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

doi:10.7503/cjcu20150185

Abstract

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

CLC Number:

O621.21

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2015, 36(8): 1530.

Figures/Tables 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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