大环硫杂冠醚的合成及对Ag(Ⅰ)和Tl(Ⅰ)的选择性萃取

doi:10.7503/cjcu20190186

摘要/Abstract

摘要：

基于冠醚配位化学和软硬酸碱理论, 设计合成了2种预期对Ag(Ⅰ)和Tl(Ⅰ)具有较强配位能力的超大环冠醚10,19-二硫杂苯并30-冠-10(DHB30C10)和10,13,17,20-四硫杂苯并31-冠-10(THB31C10). 采用溶剂萃取法考察了2种冠醚对Ag(Ⅰ)和Tl(Ⅰ)的选择萃取性能. 结果表明, 在单一体系中, DHB30C10和THB31C10对Ag(Ⅰ)的络合常数分别为9.76和13.40, 对Tl(Ⅰ)的络合常数分别为4.769和4.325. 在多元体系中, 2种冠醚对Ag(Ⅰ)均具有较强选择性, 其中DHB30C10对Cu(Ⅱ)和Ni(Ⅱ)的分离系数可达194.68和142.44, THB31C10对Cu(Ⅱ)和Ni(Ⅱ)的分离系数可达172.81和268.53, 但对Tl(Ⅰ)几乎不具有选择性. 并探讨分析了DHB30C10与THB31C10对Ag(Ⅰ)和Tl(Ⅰ)的萃取机理.

关键词: 分子设计, 硫杂冠醚, 选择性识别, 萃取, 结构模拟

Abstract:

Based on the crown ether coordination chemistry and soft and hard acid-base(HSAB) theory, two macrocyclic crown ethers of 10,19-dithiabenzo-30-crown-10(DHB30C10) and 10,13,17,20-tetrathiabenzo-3-crown-10(THB31C10) were synthesized, which potentially have excellent complex ability with Ag(Ⅰ) and Tl(Ⅰ). The extraction abilities of the two crown ethers for Ag(Ⅰ) and Tl(Ⅰ) were investigated. The results showed that in the single system, the complexing constants of DHB30C10 and THB31C10 for Ag(Ⅰ) were 9.76 and 13.40, and for Tl(Ⅰ) were 4.769 and 4.35, respectively. In the multi-system, the two crown ethers both exhibit strong selectivity to Ag(Ⅰ). The separation coefficients of DHB30C10 for Ag(Ⅰ) to Cu(Ⅱ) and Ni(Ⅱ) were 194.68 and 142.44, and the corresponding data of THB31C10 were 172.81 and 268.53, respectively. However, the two crown ethers showed poor selectivity to Tl(Ⅰ). The extraction mechanisms of DHB30C10 and THB31C10 for Ag(Ⅰ) and Tl(Ⅰ) were analyzed.

Key words: Molecular design, Thiacrown ether, Selective recognition, Extraction, Structural simulation

中图分类号:

O621
O643

TrendMD:

程衔锟, 侯雪, 田欢, 张梦龙, 魏昊, 赵卓. 大环硫杂冠醚的合成及对Ag(Ⅰ)和Tl(Ⅰ)的选择性萃取. 高等学校化学学报, 2019, 40(9): 1881.

CHENG Xiankun, HOU Xue, TIAN Huan, ZHANG Menglong, WEI Hao, ZHAO Zhuo. Synthesis of Macrocyclic Thiacrown Ethers and Their Selective Extraction for Ag(Ⅰ) and Tl(Ⅰ) ^†. Chem. J. Chinese Universities, 2019, 40(9): 1881.

图/表 7

Fig.1 Structures of 10,19-dithiabenzo-30-crown-10(A) and 10,13,17,20-tetrathiabenzo-31-crown-10(B)

Scheme 1 Synthetic routes of DHB30C10 and THB31C10

Fig.2 Change in the percent extraction of Ag(Ⅰ)(A)and Tl(Ⅰ)(B) with varying concentrations of the ligand in the organic phase

Table 1 Extraction efficiency of the crown ethers towards various ions under mulAg-system[Ag(Ⅰ)]*

Crown ether	Evaluation of extraction effect	Singleion system
Crown ether	Evaluation of extraction effect	Ag⁺	Cu²⁺		Pb²⁺		Zn²⁺		Ni²⁺		Ag⁺
DHB30C10	Extract ability(%)	65.29		0.80		12.16		3.71		1.11		61.09
	Separation coefficient			194.68		11.34		40.75		142.44
THB31C10	Extract ability(%)	93		3.62		11.83		5.32		2.36		86.65
	Separation coefficient			172.81		48.37		115.51		268.53

Table 2 Extraction efficiency of the crown ethers towards various ions under mulTl-system[Tl(Ⅰ)]*

Crown ether	Evaluation of extraction effect	Singleion system
Crown ether	Evaluation of extraction effect	Tl⁺	Cu²⁺		Pb²⁺		Zn²⁺		Ni²⁺		Tl⁺
DHB30C10	Extract ability(%)	16.83		10.80		16.40		3.91		15.64		6.54
	Separation coefficient			0.57		0.35		1.72		0.37
THB31C10	Extract ability(%)	15.06		8.48		5.46		8.07		2.62		6.6
	Separation coefficient			0.76		1.22		0.80		2.62

Fig.3 Optimized structures of DHB30C10(A) and its simulation complexes(B, C) (B) Ag(Ⅰ) complexes with DHB30C10; (C) Tl(Ⅰ) complexes with DHB30C10.

Fig.4 Optimized structure of THB31C10(A) and its simulation complexes(B, C) (B) Ag(Ⅰ) complexes with THB31C10; (C) Tl(Ⅰ) complexes with THB31C10.

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