Electrochemical Synthesis of p-(β-Hydroxyethyl Sulfone) Aniline

Authors

Hao Guo, State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
Dong-Fang Niu, State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;Follow
Shuo-Zhen Hu, State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
Xin-Sheng Zhang, State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;Follow

Corresponding Author

Dong-Fang Niu(dfniu@ecust.edu.cn);
Xin-Sheng Zhang(xszhang@ecust.edu.cn)

Abstract

Para-ester is the most important intermediate for the preparation of ethylene sulfone type reactive dyes, which is usually used in the dyeing of cellulose fibers and synthetic fibers. P-(β-hydroxyethyl sulfone) aniline is an important intermediate for the synthesis of para-ester. In this paper, p-(β-hydroxyethyl sulfone) aniline was prepared by electrochemical method, having the advantages of simple process, mild reaction condition, less environmental pollution, easy reaction control and so on. It has strong development potential and industrial application prospect. The electrochemical reduction of p-nitrophenyl-β-hydroxyethyl sulfone on a lead plate electrode to prepare p-(β-hydroxyethyl sulfone) aniline was investigated, and the reaction was carried out in a two-cell cationic diaphragm electrolytic cell. The electrolysis parameters, such as current density, electricity quantity, temperature and concentration of sulfuric acid, were firstly optimized to achieve a desirable current efficiency and excellent yield of p-(β-Hydroxyethyl Sulfone) Aniline. Under the optimal conditions (current density: 300 A·m^-2, electricity quantity: 6.0 F·mol^-1, temperature: 70℃, sulfuric acid concentration: 1.5 mol·L^-1), the current efficiency and yield of the target reaction reached 92.7% and 93.0%, respectively. Moreover, the introduction of 2.0% mass fraction of titanium sulfate additive to the electrolyte could indirectly alleviate the problem of slow diffusion rate of raw material in the late stage of electrolysis, which, in turn, could further increase the yield to 97.8%. At the later stage of reaction, as the concentration of raw materials decreased, the difference between the concentration in the body solution and the electrode surface became smaller, and the diffusion rate of raw materials from the solution to the electrode surface became slower, resulting in a slow reduction reaction rate. After adding titanium sulfate, Ti⁴⁺ was mainly diffused to the electrode surface in the late reaction solution, and Ti³⁺ with strong reducing property was reduced on the electrode surface. The p-nitrophenyl-β-hydroxyethyl sulfone and hydroxylamine intermediate of low concentrations were reduced to p-(β-hydroxyethyl sulfone) aniline, thus, improved the yield and current efficiency. The reduction of p-nitrophenyl-β-hydroxyethyl sulfone to p-(β-hydroxyethyl sulfone) aniline was determined by cyclic voltammetry and high resolution liquid-mass spectrometry. First, p-nitrophenyl-β-hydroxyethyl sulfone was reduced to hydroxylamine intermediate by 4 electrons, and then hydroxylamine intermediate was further reduced to p-(β-hydroxyethyl sulfone) aniline by 2 electrons, and the whole reaction process was a 6-electron reaction. This method provides a new process route for the syntheses of p-(β-hydroxyethyl sulfone) aniline and para-ester, which is beneficial to solve for the problems of environmental pollution and high production cost in the current production process.

Graphical Abstract

Keywords

p-nitrophenyl-β-hydroxyethyl, p-(β-hydroxyethyl sulfone) aniline, electrochemical reduction, titanium sulfate

DOI Link

https://doi.org/10.13208/j.electrochem.201203

Publication Date

2021-10-28

Online Available Date

2021-01-25

Revised Date

2021-01-10

Received Date

2020-12-03

Recommended Citation

Hao Guo, Dong-Fang Niu, Shuo-Zhen Hu, Xin-Sheng Zhang. Electrochemical Synthesis of p-(β-Hydroxyethyl Sulfone) Aniline[J]. Journal of Electrochemistry, 2021 , 27(5): 498-507.
DOI: Para-ester is the most important intermediate for the preparation of ethylene sulfone type reactive dyes, which is usually used in the dyeing of cellulose fibers and synthetic fibers. P-(β-hydroxyethyl sulfone) aniline is an important intermediate for the synthesis of para-ester. In this paper, p-(β-hydroxyethyl sulfone) aniline was prepared by electrochemical method, having the advantages of simple process, mild reaction condition, less environmental pollution, easy reaction control and so on. It has strong development potential and industrial application prospect. The electrochemical reduction of p-nitrophenyl-β-hydroxyethyl sulfone on a lead plate electrode to prepare p-(β-hydroxyethyl sulfone) aniline was investigated, and the reaction was carried out in a two-cell cationic diaphragm electrolytic cell. The electrolysis parameters, such as current density, electricity quantity, temperature and concentration of sulfuric acid, were firstly optimized to achieve a desirable current efficiency and excellent yield of p-(β-Hydroxyethyl Sulfone) Aniline. Under the optimal conditions (current density: 300 A·m^-2, electricity quantity: 6.0 F·mol^-1, temperature: 70℃, sulfuric acid concentration: 1.5 mol·L^-1), the current efficiency and yield of the target reaction reached 92.7% and 93.0%, respectively. Moreover, the introduction of 2.0% mass fraction of titanium sulfate additive to the electrolyte could indirectly alleviate the problem of slow diffusion rate of raw material in the late stage of electrolysis, which, in turn, could further increase the yield to 97.8%. At the later stage of reaction, as the concentration of raw materials decreased, the difference between the concentration in the body solution and the electrode surface became smaller, and the diffusion rate of raw materials from the solution to the electrode surface became slower, resulting in a slow reduction reaction rate. After adding titanium sulfate, Ti⁴⁺ was mainly diffused to the electrode surface in the late reaction solution, and Ti³⁺ with strong reducing property was reduced on the electrode surface. The p-nitrophenyl-β-hydroxyethyl sulfone and hydroxylamine intermediate of low concentrations were reduced to p-(β-hydroxyethyl sulfone) aniline, thus, improved the yield and current efficiency. The reduction of p-nitrophenyl-β-hydroxyethyl sulfone to p-(β-hydroxyethyl sulfone) aniline was determined by cyclic voltammetry and high resolution liquid-mass spectrometry. First, p-nitrophenyl-β-hydroxyethyl sulfone was reduced to hydroxylamine intermediate by 4 electrons, and then hydroxylamine intermediate was further reduced to p-(β-hydroxyethyl sulfone) aniline by 2 electrons, and the whole reaction process was a 6-electron reaction. This method provides a new process route for the syntheses of p-(β-hydroxyethyl sulfone) aniline and para-ester, which is beneficial to solve for the problems of environmental pollution and high production cost in the current production process.

References

[1] Tian Y(田勇), Liu C Y(刘传玉), Hu Y L(胡永玲), Zhang X B(张秀斌), Li Q(黎庆). Synjournal technology and present situation of manufacture of p-aminophenyl-β-sulf-atoethylsulfone[J]. Chem. Adhesion(化学与黏合), 2011, 33(1): 63-66.

[2] Gan H L, Yi C H. Synjournal and characterization of a novel waterborne epoxy resin dye containing diazo sulfatoethylsulfone chromophore[J]. Fiber. Polym., 2015, 16(1): 17-22.
doi: 10.1007/s12221-015-0017-x URL

[3] Zhu Z H, Jiang L M. Studies on new reactive dyes having two vinyl sulfone groups. Part II: Kinetic studies of the condensation reaction between C.I. Reactive Red 120 and m- and p-(β-sulfatoethyl-sulfonyl) aniline[J]. Dyes Pigments, 1998, 36(4): 355-363.
doi: 10.1016/S0143-7208(97)00033-8 URL

[4] Shesterkina A A, Strekalova A A, Kustov L M. Selective liquid phase hydrogenation of aromatic nitro compounds in the presence of Fe-Cu nanoparticles[J]. Russ. J. Phys. Chem. A, 2020, 94(6): 1180-1183.
doi: 10.1134/S0036024420060217 URL

[5] Lee N R, Bikovtseva A A, Cortes C M, Gallou F, Lipshutz B H. Carbonyl iron powder: a reagent for nitro group reductions under aqueous micellar catalysis conditions[J]. Org. Lett., 2017, 19(24): 6518-6521.
doi: 10.1021/acs.orglett.7b03216 URL

[6] Zhu K J(朱孔杰), Li X Q(李秀琴), Zhuang W M(庄文明). Study on synjournal of 2-chloropyridine-4-amine[J]. Shandong Chem. Ind.(山东化工), 2016, 45(15): 13-14.

[7] Mironenko R M, Belskaya O B, Stepanova L N, Gulyaeva T I, Trenikhin M V, Likholobov V A. Palladium supported on carbon nanoglobules as a promising catalyst for selective hydrogenation of nitroarenes[J]. Catal. Lett., 2020, 150(3): 888-900.
doi: 10.1007/s10562-019-02974-6 URL

[8] Yang X F, Wang A Q, Qiao B T, Li J, Liu J Y, Zhang T. Single-atom catalysts: a new frontier in heterogeneous catalysis[J]. Acc. Chem. Res., 2013, 46(8): 1740-1748.
doi: 10.1021/ar300361m URL

[9] Jadbabaei N, Slobodjian R J, Shuai D M, Zhang H C. Catalytic reduction of 4-nitrophenol by palladium-resin composites[J]. Appl. Catal. A - Gen., 2017, 543: 209-217.
doi: 10.1016/j.apcata.2017.06.023 URL

[10] Lang L M, Pan Z R, Yan J. Ni-Au alloy nanoparticles as a high performance heterogeneous catalyst for hydrogenation of aromatic nitro compounds[J]. J. Alloy. Compd., 2019, 792: 286-290.
doi: 10.1016/j.jallcom.2019.03.323 URL

[11] Zhang J W, Lu G P, Cai C. Chemoselective transfer hydrogenation of nitroarenes by highly dispersed Ni-Co BMNPs[J]. Catal. Commun., 2016, 84: 25-29.
doi: 10.1016/j.catcom.2016.05.023 URL

[12] Kaslik J, Medrik I, Ranc V, Varma R S, Zboril R, Gawande M B. Synjournal of flower-like magnetite nano-assembly: application in the efficient reduction of nitroarenes[J]. Sci. Rep., 2017, 7: 11585.
doi: 10.1038/s41598-017-09477-7 URL

[13] Hauser J L, Amberchan G, Tso M, Manley R, Bustillo K, Cooper J, Golden J H, Singaram B, Oliver S R J. A mesoporous aluminosilicate nanoparticle-supported nickel-boron composite for the catalytic reduction of nitro-arenes[J]. ACS Appl. Nano Mater., 2019, 2(3): 1472-1483.
doi: 10.1021/acsanm.8b02351

[14] Nandi D, Siwal S, Choudhary M, Mallick K. Carbon nitride supported palladium nanoparticles: an active system for the reduction of aromatic nitro-compounds[J]. Appl. Catal. A - Gen., 2016, 523(5): 31-38.
doi: 10.1016/j.apcata.2016.04.004 URL

[15] Acelas M, Sierra A F, Sierra C A. Exploring the nitro group reduction in low-solubility oligo-phenylenevinylene systems: rapid synjournal of amino derivatives[J]. Sy-nthetic Commun., 2020, 50(9): 1335-1352.

[16] Xu Y, Lv X J, Chen Y, Fu W F. Highly selective reduction of nitroarenes to anilines catalyzed using MOF-derived hollow Co₃S₄ in water under ambient conditions[J]. Catal. Commun., 2017, 101: 31-35.
doi: 10.1016/j.catcom.2017.07.001 URL

[17] Kang C, Lee J, Silvester D S. Electroreduction of 2,4,6-trinitrotoluene in room temperature ionic liquids: evidence of an EC₂ mechanism[J]. J. Phys. Chem. C, 2016, 120(20): 10997-11005.
doi: 10.1021/acs.jpcc.6b03018 URL

[18] Raheem A A, Gopi S, Kathoresan M, Praveen C. Electropolymerization of thienyl tethered comonomers and application towards the electrocatalytic reduction of nitrobenzene[J]. RSC Adv., 2019, 9(4): 1895-1902.
doi: 10.1039/C8RA08603F URL

[19] Viswanathan P, Ramaraj R. Polyelectrolyte assisted synjournal and enhanced catalysis of silver nanoparticles: electrocatalytic reduction of hydrogen peroxide and cataly-tic reduction of 4-nitroaniline[J]. J. Mol. Catal. A - Chem., 2016, 424: 128-134.
doi: 10.1016/j.molcata.2016.08.001 URL

[20] Zhang P L, Sheng X, Chen X Y, Fang Z Y, Jiang J, Wang M, Li F S, Fan L Z, Ren Y S, Zhang B B, Timmer B J J, Ahlquist M S G, Sun L C. Paired electrocatalytic oxygenation and hydrogenation of organic substrates with water as the oxygen and hydrogen source[J]. Angew. Chem. Int. Ed., 2019, 58(27): 9155-9159.
doi: 10.1002/anie.v58.27 URL

[21] Hu Y L(胡永玲), Han D W(韩大维), Tian Y(田勇). P-aminophenyl-beta-hydroxyethyl sulfone preparation method: CN, 200810137180: A[P]. 2009-02-11.

[22] Richard W, Evrard D, Gros P. New insight into 4-nitroben-zene diazonium reduction process: evidence for a grafting step distinct from NO₂ electrochemical reactivity[J]. J. Electroanal. Chem., 2012, 685: 109-115.
doi: 10.1016/j.jelechem.2012.09.014 URL

[23] Niu D F(钮东方), Zhang H H(张辉辉), Zhang X S(张新胜). Electrosynjournal of 2,6-dichloro-4-aminophenol on a three-dimensional copper mesh cathode[J]. Fine Chem.(精细化工), 2015, 32(4): 447-450+456.

[24] Lemaire A, Hapiot P, Geneste F. Ti-catalyst biomimetic sensor for the detection of nitroaromatic pollutants[J]. Anal. Chem., 2019, 91(4): 2797-2804.
doi: 10.1021/acs.analchem.8b04671 pmid: 30672286

[25] Ravi M D, Sivasankarapillai V N, Anantharaman P N. Ele-ctroreduction of m-nitroaniline to m-phenylene diamine using Ti³⁺/Ti⁴⁺ redox system[J]. B. Electrochem., 1988, 4(3): 241-244.

[26] Fan J H(樊金红), Xu W Y(徐文英), Gao T Y(高廷耀). Electrochemical reduction characteristics of nitrobenzene at the copper electrode[J]. J. Electrochem.(电化学), 2005, 11(3): 341-345.

[27] Ma C A(马淳安), Zheng Q A(郑勤安), Zhou Q(周强), Xu Y H(徐颖华). Electrosynjournal of p-aminobenzenear-senic acid[J]. J. Electrochem.(电化学), 2010, 16(1): 70-73.

[28] Ma C A(马淳安), Ge X F(葛小芳), Zhu Y H(朱英红), et al. Study on electroreduction performance and mechanism of substituted aryl nitrobenzene[J]. J. Chem. Eng. Chin. Univ.(高校化学工程学报), 2006, 20(5): 728-733.

[29] Liu Y Z, Zhang A J, Wang H, Zhang L, Lu J X. Synjournal of 1,5-diaminonaphthalene by electrochemical reduction[J]. Chinese J. Org. Chem., 2008, 28(5): 804-809.