Abstract: Mercaptan compounds are widely used as organic synthesis intermediates and fine chemicals in the fields of medicine, pesticides, electrochemistry, and organic synthesis. In China, mercaptan are in short supply and depend on import, as well as many mercaptan synthetic technology are immaturity, such as methyl mercaptan, t-butyl mercaptan 2-mercaptobenzothiazole. Therefore, the research of mercaptan synthesis is very important. Traditional mercaptan synthesis technique and methods have many defects, such as three wastes, long process, low yield; and sulfur source is single, mainly chemically active thiourea; in addition, many synthetic technique and methods don’t have universal applicability. The rise of ca-talytic science and the improvement of fine organic synthesis methods and theories provide a theoretical basis for solving these problems. With γ-Al2O3 as the carrier, transition metal oxides doped with alkali metal salt greatly increased the yield of mercaptan from hydrogen sulfide and alcohol synthesis technique; the birth of phase transfer catalyst reduced the energy consumption and production cost of halogenated hydrocarbon synthesis mercaptan technique; the discovery of many sulfur reagents and sulfur transfer reagents have broken through technical bottlenecks of many high value-added mercaptan synthesis, which has led to a large number of synthetic technique and methods have wide application range, good functional group orientation selectivity and high mercaptan yield, such as catalytic coupling, P2S5 mediated reactions. This article reviews the new developments of mercaptan synthesis in recent years. The reaction for synthesizing mercaptans is classified according to the reaction substrate and the sulfur source. Each technique is elaborated from the following aspects: the technique conditions, the catalytic system, the catalytic mechanism, and the final yield of the mercaptan. These technique such as alcohol synthesis, halogenated hydrocarbons synthesis, and syngas synthesis all using H2S as the sulfur source are highlighted. The advantages and disadvantages of each synthesis technique are analyzed. Finally, it points out that the optimization of catalytic systems and the widening of application scope of the va-rious techniquees are the main focus and the difficulty. The synthesis of mercaptans using industrial waste gas H2S and low value-added sulfur-containing compounds such as thioethers and disulfides as sulfur sources is an immportant research direction in the future.
1Pashigreva A V, Kondratieva E, Bermejo-Deval R, et al. Journal of Catalysis, 2017, 345, 308. 2 Lamonier C, Lamonier J F, Aellach B, et al. Catalysis Today, 2011, 164(1), 124. 3 Tian Y, Hu Y L, Mu C Y, et al. Chemical Engineer, 2010(4), 62(in Chinese). 田勇, 胡永玲, 穆传义, 等.化学工程师, 2010(4), 62. 4 Sheepwash E E, Rowntree P A, Schwan A L. Journal of Labelled Compounds & Radiopharmaceuticals, 2008, 51(12), 391. 5 Baltrusaitis J, Bucˇko T, Michaels W, et al. Applied Catalysis B Environmental, 2016, 187, 195. 6 Xiao G, Ma C, Xing D, et al. Organic Letters, 2016, 18(23), 6086. 7 Yatam S, Gundla R, Jadav S S, et al. Journal of Molecular Structure, 2018, 1159, 193. 8 Hamid A M A, Shehta W. Journal of the Iranian Chemical Society, 2018, 15(12), 2771. 9 Mioc M, Avram S, Bercean V, et al. Frontiers in Chemistry, DOI: 10.3389/fchem.2018.00373. 10 Shao Y D, Wang X H, Zhang M J, et al. Journal of Hainan Normal University (Natural Science), 2015 (1), 52(in Chinese). 邵艳东, 王向辉, 张美娟, 等. 海南师范大学学报(自然科学版), 2015 (1), 52. 11 Ziolek M, Kujawa J, Saur O, et al. Journal of Physical Chemistry, 1993, 97(38), 9761. 12 Bermejodeval R, Walter R M H, Gutiérrez O Y, et al. Catalysis Science & Technology, 2017, 7(19), 4437. 13 Zhang Y, Chen S, Wu M, et al. Catalysis Communications, 2012, 22(18), 48. 14 Mashkina A V, Khairulina L N. Kinetics & Catalysis, 2002, 43(5), 684. 15 Mashkina A V. Petroleum Chemistry, 2006, 46(1), 28. 16 Ziolek M, Czyzniewska J, Kujawa J, et al. Microporous & Mesoporous Materials,1998, 23(1-2), 45. 17 Calvino-Casilda V, Martin-Aranda R, Sobczak I, et al. Applied Catalysis A General, 2006, 303(1), 121. 18 Trejda M, Kujawa J, Ziolek M. Catalysis Letters, 2006, 108(3-4), 141. 19 Khaksar S A M, Zivdar M, Rahimi R. Journal of Natural Gas Science and Engineering, 2019, 61, 97. 20 Bandgar B P, Sadavarte V S. Synlett, 2000, 6, 908. 21 Wang W, Li Y, Zhang X, et al. Catalysis Communications, 2015, 69(7), 104. 22 Schoenauer S, Schieberle P. Journal of Agricultural and Food Chemistry, 2016, 64(19), 3849. 23 Schoenauer S, Schieberle P. Journal of Agricultural and Food Chemistry, 2018, 66(16), 4189. 24 Schoenauer S, Buergy A, Kreissl J, et al. Journal of Agricultural and Food Chemistry, 2019, 67(9), 2598. 25 Jha P, Mondal U, Gogoi D, et al. Journal of Molecular Catalysis A Chemical, 2016, 418-419, 30. 26 Maity S K, Pradhan N C, Patwardhan A V. Journal of Molecular Catalysis A Chemical, 2006, 250(1-2), 114. 27 Maity S K, Sen S, Pradhan N C. Chemical Engineering Science, 2009, 64(21), 4365. 28 Sen S, Pradhan N C, Patwardhan A V. Asia-Pacific Journal of Chemical Engineering, 2011, 6(2), 257. 29 Xu H. Liaoning Chemical Industry, 2007, 36(9), 589(in Chinese). 许汉. 辽宁化工, 2007, 36(9), 589. 30 Zhang Y D, Pan K L, Liang Z Y. Journal of Zhengzhou University (Engineering Science), 2012, 33(2), 44(in Chinese). 章亚东, 潘开林, 梁政勇. 郑州大学学报(工学版), 2012, 33(2), 44. 31 Li H, Guo F, Zhao L, et al. Chemical Reagents, 2009, 31(3), 221(in Chinese). 李华, 郭峰, 赵蕾, 等. 化学试剂, 2009, 31(3), 221. 32 Xing J W, Zhang Y D, Wang Z X. Chemical Industry and Engineering Progress, 2010, 29(1), 140(in Chinese). 邢军伟, 章亚东, 王振兴. 化工进展, 2010, 29(1), 140. 33 Liang Z Y, Zhang Y D, Zhang J. Journal of Chemical Engineering of Chinese Universities, 2011, 25(4), 627(in Chinese). 梁政勇, 章亚东, 张剑. 高校化学工程学报, 2011, 25(4), 627. 34 Taniguchi N. Synlett, 2005, 11, 1687. 35 Jiang Y, Qin Y, Xie S, et al. Organic Letters, 2009, 11(22), 5250. 36 Yi J, Fu Y, Xiao B, et al. Tetrahedron Letters, 2011, 52(2), 205. 37 Shu Q, Xie K, Qi J. Chinese Journal of Chemistry, 2010, 28(8), 1441. 38 Bandgar B P, Pawar S B. Journal of Chemical Research, 1999, 30(9), 212. 39 Hun J, Fox M A. Journal of Organic Chemistry, 1999, 64(13), 4959. 40 Mehdid M A, Djafri A, Roussel C, et al. Molecules, 2009, 14(11), 4634. 41 Rábai J, Menczinger B, Nemes A, et al. SynOpen, 2018, 2(1), 64. 42 Zhang B, Taylor S H, Hutchings G J. Catalysis Letters, 2003, 91(3-4), 181. 43 Wang Q, Chen A P, Xie C F, et al. Acta Chimica Sinica, 2004, 62(23), 2297(in Chinese). 王琪, 陈爱平, 谢春芳, 等. 化学学报, 2004, 62(23), 2297. 44 Chen A P, Hao Y J, Wang Q, et al. Petrochemical Technology, 2007, 36(10), 990(in Chinese). 陈爱平, 郝影娟, 王琪, 等. 石油化工, 2007, 36(10), 990. 45 Chen A, Wang Q, Li Q, et al. Journal of Molecular Catalysis A Chemical, 2008, 283(1), 69. 46 Cordova A, Blanchard P, Lancelot C, et al. ACS Catalysis, 2015, 5(5), 2966. 47 Cordova A, Blanchard P, Salembier H, et al. Catalysis Today, 2017, 292, 143. 48 Wang Q, Lu J, Chen Y Z, et al. Petrochemical Technology, 2014, 43(9), 1014(in Chinese). 王琪, 鲁骥, 陈亚中, 等. 石油化工, 2014, 43(9), 1014. 49 Huang S, He S, Deng L, et al. Procedia Engineering, 2015, 102, 684. 50 Georges F, Patrice B, Karine S, et al. U.S. patent application, US20180230093, 2018. 51 Gutiérrez O Y, Kaufmann C, Lercher J A. ACS Catalysis, 2011, 1(11), 1595. 52 Gutiérrez O Y, Kaufmann C, Hrabar A, et al. Journal of Catalysis, 2011, 280(2), 264. 53 Gutiérrez O Y, Zhong L, Zhu Y, et al. ChemCatChem, 2013, 5(11), 3249. 54 Gutiérrez O Y, Christooph K, Lercher J A. ChemCatChem, 2011, 3(9), 1480. 55 Wang W, Zhang X, Xia Z, et al. Catalysis Letters, 2015, 69(7), 1. 56 Barrault J, Boulinguiez M, Forquy C, et al. Applied Catalysis, 1988, 33(5), 309. 57 Tian Y, Xue L M, Li J L, et al. Chemistry and Adhesion, 2003 (2), 66(in Chinese). 田勇, 薛丽梅, 李嘉麟, 等. 化学与粘合, 2003 (2), 66. 58 Hu Y L, Zhang C R, Tian Y, et al. Chemical Industry and Engineering Progress, 2008, 27(5), 720(in Chinese). 胡永玲, 张春荣, 田勇, 等. 化工进展, 2008, 27(5), 720. 59 Su H L. World Sci-Tech R & D, 2007, 29(6), 11(in Chinese). 苏海兰. 世界科技研究与发展, 2007, 29(6), 11. 60 Zhang B H, Zhang Z K, Li L L, et al. Chemical Industry and Enginee-ring Progress, 2014, 33(2), 400(in Chinese). 张斌浩, 张泽凯, 李林林, 等. 化工进展, 2014, 33(2), 400. 61 Mashkina A V, Khairulina L N. Kinetics & Catalysis, 2002, 43(2), 261. 62 Chen S, Zhang Y, Wu M, et al. Applied Catalysis A General, 2012, 431-432(29), 151. 63 Chen S, Wang W, Zhang Y, et al. Journal of Molecular Catalysis A Chemical, 2012, 365, 60. 64 Maurya C, Gupta P. Synlett, 2017, 28(13), 1649. 65 Maurya C K, Mazumder A, Gupta P K. Beilstein Journal of Organic Chemistry, 2017, 13(1), 1184. 66 Liu X, Zhang S B, Dong Z B. European Journal of Organic Chemistry, 2018, 2018(39), 5406.