离子液体一步法催化合成4-乙酰胺基苯亚磺酸

文章导读

摘要离子液体作为一类同时具备优良溶剂性能与催化活性的新兴绿色催化剂，在各类反应当中有着广泛的应用。开发了以乙酰苯胺和SO₂为原料，采用离子液体一步法催化原料亚磺化反应合成4-乙酰胺基苯亚磺酸的新工艺，其中离子液体在反应过程中同时作为溶剂与催化剂。考察了多种离子液体一步法合成4-乙酰胺基苯亚磺酸，确定三乙胺盐酸盐/AlCl₃为最适宜离子液体，并进一步考察了三乙胺盐酸盐/AlCl₃自身物质的量配比、反应温度和反应时间等条件对其催化性能的影响；同时探讨了离子液体在反应中真正起催化作用的活性组分是[Al₂Cl₇]^-。离子液体一步法催化合成4-乙酰胺基苯亚磺酸最适宜反应条件为：反应温度为90℃、反应时间为4 h、n（三乙胺盐酸盐）：n（AlCl₃）=0.55：1.00（记为0.55Et₃NHCl/AlCl₃）。在最适宜反应条件下，液相收率达到89.55%。通过IR、LC-MS和¹H NMR等分析对产物结构进行了鉴定。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	梁晓通
	李国兵
	沈京华
	张旭斌

关键词： 4-乙酰氨基苯亚磺酸；亚磺化；离子液体

Abstract： Ionic liquids, as a new kind of green catalysts with excellent solvent performance and catalytic activity, have been widely used in various reactions. A new one-step synthesis process of 4-acetamidobenzenesulfinic acid using acetanilide and SO₂ has been developed in this article. Ionic liquid acts as both solvents and catalysts in the reaction. The one-step synthesis of 4-acetamidobenzenesulfinic acid from various ionic liquids are investigated. Triethylamine hydrochloride/AlCl₃ is selected as the optimum ionic liquid. The effects of the molar ratio of triethylamine hydrochloride/AlCl₃, reaction temperature and reaction time on its catalytic performance are further investigated. The real active component of ionic liquids in the reaction is[Al₂Cl₇]^-. The optimum reaction conditions for the synthesis of 4-acetamidobenzenesulfinic acid catalyzed by ionic liquids in one step are as follows:reaction temperature 90℃, reaction time 4 h, triethylamine hydrochloride/AlCl₃ molar ratio 0.55:1.00 (denoted as 0.55Et₃NHCl/AlCl₃). Under the optimum reaction conditions, the liquid yield reached 89.55%. The target product is analyzed by IR, LC-MS and ¹H NMR.

Keywords： 4-acetamidobenzenesulfinic acid； acetanilide； ionic liquid

Received 2019-06-25;

Fund:

Corresponding Authors: 李国兵,E-mail:lgbbox@tju.edu.cn。 Email: lgbbox@tju.edu.cn

About author: 梁晓通(1994-),男,硕士研究生,现从事化学反应工程方面的研究。

引用本文:

梁晓通, 李国兵, 沈京华, 张旭斌.离子液体一步法催化合成4-乙酰胺基苯亚磺酸[J]. 化学工业与工程, 2020,37(4): 7-14

Liang Xiaotong, Li Guobing, Shen Jinghua, Zhang Xubin.Catalytic Synthesis of 4-Acetamidobenzenesulfinic Acid by Ionic Liquids in One Step[J]. Chemcial Industry and Engineering, 2020,37(4): 7-14

[1] 吴珍. 4-氨基苯基-β-羟乙基砜硫酸酯的合成研究[D]. 辽宁大连:大连理工大学, 2008 Wu Zhen. Study on the synthesis of 4-aminophenyl-beta-hydroxyethyl sulfone sulfate[D]. Liaoning Dalian:Dalian University of Technology, 2008(in Chinese)
[2] 吴忠忠. 对氨基苯基-β-羟乙基砜硫酸酯的合成新工艺研究[D]. 成都:成都理工大学, 2009 Wu Zhongzhong. Study on the new synthetic technology of 2-(4-aminophenylsulfonyl)ethyl hydrogen sulfate[D]. Chengdu:Chengdu University of Technology, 2009(in Chinese)
[3] 田勇, 刘传玉, 胡永玲, 等. 对位酯的合成技术与生产现状[J]. 化学与黏合, 2011, 33(1):63-66 Tian Yong, Liu Chuanyu, Hu Yongling, et al. Synthesis technology and present situation of manufacture of p-aminophenyl-β-sulfatoethylsulfone[J]. Chemistry and Adhesion, 2011, 33(1):63-66(in Chinese)
[4] 冯雪, 张丽娜, 陈焕章. 对氨基苯基-β-羟乙基砜硫酸酯合成工艺研究进展[J]. 河北科技大学学报, 2017, 38(3):255-262 Feng Xue, Zhang Lina, Chen Huanzhang. Research progress in synthetic technology of p-aminophenyl-β-sulfatoethylsulfone[J]. Journal of Hebei University of Science and Technology, 2017, 38(3):255-262(in Chinese)
[5] 陈荣圻. 活性染料发现六十年回顾(四)[J]. 染料与染色, 2014, 51(5):26-43 Chen Rongqi. 60-Year review for the invention of reactive dye(Ⅳ)[J]. Dyestuffs and Coloration, 2014, 51(5):26-43(in Chinese)
[6] Hossen M, Imran. Study on color strength of different reactive dyes[J]. Journal of Textile Science & Engineering, 2017, doi:10.4172/2165-8064.1000293
[7] 陈焕章, 冯雪, 张悦, 等. 4-乙酰氨基苯亚磺酸合成新工艺研究[J]. 现代化工, 2018, 38(3):187-191 Chen Huanzhang, Feng Xue, Zhang Yue, et al. Study on new process for synthesis of para-acetamidobenzenesulfinic acid[J]. Modern Chemical Industry, 2018, 38(3):187-191(in Chinese)
[8] 邹晶, 魏顺安, 谭世语, 等. 合成对乙酰氨基苯磺酰氯的新工艺[J]. 世界科技研究与发展, 2012, 34(2):226-228, 246 Zou Jing, Wei Shun'an, Tan Shiyu, et al. New technology of synthesizing para-benezene chloride acetyl[J]. World Sci-Tech Research and Development, 2012, 34(2):226-228, 246(in Chinese)
[9] 杨贺勤, 刘志成, 谢在库. 绿色化工技术研究新进展[J]. 化工进展, 2016, 35(6):1575-1586 Yang Heqin, Liu Zhicheng, Xie Zaiku. Review of recent development of green chemical technologies[J]. Chemical Industry and Engineering Progress, 2016, 35(6):1575-1586(in Chinese)
[10] Truce W E, Murphy A M. The preparation of sulfinic acids[J]. Chemical Reviews, 1951, 48(1):69-124
[11] Hann R M. Some derivatives of p-fluorophenylsulfinic acid1[J]. Journal of the American Chemical Society, 1935, 57(11):2166-2167
[12] Wang T, Wang F, Shen J, et al. Convenient method for preparation of aryl sulfinates from arenes and DABSO as the SO₂ surrogates[J]. Tetrahedron Letters, 2018, 59(13):1183-1187
[13] Shen J, Wang F, Wang T, et al. Sulfination of acetanilide using liquid coordination complexes as dual catalyst and solvent[J]. Molecular Catalysis, 2019, 462:56-60
[14] Petkovic M, Seddon K R, Rebelo L P N, et al. Ionic liquids:A pathway to environmental acceptability[J]. Chemical Society Reviews, 2011, 40(3):1383-1403
[15] Welton T. Room-Temperature ionic liquids. Solvents for synthesis and catalysis[J]. Chemical Reviews, 1999, 99(8):2071-2084
[16] Hallett J P, Welton T. Room-Temperature ionic liquids:Solvents for synthesis and catalysis[J]. Chemical Reviews, 2011, 111(5):3508-3576
[17] Cai X, Cui S, Qu L, et al. Alkylation of benzene and dichloromethane to diphenylmethane with acidic ionic liquids[J]. Catalysis Communications, 2008, 9(6):1173-1177
[18] Hu P, Zhang R, Meng X, et al. Structural and spectroscopic characterizations of amide-AlCl₃-based ionic liquid analogues[J]. Inorganic Chemistry, 2016, 55(5):2374-2380
[19] Knoevenagel E, Kenner J. Zur darstellung von sulfinsäuren[J]. Berichte Der Deutschen Chemischen Gesellschaft, 1908, 41(3):3315-3322
[20] Csihony S, Mehdi H, Horváth I. In situ infrared spectroscopic studies of the Friedel-Crafts acetylation of benzene in ionic liquids using AlCl₃ and FeCl₃[J]. Green Chemistry, 2001, 3(6):307-309
[21] Yuan X, Min C, Dai Q, et al. Friedel-Crafts acylation of anthracene with oxalyl chloride catalyzed by ionic liquid of[bmim]Cl/AlCl₃[J]. Chemical Engineering Journal, 2009, 146(2):266-269
[22] Boon J A, Levisky J A, Pflug J L, et al. Friedel-Crafts reactions in ambient-temperature molten salts[J]. The Journal of Organic Chemistry, 1986, 51(4):480-483