CN1264814C - Method for preparing chlorine sulfonyl isocyanic ester - Google Patents
Method for preparing chlorine sulfonyl isocyanic ester Download PDFInfo
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- CN1264814C CN1264814C CN 03127621 CN03127621A CN1264814C CN 1264814 C CN1264814 C CN 1264814C CN 03127621 CN03127621 CN 03127621 CN 03127621 A CN03127621 A CN 03127621A CN 1264814 C CN1264814 C CN 1264814C
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- chlorocyanogen
- temperature
- chlorosulfonyl isocyanate
- sulfur trioxide
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Abstract
The present invention discloses a method for preparing chlorosulfonyl isocyanate. The technical scheme provided by the present invention is realized by that a reactor which is provided with 8 to 30 % of sodium cyanide mother liquor, chlorine gas is simultaneously lead into the reactor, and products of chlorosulfonyl isocyanate are treated by drying, and then are communicated into a reactor filled with sulfur trioxide; the reaction is controlled at the temperature of-20 to 100 DEG C to obtain chlorinating coke sulfonyl isocyanate and 2, 6-dichloro 1, 3, 4, 5-oxygen, nitrogen, thia six-membered rings which are decomposed at the temperature of 100 to 200 DEG C for removing unreacted sulfur trioxide and chlorine cyanogen; obtained mother liquor is distilled, and distillation fractions in the temperature from 106 to 107 DEG C are collected to obtain high purity chlorosulfonyl isocyanate. The present invention has the advantages of simple technology, easy operation, high product purity, less environment pollution, low cost, wide raw material source, etc. The chlorosulfonyl isocyanate not only can be used as chloridizing agents and dehydrating agents, but also is important medicine intermediate bodies, etc.
Description
The technical field is as follows: the invention relates to a preparation method of chlorosulfonyl isocyanate. In particular to a preparation method for refining chlorosulfonyl isocyanate by using three chemical raw materials of chlorine, sodium cyanide and sulfur trioxide and adopting high temperature and thermal decomposition.
Background art: chlorosulfonyl isocyanate is a very active organic synthesis intermediate, and compounds such as radicals, amino groups, carboxyl groups and the like of the chlorosulfonyl isocyanate undergo addition reaction to form compounds such as carbamate, carbamide and the like. The chlorosulfonyl can react with olefin phenol sulfonamide and water molecules to generate a series of compounds such as hydrocarbyl sulfonyl isocyanate, aryl carbamate sulfonyl chloride, aminosulfonyl ester and the like under the condition of retaining the isocyanate group. In addition, chlorosulfonyl isocyanate can also be used as a chlorinating agent and a dehydrating agent.
Chlorosulfonyl isocyanate replaces trichloroisocyanate to react with 3-hydroxymethyl in 7-ACA (7-aminocephalosporanic acid) to form amide for synthesizing cefoxitin and cefuroxime medicaments since the nineties of the twentieth century, so that chlorosulfonyl isocyanate becomes an important medical intermediate.
At present, chlorosulfonyl isocyanate is prepared by reacting urea with chlorosulfonic acid under normal conditions, distilling and refining. In Japanese patent No. JP77855 and EP294613, chlorocyanogen and sulfur trioxide are reacted in a molar ratio of 1: 1, and chlorosulfonyl isocyanate is obtained by distillation, which is difficult to control the reaction conditions in industrial scale-up and to realize mass production.
The invention content is as follows: the invention aims to overcome the defects of the existing technology for preparing the chlorosulfonyl isocyanate, and provides a production method for preparing the chlorosulfonyl isocyanate by using chlorine, sodium cyanide and sulfur trioxide as raw materials.
The technical scheme provided by the invention is realized by introducing mother liquor containing 8-30% of sodium cyanide and chlorine into a reactor at the same time, drying the product chlorocyanogen, introducing the product chlorocyanogen into the reactor containing sulfur trioxide, controlling the reaction temperature to be between 20 ℃ below zero and 100 ℃ for reaction to obtain chlorinated pyrosulfuryl isocyanate and 2, 6-dichloro-1, 3, 4, 5-oxygen, nitrogen,sulfur and aza-hexatomic ring-4, 4-dioxide, decomposing the product at 100 ℃ to 200 ℃ to remove unreacted sulfur trioxide and chlorocyanogen, distilling the obtained mother liquor, collecting fractions at 106 ℃ to 107 ℃ and obtaining the high-purity chlorosulfonyl isocyanate.
The reaction principle is as follows:
the preparation method has the advantages that chlorine, sodium cyanide and sulfur trioxide are used as raw materials, chlorosulfonyl isocyanate is prepared by high-temperature decomposition, so that the product has simple process, high yield and high purity, the pollution of three wastes is greatly reduced, the cost is low, the raw materials are widely available, and the like.
The specific embodiment is as follows: the invention will be further understood by the following examples.
Example 1: adding 1000ml of 16% sodium cyanide solution into a 2000ml reaction bottle, slowly introducing the solution and chlorine gas into a glass reactor to obtain chlorocyanogen gas, drying the chlorocyanogen gas by calcium chloride, introducing the chlorocyanogen gas into the reaction bottle with a stirrer, and filling 200 g of SO3The reactor is reacted for 3 hours at the temperature of minus 20 ℃ to 50 ℃, after the gas is introduced, the temperature is kept for 30 minutes, then the temperature is raised to 120 ℃ to 135 ℃ for reflux for 3 hours, all the chlorocyanogen and sulfur trioxide are removed, the chlorocyanogen and the sulfur trioxide are collected and reused, the reactor is arranged on a rectifying device for rectification, and 390 g of distillate at the temperature of 106 ℃ to 107 ℃ is collected.
Example 2: adding 1000ml of 21% sodium cyanide solution into a 2000ml reaction bottle, slowly introducing the solution and chlorine gas into a glass reactor to obtain chlorocyanogen gas, drying the chlorocyanogen gas by calcium chloride, introducing the dried chlorocyanogen gas into a reaction bottle with a stirring belt, and filling 200 g of SO3The reactor is reacted for 3 hours at the temperature of 25-60 ℃, after the gas is introduced, the temperature is kept for 30 minutes, then the temperature is raised to 127-plus-150 ℃ for reflux for 3 hours, all the chlorocyanogen and the sulfur trioxide are removed, the chlorocyanogen and the sulfur trioxide are collected and reused, a rectifying device is arranged for rectification, and the distillate at the temperature of 106-107 ℃ is collected to obtain 400 g.
Example 3: 500 g of a mixture of 2, 6-dichloro-1, 3, 4, 5-oxygen, nitrogen, sulfur, aza-hexatomic ring-4, 4-dioxide and chlorinated pyrosulfuryl isocyanate is added into a 1000ml three-necked flask, the mixture is heated to the temperature of 120 ℃ and 135 ℃ and refluxed for 3 hours, and after the reaction is finished, 370 g of chlorosulfonyl isocyanate is obtained by rectification in a rectifying tower.
Claims (4)
1. A preparation method for preparing chlorosulfonyl isocyanate by using chlorine, sodium cyanide and sulfur trioxide as raw materials is characterized by comprising the following steps of: introducing mother liquor containing 8-30% of sodium cyanide and chlorine gas into a reactor simultaneously, drying the product chlorocyanogen, introducing the product chlorocyanogen into the reactor containing sulfur trioxide, controlling the reaction temperature to be-20-100 ℃ to react to obtain chlorinated pyrosulfuryl isocyanate and 2, 6-dichloro-1, 3, 4, 5-oxygen, nitrogen, sulfur and aza-hexatomic ring-4, 4-dioxide, decomposing at100-200 ℃ to remove unreacted sulfur trioxide and chlorocyanogen, distilling the obtained mother liquor, collecting fractions at 106-107 ℃ to obtain high-purity chlorosulfonyl isocyanate,
the reaction principle is as follows:
2. the method for producing chlorosulfonyl isocyanate according to claim 1, wherein: introducing mother liquor of 16 percent sodium cyanide and chlorine gas into a reactor simultaneously, drying the product chlorocyanogen by calcium chloride, then introducing the product chlorocyanogen into the reactor filled with sulfur trioxide, controlling the reaction temperature to be between 20 ℃ below zero and 50 ℃ for reaction for 3 hours, preserving the temperature for 30 minutes after the gas introduction is finished, then heating to 120 ℃ to 135 ℃ for reflux for 3 hours, removing all chlorocyanogen and sulfur trioxide, collecting the chlorocyanogen and the sulfur trioxide for reuse, installing a rectifying device for rectification, and collecting fractions at 106 ℃ to 107 ℃ to obtain chlorosulfonyl isocyanate.
3. The method for producing chlorosulfonyl isocyanate according to claim 1, wherein: slowly introducing 21% sodium cyanide solution and chlorine gas into a glass reactor,preparing chlorocyanogen gas, drying by calcium chloride, introducing into a reactor with stirring to contain SO3The reactor is reacted for 3 hours at the temperature of 25-60 ℃, after the gas is introduced, the temperature is kept for 30 minutes, then the temperature is raised to 127-plus-150 ℃ for reflux for 3 hours, all the chlorocyanogen and the sulfur trioxide are removed, the chlorocyanogen and the sulfur trioxide are collected and reused, a rectifying device is arranged for rectification, and the distillate at the temperature of 106-107 ℃ is collected to obtain the chlorosulfonyl isocyanate.
4. The method for producing chlorosulfonyl isocyanate according to claim 1, wherein: heating the mixture of 2, 6-dichloro-1, 3, 4, 5-oxygen, nitrogen, sulfur, aza-hexatomic ring-4, 4-dioxide and chlorinated pyrosulfuryl isocyanate to the temperature of 120 ℃ and 135 ℃, refluxing for 3 hours, and rectifying by using a rectifying tower after the reaction is finished to obtain the chlorosulfonyl isocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03127621 CN1264814C (en) | 2003-07-04 | 2003-07-04 | Method for preparing chlorine sulfonyl isocyanic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03127621 CN1264814C (en) | 2003-07-04 | 2003-07-04 | Method for preparing chlorine sulfonyl isocyanic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1566085A CN1566085A (en) | 2005-01-19 |
| CN1264814C true CN1264814C (en) | 2006-07-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03127621 Expired - Fee Related CN1264814C (en) | 2003-07-04 | 2003-07-04 | Method for preparing chlorine sulfonyl isocyanic ester |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891657B (en) * | 2010-07-15 | 2011-08-31 | 营口三征新科技化工有限公司 | Manufacturing method of chlorosulfonyl isocyanate |
| CN104447438A (en) * | 2014-11-20 | 2015-03-25 | 沈阳化工大学 | Method for producing chlorosulfonyl isocyanate by taking cyanogen chloride and sulfur trioxide as raw materials |
| CN109400506B (en) * | 2018-11-14 | 2021-04-13 | 四平市精细化学品有限公司 | Synthesis method of high-purity chlorosulfonyl isocyanate |
| CN112321462B (en) * | 2020-11-02 | 2023-02-24 | 四平市精细化学品有限公司 | Method for synthesizing chlorosulfonyl isocyanate by continuous method |
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| CN1566085A (en) | 2005-01-19 |
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Owner name: HEBEI ZHONGRUN PHARMACEUTICAL CO.LTD., SHIYAO GRO Free format text: FORMER OWNER: SIPING FINE CHEMICALS LIMITED COMPANY Effective date: 20081121 |
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Effective date of registration: 20081121 Address after: 47, Feng Shou Road, Shijiazhuang, Hebei, zip code: 050041 Co-patentee after: Siping City Fine Chemicals Co., LTD Patentee after: Hebei Zhong run Pharmaceutical Co., Ltd. Address before: No. 1, Beishan West Road, MTR Eastern District, Siping City, Jilin Province, China: 136001 Patentee before: Siping City Fine Chemicals Co., LTD |
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Owner name: CSPC PHARMACEUTICAL GROUP ZHONGNUO PHARMACEUTICAL Free format text: FORMER NAME: CSPC HEBEI ZHONGRUN PHARMACEUTICAL CO., LTD. |
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Address after: 050041 No. 47 Harvest Road, Hebei, Shijiazhuang Co-patentee after: Siping City Fine Chemicals Co., LTD Patentee after: Zhongnuo Pharmaceutical (Shijiazhuang) Co., Ltd., Shiyao Group Address before: 050041 No. 47 Harvest Road, Hebei, Shijiazhuang Co-patentee before: Siping City Fine Chemicals Co., LTD Patentee before: CSPC Hebei Zhongrun Pharmaceutical Co., Ltd. |
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Granted publication date: 20060719 Termination date: 20130704 |