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
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