Citation: ZHOU Shuang, DONG Yong-Ming, JIANG Heng, LI Fei, GONG Hong. β-Hydroxyethylation of Thiols Catalyzed by Alkali Metal Inorganic Acid Salts[J]. Chinese Journal of Inorganic Chemistry, ;2020, 36(4): 636-642. doi: 10.11862/CJIC.2020.080 shu

β-Hydroxyethylation of Thiols Catalyzed by Alkali Metal Inorganic Acid Salts

School of Chemical and Material Science, Liaoning Shihua University, Fushun, Liaoning 113001, China

Corresponding author: JIANG Heng, hjiang78@hotmail.com
Received Date: 10 July 2019
Revised Date: 22 December 2019

Figures(4)

For the β-hydroxyethylation of sulfur atoms in thiols, there should be a strong interaction between the -SH group and the methylene carbon of ethylene carbonate (EC). However, the nucleophilicity of -SH group is insufficient to interact with the methylene carbon of EC. Therefore, a catalyst should be required to activate -SH group. Under the conditions of atmospheric pressure, solvent-free and 120℃, 14 kinds of alkali metal mineral acid salts (MA, M=Li⁺, Na⁺ and K⁺) were investigated for the S-hydroxyethylation of n-octyl mercaptan with EC. When A^- of MA are the same, the ionic radius and polarizability of Li⁺, Na⁺ and K⁺ increase sequentially, the ability of MA to activate SH group also increase sequentially. The general rule is that the catalytic activity of the potassium salt is higher than that of the corresponding sodium salt, while the lithium salt has no catalytic activity. In various inorganic acid potassium salts, the catalytic activity of KA has a positive correlation with the pK_a of its corresponding conjugate acid HA. The catalytic activity of KA is lower when its conjugate acid HA is more acidic. In order to explore the universality of the mechanism of potassium salt catalytic activation of -SH, K₃PO₄ was used as catalyst to investigate the catalytic activity of β-hydroxyethylation of six different structures of thiols with EC at different reaction temperatures. Due to the acidic difference of mercaptan, the rule is that the stronger the acidity of the mercaptan, the higher the reactivity, and the easier the S-H bond is to dissociate. The advantages of the reaction are as follows:no solvent is involved, the molar ratio of mercaptan to EC is close to the theoretical amount, the selectivity of the product β-hydroxyethyl sulfide is >99%, no halogen containing reactant involved and therefore no halogen salt byproduct is formed in the final product.
- β-hydroxyethylation,
- alkali metal inorganic acid salts,
- aliphatic thiols,
- β-hydroxyethyl sulfides
1. [1]
  Liu L, Qiang J, Bai S, et al. Appl. Organomet. Chem., 2017, 31(11):e3810 doi: 10.1002/aoc.3810
2. [2]
  Feng M, Tang B H, Liang S, et al. Curr. Top. Med. Chem., 2016, 16(11):1200-1216 doi: 10.2174/1568026615666150915111741
3. [3]
  Qiao Z, Jiang X. Org. Biomol. Chem., 2017, 15(9):1942-1946 doi: 10.1039/C6OB02833K
4. [4]
  Sun S, He Z, Huang M, et al. Bioorg. Med. Chem., 2018, 26(9):2381-2391 doi: 10.1016/j.bmc.2018.03.039
5. [5]
  Carlson D A. Kirk-Othmer Encyclopedia of Chemical Technology:Vol.21 4th Ed. Kroschwitz J I, Howe-Grant M. Ed., New York:John Wiley & Sons, 2000:112-124
6. [6]
  WANG Ming, WANG Cui-Hong, JIANG Xue-Feng. Chinese J. Org. Chem., 2019, 39(8):2139-2147
7. [7]
  XIAO Cai-Qin, XU Xin-Bing, RU Li-Jun. Chinese Journal of Synthetic Chemistry, 2019, 27(4):316-327
8. [8]
  LIU Ji-Wei, GUAN Shu-Xia, GU Chang-Sheng. Chinese J. Inorg. Chem., 2018, 34(11):2081-2087 doi: 10.11862/CJIC.2018.254
9. [9]
  WANG Hong-Yan, WEI Xu-Ning. Chin. J. Appl. Chem., 2018, 35(10):1184-1189 doi: 10.11944/j.issn.1000-0518.2018.10.170406
10. [10]
  TANG Hai-Yan, ZHANG Ya-Dong, WANG Zhen-Xing. Speciality Petrochemicals, 2010, 27(3):23-26 doi: 10.3969/j.issn.1003-9384.2010.03.007
11. [11]
  Watts R F, Murakami Y, Richard K M, et al. US Patent, 6337309. 2002-1-8.
12. [12]
  Lachut F J. US Patent, 6432884. 2002-8-13.
13. [13]
  Veierov D. US Patent, 6001874. 1999-12-14.
14. [14]
  Imenez D, Janssen G, Long D, et al. US Patent, 9295250. 2016-03-29.
15. [15]
  Byers R E. J. Tree Fruit Prod., 1999, 2(2):59-78 doi: 10.1300/J072v02n02_06
16. [16]
  Klimpel R R, Hansen R D, Strojny E J. US Patent, 4735711. 1988-4-5.
17. [17]
  Shaw J E. US Patent, 5283368. 1994-2-1.
18. [18]
  Lissel M, Schmidt S, Neumann B. Synthesis, 1986, 17(43):382-383
19. [19]
  Carlson W W. US Patent, 2448767. 1948-09-07.
20. [20]
  Upare P P, Kinage A K, Shingote S K, et al. Green Chem. Lett. Rev., 2012, 5(1):19-26
21. [21]
  Wang P, Fei Y, Long Y, et al. J. CO₂ Util., 2018, 28:403-407 doi: 10.1016/j.jcou.2018.10.020
22. [22]
  Zhang Q, Yuan H Y, Fukaya N, et al. ACS Sustainable Chem. Eng., 2018, 6(5):6675-6681 doi: 10.1021/acssuschemeng.8b00449
23. [23]
  Zheng T, Wu Z, Xie Q, et al. J. Am. Oil Chem. Soc., 2018, 95(1):79-88 doi: 10.1002/aocs.12023
24. [24]
  Sankar M, Nair C M, Murty K, et al. Appl. Catal. A, 2006, 312:108-114 doi: 10.1016/j.apcata.2006.06.034
25. [25]
  Busca G. Ind. Eng. Chem. Res., 2009, 48(14):6486-6511 doi: 10.1021/ie801878d
26. [26]
  Speight J G. Lange's Handbook of Chemistry. 6th Ed. New York:McGraw-Hill, 2005:330-330
27. [27]
  Marino T, Russo N, Toscano M. J. Phys. Chem. B, 2003, 107(11):2588-2594 doi: 10.1021/jp027063j
28. [28]
  Ho T L. Chem. Rev., 1975, 75(1):1-20 doi: 10.1021/cr60293a001
29. [29]
  Lian P, Johnston R C, Parks J M, et al. J. Phys. Chem. A, 2018, 122(17):4366-4374 doi: 10.1021/acs.jpca.8b01751
30. [30]
  Zheng Y, Zheng W, Zhu D, et al. New J. Chem., 2019, 43(13):5239-5254 doi: 10.1039/C8NJ06259E
31. [31]
  Patai S. The Chemistry of the Thiol Group. London:John Wlley & Sons, 1974:396-398
32. [32]
  Hunter N E, Seybold P G. Mol. Phys., 2014, 112(3/4):340-348
33. [33]
  Tundo P, Rossi L, Loris A. J. Org. Chem., 2005, 70(6):2219-2224 doi: 10.1021/jo048532b
1. [1]
  Tiantian MA , Sumei LI , Chengyu ZHANG , Lu XU , Yiyan BAI , Yunlong FU , Wenjuan JI , Haiying YANG . Methyl-functionalized Cd-based metal-organic framework for highly sensitive electrochemical sensing of dopamine. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 725-735. doi: 10.11862/CJIC.20230351
2. [2]
  Zhengyu Zhou , Huiqin Yao , Youlin Wu , Teng Li , Noritatsu Tsubaki , Zhiliang Jin . Synergistic Effect of Cu-Graphdiyne/Transition Bimetallic Tungstate Formed S-Scheme Heterojunction for Enhanced Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(10): 2312010-. doi: 10.3866/PKU.WHXB202312010
3. [3]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
4. [4]
  Yan LIU , Jiaxin GUO , Song YANG , Shixian XU , Yanyan YANG , Zhongliang YU , Xiaogang HAO . Exclusionary recovery of phosphate anions with low concentration from wastewater using a CoNi-layered double hydroxide/graphene electronically controlled separation film. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1775-1783. doi: 10.11862/CJIC.20240043
5. [5]
  Ruiqing LIU , Wenxiu LIU , Kun XIE , Yiran LIU , Hui CHENG , Xiaoyu WANG , Chenxu TIAN , Xiujing LIN , Xiaomiao FENG . Three-dimensional porous titanium nitride as a highly efficient sulfur host. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 867-876. doi: 10.11862/CJIC.20230441
6. [6]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
7. [7]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
8. [8]
  Zeyuan WANG , Songzhi ZHENG , Hao LI , Jingbo WENG , Wei WANG , Yang WANG , Weihai SUN . Effect of I₂ interface modification engineering on the performance of all-inorganic CsPbBr₃ perovskite solar cells. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1290-1300. doi: 10.11862/CJIC.20240021
9. [9]
  Cheng PENG , Jianwei WEI , Yating CHEN , Nan HU , Hui ZENG . First principles investigation about interference effects of electronic and optical properties of inorganic and lead-free perovskite Cs₃Bi₂X₉ (X=Cl, Br, I). Chinese Journal of Inorganic Chemistry, 2024, 40(3): 555-560. doi: 10.11862/CJIC.20230282
10. [10]
  Guimin ZHANG , Wenjuan MA , Wenqiang DING , Zhengyi FU . Synthesis and catalytic properties of hollow AgPd bimetallic nanospheres. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 963-971. doi: 10.11862/CJIC.20230293
11. [11]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
12. [12]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
13. [13]
  Endong YANG , Haoze TIAN , Ke ZHANG , Yongbing LOU . Efficient oxygen evolution reaction of CuCo₂O₄/NiFe-layered bimetallic hydroxide core-shell nanoflower sphere arrays. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 930-940. doi: 10.11862/CJIC.20230369
14. [14]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
15. [15]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
16. [16]
  Qiuyang LUO , Xiaoning TANG , Shu XIA , Junnan LIU , Xingfu YANG , Jie LEI . Application of a densely hydrophobic copper metal layer in-situ prepared with organic solvents for protecting zinc anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1243-1253. doi: 10.11862/CJIC.20240110
17. [17]
  Jing SU , Bingrong LI , Yiyan BAI , Wenjuan JI , Haiying YANG , Zhefeng Fan . Highly sensitive electrochemical dopamine sensor based on a highly stable In-based metal-organic framework with amino-enriched pores. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1337-1346. doi: 10.11862/CJIC.20230414
18. [18]
  Youlin SI , Shuquan SUN , Junsong YANG , Zijun BIE , Yan CHEN , Li LUO . Synthesis and adsorption properties of Zn(Ⅱ) metal-organic framework based on 3, 3', 5, 5'-tetraimidazolyl biphenyl ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1755-1762. doi: 10.11862/CJIC.20240061

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(417)
HTML views(111)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142