4,13-二硫杂苯并-18-冠-6的合成及对Ag+的选择性萃取

doi:10.7503/cjcu20170760

摘要/Abstract

摘要：

以邻苯二酚为原料, 经酯化、还原及亲核取代反应合成了4,13-二硫杂苯并-18-冠-6(DSB18C6); 采用核磁共振氢谱(¹H NMR)和X射线单晶衍射分析对化合物进行了结构表征; 采用溶剂萃取法考察了其银离子选择键合行为. 结果表明, 该类冠醚对Ag⁺表现出很高的萃取性能和选择性, 在多种离子(Cu²⁺, Pb²⁺, Zn²⁺, Ni²⁺)共存的复杂体系中, DSB18C6对Ag⁺的萃取效率高达95%.

关键词: 冠醚合成, 晶体结构, 选择性识别

Abstract:

4,13-Dithio benzene and-18-crown-6(DSB18C6) was synthesized by esterification, reduction and nucleophilic substitution reaction. The structural characterization was performed using proton nuclear magnetic resonance spectroscopy and X-ray single crystal diffraction, the selective binding to Ag⁺ was investigated by solvent extraction. The results show that DSB18C6 has a high selective extraction ability for Ag⁺ in the co-existence of Cu²⁺, Pb²⁺, Zn²⁺ and Ni²⁺ ions. The extraction efficiency of DSB18C6 to Ag⁺ was 95%.

Key words: Crown ether synthesis, Crystal structure, Selective identification

中图分类号:

O621

TrendMD:

田欢, 张梦龙, 王莉莎, 童碧海, 赵卓. 4,13-二硫杂苯并-18-冠-6的合成及对Ag⁺的选择性萃取. 高等学校化学学报, 2018, 39(6): 1191.

TIAN Huan, ZHANG Menglong, WANG Lisha, TONG Bihai, ZHAO Zhuo. Synthesis of 4,13-Dithio Benzene and-18-Crown-6 and Its Selective Extractability on A $g + †$ . Chem. J. Chinese Universities, 2018, 39(6): 1191.

图/表 7

Scheme 1 Synthetic routes of DSB18C6

Table 1 Crystal structure parameters of DSB18C6

Empirical formula	C₁₆H₂₄O₄S₂	D_c/(Mg·m^-3)	1.295
Formula weight	344.47	Absorption coefficient/mm^-1	0.315
T/K	296(2)	F(000)	736
λ/nm	0.071073	Crystal size	0.20 mm ×0.18 mm ×0.15 mm
Crystal system, space group	Monoclinic, P2₁/c	θ range/(°)	2.374—27.503
a/nm	1.7247(3)	h/k/l range	-22≤h≤22, -4≤k≤6, -26≤l≤23
b/nm	0.51063(9)	Reflections collected/unique	10330/3986 [R_int=0.0399]
c/nm	2.0157(4)	Absorption correction	Semi-empirical from equivalents
α/(°)	90	Data/restraints/parameters	3986/270/227
β/(°)	95.763(2)	Goodness of fit	0.988
γ/(°)	90	Final $R 1 a$ [I>2σ(I)]	0.0635
V/nm³	1.7662(5)	w $R 2 b$ (all data)	0.2264
Z	4

Table 1 Crystal structure parameters of DSB18C6

Empirical formula	C₁₆H₂₄O₄S₂	D_c/(Mg·m^-3)	1.295
Formula weight	344.47	Absorption coefficient/mm^-1	0.315
T/K	296(2)	F(000)	736
λ/nm	0.071073	Crystal size	0.20 mm ×0.18 mm ×0.15 mm
Crystal system, space group	Monoclinic, P2₁/c	θ range/(°)	2.374—27.503
a/nm	1.7247(3)	h/k/l range	-22≤h≤22, -4≤k≤6, -26≤l≤23
b/nm	0.51063(9)	Reflections collected/unique	10330/3986 [R_int=0.0399]
c/nm	2.0157(4)	Absorption correction	Semi-empirical from equivalents
α/(°)	90	Data/restraints/parameters	3986/270/227
β/(°)	95.763(2)	Goodness of fit	0.988
γ/(°)	90	Final $R 1 a$ [I>2σ(I)]	0.0635
V/nm³	1.7662(5)	w $R 2 b$ (all data)	0.2264
Z	4

Fig.1 Single crystal struture of DSB18C6

Table 2 Bond lengths(nm) of DSB18C6

S1—C8	0.1790(4)	C7—H7A	0.097	C15—H15A	0.097
S1—C9	0.1814(5)	C7—H7B	0.097	C15—H15B	0.097
S2—C14A	0.1767(8)	C8—H8A	0.097	C16—O2	0.1424(4)
S2—C15	0.1782(4)	C8—H8B	0.097	C16—H16A	0.097
S2—C14B	0.1920(10)	C9—C10	0.1467(6)	C16—H16B	0.097
C1—O1	0.1370(4)	C9—H9A	0.097	C14A—C13A	0.1504(15)
C1—C2	0.1377(4)	C9—H9B	0.097	C14A—H14A	0.097
C1—C6	0.1388(4)	C10—O3	0.1367(6)	C14A—H14B	0.097
C2—C3	0.1386(5)	C10—H10A	0.097	C13A—O4A	0.1547(15)
C2—H2	0.093	C10—H10B	0.097	C13A—H13A	0.097
C3—C4	0.1359(5)	C11—O3	0.1316(5)	C13A—H13B	0.097
C3—H3	0.093	C11—C12	0.1411(7)	C14B—C13B	0.1504(15)
C4—C5	0.1378(5)	C11—H11A	0.097	C14B—H14C	0.097
C4—H4	0.093	C11—H11B	0.097	C14B—H14D	0.097
C5—C6	0.1370(4)	C12—O4A	0.1282(10)	C13B—O4B	0.1504(14)
C5—H5	0.093	C12—O4B	0.1358(10)	C13B—H13C	0.097
C6—O2	0.1370(4)	C12—H12A	0.097	C13B—H13D	0.097
C7—O1	0.1427(4)	C12—H12B	0.097
C7—C8	0.1502(5)	C15—C16	0.1500(5)

Fig.2 Change in the percent extraction of Ag+ with varing concentrations of the ligand in organic phase(A) and plot of lgD vs. lg[4]org(B)

Table 3 Extractability of DSB18C6 towards various ions under binary-systems and multi-system*

System	Extractability of impurity ion(%)	Extractability of Ag⁺(%)	Separation factor, S
Cu²⁺+Ag⁺	2.2(Cu²⁺)	89	360
Pb²⁺+Ag⁺	6.5(Pb²⁺)	79	54
Zn²⁺+Ag⁺	0.03(Zn²⁺)	88	24437
Ni²⁺+Ag⁺	1.6(Ni²⁺)	91	622
Ag⁺+Cu²⁺+Pb²⁺+Zn²⁺+Ni²⁺	1.8(Cu²⁺)	95	1037
	0.8(Pb²⁺)		2356
	0.1(Zn²⁺)		18981
	0.7(Ni²⁺)		2695

Table 4 Extractability of DSB18C6 towards various ions under multi-system*

Ion	Cu²	Pb²⁺	Zn²⁺	Ni²⁺	Ag⁺
Extractability(%)	9.5	12.3	8.7	8.9	93.4

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