Supplementary Material

Fatty acids in Heterocyclic Synthesis. Part XIV: Synthesis of Surface Active Agents from Some Novel Class of Oxadiazole, Thiadiazole and Triazole Derivatives having Microbiological Activities

Iman A. Gad El-Karim*, Mahasen S. Amine, Amal A. Mahmoud, Alaa. S. Gouda

Department of Chemistry, Faculty of science, Benha University, Benha, Egypt P.O.:13518.

*E-mail:

Characteristic dataof 2-amino-5-heptadecyl-1,3,4-oxadiazole (1): mp 102-104 oC;IR (KBr) ν (cm-1): 3216, 3158 (NH’s), 2919, 2850 (aliphatic CH stretching), 1690, 1662, 1589 (C=N’s stretching) beside bands at 1109 and 1058 cm-1 for C-O and 721 cm-1. 1H-NMR (DMSO-d6) δ(ppm): 6.80 (s, 1H, NH, D2O exchangeable), 5.52 (s, 2H, NH2, D2O exchangeable), 2.71 (t, 2H, CH2, J = 7.3 Hz), 1.71 (m, 2H, CH2, J = 7.3 Hz), 1.28 (m, 28H, 14 CH2 of alkyl chain), 0.88 (t, 3H, CH3, J = 7.8 Hz); 13C-NMR (DMSO-d6) δ (ppm): 169, 163 (2C=N), and aliphatic saturated carbons at 32.4, 31.9, 29.6 (10C), 29.3 (2C), 28.2, 22.7 and 14.1 (terminal CH3); MS: m/z (% rel.int.): 323 (1.0) [M˙+], 280 (2.4), 266 (4.4), 112 (40) 99(100), 58 (18.1), 56 (16.6). Anal. Calcd.(%) for C19H37N3O: C; 70.54, H; 11.53, N; 12.99. Found: C; 70.23, H; 11.29, N; 12.81.

Characteristic data of (4-chloro-benzylidene)-(5-heptadecyl-[1,3,4]oxadiazol-2-yl)-amine (2).mp 136-138 oC;IR (KBr) ν (cm-1): 3060 (aromatic CH), 2920, 2852 (aliphatic CH), 1650, 1599, 1464, 1098, 714; 1H-NMR (DMSO-d6)δ(ppm): 8.59 (s, 1H, CH=N), 7.77- 7.52 ( m, 4H, ArH), 2.74 (t, 2H, CH2, J = 7.3 Hz), 1.76 (m, 2H, CH2, J = 7.3 Hz), 1.27 (m, 28H, 14 CH2 of alkyl chain), 0.86 (t, 3H, CH3, J = 7.46 Hz); 13C-NMR (DMSO-d6) δ (ppm): 160 (N=CH-), 158, 155 (2C=N), 136.6 (C-Cl), 134 (-C-CH=N-), 130.6 (2C, ArH), 128.9 (2C, ArH), and aliphatic saturated carbons at 32.6, 32.3, 29.8 (10C), 29.5(2C), 28.2, 22.8 and 14.2 (terminal CH3); MS m/z (% rel.int.): 447 (0.04) [M˙+ +2], 445 (0.15) [M˙+], 128 (45.68), 115 (100), 97 (47.1), 57 (24.41). Anal. Calcd. (%) for C26H40ClN3O: C; 70.01, H; 9.04, N; 9.42, Cl; 7.95. Found: C; 70.13, H; 9.29, N; 9.61, Cl; 8.05.

Characteristic data ofN-(5-heptadecyl-[1,3,4]oxadiazol-2-yl)-acetamide (3): mp 85-87oC;IR(KBr) ν (cm-1): 3265 (NH), 2919, 2850 (aliphatic CH), 1681 (C=O of amide), 1592, 1526 (C=N’s) and 720; 1H-NMR (DMSO-d6) δ(ppm): 9.15 (s, 1H, NH, D2O exchangeable), 2.59 (t, 2H, CH2, J = 7.2 Hz), 2.04 ( s, 3H, CH3CO-), 1.61 (m, 2H, CH2, J = 7.2 Hz), 1.28 (m, 28H, 14CH2 of alkyl chain), 0.89 (t, 3H, CH3, J = 7.2 Hz); 13C-NMR (DMSO-d6) δ (ppm): 169.2 (N=C-NH-), 168.8 (C=O), 163.3 (C=N), and aliphatic saturated carbons at 32.3, 31.9, 29.6 (10C), 29.3, 29.1, 28.2, 22.7, 24.1 (CH3CO) and 14.2 (terminal CH3); MS m/z (% rel. int.): 366 (0.90 ) [M˙+ +1], 322 (0.85), 307 (0.86 ), 126 (0.14), 111 (27.55) and 57 (100). Anal. Calcd. (%) for C21H39N3O2: C; 69.00, H; 10.75, N; 11.49. Found: C; 69.13, H; 10.29, N; 11.61.

Characteristic data of2-chloro-N-(5-heptadecyl-[1,3,4]oxadiazol-2-yl)-acetamide (4): mp 132-134oC;IR(KBr) ν (cm-1): 3214 (NH), 2918, 2850 (aliphatic CH), 1684 (C=O of amide), 1591 (C=N’s), 662 (C-Cl); 1H-NMR (DMSO-d6) δ(ppm): 9.15 (s, 1H, NH, D2O exchangeable), 4.21 ( s, 2H, CH2CO-), 2.68 (t, 2H, CH2, J = 7.1 Hz), 1.69 (m, 2H, CH2, J = 7.2 Hz), 1.28 (m, 28H, 14CH2 of alkyl chain), 0.90 (t, 3H, CH3, J = 7.31 Hz); 13C-NMR (DMSO-d6) δ (ppm): 169.3 (N=C-NH-), 165.8 (C=O), 163.2 (C=N), 42.6 (CH2Cl) and aliphatic saturated carbons at 32.4, 31.9, 29.7 (10C), 29.3, 29.0, 28.2, 22.7 and 14.2 (terminal CH3); MS m/z (% rel. int.): 399 (0.10) [M˙+] , 350 (1.23%), 323 (23.40), 322 (12.03), 266 (27.80), 239 (12.02), 111 (18.25) and 99 (100). Anal. Calcd. (%) for C21H38ClN3O2: C; 63.06, H; 9.58, N; 10.51, Cl; 8.86. Found: C; 63.23, H; 10.19, N; 10.62, Cl; 8.65.

Characteristic data of2-[(5-heptadecyl-[1,3,4]oxadiazol-2-yl)amino]acetic acid (5): mp 126-128oC;IR(KBr) ν (cm-1) : 3400-2950 (carboxylic OH), 2920, 2850 (aliphatic CH), 1717 (C=O of acid); 1H-NMR (DMSO-d6) δ(ppm):, 11.1 (s, 1H, OH carboxylic), 4.0 (s, 1H, NH, D2O exchangeable), 3.67 ( s, 2H, CH2NH-), 2. 75 (t, 2H, CH2, J = 7.2 Hz), 1.74 (m, 2H, CH2, J = 7.2 Hz), 1.24 (m, 28H, 14CH2 of alkyl chain), 0.89 (t, 3H, CH3, J = 7.3 Hz); 13C-NMR (DMSO-d6) δ (ppm): 172.2 (C=O), 169.1, 163.2 (2C=N), 45.4 (CH2CO) and aliphatic saturated carbons at 32.4, 31.9, 29.7 (10C), 29.3, 29.2, 28.2, 22.7, 14.2 (terminal CH3) and; MS m/z (% rel.int.): 383 (1.99) [M˙++2] , 337 (1.78), 198 (100). Anal. Calcd. (%) for C21H39N3O3: C; 66.14, H; 10.24, N; 11.02 Found: C; 66.45, H; 10.51, N; 10.69.

Characteristic data of2-heptadecylimidazo[2,1-b][1,3,4]oxadiazol-6(5H)-one (6): mp 149-151oC;IR (KBr) ν (cm-1) : 2920, 2851 (aliphatic CH), 1674 (C=O of cyclic amide), 1582 (C=N’s); 1H-NMR (DMSO-d6) δ(ppm): 2.86 ( s, 2H, CH2CO-), 1.75 (t, 2H, CH2, J = 7.1 Hz), 1.26 (m, 30H, 15CH2 of alkyl chain), 0.87 (t, 3H, CH3, J = 7.29 Hz); 13C-NMR (DMSO-d6) δ (ppm): 168 (C=O), 163.1, 157 (2C=N), 59.9(CH2-CO), and aliphatic saturated carbons at 31.9, 30.2, 29.5 (10C), 29.3(2C), 27.9, 22.8 and 14.3 (terminal CH3); MS m/z (% rel.int.): 364 (0.81) [M˙+ +1] , 363 (0.68) [M˙+], 323 (23.40), 266 (27.88), 99 (100). Anal. Calcd. (%) for C21H37N3O2: C; 69.38, H; 10.26, N; 11.56. Found: C; 69.55, H; 10.41, N; 11.68.

Characteristic data of2-heptadecylimidazo[2,1-b][1,3,4]oxadiazol-5(6H)-one (7): mp 161-163oC;IR(KBr) ν (cm-1): 2919, 2850 (aliphatic CH), 1681 (C=O of cyclic amide), 1577 (C=N’s); 1H-NMR (DMSO-d6) δ(ppm): 2.88 (s, 2H, CH2CO-), 1.73 (t, 2H, CH2, J = 7.1 Hz), 1.25 (m, 30H, 15CH2 of alkyl chain), 0.87 (t, 3H, CH3, J = 7.24 Hz); 13C-NMR (DMSO-d6) δ (ppm): 173 (C=O), 162.8, 158.3 (2C=N), 51.5(CH2-CO), and aliphatic saturated carbons at 31.9, 30.2, 29.6 (10C), 29.3(2C), 22.7, 19.8, 14.1 (terminal CH3); MS m/z (% rel. int.): 364 (0.81) [M˙+ +1], 99 (100). Anal. Calcd. (%) for C21H37N3O2: C; 69.38, H; 10.26, N; 11.56. Found: C; 69.55, H; 10.41, N; 11.68.

Characteristic data of2-amino-5-heptadecyl-1,3,4-thiadiazole (8): mp 110-112oC;IR(KBr) ν (cm-1): 3300, 3216 (NH’s), 2920, 2850 (aliphatic CH), 1623, 1590 (C=N’s) beside the characteristic bands for thiadiazole ring in the region of (1200-1100) and (1000-880); 1H-NMR (DMSO-d6) δ(ppm): 5.70 (s, 2H, NH2, , D2O exchangeable), 2.72 (t, 2H, CH2, J = 7.13 Hz), 1.63 (m, 2H, CH2, J = 7.13 Hz), 1.27 (m, 28H, 14 CH2 of alkyl chain), 0.87 (t, 3H, CH3, J = 8.4 Hz); 13C-NMR (DMSO-d6) δ (ppm): 167.9, 161.3 (2C=N) and aliphatic saturated carbons at 31.9, 31.2, 29.6 (10C), 29.1(2C), 28.6, 22.7, 14.1 (terminal CH3); MS m/z (% rel. int.): 340 (1.14) [M˙++1] , 339 (1.36) [M˙+], 128 (36.01) and 115(100). Anal. Calcd. (%) for C19H37N3S: C; 67.20, H; 10.98, N; 12.37, S; 9.44. Found: C; 66.91, H; 10.64, N; 12.08, S; 9.13.

Characteristic data of3-amino-5-heptadecyl[1,2,4]triazol-4-ol (9): mp 104-106oC;IR(KBr) ν (cm-1): 3301 (OH), 3223, 3120 (NH’s), 2920,2852 (aliphatic CH), 1662 (C=N); 1H-NMR (DMSO-d6) δ(ppm): 8.85 (s, 1H, OH, D2O exchangeable ), 7.91, 4.93 (s, 2H, NH2, D2O exchangeable), 2.59 (t, 2H, CH2, J = 7.1 Hz), 1.59 (m, 2H, CH2, J = 7.3 Hz), 1.27 (m, 28H, 14 CH2 of alkyl chain), 0.89 (t, 3H, CH3, J = 7.4 Hz); 13C-NMR (DMSO-d6) δ (ppm): 158.7, 154.6 (2C=N) and aliphatic saturated carbons at 31.8, 29.6 (10C), 29.3, 29.1, 22.8, 22.6, 22.1 and 14.1 (terminal CH3); MS m/z (% rel.int.): 339 (3.58) [M˙+ +1], 266 (0.53), 128 (36.1), 115(100), 71 (8.32) and 57 (16.02) Anal. Calcd. (%) for C19H38N4O: C; 67.41, H; 11.31, N; 16.55. Found: C; 67.53, H; 11.22, N; 16.78.

Characteristic data of5-heptadecyl[1,2,4]triazole-3,4-diamine (10): mp 94-96oC;IR(KBr) ν (cm-1): 3318, 3292, 3181, 3170 (NH’s), 2918, 2849 (aliphatic CH), 1631, 1535 (C=N’s); 1H-NMR (DMSO-d6) δ(ppm): 7.26, 5.68 (s, 4H, 2-NH2, D2O exchangeable), 2.68 (t, 2H, CH2, J = 7.6 Hz), 1.67 (m, 2H, CH2, J = 7.6 Hz), 1.25 (m, 28H, 14 CH2 of alkyl chain), 0.88 (t, 3H, CH3, J = 6.88 Hz); 13C-NMR (DMSO-d6) δ (ppm): 154.7, 151.6 (2C=N) and aliphatic saturated carbons at 31.9, 29.6 (10C), 29.3, 29.1, 22.8, 22.6, 22.1 and 14.1 (terminal CH3); MS m/z (% rel. int.): 338 (0.26) [M˙+ +1], 337 (0.25) [M˙+ ], 310 (0.37%), 284 (31.26%), 256 (100) and129 (10.66). Anal. Calcd. (%) for C19H39N5: C; 67.61, H; 11.65, N; 20.75. Found: C; 67.54, H; 11.41, N; 20.58.

Characteristic data of6-heptadecyl[1,2,4]triazolo[3,4-b][1,3,4]oxadiazol-3-amine (11): mp 130-132 oC; IR(KBr) ν (cm-1) : 3228 (NH’s), 2919, 2848 (aliphatic CH), 1600 (C=N’s), 1180 (C-O-C ether linkage); 1H-NMR(DMSO-d6) δ(ppm): 6.8 (s, 2H, NH2, D2O exchangeable), 2.78 (t, 2H, CH2, J = 7.65 Hz), 1.76 (m, 2H, CH2, J = 7.65 Hz), 1.26 (m, 28H, 14 CH2 of alkyl chain), 0.873 (t, 3H, CH3, J = 7.65 Hz); 13C-NMR (DMSO-d6) δ (ppm): 158 (N=C-O), 148, 143 (2 C=N), and aliphatic saturated carbons at 32.0, 31.8, 29.9 (10C), 28.2, 25.6, 25.1, 22.2 and 14.1 (terminal CH3); MS m/z (% rel. int.): 363 (6.9) [M˙+], 236 (4.3), 194 (12.9), 124 (12.1), 97 (19.0), 70 (42.2), 57 (51.7) and 55 (100). Anal. Calcd. (%) for C20H37N5O: C; 66.08, H; 10.26, N; 19.26. Found: C; 66.14, H; 10.31, N; 19.31.

Characteristic data ofethyl-N-[amino(hydrazinylidene)methyl]heptadecylhydrazonoate (12): mp 98-100oC;IR (KBr) ν (cm-1): 3310, 3121 (NH’s), 2919, 2849 (aliphatic CH), 1662, 1589 (C=N’s); 1H-NMR (DMSO-d6) δ(ppm): 8.61, 6.98 (s, 4H, 2 NH2, D2O exchangeable), 7.05 (s, 1H, NH), 4.13 (q, 2H, CH2-O, J= 7.81), 1.68 (t, 2H, CH2, J = 7.59 Hz), 1.48 (m, 2H, CH2, J = 7.55 Hz), 1.38 (t, 3H, CH3-CH2O, J= 7.81), 1.26 (m, 28H, 14 CH2 of alkyl chain), 0.871 (t, 3H, CH3, J = 7.59 Hz); 13C-NMR (DMSO-d6) δ (ppm): 162.7 (OC=N), 148.9 (HNC=N), 60.9 (OCH2) and aliphatic saturated carbons at 31.9, 29.7 (10C), 29.1 (2C), 23.9, 22.7, 20.1 and 15.3, 14.1 (two terminal CH3); MS m/z (% rel. int.): 383 (11.8) [M˙+], 310 (5.9), 265 (12.9), 127 (18.8), 73 (32.9), 59 (100) and 58 (27.1) Anal. Calcd. (%) for C21H45N5O: C; 65.75, H; 11.82, N; 18.26. Found: C; 65.58, H; 12.01, N; 18.39.

Figure S(a-i) Variation of surface tension vs log concentration of nonionic surfactants (Ia-c)-(IXa-c)used in the determination of CMC

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