Synthesis of 4,13-Dithio Benzene and-18-Crown-6 and Its Selective Extractability on Ag+†

doi:10.7503/cjcu20170760

Abstract

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

CLC Number:

O621

TrendMD:

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 $g + †$ [J]. Chem. J. Chinese Universities, 2018, 39(6): 1191.

Figures/Tables 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

References 21

[1]	Hou S. B., Wang X., Cui J. Y., Yang X. Y., Jia H., Lin H., Precious Metal, 2014, S1, 12—14
	(侯绍彬, 王兴, 崔家友, 杨晓宇, 贾辉, 林浩. 贵金属, 2014, S1, 12—14)
[2]	Condomitti U., Silveira A. T., Condomitti G. W., Toma S. H., Araki K., Toma H. E., Hydrometallurgy, 2014, 8, 241—245
[3]	Han Z., Wei J., Zhao M., Hu J., Hydrometallurgy, 2008, 92, 148—151
[4]	Virolainen S., Tyster M., Haapalainen M., Sainio T., Hydrometallurgy, 2015, 152, 100—106
[5]	Zheng T., Han Y., Liu N., Chem. Res. Chinese Universities, 2016, 32(2), 184—187
[6]	Gao Z. Z., Yang L. G., Bai D., Chen L. X., Tao Z., Xiao X., Chem. J. Chinese Universities, 2017, 38(2), 212—216
	(高中政, 杨立国, 白东, 陈丽霞, 陶朱, 肖昕. 高等学校化学学报, 2017, 38(2), 212—216)
[7]	Zhang Z. Y., Chen H. W., Yu H. L., Yang X., Liang Z. W., J. Chin. Coal. Soc., 2017, 42(3), 768—774
	(张志远, 陈鸿伟, 于海龙, 杨新, 梁占伟. 煤炭学报, 2017, 42(3), 768—774)
[8]	Zhang H. Y., Yang Y. W., Liu Y.,Chem. J. Chinese Universities, 2000, 21(12), 1858—1860
	(张衡益, 杨英威, 刘育. 高等学校化学学报, 2000, 21(12), 1858—1860)
[9]	Duan Z. Y., Zhang H. Y., Liu Y., Acta Chim. Sinica, 2005, 63(8), 752—756
	(段中余, 张衡益, 刘育. 化学学报, 2005, 63(8), 752—756)
[10]	Pedersen C. J., J. Am. Chem. Soc., 1967, 89(26), 7017—7036
[11]	Jabbari A., Hasani M., Shamsipur M., J. Incl. Phenom. Molec. Rec. Chem., 1993, 15(4), 329—340
[12]	Mao H., Preparation of Dibenzo-18-crown-6 with Ultrasonic Synthesis and the Study of Its Potassium Ion Comple., Chengdu University of Technolog., Chengdu, 2008
	(毛晖. 超声波合成法制备二苯并-18-冠-6及其络合钾离子的研究, 成都: 成都理工大学, 2008)
[13]	Zhao W. J., Han S. Y., Liu E. M., Chem. Reagents, 2016, 28(5), 419—422
	(赵文静, 韩思远, 刘二美. 化学试剂, 2016, 28(5), 419—422)
[14]	Shu Y. Z., Wu J. Z., Deng W. Q., Qian H. J., J. Nuclear and Radiochemistry, 2017, 39(2), 151—157
	(束玉珍, 吴继宗, 邓惟勤, 钱红娟. 核化学与放射化学, 2017, 39(2), 151—157)
[15]	Golebiowski J., Lamare V., Ruiz-López M. F., J. Comput. Chem., 2002, 23(7), 724—731
[16]	Bajaj A. V., Poonia N. S., Coord. Chem. Rev., 1988, 87(49), 55—213
[17]	Peng Y. Q., Zhong H., Wang S., Zhang Q., Precious Metal, 2010, 31(1), 25—28
	(彭亚勤, 钟宏, 王帅, 张骞. 贵金属, 2010, 31(1), 25—28)
[18]	Han J. R., Zhang H. Y., Liu Y., Chem. J. Chinese Universities, 2005, 26(7), 1273—1276
	(韩建荣, 张衡益, 刘育. 高等学校化学学报, 2005, 26(7), 1273—1276)
[19]	Roper E. D., Talanov V. S., Butcher R. J., Supramol. Chem., 2008, 20(1/2), 217—229
[20]	Zhu T., Li Z., Solvent Extraction(Modern Separation Science and Technology Series), Chemical Industry Press, Beijing, 2008, 5—160
	(朱屯, 李洲. 溶剂萃取(现代分离科学与技术丛书), 北京: 化学工业出版社, 2008, 5—160)
[21]	Elwakeel K. Z., El-Sayed G. O., Darweesh R S., Int. J. Miner. Process, 2013, 120(5), 26—34