CN102633696A - Method and technology for preparing p-substituted alkyl benzene sulfonyl chloride by two-step synthesis - Google Patents
Method and technology for preparing p-substituted alkyl benzene sulfonyl chloride by two-step synthesis Download PDFInfo
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Abstract
The invention relates to a method and a technology for preparing p-substituted alkyl benzene sulfonyl chloride by two-step synthesis, and the method comprises the steps of: 1) adding alkylbenzene and an inorganic salt catalyst into a reaction kettle, slowly adding chlorosulfonic acid for the first time at the temperature of -5 to 40 DEG C when stirring, carrying out sulfonation reaction, and then carrying out heat preservation; 2) slowly adding chlorosulfonic acid for the second time at the temperature of 10 to 60 DEG C when stirring, carrying out acyl chlorination reaction, and carrying out heat preservation to obtain a sulfonated material; and 3) separating and purifying by an ice water precipitation method, to obtain the p-substituted alkyl benzene sulfonyl chloride. The invention has the advantages that a two-step method is adopted to respectively control the sulfonation reaction and the acyl chlorination reaction under the different reaction conditions, so that the generation of various isomers are effectively inhibited and reduced; the inorganic salt catalyst can be used for inhibiting the generation of sulfoxide by-products in the sulfonation reaction, so that the yield of the p-substituted alkyl benzene sulfonyl chloride is improved to 95-100%; and the problems of much dosage of the chlorosulfonic acid, difficult treatment for three wastes, low product yield, poor quality and the like in the existing method and technology can be solved.
Description
Technical field
The present invention relates to the preparation method of para-orientation alkylbenzene sulfonyl chloride, particularly a kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps.
Background technology
The para-orientation alkylbenzene sulfonyl chloride is the important intermediate that is widely used in medicine, dyestuff, pigment, auxiliary agent etc.The domestic method of producing the para-orientation alkylbenzene sulfonyl chloride is gone up in industry at present, is korenyl and excessive chlorsulfonic acid to be reacted make.In order to improve the yield of SULPHURYL CHLORIDE product, often need impel to react completely with a large amount of chlorsulfonic acids, nonetheless, the yield of para-orientation alkylbenzene sulfonyl chloride product also has only about 80% usually, and product yield is lower, and is second-rate.
In fact; The reaction that utilizes korenyl and chlorsulfonic acid to prepare the para-orientation alkylbenzene sulfonyl chloride is carried out in two steps; At first be korenyl and chlorsulfonic acid generation sulfonation reaction; Generating the para-orientation alkyl benzene sulphonate(ABS), is para-orientation alkyl benzene sulphonate(ABS) and chlorsulfonic acid generation acyl chloride reaction then, generates the para-orientation alkylbenzene sulfonyl chloride.Discover that korenyl reacts with a large amount of excessive chlorsulfonic acids, can cause a large amount of generations of multiple isomer and sulfoxide class by product; Cause product yield to reduce; Production cost is higher, and problems such as quantity of three wastes is big, difficult treatment should not be applied in actual production.
Summary of the invention
The objective of the invention is to above-mentioned existing problems; A kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps is provided; This preparation method controls reaction conditions through substep and carries out sulfonation reaction and acyl chloride reaction respectively; Effectively reduce the generation of various isomer, effectively suppressed the generation of sulfoxide compound through the adding of part inorganic salt; Utilize in addition that the para-orientation alkylbenzene sulfonyl chloride is insoluble in water or water-fast character under the low temperature, adopt frozen water dilution liberation method separating prod, prepare high yield, highly purified para-orientation alkylbenzene sulfonyl chloride.
Technical scheme of the present invention:
A kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps, step is following:
1) adds korenyl and inorganic salt catalyst in the reaction kettle, stir down and carry out sulfonation reaction, and carry out insulation reaction after finishing in slow adding-5 ℃～40 ℃ first time chlorsulfonic acid;
2) stir down in 10 ℃-60 ℃ second time the slow chlorsulfonic acid that adds carries out acyl chloride reaction, and carry out insulation reaction after finishing and obtain the sulfonation material;
3) adopt the frozen water liberation method to separate and purification para-orientation alkylbenzene sulfonyl chloride; Method is under agitation above-mentioned sulfonation material to be added in the frozen water slowly to separate out; Standing separation is collected organic matter layer or is filtered the collection filter cake then, can make target product para-orientation alkylbenzene sulfonyl chloride.
Said korenyl is toluene, ethylbenzene, n-propylbenzene, isopropyl benzene, n-butylbenzene, isobutyl-benzene or tert.-butylbenzene.
Said inorganic salt are the mixture of one or more arbitrary proportions in sodium sulfate, vitriolate of tartar, sal epsom, calcium sulfate, ferric sulfate, ammonium sulfate, sodium pyrosulfate, sal enixum, magnesium hydrogen sulfate, calcium bisulfate, monoammonium sulfate, sodium-chlor, Repone K, calcium chloride, magnesium chloride, iron(ic)chloride, ammonium chloride, Sodium Bromide, Potassium Bromide, magnesium bromide, Calcium Bromide and the brometo de amonio, and the mol ratio of inorganic salt and korenyl is 0.001-0.50: 1.
The purity of said chlorsulfonic acid is >=92%, and the consumption of chlorsulfonic acid and the mol ratio of korenyl are 1.0-1.5 for the first time: 1, and the consumption of chlorsulfonic acid and the mol ratio of korenyl are 1.5-3.5 for the second time: 1.
The technology of said sulfonation reaction is: temperature of reaction is-5 ℃～40 ℃, and soaking time is 0.01-3.0 hour.
The technology of said acyl chloride reaction is: temperature of reaction is 10 ℃-60 ℃, and soaking time is 0.1-10.0 hour.
In the said frozen water liberation method consumption of frozen water be the sulfonation quality of material 0.5-5.0 doubly.
Beneficial effect of the present invention: take two-step approach under the differential responses condition, to control sulfonation reaction and chlorine acylation respectively, optimized sulfonation reaction and chlorine acylation processing condition, effectively suppress and reduced the generation of various isomer.Adopt inorganic salt catalyst effectively to suppress the production of sulfoxide class by product in the sulfonation reaction process, thereby improved the yield of para-orientation alkylbenzene sulfonyl chloride, yield can reach 95～100%, has reduced the chlorsulfonic acid consumption simultaneously.Problem such as solved in existing method and the technology that the chlorsulfonic acid consumption is big, three wastes difficult treatment, product yield are low, of poor quality.
Embodiment
Below in conjunction with embodiment the present invention is further specified, but embodiment does not limit protection scope of the present invention.
Embodiment 1:
A kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps, step is following:
1) in the 1000mL four-hole bottle, add toluene 55.2g, stir adding sodium sulfate 3.6g down; Ice bath is cooled to below 5 ℃, and control reaction temperature is 5-15 ℃, controls 1.0-1.5 hour; For the first time drip chlorsulfonic acid 77.0g from tap funnel is slow, finish, in 10-15 ℃ of insulation reaction 0.5 hour;
2) control reaction temperature is 15～25 ℃, controls 0.5-1.0 hour, drips secondary chlorsulfonic acid 145.0g slowly from tap funnel, finishes, and obtains the sulfonation material in 2.0 hours in 20～25 ℃ of insulation reaction;
3) in the 1000mL beaker, add mixture of ice and water 150g, start stirring, above-mentioned sulfonation material is added in the frozen water slowly, in maintenance effect below 15 ℃ 15 minutes, cross and filter white solid 4-Methyl benzenesulfonyl chlorine 106.6g, yield 93.3%, m.p.65-67 ℃.
Embodiment 2:
A kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps, step is following:
1) in the 1000mL four-hole bottle, add toluene 55.2g, stir adding sodium sulfate 7.2g down; Ice bath is cooled to below 10 ℃, and control reaction temperature is 10-18 ℃, controls 1.5-2.0 hour; Drip a chlorsulfonic acid 79.5g from tap funnel is slow, finish, in 15-20 ℃ of insulation reaction 0.5 hour;
2) control reaction temperature is 18-25 ℃, controls 0.5-1.0 hour, drips secondary chlorsulfonic acid 148.0g slowly from tap funnel, finishes, and obtains the sulfonation material in 2.0 hours in 20-25 ℃ of insulation reaction;
3) in the 1000mL beaker, add mixture of ice and water 200g, start stirring, above-mentioned sulfonation material is added in the frozen water slowly, in maintenance effect below 15 ℃ 25 minutes, suction filtration got white solid 4-Methyl benzenesulfonyl chlorine 105.8g, yield 92.6%, m.p.65-67 ℃.
Embodiment 3:
A kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps, step is following:
1) in the 1000mL four-hole bottle, add ethylbenzene 63.6g, stir adding sodium sulfate 3.6g down; Ice bath is cooled to below 5 ℃, and control reaction temperature is 5-15 ℃, controls 1.5-2.0 hour; Drip a chlorsulfonic acid 77.0g from tap funnel is slow, finish, in 10-15 ℃ of insulation reaction 0.5 hour;
2) control reaction temperature is 15-25 ℃, controls 1.0-1.5 hour, drips secondary chlorsulfonic acid 145.0g slowly from tap funnel, finishes, and obtains the sulfonation material in 2.0 hours in 20-25 ℃ of insulation reaction;
3) in the 1000mL beaker; Add mixture of ice and water 150g, start stirring, add above-mentioned sulfonation material in the frozen water slowly; In maintenance effect below 15 ℃ 15 minutes; Place separating funnel to leave standstill 30 minutes material, tell lower floor's organic layer and make 4-ethylbenzene SULPHURYL CHLORIDE 116.8g, yield 95.1%.
Embodiment 4:
A kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps, step is following:
1) in the 1000mL four-hole bottle, add ethylbenzene 63.6g, stir adding sodium sulfate 7.2g down; Ice bath is cooled to below 10 ℃, and control reaction temperature is 10-18 ℃, controls 2.0-2.5 hour; Drip a chlorsulfonic acid 79.5g from tap funnel is slow, finish, in 15-20 ℃ of insulation reaction 0.2 hour;
2) control reaction temperature is 18-25 ℃, controls 1.0-1.5 hour, drips secondary chlorsulfonic acid 148.0g slowly from tap funnel, finishes, and obtains the sulfonation material in 2.0 hours in 20-25 ℃ of insulation reaction;
3) in the 1000mL beaker; Add mixture of ice and water 200g, start stirring, add above-mentioned sulfonation material in the frozen water slowly; In maintenance effect below 15 ℃ 25 minutes; Place separating funnel to leave standstill 30 minutes material, tell lower floor's organic layer and make 4-ethylbenzene SULPHURYL CHLORIDE 117.0g, yield 95.4%.
Embodiment 5:
A kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps, step is following:
1) in the 1000mL four-hole bottle, add isopropyl benzene 72.0g, stir adding vitriolate of tartar 5.6g down; Ice bath is cooled to below 5 ℃, and control reaction temperature is 5-15 ℃, controls 1.5-2.0 hour; Drip a chlorsulfonic acid 77.0g from tap funnel is slow, finish, in 10-15 ℃ of insulation reaction 0.5 hour;
2) control reaction temperature is 15-25 ℃, controls 1.0-1.5 hour, drips secondary chlorsulfonic acid 145.0g slowly from tap funnel, finishes, and obtains the sulfonation material in 2.0 hours in 20～25 ℃ of insulation reaction;
3) in the 1000mL beaker; Add mixture of ice and water 150g, start stirring, add above-mentioned sulfonation material in the frozen water slowly; In maintenance effect below 15 ℃ 15 minutes; Place separating funnel to leave standstill 30 minutes material, tell lower floor's organic layer and make 4-isopropyl benzene SULPHURYL CHLORIDE 128.8g, yield 98.3%.
Embodiment 6:
A kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps, step is following:
1) in the 1000mL four-hole bottle, add isopropyl benzene 72.0g, stir adding sodium sulfate 7.2g down; Ice bath is cooled to below 10 ℃, and control reaction temperature is 10-18 ℃, controls 2.5-3.0 hour; Drip a chlorsulfonic acid 79.5g from tap funnel is slow, finish, in 15-20 ℃ of insulation reaction 0.5 hour;
2) control reaction temperature is 18-25 ℃, controls 1.0-1.5 hour, drips secondary chlorsulfonic acid 148.0g slowly from tap funnel, finishes, and obtains the sulfonation material in 3.0 hours in 20-25 ℃ of insulation reaction;
3) in the 1000mL beaker; Add mixture of ice and water 200g, start stirring, add above-mentioned sulfonation material in the frozen water slowly; In maintenance effect below 15 ℃ 25 minutes; Place separating funnel to leave standstill 30 minutes material, tell lower floor's organic layer and make 4-isopropyl benzene SULPHURYL CHLORIDE 126.5g, yield 96.5%.
Embodiment 7:
A kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps, step is following:
1) in the 1000mL four-hole bottle, add tert.-butylbenzene 80.4g, stir adding sodium sulfate 3.6g down; Ice bath is cooled to below 5 ℃, and control reaction temperature is 5-15 ℃, controls 1.0-1.5 hour; Drip a chlorsulfonic acid 77.0g from tap funnel is slow, finish, in 10-15 ℃ of insulation reaction 0.5 hour;
2) control reaction temperature is 15-25 ℃, controls 1.0-1.5 hour, drips secondary chlorsulfonic acid 145.0g slowly from tap funnel, finishes, and obtains the sulfonation material in 2.0 hours in 20-25 ℃ of insulation reaction;
3) in the 1000mL beaker, add mixture of ice and water 150g, start stirring; Above-mentioned sulfonation material is added in the frozen water slowly,, cross and filter white solid 4-tert.-butylbenzene SULPHURYL CHLORIDE 137.4g in maintenance effect below 15 ℃ 15 minutes; Yield 98.5%, m.p.76-78 ℃.
Embodiment 8:
A kind of synthetic method and technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps, step is following:
1) in the 1000mL four-hole bottle, add tert.-butylbenzene 80.4g, stir adding vitriolate of tartar 6.8g down; Ice bath is cooled to below 10 ℃; Control reaction temperature is 10-18 ℃, controls 1.5-2.0 hour, from chlorsulfonic acid 79.5g of the slow dropping of tap funnel; Finish, in 15-20 ℃ of insulation reaction 0.5 hour;
2) control reaction temperature is 18-25 ℃, controls 0.5-1.0 hour, drips secondary chlorsulfonic acid 148.0g slowly from tap funnel, finishes, and obtains the sulfonation material in 2.5 hours in 20-25 ℃ of insulation reaction;
3) in the 1000mL beaker, add mixture of ice and water 200g, start stirring; Above-mentioned sulfonation material is added in the frozen water slowly, and in maintenance effect below 15 ℃ 25 minutes, suction filtration got white solid 4-tert.-butylbenzene SULPHURYL CHLORIDE 136.8g; Yield 98.0%, m.p.76-78 ℃.
Claims (7)
1. a step is synthesized method and the technology for preparing the para-orientation alkylbenzene sulfonyl chloride, it is characterized in that step is following:
1) adds korenyl and inorganic salt catalyst in the reaction kettle, stir down and carry out sulfonation reaction, and carry out insulation reaction after finishing in slow adding-5 ℃～40 ℃ first time chlorsulfonic acid;
2) stir down in 10 ℃-60 ℃ second time the slow chlorsulfonic acid that adds carries out acyl chloride reaction, and carry out insulation reaction after finishing and obtain the sulfonation material;
3) adopt the frozen water liberation method to separate and purification para-orientation alkylbenzene sulfonyl chloride; Method is under agitation above-mentioned sulfonation material to be added in the frozen water slowly to separate out; Standing separation is collected organic matter layer or is filtered the collection filter cake then, can make target product para-orientation alkylbenzene sulfonyl chloride.
2. according to said synthetic method and the technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps of claim 1, it is characterized in that: said korenyl is toluene, ethylbenzene, n-propylbenzene, isopropyl benzene, n-butylbenzene, isobutyl-benzene or tert.-butylbenzene.
3. according to said synthetic method and the technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps of claim 1; It is characterized in that: said inorganic salt are the mixture of one or more arbitrary proportions in sodium sulfate, vitriolate of tartar, sal epsom, calcium sulfate, ferric sulfate, ammonium sulfate, sodium pyrosulfate, sal enixum, magnesium hydrogen sulfate, calcium bisulfate, monoammonium sulfate, sodium-chlor, Repone K, calcium chloride, magnesium chloride, iron(ic)chloride, ammonium chloride, Sodium Bromide, Potassium Bromide, magnesium bromide, Calcium Bromide and the brometo de amonio, and the mol ratio of inorganic salt and korenyl is 0.001-0.50: 1.
4. according to said synthetic method and the technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps of claim 1; It is characterized in that: the purity of said chlorsulfonic acid is >=92%; The consumption of chlorsulfonic acid and the mol ratio of korenyl are 1.0-1.5 for the first time: 1, and the consumption of chlorsulfonic acid and the mol ratio of korenyl are 1.5-3.5 for the second time: 1.
5. according to said synthetic method and the technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps of claim 1, it is characterized in that: the technology of said sulfonation reaction is: temperature of reaction is-5 ℃～40 ℃, and soaking time is 0.01-3.0 hour.
6. according to said synthetic method and the technology for preparing the para-orientation alkylbenzene sulfonyl chloride of two steps of claim 1, it is characterized in that: the technology of said acyl chloride reaction is: temperature of reaction is 10 ℃-60 ℃, and soaking time is 0.1-10.0 hour.
7. according to said synthetic method and the technology that prepare the para-orientation alkylbenzene sulfonyl chloride of two steps of claim 1, it is characterized in that: the consumption of frozen water is 0.5-5.0 a times of sulfonation quality of material in the said frozen water liberation method.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105037224A (en) * | 2015-05-27 | 2015-11-11 | 南通沃兰化工有限公司 | Method for reducing loss and improving yield during acyl chloride hydrolysis process |
| CN105503671A (en) * | 2015-12-22 | 2016-04-20 | 嘉兴学院 | Preparation method of p-toluene sulfonyl chloride |
| CN108069935A (en) * | 2017-12-25 | 2018-05-25 | 天津瑞岭化工有限公司 | A kind of preparation method of 2,4- diethyl thioxanthones |
| CN108084062A (en) * | 2017-12-25 | 2018-05-29 | 天津瑞岭化工有限公司 | A kind of preparation method of 2,4- disubstituted benzenes sulfonic acid chloride |
| CN108752242A (en) * | 2018-06-28 | 2018-11-06 | 金华双宏化工有限公司 | For the method for sulfonating of low cloud density aromatic hydrocarbons |
| CN109456232A (en) * | 2018-12-17 | 2019-03-12 | 苏州华道生物药业股份有限公司 | A kind of preparation process of pair of ethyl beneznesulfonamide |
| CN110156643A (en) * | 2019-06-24 | 2019-08-23 | 新乡市锦源化工有限公司 | A kind of N-acetylsulfanilyl chloride efficient catalytic preparation method |
| CN116769493A (en) * | 2023-05-11 | 2023-09-19 | 大庆轩隆化工有限公司 | Petroleum alkylbenzene sulfonate surfactant for oil displacement and preparation method thereof |
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Cited By (9)
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|---|---|---|---|---|
| CN105037224A (en) * | 2015-05-27 | 2015-11-11 | 南通沃兰化工有限公司 | Method for reducing loss and improving yield during acyl chloride hydrolysis process |
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| CN108084062A (en) * | 2017-12-25 | 2018-05-29 | 天津瑞岭化工有限公司 | A kind of preparation method of 2,4- disubstituted benzenes sulfonic acid chloride |
| CN108752242A (en) * | 2018-06-28 | 2018-11-06 | 金华双宏化工有限公司 | For the method for sulfonating of low cloud density aromatic hydrocarbons |
| CN108752242B (en) * | 2018-06-28 | 2021-01-01 | 金华双宏化工有限公司 | Sulfonation method for low electron cloud density aromatic hydrocarbon |
| CN109456232A (en) * | 2018-12-17 | 2019-03-12 | 苏州华道生物药业股份有限公司 | A kind of preparation process of pair of ethyl beneznesulfonamide |
| CN110156643A (en) * | 2019-06-24 | 2019-08-23 | 新乡市锦源化工有限公司 | A kind of N-acetylsulfanilyl chloride efficient catalytic preparation method |
| CN116769493A (en) * | 2023-05-11 | 2023-09-19 | 大庆轩隆化工有限公司 | Petroleum alkylbenzene sulfonate surfactant for oil displacement and preparation method thereof |
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Application publication date: 20120815 |