CN105503671A - Preparation method of p-toluene sulfonyl chloride - Google Patents
Preparation method of p-toluene sulfonyl chloride Download PDFInfo
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- CN105503671A CN105503671A CN201510976350.6A CN201510976350A CN105503671A CN 105503671 A CN105503671 A CN 105503671A CN 201510976350 A CN201510976350 A CN 201510976350A CN 105503671 A CN105503671 A CN 105503671A
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- toluenesulfonic acid
- chloroform
- toluenesulfonyl chloride
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- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 140
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000012074 organic phase Substances 0.000 claims abstract description 37
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 33
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010410 layer Substances 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000012044 organic layer Substances 0.000 claims abstract description 15
- 239000006184 cosolvent Substances 0.000 claims abstract description 14
- 239000002608 ionic liquid Substances 0.000 claims abstract description 14
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims description 19
- 239000002699 waste material Substances 0.000 claims description 19
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 23
- 238000009826 distribution Methods 0.000 abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000032798 delamination Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 150000001263 acyl chlorides Chemical class 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 16
- 238000004811 liquid chromatography Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- -1 arylsulfonyl chloride Chemical compound 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- LLLLWIUPYCSYJE-UHFFFAOYSA-N phosphoryl trichloride sulfuryl dichloride Chemical compound S(=O)(=O)(Cl)Cl.P(=O)(Cl)(Cl)Cl LLLLWIUPYCSYJE-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical group 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- LAYPMCGIWDGYKX-UHFFFAOYSA-N trichloromethyl hydrogen carbonate Chemical compound OC(=O)OC(Cl)(Cl)Cl LAYPMCGIWDGYKX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种制备对甲苯磺酰氯的方法，包括以下步骤：(1)将对甲苯磺酸溶于氯仿中，加入离子液助溶剂，在0～40℃条件下均匀搅拌，滴加氯磺酸；(2)滴加结束后，继续恒温反应1.5～4h；(3)反应结束后，加水除去过量的氯磺酸，并于分液漏斗中分液，得到废酸和有机层；(4)有机层加水洗涤，从有机相中萃取得到对甲苯磺酸水溶液，分液去除废水后得到产品层。(5)蒸馏除去氯仿，得到对甲苯磺酰氯成品。本发明使用低毒溶剂氯仿，由于用离子液作为助溶剂，对甲苯磺酸与氯磺酸进行酰氯化反应，反应进行到一定程度，副产物硫酸和有机层分层，离子液助溶剂改变了对甲苯磺酸的分配系数，从而提高了对甲苯磺酰氯的产率。A method for preparing p-toluenesulfonyl chloride, comprising the following steps: (1) dissolving p-toluenesulfonic acid in chloroform, adding an ionic liquid co-solvent, uniformly stirring at 0-40°C, and dripping chlorosulfonic acid; 2) After the dropwise addition, continue the constant temperature reaction for 1.5 to 4 hours; (3) After the reaction, add water to remove excess chlorosulfonic acid, and separate liquids in a separatory funnel to obtain spent acid and an organic layer; (4) Organic layer Wash with water, extract from the organic phase to obtain an aqueous solution of p-toluenesulfonic acid, and separate to remove waste water to obtain a product layer. (5) Distill off chloroform to obtain p-toluenesulfonyl chloride finished product. The present invention uses low-toxicity solvent chloroform, owing to use ionic liquid as cosolvent, p-toluenesulfonic acid and chlorosulfonic acid carry out acyl chloride reaction, reaction is carried out to a certain extent, by-product sulfuric acid and organic layer delamination, ionic liquid cosolvent has changed The distribution coefficient of p-toluenesulfonic acid, thereby improving the productive rate of p-toluenesulfonyl chloride.
Description
技术领域technical field
本发明涉及一种制备对甲苯磺酰氯的方法，属有机化学领域。The invention relates to a method for preparing p-toluenesulfonyl chloride, belonging to the field of organic chemistry.
背景技术Background technique
磺酰氯是一类重要的精细有机化工中间体，广泛用于多种医药、农药、染料的合成过程中，其中芳基磺酰氯是合成磺胺类药物、染料、杀虫剂的重要中间体。磺酰氯可以看作磺酸中的羟基被氯取代的产物，是磺酸的衍生物。目前对甲苯磺酰氯的工业生成是通过对甲苯磺酸加入酰氯化试剂氯磺酸合成的，虽然反应条件温和，但是，在转化率到达80％左右时就停止反应，大量未反应的原料对甲苯磺酸溶于副产物硫酸中，造成转化率不高、废酸水中COD过高的问题。目前已报道的合成对甲苯磺酰氯的文章比较多，但在实际生产中都存在一些问题。《高校化学工程学报》第18卷第2期(出版日期2004-4-25)陈钟秀的文章“对甲苯磺酰氯合成研究”一文报道了以对甲苯磺酸和三氯氧磷为原料合成对甲苯磺酰氯，其所用原料三氯氧磷具有刺激性气味，剧毒，产生的亚磷酸较难除去，不利于大规模工业生产；专利文献“CN1687024”报道了以芳基磺酸钠和三光气(双(三氯甲基)碳酸酯)为原料，以有机胺为催化剂，在惰性有机溶剂中回流反应得到芳基磺酰氯，该专利中的后续处理方法仍采用传统的提纯方法，需要在滤液脱溶后再进行减压精馏操作，在工业上应用时需要增加后续提纯操作的设备投入；专利文献“CN102633687”报道了烷基苯在搅拌下于0℃-45℃温度一次性缓速加入氯磺酸、无机盐催化剂，保温反应0.1-10小时，可得到磺化物料，采用冰水析出法分离和提纯对位取代烷基苯磺酰氯，此方法氯磺酸用量过大，三废问题严重，对环境污染严重；专利文献“CN103588683”报道了以甲苯、氯磺酸、氯化铵、吡啶和氨基磺酸为原料，经过氯磺化反应后，将反应液冷却、真空抽滤、溶剂萃取、结晶、干燥后得对甲苯磺酰氯，该专利后续处理方法也采用传统的提纯方法，需要在滤液脱溶后再进行减压精馏操作，在工业上应用时需要增加后续提纯操作的设备投入。Sulfonyl chloride is an important class of fine organic chemical intermediates, which are widely used in the synthesis of various medicines, pesticides, and dyes. Among them, arylsulfonyl chloride is an important intermediate for the synthesis of sulfonamide drugs, dyes, and insecticides. Sulfonyl chloride can be regarded as a product in which the hydroxyl group in sulfonic acid is replaced by chlorine, and it is a derivative of sulfonic acid. At present, the industrial generation of p-toluenesulfonyl chloride is synthesized by adding p-toluenesulfonic acid to the acid chloride reagent chlorosulfonic acid. Although the reaction conditions are mild, the reaction is stopped when the conversion rate reaches about 80%, and a large amount of unreacted raw material p-toluene Sulfonic acid dissolves in the by-product sulfuric acid, resulting in low conversion rate and high COD in waste acid water. There are many articles on the synthesis of p-toluenesulfonyl chloride reported so far, but there are some problems in actual production. The article "Research on the Synthesis of p-Toluenesulfonyl Chloride" by Chen Zhongxiu, Vol. 18, No. 2 of "Journal of Chemical Engineering of Universities" reported the synthesis of p-toluene from p-toluenesulfonic acid and phosphorus oxychloride Sulfonyl chloride, its used raw material phosphorus oxychloride has pungent odor, is highly toxic, and the phosphorous acid that produces is difficult to remove, is unfavorable for large-scale industrial production; Two (trichloromethyl) carbonate) is raw material, with organic amine as catalyst, reflux reaction in inert organic solvent obtains aryl sulfonyl chloride, the follow-up treatment method in this patent still adopts traditional purification method, needs to remove in filtrate After melting, the vacuum distillation operation is carried out, and the equipment input for subsequent purification operations needs to be increased in industrial applications; the patent document "CN102633687" reports that alkylbenzene is slowly added to chlorine at a temperature of 0°C-45°C under stirring. Sulfonic acid, inorganic salt catalyst, heat preservation reaction for 0.1-10 hours, can obtain sulfonated materials, use ice water precipitation method to separate and purify p-substituted alkylbenzenesulfonyl chloride, this method uses too much chlorosulfonic acid, and the three wastes problem is serious, Serious environmental pollution; patent literature "CN103588683" reports that toluene, chlorosulfonic acid, ammonium chloride, pyridine and sulfamic acid are used as raw materials, after chlorosulfonation reaction, the reaction solution is cooled, vacuum filtered, solvent extracted, After crystallization and drying, p-toluenesulfonyl chloride is obtained. The follow-up treatment method of this patent also adopts the traditional purification method, which requires vacuum distillation after the filtrate is desolvated. When it is applied in industry, it needs to increase the investment in equipment for subsequent purification operations.
发明内容Contents of the invention
本发明旨在提出一种对甲苯磺酸与氯磺酸进行酰氯化反应的新方法制备对甲苯磺酰氯，可提高对甲苯磺酰氯的产率，一种制备对甲苯磺酰氯的方法。The present invention aims to propose a new method for preparing p-toluenesulfonyl chloride by acid chlorination reaction between p-toluenesulfonic acid and chlorosulfonic acid, which can improve the yield of p-toluenesulfonyl chloride, and a method for preparing p-toluenesulfonyl chloride.
这种制备对甲苯磺酰氯的方法，包括以下步骤：This method for preparing p-toluenesulfonyl chloride comprises the following steps:
(1)将对甲苯磺酸溶于氯仿中，加入离子液助溶剂，在0～40℃条件下均匀搅拌，滴加氯磺酸；(1) Dissolve p-toluenesulfonic acid in chloroform, add ionic liquid co-solvent, stir evenly at 0-40°C, and add chlorosulfonic acid dropwise;
(2)滴加结束后，继续恒温反应1.5～4h；(2) After the dropwise addition, continue the constant temperature reaction for 1.5 to 4 hours;
(3)反应结束后，加水除去过量的氯磺酸，并于分液漏斗中分液，得到废酸和有机层；(3) After the reaction finishes, add water to remove excessive chlorosulfonic acid, and separate liquid in separating funnel, obtain spent acid and organic layer;
(4)有机层加水洗涤，从有机相中萃取得到对甲苯磺酸水溶液，分液去除废水后得到产品层。(4) The organic layer is washed with water, extracted from the organic phase to obtain an aqueous solution of p-toluenesulfonic acid, and the product layer is obtained after liquid separation and removal of waste water.
(5)蒸馏回收氯仿，得到对甲苯磺酰氯成品。(5) Distill and recover chloroform to obtain p-toluenesulfonyl chloride finished product.
本发明使用溶剂氯仿，由于用离子液作为助溶剂，对甲苯磺酸与氯磺酸进行酰氯化反应，反应进行到一定程度，副产物硫酸和有机层分层，离子液助溶剂改变了对甲苯磺酸的分配系数，从而提高了对甲苯磺酰氯的产率。The present invention uses solvent chloroform, owing to use ionic liquid as cosolvent, p-toluenesulfonic acid and chlorosulfonic acid carry out acyl chlorination reaction, reaction is carried out to a certain extent, by-product sulfuric acid and organic layer delamination, ionic liquid cosolvent has changed p-toluene The partition coefficient of sulfonic acid is improved, thereby improving the productive rate of p-toluenesulfonyl chloride.
具体实施方式detailed description
这种制备对甲苯磺酰氯的方法包括以下步骤：This method for preparing p-toluenesulfonyl chloride comprises the following steps:
(1)将对甲苯磺酸溶于氯仿中，加入离子液助溶剂，在0～40℃条件下均匀搅拌，作为底物，滴加氯磺酸进行反应，反应式如下：(1) Dissolve p-toluenesulfonic acid in chloroform, add ionic liquid co-solvent, and stir evenly under the condition of 0-40°C. As a substrate, add chlorosulfonic acid dropwise for reaction. The reaction formula is as follows:
(2)滴加结束后，继续恒温反应1.5～4h；(2) After the dropwise addition, continue the constant temperature reaction for 1.5 to 4 hours;
(3)反应结束后，加水除去过量的氯磺酸，并于分液漏斗中分液，得到废酸和有机层；(3) After the reaction finishes, add water to remove excessive chlorosulfonic acid, and separate liquid in separating funnel, obtain spent acid and organic layer;
(4)有机层加水洗涤，从有机相中萃取得到对甲苯磺酸水溶液，分液去除废水后得到产品层。(4) The organic layer is washed with water, extracted from the organic phase to obtain an aqueous solution of p-toluenesulfonic acid, and the product layer is obtained after liquid separation and removal of waste water.
(5)蒸馏，得到对甲苯磺酰氯成品。氯仿可以回收再利用。(5) Distillation to obtain p-toluenesulfonyl chloride finished product. Chloroform can be recycled and reused.
(6)计算对甲苯磺酸的分配系数。通过液相色谱分析，得出对甲苯磺酸在废酸中和有机层中的浓度，对甲苯磺酸分配系数计算如下：(6) Calculate the partition coefficient of p-toluenesulfonic acid. Through liquid chromatography analysis, draw the concentration of p-toluenesulfonic acid in waste acid and in the organic layer, p-toluenesulfonic acid distribution coefficient is calculated as follows:
其中：kA为分配系数；m水A为水中TsOH(对甲苯磺酸)的质量，是通过TsOH在液相色谱中做出来的工作曲线计算而得；m有机层为有机层的质量；yA为TsOH在氯仿中的浓度；xA为TsOH在硫酸中的浓度。Wherein: k A is distribution coefficient; m water A is the quality of TsOH (p-toluenesulfonic acid) in water, is calculated by the working curve that TsOH is done in liquid chromatography; m organic layer is the quality of organic layer; y A is the concentration of TsOH in chloroform; x A is the concentration of TsOH in sulfuric acid.
(7)将所得产品直接称量，计算得出对甲苯磺酰氯的产率。(7) Gained product is directly weighed, calculates the productive rate of p-toluenesulfonyl chloride.
这种制备对甲苯磺酰氯的方法中，第一步中各原料的加入量以摩尔质量计可以为：对甲苯磺酸∶氯磺酸＝1∶(1～4)；助溶剂离子液的加入量为对甲苯磺酸质量的1％～4％；氯仿加入量以质量计可以为：对甲苯磺酸∶氯仿＝1∶(1～4)。In this method for preparing p-toluenesulfonyl chloride, the addition of each raw material in the first step can be in terms of molar mass: p-toluenesulfonic acid: chlorosulfonic acid=1: (1～4); The amount is 1%-4% of the mass of p-toluenesulfonic acid; the amount of chloroform added in terms of mass can be: p-toluenesulfonic acid:chloroform=1:(1-4).
本方法中的离子液助溶剂指：[Bmim]Br、[Bmim]BF4、[Bmim]EtOSO3、[BuPy]Br、[BuPy]BF4或[BuPy]EtOSO3中的一种。The ionic liquid co-solvent in this method refers to one of [Bmim]Br, [Bmim]BF 4 , [Bmim]EtOSO 3 , [BuPy]Br, [BuPy]BF 4 or [BuPy]EtOSO 3 .
本发明的方法由于用离子液作为助溶剂，对甲苯磺酸与氯磺酸进行酰氯化反应，反应进行到一定程度，副产物硫酸和有机层分层，离子液助溶剂改变了对甲苯磺酸的分配系数，从而提高了对甲苯磺酰氯的产率。离子液助溶剂提高了对甲苯磺酸在有机层中的分配系数，从原来的0.0178提高到0.0494，产率从原来的78.82％提高到88.19％。The method of the present invention owing to use ionic liquid as cosolvent, p-toluenesulfonic acid and chlorosulfonic acid carry out acyl chlorination reaction, reaction is carried out to a certain extent, by-product sulfuric acid and organic layer delamination, ionic liquid cosolvent has changed p-toluenesulfonic acid The distribution coefficient, thereby improving the productive rate of p-toluenesulfonyl chloride. The ionic liquid co-solvent improves the distribution coefficient of p-toluenesulfonic acid in the organic layer from 0.0178 to 0.0494, and the yield increases from 78.82% to 88.19%.
实施例1：Example 1:
将0.1mol(19.02g)的对甲苯磺酸(带结晶水，下同)和0.38g[BuPy]EtOSO3溶于47.55g氯仿中，均匀搅拌，25℃条件下滴加0.15mol(17.48g)氯磺酸。恒温反应2.5h后加入0.1mol(1.8g)蒸馏水，除去过量的氯磺酸。反应液分层，通过分液漏斗分液得到废酸和有机相，有机相中加入10g蒸馏水洗涤，除去有机相中残留的对甲苯磺酸，分液得到废水和产品层。对甲苯磺酸的分配系数为对甲苯磺酸在有机相中的浓度和在废酸中浓度的比值。通过液相色谱分析，对甲苯磺酸的分配系数为0.0494；通过蒸馏有机相回收氯仿，得到对甲苯磺酰氯16.67g，产率为87.51％。Dissolve 0.1mol (19.02g) of p-toluenesulfonic acid (with crystal water, the same below) and 0.38g [BuPy]EtOSO 3 in 47.55g of chloroform, stir evenly, and add 0.15mol (17.48g) dropwise at 25°C Chlorosulfonic acid. After constant temperature reaction for 2.5 h, 0.1 mol (1.8 g) of distilled water was added to remove excess chlorosulfonic acid. The reaction solution was separated into layers, and the waste acid and the organic phase were obtained by liquid separation through a separatory funnel. 10 g of distilled water was added to the organic phase for washing to remove residual p-toluenesulfonic acid in the organic phase, and the waste water and the product layer were obtained by liquid separation. The distribution coefficient of p-toluenesulfonic acid is the ratio of the concentration of p-toluenesulfonic acid in the organic phase to the concentration in the spent acid. Analysis by liquid chromatography showed that the distribution coefficient of p-toluenesulfonic acid was 0.0494; the chloroform was recovered by distillation of the organic phase to obtain 16.67 g of p-toluenesulfonyl chloride with a yield of 87.51%.
实施例2：Example 2:
将0.1mol(19.02g)的对甲苯磺酸和0.19g[Bmim]EtOSO3溶于47.55g氯仿中，均匀搅拌，25℃条件下滴加0.1mol(11.65g)氯磺酸。加完后恒温反应3h后加入0.05mol(0.9g)蒸馏水，除去过量的氯磺酸。反应液分层，通过分液漏斗分液得到废酸和有机相，有机相中加入10g蒸馏水洗涤，萃取有机相中残留的对甲苯磺酸，分液得到废水和产品层。对甲苯磺酸的分配系数为对甲苯磺酸在产品层中的浓度和在废酸中浓度的比值。通过液相色谱分析，对甲苯磺酸的分配系数为0.0449；通过蒸馏有机相回收氯仿，得到对甲苯磺酰氯15.91g，产率为83.51％。Dissolve 0.1 mol (19.02 g) of p-toluenesulfonic acid and 0.19 g of [Bmim]EtOSO 3 in 47.55 g of chloroform, stir evenly, and add 0.1 mol (11.65 g) of chlorosulfonic acid dropwise at 25°C. After the addition, 0.05 mol (0.9 g) of distilled water was added after constant temperature reaction for 3 h to remove excess chlorosulfonic acid. The reaction solution was separated into layers, and the waste acid and the organic phase were obtained by liquid separation through a separatory funnel. 10 g of distilled water was added to the organic phase for washing, the residual p-toluenesulfonic acid in the organic phase was extracted, and the waste water and the product layer were obtained by liquid separation. The distribution coefficient of p-toluenesulfonic acid is the ratio of the concentration of p-toluenesulfonic acid in the product layer to the concentration in the waste acid. Analysis by liquid chromatography showed that the distribution coefficient of p-toluenesulfonic acid was 0.0449; the chloroform was recovered by distillation of the organic phase to obtain 15.91 g of p-toluenesulfonyl chloride with a yield of 83.51%.
实施例3：Example 3:
将0.1mol(19.02g)的对甲苯磺酸和0.57g[Bmin]BF4溶于19.02g氯仿中，均匀搅拌，25℃条件下滴加0.15mol(17.4g)氯磺酸。加完后恒温反应2h后加入0.1mol(1.8g)蒸馏水，除去过量的氯磺酸。反应液分层，通过分液漏斗分液得到废酸和有机相，有机相中加入10g蒸馏水洗涤，萃取有机相中残留的对甲苯磺酸，分液得到废水和产品层。对甲苯磺酸的分配系数为对甲苯磺酸在产品层中的浓度和在废酸中浓度的比值。通过液相色谱分析，对甲苯磺酸的分配系数为0.0371；通过蒸馏有机相回收氯仿，得到对甲苯磺酰氯15.39g，产率为80.79％。。Dissolve 0.1mol (19.02g) of p-toluenesulfonic acid and 0.57g of [Bmin]BF 4 in 19.02g of chloroform, stir evenly, and add 0.15mol (17.4g) of chlorosulfonic acid dropwise at 25°C. After the addition, 0.1 mol (1.8 g) of distilled water was added after constant temperature reaction for 2 h to remove excess chlorosulfonic acid. The reaction solution was separated into layers, and the waste acid and the organic phase were obtained by liquid separation through a separatory funnel. 10 g of distilled water was added to the organic phase for washing, the residual p-toluenesulfonic acid in the organic phase was extracted, and the waste water and the product layer were obtained by liquid separation. The distribution coefficient of p-toluenesulfonic acid is the ratio of the concentration of p-toluenesulfonic acid in the product layer to the concentration in the waste acid. Analysis by liquid chromatography showed that the distribution coefficient of p-toluenesulfonic acid was 0.0371; the chloroform was recovered by distillation of the organic phase to obtain 15.39 g of p-toluenesulfonyl chloride with a yield of 80.79%. .
实施例4：Example 4:
将0.1mol(19.02g)的对甲苯磺酸和0.38g[Bmin]Br溶于38.04g氯仿中，均匀搅拌，25℃条件下滴加0.25mol(29.13g)氯磺酸。加完后恒温反应2.5h后加入0.2mol(3.6g)蒸馏水，除去过量的氯磺酸。反应液分层，通过分液漏斗分液得到废酸和有机相，有机相中加入10g蒸馏水洗涤，萃取有机相中残留的对甲苯磺酸，分液得到废水和产品层。对甲苯磺酸的分配系数为对甲苯磺酸在产品层中的浓度和在废酸中浓度的比值。通过液相色谱分析，对甲苯磺酸的分配系数为0.0437；通过蒸馏有机相回收氯仿，得到对甲苯磺酰氯15.77g，产率为82.77％。Dissolve 0.1mol (19.02g) of p-toluenesulfonic acid and 0.38g of [Bmin]Br in 38.04g of chloroform, stir evenly, and add 0.25mol (29.13g) of chlorosulfonic acid dropwise at 25°C. After the addition, 0.2 mol (3.6 g) of distilled water was added after constant temperature reaction for 2.5 h to remove excess chlorosulfonic acid. The reaction solution was separated into layers, and the waste acid and the organic phase were obtained by liquid separation through a separatory funnel. 10 g of distilled water was added to the organic phase for washing, the residual p-toluenesulfonic acid in the organic phase was extracted, and the waste water and the product layer were obtained by liquid separation. The distribution coefficient of p-toluenesulfonic acid is the ratio of the concentration of p-toluenesulfonic acid in the product layer to the concentration in the waste acid. Analysis by liquid chromatography showed that the distribution coefficient of p-toluenesulfonic acid was 0.0437; the chloroform was recovered by distillation of the organic phase to obtain 15.77 g of p-toluenesulfonyl chloride with a yield of 82.77%.
实施例5：Example 5:
将0.1mol(19.02g)的对甲苯磺酸和0.76g[Bmim]EtOSO3溶于47.55g氯仿中，均匀搅拌，25℃条件下滴加0.3mol(34.95g)氯磺酸。加完后恒温反应2.5h后加入0.25mol(4.5g)蒸馏水，除去过量的氯磺酸。反应液分层，通过分液漏斗分液得到废酸和有机相，有机相中加入10g蒸馏水洗涤，萃取有机相中残留的对甲苯磺酸，分液得到废水和产品层。对甲苯磺酸的分配系数为对甲苯磺酸在产品层中的浓度和在废酸中浓度的比值。通过液相色谱分析，对甲苯磺酸的分配系数为0.0497；通过蒸馏有机相回收氯仿，得到对甲苯磺酰氯16.80g，产率为88.19％。Dissolve 0.1 mol (19.02 g) of p-toluenesulfonic acid and 0.76 g of [Bmim]EtOSO 3 in 47.55 g of chloroform, stir evenly, and add 0.3 mol (34.95 g) of chlorosulfonic acid dropwise at 25°C. After the addition, 0.25 mol (4.5 g) of distilled water was added after constant temperature reaction for 2.5 h to remove excess chlorosulfonic acid. The reaction solution was separated into layers, and the waste acid and the organic phase were obtained by liquid separation through a separatory funnel. 10 g of distilled water was added to the organic phase for washing, the residual p-toluenesulfonic acid in the organic phase was extracted, and the waste water and the product layer were obtained by liquid separation. The distribution coefficient of p-toluenesulfonic acid is the ratio of the concentration of p-toluenesulfonic acid in the product layer to the concentration in the waste acid. Analysis by liquid chromatography showed that the distribution coefficient of p-toluenesulfonic acid was 0.0497; the chloroform was recovered by distillation of the organic phase to obtain 16.80 g of p-toluenesulfonyl chloride with a yield of 88.19%.
实施例6：Embodiment 6:
将0.1mol(19.02g)的对甲苯磺酸和0.38g[BuPy]Br溶于66.57g氯仿中，均匀搅拌，25℃条件下滴加0.15mol(17.48g)氯磺酸。加完后恒温反应2.5h后加入0.1mol(1.8g)蒸馏水，除去过量的氯磺酸。反应液分层，通过分液漏斗分液得到废酸和有机相，有机相中加入10g蒸馏水洗涤，萃取有机相中残留的对甲苯磺酸，分液得到废水和产品层。对甲苯磺酸的分配系数为对甲苯磺酸在产品层中的浓度和在废酸中浓度的比值。通过液相色谱分析，对甲苯磺酸的分配系数为0.0413；通过蒸馏有机相回收氯仿，得到对甲苯磺酰氯15.56g，产率为81.66％。Dissolve 0.1mol (19.02g) of p-toluenesulfonic acid and 0.38g of [BuPy]Br in 66.57g of chloroform, stir evenly, and add 0.15mol (17.48g) of chlorosulfonic acid dropwise at 25°C. After the addition, 0.1 mol (1.8 g) of distilled water was added after constant temperature reaction for 2.5 h to remove excess chlorosulfonic acid. The reaction solution was separated into layers, and the waste acid and the organic phase were obtained by liquid separation through a separatory funnel. 10 g of distilled water was added to the organic phase for washing, the residual p-toluenesulfonic acid in the organic phase was extracted, and the waste water and the product layer were obtained by liquid separation. The distribution coefficient of p-toluenesulfonic acid is the ratio of the concentration of p-toluenesulfonic acid in the product layer to the concentration in the waste acid. Analysis by liquid chromatography showed that the distribution coefficient of p-toluenesulfonic acid was 0.0413; the chloroform was recovered by distillation of the organic phase to obtain 15.56 g of p-toluenesulfonyl chloride with a yield of 81.66%.
实施例7：Embodiment 7:
将0.1mol(19.02g)的对甲苯磺酸和0.38g[BuPy]EtOSO3溶于28.53g氯仿中，均匀搅拌，25℃条件下滴加0.15mol(17.48g)氯磺酸。加完后恒温反应2.5h后加入0.1mol(1.8g)蒸馏水，除去过量的氯磺酸。反应液分层，通过分液漏斗分液得到废酸和有机相，有机相中加入10g蒸馏水洗涤，萃取有机相中残留的对甲苯磺酸，分液得到废水和产品层。对甲苯磺酸的分配系数为对甲苯磺酸在产品层中的浓度和在废酸中浓度的比值。通过液相色谱分析，对甲苯磺酸的分配系数为0.0472；通过蒸馏有机相回收氯仿，得到对甲苯磺酰氯16.43g，产率为86.24％。0.1mol (19.02g) of p-toluenesulfonic acid and 0.38g of [BuPy]EtOSO 3 were dissolved in 28.53g of chloroform, stirred evenly, and 0.15mol (17.48g) of chlorosulfonic acid was added dropwise at 25°C. After the addition, 0.1 mol (1.8 g) of distilled water was added after constant temperature reaction for 2.5 h to remove excess chlorosulfonic acid. The reaction solution was separated into layers, and the waste acid and the organic phase were obtained by liquid separation through a separatory funnel. 10 g of distilled water was added to the organic phase for washing, the residual p-toluenesulfonic acid in the organic phase was extracted, and the waste water and the product layer were obtained by liquid separation. The distribution coefficient of p-toluenesulfonic acid is the ratio of the concentration of p-toluenesulfonic acid in the product layer to the concentration in the waste acid. Analysis by liquid chromatography showed that the distribution coefficient of p-toluenesulfonic acid was 0.0472; the chloroform was recovered by distillation of the organic phase to obtain 16.43 g of p-toluenesulfonyl chloride with a yield of 86.24%.
实施例8：Embodiment 8:
将0.1mol(19.02g)的对甲苯磺酸和0.38g[BuPy]EtOSO3溶于38.04g氯仿中，均匀搅拌，25℃条件下滴加0.15mol(17.48g)氯磺酸。加完后恒温反应4h后加入0.1mol(1.8g)蒸馏水，除去过量的氯磺酸。反应液分层，通过分液漏斗分液得到废酸和有机相，有机相中加入10g蒸馏水洗涤，萃取有机相中残留的对甲苯磺酸，分液得到废水和产品层。对甲苯磺酸的分配系数为对甲苯磺酸在产品层中的浓度和在废酸中浓度的比值。通过液相色谱分析，对甲苯磺酸的分配系数为0.0481；通过蒸馏有机相回收氯仿，得到对甲苯磺酰氯16.52g，产率为86.71％。0.1mol (19.02g) of p-toluenesulfonic acid and 0.38g of [BuPy]EtOSO 3 were dissolved in 38.04g of chloroform, stirred evenly, and 0.15mol (17.48g) of chlorosulfonic acid was added dropwise at 25°C. After the addition, 0.1 mol (1.8 g) of distilled water was added after constant temperature reaction for 4 hours to remove excess chlorosulfonic acid. The reaction solution was separated into layers, and the waste acid and the organic phase were obtained by liquid separation through a separatory funnel. 10 g of distilled water was added to the organic phase for washing, the residual p-toluenesulfonic acid in the organic phase was extracted, and the waste water and the product layer were obtained by liquid separation. The distribution coefficient of p-toluenesulfonic acid is the ratio of the concentration of p-toluenesulfonic acid in the product layer to the concentration in the waste acid. Analysis by liquid chromatography showed that the distribution coefficient of p-toluenesulfonic acid was 0.0481; the chloroform was recovered by distillation of the organic phase to obtain 16.52 g of p-toluenesulfonyl chloride with a yield of 86.71%.
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