Synthesis of Macrocyclic Thiacrown Ethers and Their Selective Extraction for Ag(Ⅰ) and Tl(Ⅰ) †

doi:10.7503/cjcu20190186

Abstract

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

CLC Number:

O621
O643

TrendMD:

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) ^†[J]. Chem. J. Chinese Universities, 2019, 40(9): 1881.

Figures/Tables 7

References 33

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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

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

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

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