基于(R)-四氢噻唑-2-硫酮-4-甲酸盐的手性离子液体的合成及性质

doi:10.7503/cjcu20150185

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (8): 1530.doi: 10.7503/cjcu20150185

基于(R)-四氢噻唑-2-硫酮-4-甲酸盐的手性离子液体的合成及性质

王斌, 罗海燕, 张永红, 孙亚栋, 刘晨江()

新疆大学理化测试中心, 石油化工天然气精细化工教育部暨自治区重点实验室, 乌鲁木齐 830046

收稿日期:2015-03-09 出版日期:2015-08-10 发布日期:2015-06-30
作者简介:联系人简介: 刘晨江, 男, 博士, 教授, 主要从事有机合成方法学和功能杂环化合物的合成研究. E-mail:cjliuxj@126.com
基金资助:
国家自然科学基金(批准号: 21162025, 21262035)、新疆维吾尔自治区自然科学基金(批准号: 2012211A015)和新疆维吾尔自治区青年科技创新人才培养工程(批准号: 2014721004)资助

Synthesis and Properties of Chiral Ionic Liquid Based on (R)-Thiazolidine-2-thione-4-carboxylate^†

WANG Bin, LUO Haiyan, ZHANG Yonghong, SUN Yadong, LIU Chenjiang^*()

Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education & Xinjiang Uygur Autonomous Region, Physics and Chemistry Detecting Center, Xinjiang University, Urumqi 830046, China

Received:2015-03-09 Online:2015-08-10 Published:2015-06-30
Contact: LIU Chenjiang E-mail:cjliuxj@126.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21162025, 21262035), the Natural Science Foundation of Xinjiang Uygur Autonomous Region, China(No.2012211A015) and the Program for Outstanding Youth Science and Technology Innovation Talents Training in Xinjiang Uygur Autonomous Region, China(No.2014721004)

摘要/Abstract

摘要：

在室温下将(R)-四氢噻唑-2-硫酮-4-甲酸与氢氧化N-烷基吡啶或氢氧化1,3-二烷基苯并咪唑反应, 合成了6种新型手性离子液体; 其结构经核磁共振波谱(¹H NMR, ¹³C NMR)、红外光谱(IR)和电喷雾质谱(ESI-MS)表征; 测定了其旋光度和pH值, 并对其溶解性、电导率及热稳定性进行了研究. 结果表明, 合成的6种离子液体均为弱酸性, 室温下可溶解于极性较强的有机溶剂; 当其水溶液浓度为1×10^-3 mol/L时, 电导率随着温度的升高而增大; 在150和250 ℃有2个失重阶段, 可能是阴、阳离子分别失重的过程, 热稳定性较好.

关键词: (R)-四氢噻唑-2-硫酮-4-甲酸, 离子液体, 溶解性, 电导率, 热稳定性

Abstract:

A novel series of chiral ionic liquids from (R)-thiazolidine-2-thione-4-carboxylic acid and hydro-xide 1,3-dialkylbenzimidazole or hydroxide 1-alkyl pyridine was synthesized. The structures of the ionic liquids were confirmed by ¹H NMR,¹³C NMR, IR and ESI-MS. The optical rotation and pH value of the chiral ionic liquids were determined. Furthermore, the solubility, electrical conductivity and thermal stability of the ionic liquids were studied as well. The results revealed that the ionic liquids with weak acidity and good solubility in strongly polar organic solvents under room temperature. When the concentration of the ionic liquids in the aqueous solution was 1×10^-3 mol/L, increasing the conductivity was almost proportional to the temperature increases. The TGA results showed that the ionic liquids had two mass loss process under 150 and 250 ℃, caused by anion and cation, respectively.

Key words: (R)-Thiazolidine-2-thione-4-carboxylic acid, Chiral ionic liquid, Solubility, Conductivity, Thermal stability

中图分类号:

O621.21

TrendMD:

王斌, 罗海燕, 张永红, 孙亚栋, 刘晨江. 基于(R)-四氢噻唑-2-硫酮-4-甲酸盐的手性离子液体的合成及性质. 高等学校化学学报, 2015, 36(8): 1530.

WANG Bin, LUO Haiyan, ZHANG Yonghong, SUN Yadong, LIU Chenjiang. Synthesis and Properties of Chiral Ionic Liquid Based on (R)-Thiazolidine-2-thione-4-carboxylate^†. Chem. J. Chinese Universities, 2015, 36(8): 1530.

图/表 6

Scheme 1 Synthesis routes of chiral ionic liquids 3a—3f

Table 1 Specific rotation, ESI-MS and IR data for chiral ionic liquids 3a—3f

Ionic liquid	[α $] D 20$ /(°) (c=0.10, CH₃OH)	ESI-MS, m/z	IR(KBr), $ν ˙ max$ /cm^-1
3a	-67.00	108.1[M]⁺, 161.9[M]^-	3397, 3131, 2963, 1609, 1448, 1384, 1043, 973, 851, 647
3b	-71.00	136.1[M]⁺, 161.9[M]^-	3398, 3129, 2872, 1610, 1447, 1276, 1043, 972, 852, 647
3c	-55.00	192.2[M]⁺, 161.9[M]^-	3394, 3128, 2855, 1610, 1487, 1276, 1381, 973, 852, 683, 646
3d	-67.00	175.1[M]⁺, 161.9[M]^-	3393, 2935, 2872, 1610, 1564, 1489, 1213, 1086, 973, 849, 755, 645
3e	-60.00	203.1[M]⁺, 161.9[M]^-	3401, 2959, 2933, 1612, 1563, 1489, 1213, 1086, 972, 849, 751, 646
3f	-63.00	231.2[M]⁺, 161.9[M]^-	3403, 2961, 2935, 1614, 1565, 1492, 1216, 1088, 975, 851, 753, 648

Table 1 Specific rotation, ESI-MS and IR data for chiral ionic liquids 3a—3f

Ionic liquid	[α $] D 20$ /(°) (c=0.10, CH₃OH)	ESI-MS, m/z	IR(KBr), $ν ˙ max$ /cm^-1
3a	-67.00	108.1[M]⁺, 161.9[M]^-	3397, 3131, 2963, 1609, 1448, 1384, 1043, 973, 851, 647
3b	-71.00	136.1[M]⁺, 161.9[M]^-	3398, 3129, 2872, 1610, 1447, 1276, 1043, 972, 852, 647
3c	-55.00	192.2[M]⁺, 161.9[M]^-	3394, 3128, 2855, 1610, 1487, 1276, 1381, 973, 852, 683, 646
3d	-67.00	175.1[M]⁺, 161.9[M]^-	3393, 2935, 2872, 1610, 1564, 1489, 1213, 1086, 973, 849, 755, 645
3e	-60.00	203.1[M]⁺, 161.9[M]^-	3401, 2959, 2933, 1612, 1563, 1489, 1213, 1086, 972, 849, 751, 646
3f	-63.00	231.2[M]⁺, 161.9[M]^-	3403, 2961, 2935, 1614, 1565, 1492, 1216, 1088, 975, 851, 753, 648

Table 2 1H NMR and 13C NMR data for ionic liquids 3a—3f

Ionic liquid	¹H NMR(400 MHz, D₂O), δ	¹³C NMR(100 MHz, D₂O), δ
3a	1.65(t, J=7.2 Hz, 3H, CH₃), 3.66(m, 1H, SCH), 3.82(m, 1H, SCH), 4.66(m, 2H, CH₂), 4.81(m, 1H, NCH), 8.06—8.88(m, 5H, ArH)	15.8, 36.9, 57.5, 66.7, 128.4, 143.9, 144.1, 144.2, 145.6, 175.6, 201.6
3b	0.95(t, J=7.2 Hz, 3H, CH₃), 1.37(m, 2H, CH₂), 2.01(m, 2H, CH₂), 3.66(m, 1H, SCH), 3.92(m, 1H, SCH), 4.62(t, J=7.2 Hz, 2H, CH₂), 4.77(m, 1H, NCH), 8.05—8.86(m, 5H, ArH)	12.8, 18.9, 32.7, 37.0, 61.9, 66.9, 128.3, 144.3, 145.6, 175.8, 201.5
3c	0.84(t, J=7.2 Hz, 3H, CH₃), 1.2—1.4(m, 10H, 5CH₂), 2.02(m, 2H, CH₂), 3.66(m, 1H, SCH), 3.91(m, 1H, SCH), 4.61(m, 2H, CH₂), 4.81(m, 1H, NCH), 8.05—8.85(m, 5H, ArH)	13.5, 22.1, 25.3, 28.2, 28.3, 30.6, 31.1, 36.8, 62.2, 66.6, 128.3, 144.3, 145.6, 175.5, 201.6
3d	1.56(t, J=7.2 Hz, 6H, 2CH₃), 3.57(m, 1H, SCH), 3.84(m, 1H, SCH), 4.47(m, 4H, 2CH₂), 4.72(m, 1H, NCH), 7.63—9.26(m, 5H, ArH)	13.7, 37.0, 42.1, 66.9, 113.2, 126.8, 131.5, 139.9, 176.0, 201.4
3e	0.93(t, J=7.2 Hz, 3H, CH₃), 1.37(m, 2H, CH₂), 1.62(t, J=7.2 Hz, 3H, CH₃), 1.97(m, 2H, CH₂), 3.65(m, 1H, SCH), 3.90(m, 1H, SCH), 4.51(m, 4H, 2CH₂), 4.81(m, 1H, NCH), 7.68—9.31(m, 5H, ArH)	12.8, 13.7, 19.2, 30.6, 36.7, 42.5, 47.1, 66.4, 107.3, 113.3, 113.4, 126.9, 131.5, 131.7, 140.2, 175.3, 201.7
3f	0.93(t, J=7.2 Hz, 6H, CH₃), 1.35(m, 4H, 2CH₂), 1.97(m, 4H, 2CH₂), 3.64(m, H, SCH), 3.90(m, 1H, SCH), 4.50(t, J=7.2 Hz, 4H, 2CH₂), 4.80(m, 1H, NCH), 7.68—9.34(m, 5H, ArH)	12.8, 19.2, 30.5, 36.8, 42.5, 47.1, 66.6, 66.9, 107.3, 113.4, 126.9, 131.7, 140.6, 175.5, 201.6

Table 3 Solubility data of chiral ionic liquids 3a—3f*

Ionic liquid	Solubility
Ionic liquid	H₂O	DMSO	CH₃CN	DMF	CH₃OH	C₂H₅OH	CH₃COOC₂H₅	Et₂O	CH₂Cl₂	CHCl₃	Toluene
3a	m	m	m	m	m	pm	sm	im	im	im	im
3b	m	m	m	m	m	pm	sm	im	im	im	im
3c	m	m	m	m	pm	sm	im	im	im	im	im
3d	m	m	m	m	m	pm	sm	im	im	im	im
3e	m	m	m	m	m	pm	sm	im	im	im	im
3f	m	m	m	m	m	sm	sm	im	im	im	im

Fig.1 Relationship between temperature and conductivity of chiral ionic liquids 3a—3f

Fig.2 Thermal stability of the chiral ionic liquids 3a—3f

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基于(R)-四氢噻唑-2-硫酮-4-甲酸盐的手性离子液体的合成及性质

Synthesis and Properties of Chiral Ionic Liquid Based on (R)-Thiazolidine-2-thione-4-carboxylate^†

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基于(R)-四氢噻唑-2-硫酮-4-甲酸盐的手性离子液体的合成及性质

Synthesis and Properties of Chiral Ionic Liquid Based on (R)-Thiazolidine-2-thione-4-carboxylate†

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Synthesis and Properties of Chiral Ionic Liquid Based on (R)-Thiazolidine-2-thione-4-carboxylate^†