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General preparation method of sulfonyl chloride

A technology of sulfonyl chloride and oxidative chlorination, which is applied to the preparation of sulfonic acid, the preparation of organic compounds, chemical instruments and methods, etc., and can solve problems such as operational hazards, generation of acidic or toxic by-products, excessive use, etc.

Inactive Publication Date: 2013-10-16
BEIJING UNIV OF CHEM TECH
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AI Technical Summary

Problems solved by technology

The first method has disadvantages such as harsh reaction conditions, long reaction time, low functional group tolerance, excessive use of chlorinated reagents, and generation of acidic or toxic by-products; the second method has made considerable progress in the past century. progress, but still faces shortcomings
For example, some oxidative chlorination reagents are not easy to obtain (O3-SOCl2, Kv?rn?, L. Werder, M. Hauser, H. Carreira, E. M. Org. Lett.2005, 7, 1145.), some operationally hazardous (SO2Cl2 -KNO3: Park, Y. J. Shin H. H. Kim, Y. H. Chem. Lett.1992, 1483. Br2-POCl3: Meinzer, A. Breckel, A. Thaher, B. A. Manicone N. Otto, H.-H.Helv. Chim. Acta2004, 87, 90. H2O2-SOCl2: Monnee, M. C. F. Marijne, M. F. Brouwer A. J. Liskamp, ​​R. M. J. Tetrahedron Lett. 2000, 41, 7991; Piatek, A. Chapuis, C. Jurczak, J. Helv. Chim. Acta2002, 85, 1973; Humljan, J. Gobec, S. Tetrahedron Lett.2005, 46, 4069; Bahrami, K. Khodaei M. M. Soheilizad. M. J. Org. Chem. 2009, 74, 9287.), and some can cause heavy metal pollution (H2O2-ZrCl 4: Bahrami, K. Khodaei, M. M. Soheilizad, M. Synlett2009, 2773. KMnO4-HCl: Zhen Xiaoli, Kang Ruhong, Han Jianrong, Chemical Bulletin, 1996, 37.), some produce organic by-products that interfere with product purification (HCl-silica PhIO: Soh miya, H. Kimura, T. Fujita, M. Ando, ​​T. Chem. Lett.1992, 891; Sohmiya, H. Kimura, T. Fujita, M. T. Ando, ​​Tetrahedron i>1998,54, 13737. N-Chlorosuccinimide-HCl: Kim, D. W. Ko, Y. K. Kim, S. H. Synthesis1992, 1203; Nishiguchi, A . Maeda, K. Miki, S. Synthesis2006, 4131; Veisi, H. Ghorbani-Vagheit, R. Hemmatia S. Mahmoodic, J. Synlett2011, 2315; Liu, J. Hou, S. L. Xu, J. X. Phosphous, Sulfur Sillicon Relat. Elem.2011, 186, 2377; Meng, F. H. Chen, N. Xu, J. X. Sci. China: Chem.2012,55, 2548. Yang, Z. H. Xu, J. X. Synthesis2013, 45, 1675 Chlorotrimethylsilane-Potassium Nitrate: Surya Prakash, G. K. Mathew, T. Panja, C. Olah, G. A. J. Org. Chem.2007, 72, 5847 .Trichloroisocyanuric acid: Massah, A. R. Sayadi, S. Ebrahimi, S. RSC Adv.2012, 2, 6606. 2,4-Dichloro-5, 5-Dimethylhydantoin: Pu, Y.-M. Christesen A. Ku, Y.-Y. Tetrahedron Lett.2010, 51, 418. tert-butyl hypochlorite: Joyard, Y. Papamicael, C. Bohn, P. Bischoff, L. Org. Lett.2013, 15, 2294.)

Method used

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  • General preparation method of sulfonyl chloride
  • General preparation method of sulfonyl chloride

Examples

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Embodiment 1

[0057] Benzylsulfonyl chloride 2a preparation of

[0058] Thiourea (0.387 g, 5 mmol) and benzyl chloride (0.633 g, 5 mmol) were dissolved in 5 mL of ethanol. After reflux for 30 min, the solvent was removed under reduced pressure to obtain a white solid. The white solid was slowly added dropwise to NaClO 2 (1.61 g, 15 mmol, 85% purity), in a mixed system of concentrated HCl (3 mL) and MeCN (10 mL). During the feeding process, use a water bath to control the temperature in the reaction system at 10-20 oC between. After the addition, continue to stir the reaction for 30 min, remove acetonitrile under reduced pressure at low temperature, add 25 mL of water, filter the solid in the system, and dry to obtain the product colorless crystal benzylsulfonyl chloride 3a , melting point 90-91°C, 0.781 g, yield 82%. 1 H NMR (400 MHz, CDCl 3 ) δ: 7.61~7.35 (m, 4H), 5.12 (s, 2H).

Embodiment 2

[0060] p-methylbenzylsulfonyl chloride 2b preparation of

[0061] According to the method described in Example 1, using p-methylbenzyl chloride and thiourea as raw materials, p-methylbenzylsulfonyl chloride was obtained as colorless crystals, melting point 86-88°C, 0.665 g, yield 65%. 1 H NMR (400 MHz, CDCl 3 ) δ: 7.38~7.26 (m, 4H), 4.83 (s, 2H), 2.39 (s, 3H).

Embodiment 3

[0063] 4-chlorobenzylsulfonyl chloride 2c preparation of

[0064] According to the method described in Example 1, using p-chlorobenzyl chloride and thiourea as raw materials, p-chlorobenzylsulfonyl chloride was obtained as colorless crystals with a melting point of 90-92°C, 1.080 g, and a yield of 96%. 1 H NMR (400 MHz, CDCl 3 ) δ: 7.46~7.42 (m, 4H), 4.83 (s, 2H).

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Abstract

The invention provides a general preparation method of sulfonyl chloride. The preparation method is characterized in that S-alkyl isothiourea salt, mercaptan, thiophenol, disulfide, thiol acetate, ethanethioate, xanthogenate and other sulfur-containing compounds are used as raw materials to prepare the sulfonyl chloride through the oxidation and chlorination of chlorous acid or its salt under acidic conditions. In the preparation method, the raw materials come from wide sources and are easily available, the operation is convenient, no toxic or polluting raw materials are needed, and no poisonous and harmful byproducts and organic byproducts are generated. Therefore, the preparation method is suitable for industrial production and can be applied to the preparation of optically active sulfonyl chloride and compounds containing a plurality of chlorosulfonyl. The obtained compounds may be used as the raw materials of organic, drugs, dyes, antibacterial agents, surfactants and plant-growth regulators.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of sulfonyl chloride. Background technique [0002] Sulfonyl chlorides are a very important class of compounds widely used as intermediates and starting materials in organic and pharmaceutical synthesis (Hoyle, J. In the Chemistry of Sulfonic Acids, Esters and Their Derivatives (The Chemistry of Functional Groups) ; Kociensky, P. J. Protecting Groups ; Thieme: New York, 1994.), is an important source of sulfonyl groups. [0003] Due to the important role and wide application of sulfonyl chloride, a variety of preparation methods for sulfonyl chloride have been developed. In general, alkylsulfonyl chlorides can be prepared by the following two methods: (1) direct chlorination of alkylsulfonic acids or their salts with chlorinating reagents (Bossard, H. H. Mory, R. Schmid M.; Zollinger, H. . Helv. Chim. Acta 1959, 42 , 1653; Albrigh...

Claims

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Application Information

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IPC IPC(8): C07C303/16C07C303/02C07C309/81C07C309/84C07C309/80C07C309/86C07C309/82
Inventor 许家喜杨占会
Owner BEIJING UNIV OF CHEM TECH
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