Supplementary material
Synthesis, Characterization and Evaluation of the Surface Active Properties of Novel Cationic Imidazolium Gemini Surfactants
Pankaj Patiala, ArifaShaheen*b and Ishtiaque Ahmad*a
aDepartment of Chemistry, Guru Nanak Dev University, Amritsar-143005, India
bUniversity College of Engineering, Punjabi University, Patiala-147002, India
E-mail address:,
Data
Synthesis of 1-(1-H-imidazol-1-yl-3-alkoxy)propane-2-ol (4-6): yellow oily liquid, Yield, 92.5%. The IR (KBr Pellet, cm-1):1126, 1564, 1572, 2849, 2918, and 3343. 1H NMR (δ ppm, CDCl3): ): 0.85- 0.87 (t, 3H, CH3), 1.23-1.25(s, chain 26H, (-CH2-)13, 24H, (-CH2-)12, 22H,(-CH2-)10), 1.55-1.58(m, 2H, CH2next to terminal methyl group), 3.33-3.36(d, OH), 3.40-3.42(t, 2H, OCH2), 3.93-3.95(d, 2H, CH2O), 3.97-4.04(d, 4H, NCH2), 4.12-4.17(m, 1H, CHOH), 6.93-6.95(d, α CH to +ve Nitrogen of imidazole),7.22-7.27(d, β CH to +ve Nitrogen of imidazole), 7.41-7.42(s, sandwiched proton between nitrogen of imidazole). 75MHz13C/DEPT NMR (δ ppm, CDCl3): 14.07-14.10(terminal methyl carbon), 22.64-22.67(CH3CH2), 25.82-26.10(OCH2CH2), 29.05-29.52 (chain methylene carbons),31.88-31.90 (CH3CH2CH2), 49.97-50.17 (NCH2), 69.21-69.58(secondary carbon attached to hydroxyl group), 71.47-71.57 (OCH2), 71.78-71.80 (CH2O), 119.75-119.52 (NCHCHN), 128.48-128.92((NCHCHN), 137.71-137.79 (sandwiched carbon between nitrogen of imidazole). ESI-MS positive ions at m/z (relative intensity %) 367.3 (100 %) {(M- 2Br)-1)}+, 368.3(40%) (M-2Br)+, 338.2 (100 %), {(M- 2Br)-1)}+, 339.3(52%) (M-2Br)+, 310.4 (100%) {(M- 2Br)-1)}+, 311.4 (40%) (M-2Br)+.
Synthesis of 1,2-bis(1(3-alkoxy-2-hydroxypropyl)-1-H-imidazol-3-ium)ethane bromide(7).White solid, Yield, 92.5%.Melting point 127 0C. The IR (KBr Pellet, cm-1): 1126, 1564, 1572, 2849, 2918 and 3343. 1H NMR (δ ppm, CDCl3): 0.88(t, 6H, 2XCH3), 1.27(br,s, chain 52H, 2X(-CH2-)13, 1.57(m, 4H, 2XCH2next to terminal methyl groups), 3.45(d, 2H, 2XOH), 3.47(t, 4H, 2XOCH2), 3.58(d, 4H, 2XCH2O), 3.60(d, 4H, 2XNCH2), 4.26(m, 2H, 2XCHOH), 4.52(t, 4H, ImCH2CH2Im), 7.28(s, 2H, 2XαCH to +ve Nitrogen of imidazole), 7.32(s, 2H, 2Xβ CH to +ve Nitrogen of imidazole), 9.32(s, 2H, sandwiched proton between nitrogen of imidazole). 75MHz13C/DEPT NMR (δ ppm, CDCl3): 14.45(terminal methyl carbons), 22.26(CH3CH2), 26.07(OCH2CH2), 29.22(chain methylene carbons), 29.68(CH3CH2CH2), 48.24(ImCH2CH2Im), 50.02(NCH2), 67.38 (secondary carbon attached to hydroxyl group), 71.00(OCH2), 71.87(CH2O), 103.54(NCHCHN), 123.21(sandwiched carbon between nitrogen of imidazole). ESI-MS positive ions at m/z (relative intensity %) 761.2 (100%) {(M- 2Br)-1)}+, 762.2(40%) (M-2Br)+.
Synthesis of 1,3-bis(1(3-alkoxy-2-hydroxypropyl)-1-H-imidazol-3-ium)propane bromide (8).White solid, Yield, 92.5%.Melting point 132 0C. The IR (KBr Pellet, cm-1): 1126, 1564, 1572, 2849, 2918 and 3343. 1H NMR (δ ppm, CDCl3): 0.88(t, 6H, 2XCH3), 1.26(br,s, chain 52H, 2X(-CH2-)13, 1.56(m, 4H, 2XCH2next to terminal methyl groups), 2.72(t,2H,ImCH2CH2CH2Im), 3.36(d, 2H, 2XOH), 3.45(t, 4H, 2XOCH2), 3.58(d, 4H, 2XCH2O), 4.22(d, 4H, 2XNCH2), 4.41(m, 2H, 2XCHOH), 4.61(t, 4H, ImCH2CH2CH2Im), 7.34(s, 2H, 2XαCH to +ve Nitrogen of imidazole), 7.97(s, 2H, 2Xβ CH to +ve Nitrogen of imidazole), 9.61(s, 2H, sandwiched proton between nitrogen of imidazole). 75MHz13C/DEPT NMR (δ ppm, CDCl3): 14.14(terminal methyl carbons), 22.63(CH3CH2), 26.13(OCH2CH2), 29.29(chain methylene carbons), 29.84(CH3CH2CH2), 31.86(ImCH2CH2CH2Im), 46.78(ImCH2CH2Im), 53.42(NCH2), 67.38(secondary carbon attached to hydroxyl group), 71.28(OCH2), 71.84(CH2O), 123.54(NCHCHN), 137.21(sandwiched carbon between nitrogen of imidazole). ESI-MS positive ions at m/z (relative intensity %) 773.8 (60 %) {(M- 2Br)-1)}+, 774.8(40%) (M-2Br)+.
Synthesis of 1,2-bis(1(3-alkoxy-2-hydroxypropyl)-1-H-imidazol-3-ium)ethane bromide (9).White solid, Yield, 92.5%.Melting point 117 0C. The IR (KBr Pellet, cm-1): 1126, 1564, 1572, 2849, 2918 and 3343. 1H NMR (δ ppm, CDCl3): 0.81(t, 6H, 2XCH3), 1.18(br,s, chain 44H, 2X(-CH2-)11, 1.49(m, 4H, 2XCH2next to terminal methyl groups), 3.29(d, 2H, 2XOH), 3.36(t, 4H, 2XOCH2), 3.51(d, 4H, 2XCH2O), 4.18(d, 4H, 2XNCH2), 4.20(m, 2H, 2XCHOH), 4.35(t, 4H, ImCH2CH2Im), 7.34(s, 2H, 2XαCH to +ve Nitrogen of imidazole), 7.97(s, 2H, 2Xβ CH to +ve Nitrogen of imidazole), 9.61(s, 2H, sandwiched proton between nitrogen of imidazole). 75MHz13C/DEPT NMR (δ ppm, CDCl3): 13.49(terminal methyl carbons), 22.45(CH3CH2), 26.23(OCH2CH2), 29.09(chain methylene carbons), 29.84(CH3CH2CH2), 46.78(ImCH2CH2Im), 53.42(NCH2), 67.38(secondary carbon attached to hydroxyl group), 71.28(OCH2), 71.84(CH2O), 123.54(NCHCHN), 137.21(sandwiched carbon between nitrogen of imidazole). ESI-MS positive ions at m/z (relative intensity %) 704.2 (60 %) {(M- 2Br)-1)}+, 705.2(40%) (M-2Br)+.
Synthesis of 1,2-bis(1(3-alkoxy-2-hydroxypropyl)-1-H-imidazol-3-ium)propane bromide (10).White solid, Yield, 92.5%.Melting point 123 0C. The IR (KBr Pellet, cm-1): 1126, 1564, 1572, 2849, 2918 and 3343. 1H NMR (δ ppm, CDCl3): 0.80(t, 6H, 2XCH3), 1.18(br,s, chain 44H, 2X(-CH2-)11, 1.47(m, 4H, 2XCH2next to terminal methyl groups), 2.72(t, 2H,ImCH2CH2CH2Im), 3.29(d, 2H, 2XOH), 3.36(t, 4H, 2XOCH2), 3.51(d, 4H, 2XCH2O), 4.15(d, 4H,2XNCH2), 4.18(m, 2H, 2XCHOH), 4.35(t, 4H, ImCH2CH2CH2Im), 7.34(s, 2H, 2XαCH to +ve Nitrogen of imidazole),7.97(s, 2H, 2Xβ CH to +ve Nitrogen of imidazole), 9.61(s, 2H, sandwiched proton between nitrogen of imidazole). 75MHz13C/DEPT NMR (δ ppm, CDCl3): 13.35(terminal methyl carbons), 22.63(CH3CH2), 26.13(OCH2CH2), 29.29(chain methylene carbons), 29.84(CH3CH2CH2), 31.86(ImCH2CH2CH2Im), 46.78(ImCH2CH2Im), 53.42(NCH2), 67.38(secondary carbon attached to hydroxyl group), 71.28(OCH2), 71.84(CH2O), 123.54(NCHCHN), 137.21(sandwiched carbon between nitrogen of imidazole). ESI-MS positive ions at m/z (relative intensity %) 717.8 (100 %) {(M- 2Br)-1)}+, 718.8(60%) (M-2Br)+.
Synthesis of 1,2-bis(1(3-alkoxy-2-hydroxypropyl)-1-H-imidazol-3-ium)ethane bromide (11).White solid, Yield, 92.5%. Melting point 104 0C. The IR (KBr Pellet, cm-1): 1126, 1564, 1572, 2849, 2918 and 3343. 1H NMR (δ ppm, CDCl3): 0.81(t, 6H, 2XCH3), 1.19(br,s, chain 36H, 2X(-CH2-)9, 1.48(m, 4H, 2XCH2next to terminal methyl groups), 3.29(d, 2H, 2XOH), 3.36(t, 4H, 2XOCH2), 3.51(d, 4H, 2XCH2O), 4.12(d, 4H, 2XNCH2), 4.35(m, 2H, 2XCHOH), 5.10(t, 4H, ImCH2CH2CH2Im), 7.27(s, 2H, 2XαCH to +ve Nitrogen of imidazole), 8.01(s, 2H, 2Xβ CH to +ve Nitrogen of imidazole), 9.52(s, 2H, sandwiched proton between nitrogen of imidazole). 75MHz 13C/DEPT NMR (δ ppm, CDCl3): 13.49(terminal methyl carbons), 22.45(CH3CH2), 26.28(OCH2CH2), 29.29(chain methylene carbons), 31.95(CH3CH2CH2), 46.78(ImCH2CH2Im), 53.42(NCH2), 67.38(secondary carbon attached to hydroxyl group), 71.28(OCH2), 71.84(CH2O), 123.54(NCHCHN), 136.21(sandwiched carbon between nitrogen of imidazole). ESI-MS positive ions at m/z (relative intensity%) 648.5(100%) {(M- 2Br)-1)}+, 649.5(60%) (M-2Br)+.
Synthesis of 1,2-bis(1(3-alkoxy-2-hydroxypropyl)-1-H-imidazol-3-ium)propane bromide (12).White solid, Yield, 92.5%.Melting point 113 0C. The IR (KBr Pellet, cm-1): 1126, 1564, 1572, 2849, 2918 and 3343. 1H NMR (δ ppm, CDCl3): 0.81(t, 6H, 2XCH3), 1.87(br,s, chain 36H, 2X(-CH2-)9, 1.49(m, 4H, 2XCH2next to terminal methyl groups), 2.72(t,2H, ImCH2CH2CH2Im), 3.30(d, 2H, 2XOH), 3.36(t, 4H, 2XOCH2), 3.51(d, 4H, 2XCH2O), 3.89(d, 4H, 2XNCH2), 4.25(m, 2H, 2XCHOH), 4.30(t, 4H, ImCH2CH2CH2Im), 7.21(s, 2H, 2XαCH to +ve Nitrogen of imidazole), 7.44(s, 2H, 2Xβ CH to +ve Nitrogen of imidazole), 9.21(s, 2H, sandwiched proton between nitrogen of imidazole). 75MHz 13C/DEPT NMR (δ ppm, CDCl3): 13.96(terminal methyl carbons), 22.75(CH3CH2), 25.87(OCH2CH2), 29.29(chain methylene carbons), 31.35(CH3CH2CH2), 31.86(ImCH2CH2CH2Im), 48.78(ImCH2CH2Im), 53.42(NCH2), 67.38(secondary carbon attached to hydroxyl group), 71.28(OCH2), 71.84(CH2O), 110.54(NCHCHN), 123.05(sandwiched carbon between nitrogen of imidazole). ESI-MS positive ions at m/z (relative intensity %) 662.8 (100 %) {(M- 2Br)-1)}+, 663.8(60%) (M-2Br)+.
Specific conductivity and surface tension plots of gemini surfactants (8-12):
(8)
(9)
(10)
(11)
(12)
(8)
(9)
(10)
(11)
(12)