring for dissolving, cooling to 30 ℃, separating out crystals, filtering, and drying; the filtrate is refined after the methanol is recovered by distillation, and 242.01g of N, N, N, N-tetraallyloxybis-benzenesulfonamide is obtained, the detection content is 99.28 percent, and the experimental yield is 97.18 percent.
Example 2
200g of water and 100.1g (content 99%, 1.02mol, mol ratio 2.04) of diallylamine are added into a 1000ml four-mouth bottle, heated to 60 ℃ in a water bath, 140g (content 30%, 1.05mol, mol ratio 2.1) of liquid alkali is added into a dropping funnel, and the dropping funnel is mounted on the four-mouth bottle for standby.
Weighing 4 parts of 4, 4-oxybis benzene sulfonyl chloride, namely 92.75g, 30.92g, 30.92g and 30.91g respectively, weighing 185.5g (with the content of 99 percent and 0.5 mol) of the total amount of the materials for later use, adding the 4, 4-oxybis benzene sulfonyl chloride in four batches after the temperature is raised to 60 ℃, firstly adding 1/2 of the total amount, adding 1/3 of the residual amount every time for three times, slowly dropwise adding liquid alkali after adding the 4, 4-oxybis benzene sulfonyl chloride each time, controlling the pH value to be 8-10, detecting the pH value to be 8-10 after the materials are added, keeping the temperature to be 65 ℃ for reaction for 2 hours, sampling and detecting that the raw materials are completely reacted, cooling to 30 ℃, adding hydrochloric acid to adjust the pH to be 6-7, filtering, refining a filter cake, and removing the filtrate which is sodium chloride salt wastewater to treat the wastewater.
Adding the filter cake into a 1000ml four-mouth bottle, adding 365g of methanol (mass ratio of filter cake to methanol is about 1: 1.5), heating to 60 ℃, stirring for dissolving, cooling to 30 ℃, separating out crystals, filtering, and drying; the filtrate is refined after the methanol is recovered by distillation, and 242.01g of N, N, N, N-tetraallyloxybis-benzenesulfonamide is obtained, the detection content is 98.74 percent, and the experimental yield is 97.01 percent.
Example 3
200g of water and 103.05g of diallylamine (content 99%, 1.05mol, mol ratio 2.1) are added into a 1000ml four-mouth bottle, heated to 60 ℃ in a water bath, and 133.33g of liquid alkali (content 30%, 1mol, mol ratio 2.0) is added into a dropping funnel and is mounted on the four-mouth bottle for standby.
Weighing 4 parts of 4, 4-oxybis benzene sulfonyl chloride, namely 92.75g, 30.92g, 30.92g and 30.91g respectively, weighing 185.5g (with the content of 99 percent and 0.5 mol) of the total amount of the materials for later use, adding the 4, 4-oxybis benzene sulfonyl chloride in four batches after the temperature is raised to 60 ℃, firstly adding 1/2 of the total amount, adding 1/3 of the residual amount every time for three times, slowly dropwise adding liquid alkali after adding the 4, 4-oxybis benzene sulfonyl chloride each time, controlling the pH value to be 8-10, detecting the pH value to be 8-10 after the materials are added, keeping the temperature to be 70 ℃ for reaction for 2 hours, sampling and detecting that the raw materials are completely reacted, cooling to 30 ℃, adding hydrochloric acid to adjust the pH to be 6-7, filtering, refining a filter cake, and removing the filtrate which is sodium chloride salt wastewater to treat the wastewater.
Adding the filter cake into a 1000ml four-mouth bottle, adding 365g of methanol (mass ratio of filter cake to methanol is about 1: 1.5), heating to 60 ℃, stirring for dissolving, cooling to 30 ℃, separating out crystals, filtering, and drying; the filtrate is refined after the methanol is recovered by distillation, and 242.03g of N, N, N, N-tetraallyloxybis-benzenesulfonamide is obtained, the detection content is 99.38 percent, and the experimental yield is 97.35 percent.
Example 4
200g of water and 102.06g of diallylamine (content 99%, 1.04mol, mol ratio 2.08) are added into a 1000ml four-mouth bottle, heated to 60 ℃ in a water bath, and 137.33g of liquid alkali (content 30%, 1.04mol, mol ratio 2.08) is added into a dropping funnel and is mounted on the four-mouth bottle for standby.
Weighing 4 parts of 4, 4-oxybis benzene sulfonyl chloride, namely 92.75g, 30.92g, 30.92g and 30.91g respectively, weighing 185.5g (with the content of 99 percent and 0.5 mol) of the total amount of the materials for later use, adding the 4, 4-oxybis benzene sulfonyl chloride in four batches after the temperature is raised to 60 ℃, firstly adding 1/2 of the total amount, adding 1/3 of the residual amount every time for three times, slowly dropwise adding liquid alkali after adding the 4, 4-oxybis benzene sulfonyl chloride each time, controlling the pH value to be 8-10, detecting the pH value to be 8-10 after the materials are added, keeping the temperature to be 75 ℃ for reaction for 2 hours, sampling and detecting that the raw materials are completely reacted, cooling to 30 ℃, adding hydrochloric acid to adjust the pH to be 6-7, filtering, refining a filter cake, and removing the filtrate which is sodium chloride salt wastewater to treat the wastewater.
Adding the filter cake into a 1000ml four-mouth bottle, adding 365g of methanol (mass ratio of filter cake to methanol is about 1: 1.5), heating to 60 ℃, stirring for dissolving, cooling to 30 ℃, separating out crystals, filtering, and drying; the filtrate is refined after the methanol is recovered by distillation, and 240.79g of N, N, N, N-tetraallyloxybis-benzenesulfonamide is obtained, the detection content is 99.48 percent, and the experimental yield is 97.58 percent.
Example 5
200g of water and 100.1g (content 99%, 1.02mol, mol ratio 2.04) of diallylamine are added into a 1000ml four-mouth bottle, heated to 60 ℃ in a water bath, 140g (content 30%, 1.05mol, mol ratio 2.1) of liquid alkali is added into a dropping funnel, and the dropping funnel is mounted on the four-mouth bottle for standby.
Weighing 4 parts of 4, 4-oxybis benzene sulfonyl chloride, namely 92.75g, 30.92g, 30.92g and 30.91g respectively, weighing 185.5g (with the content of 99 percent and 0.5 mol) of the total amount of the materials for later use, adding the 4, 4-oxybis benzene sulfonyl chloride in four batches after the temperature is raised to 60 ℃, firstly adding 1/2 of the total amount, adding 1/3 of the residual amount every time for three times, slowly dropwise adding liquid alkali after adding the 4, 4-oxybis benzene sulfonyl chloride each time, controlling the pH value to be 8-10, detecting the pH value to be 8-10 after the materials are added, keeping the temperature to be 68 ℃ for reaction for 2 hours, sampling and detecting that the raw materials are completely reacted, cooling to 30 ℃, adding hydrochloric acid to adjust the pH to be 6-7, filtering, refining a filter cake, and removing the filter cake, wherein the filtrate is sodium chloride wastewater and treating the wastewater.
Adding the filter cake into a 1000ml four-mouth bottle, adding 365g of methanol (mass ratio of filter cake to methanol is about 1: 1.5), heating to 60 ℃, stirring for dissolving, cooling to 30 ℃, separating out crystals, filtering, and drying; the filtrate is refined after the methanol is recovered by distillation, and 240.9g of N, N, N, N-tetraallyloxybis-benzenesulfonamide is obtained, the detection content is 99.39 percent, and the experimental yield is 97.61 percent.
The N, N, N, N-tetraallyloxybisbenzenesulfonamide prepared in examples 1 to 5 was sampled and examined by liquid chromatography:
1. pretreatment of samples
According to the formula, N, N, N-tetraallyloxybisbenzenesulfonamide: acetonitrile = 1: dissolving the mixture in a volume ratio of 20, filtering the dissolved mixture by using an organic filter membrane of 0.45 mu m, and injecting the sample.
Preparing a standard substance: n, N-tetraallyloxybisbenzenesulfonamide standard: acetonitrile = 1: dissolving the mixture in a volume ratio of 20, filtering the dissolved mixture by using an organic filter membrane of 0.45 mu m, and injecting the sample.
2. Conditions for liquid chromatography
The liquid chromatography analysis conditions of the samples and the standard products prepared in the examples 1, 4 and 5 are as follows:
a chromatographic column: agilentextended C18, 250 × 4.6mm (inner diameter), 5 μm (particle size);
mobile phase: acetonitrile: water = 40: 60 (V/V);
and (3) an elution mode: isocratic elution;
flow rate: 1.0 ml/min;
detection wavelength: 224 nm;
column temperature: 30 ℃;
sample introduction amount: 10 mul.
The conditions for liquid chromatography analysis of the samples and standards prepared in examples 2-3 were as follows:
a chromatographic column: agilentextended C18, 250 × 4.6mm (inner diameter), 5 μm (particle size);
mobile phase: acetonitrile: water = 50: 50 (V/V);
and (3) an elution mode: isocratic elution;
flow rate: 1.0 ml/min;
detection wavelength: 224 nm;
column temperature: 30 ℃;
sample introduction amount: 10 mul.
3. Map creation and result analysis
Analyzing and recording the liquid chromatogram of the N, N, N, N-tetraallyloxybisbenzenesulfonamide sample and the standard substance by using liquid chromatogram workstation software, and calculating the relative content of each chromatogram peak by adopting an area normalization method.
Since the mobile phase composition ratios of examples 2 and 3 were different from those of examples 1, 4 and 5, the retention times of the N, N-tetraallyloxybisbenzenesulfonyl-derived peaks were different.
The results are shown in FIGS. 2-8.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. A preparation method of N, N, N, N-tetraallyloxybis-benzenesulfonamide is characterized by comprising the following steps:
(1) amination reaction: mixing diallylamine and water, heating to 60 ℃, adding 4, 4-oxo-bis-benzenesulfonyl chloride in portions, and simultaneously dropwise adding liquid alkali, wherein the reaction pH is controlled to be 8-10;
(2) cooling and filtering: after the amination reaction is finished, cooling to 30 ℃, adding hydrochloric acid for neutralization, and filtering to obtain a filter cake and a brine filtrate;
(3) dissolving and recrystallizing: and adding methanol into the filter cake, heating to 60 ℃, stirring for dissolving, cooling to 30 ℃, separating out crystals, performing suction filtration to obtain a solid and a methanol filtrate, and drying the solid to obtain the N, N, N, N-tetraallyloxybis-benzenesulfonamide.
2. The process for producing N, N-tetraallyloxybis-benzenesulfonamide according to claim 1, wherein in step (1), the molar ratio of the 4, 4-oxybis-benzenesulfonyl chloride, the diallylamine and the liquid base is 1: 2.0-2.1: 2.0 to 2.1.
3. The method for preparing N, N, N, N-tetraallyloxybisbenzenesulfonamide according to claim 1, wherein in step (1), the temperature of the dropwise addition of the liquid base is 60 to 75 ℃, and the reaction temperature after the dropwise addition is 60 to 75 ℃ is maintained.
4. The process for producing N, N, N, N-tetraallyloxybis-benzenesulfonamide according to claim 1, wherein in step (1), the 4, 4-oxybis-benzenesulfonyl chloride is added in four times, the first addition is 1/2 of the total addition of the 4, 4-oxybis-benzenesulfonyl chloride, and the last addition is 1/3 of the remaining amount of the 4, 4-oxybis-benzenesulfonyl chloride.
5. The process for producing N, N-tetraallyloxybisbenzenesulfonamide according to claim 1, wherein in step (1), the concentration by mass of the liquid alkali is 30%.
6. The method for producing N, N-tetraallyloxybisbenzenesulfonamide according to claim 1, wherein in step (2), the pH after neutralization is =6 to 7.
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Citations (7)
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|---|---|---|---|---|
| US3725476A (en) * | 1971-09-15 | 1973-04-03 | Stepsan Chem Co | Unsaturated amides of oxybis (benzenesulfonic acid) |
| US3856858A (en) * | 1972-11-06 | 1974-12-24 | Grace W R & Co | Sulfonamides related to n,n,n{40 -tetra allyl diphenylether-4,4{40 disulfonamide |
| US3870768A (en) * | 1971-09-15 | 1975-03-11 | Stepan Chemical Co | Unsaturated amides of oxybis(benzenesulfonic acid) and their use as cross-linking agents |
| US3915825A (en) * | 1972-11-06 | 1975-10-28 | Grace W R & Co | Curable compositions comprising a tetraallylsulfonamide and a polythiol |
| US3959366A (en) * | 1972-11-06 | 1976-05-25 | W. R. Grace & Co. | Polyenes from diphenyl ethers |
| CN104710423A (en) * | 2009-12-14 | 2015-06-17 | 默沙东有限责任公司 | Mk2 inhibitors |
| CN105712909A (en) * | 2014-12-05 | 2016-06-29 | 中国石油天然气股份有限公司 | Disulfonate compounds for the preparation of olefin polymerization catalysts |
-
2022
- 2022-01-26 CN CN202210089950.0A patent/CN114105834B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725476A (en) * | 1971-09-15 | 1973-04-03 | Stepsan Chem Co | Unsaturated amides of oxybis (benzenesulfonic acid) |
| US3870768A (en) * | 1971-09-15 | 1975-03-11 | Stepan Chemical Co | Unsaturated amides of oxybis(benzenesulfonic acid) and their use as cross-linking agents |
| US3856858A (en) * | 1972-11-06 | 1974-12-24 | Grace W R & Co | Sulfonamides related to n,n,n{40 -tetra allyl diphenylether-4,4{40 disulfonamide |
| US3915825A (en) * | 1972-11-06 | 1975-10-28 | Grace W R & Co | Curable compositions comprising a tetraallylsulfonamide and a polythiol |
| US3959366A (en) * | 1972-11-06 | 1976-05-25 | W. R. Grace & Co. | Polyenes from diphenyl ethers |
| CN104710423A (en) * | 2009-12-14 | 2015-06-17 | 默沙东有限责任公司 | Mk2 inhibitors |
| CN105712909A (en) * | 2014-12-05 | 2016-06-29 | 中国石油天然气股份有限公司 | Disulfonate compounds for the preparation of olefin polymerization catalysts |
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