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K. Wermann et al. / Tetrahedron 61 (2005) 673–685
203 8C. IR (KBr) nZ1618 cmK1 (C]N, exocyclic). 1H
NMR (DMSO): dZ1.05 (t, 3H, CH3), 1.18 (t, 3H, CH3),
1.16–2.06 (m, 10H, CH2 cyclohexyl), 2.44 (m, 2H, CH2), 2.55
(m, 2H, CH2), 4.18 (1H br, CHcyclohexyl), 4.61–4.75 (dd, 2H,
CH2), 6.72–7.20 (m, 9H, CHph), 7.40 (s, 1H, sp3CH), 9.20 (s
br, 1H, NH), 9.93 (s br, 1H, OH). 13C NMR (DMSO): dZ
11.7, 11.4, 18.1, 24.1, 25.1, 33.6, 34.0, 43.8, 52.6, 66.3,
115.1, 119.1, 124.7, 127.2, 127.4, 128.3, 128.7, 136.9,
147.8, 150.9, 151.4, 152.3, 153.0, 156.2. MS (DCI/H2O),
m/z (%): 519 (100) [C28H35N7OS]C. Anal. calcd for
C28H35N7OS (517.69): C, 64.96; H, 6.81; N, 18.94; O,
3.09; S, 6.19. Found: C, 64.59; H, 7.32; N, 18.95; S, 5.96.
19.94; O, 3.25; S, 6.52. Found: C, 63.03; H, 7.09; N, 20.31;
S, 6.36.
4.4.17. N-(4-Methoxyphenyl)-2-(4-methylphenyl)-N0-(4-
benzyl-5-methyl-4H-1,2,4-triazol-3-yl)-5-methyl-1,3,4-
thiadiazole-3(2H)-carboximidamid (8s), (SV B). Yield
25%; mp 63 8C. IR (KBr) nZ1627 cmK1 (C]N, exo-
1
cyclic). H NMR (CDCl3): dZ1.92 (s, 3H, CH3), 2.07 (s,
3H, CH3), 2.18 (s, 3H, CH3), 3.73 (s, 3H, OCH3), 4.55–4.76
(dd, 2H, CH2), 6.71–7.19 (m, 13H, CHph), 7.22 (s, 1H,
sp3CH), 10.39 (s, br, 1H, NH). 13C NMR (CDCl3): dZ11.3,
16.6, 21.2, 45.2, 55.5, 72.9, 113.6, 124.6, 125.9, 126.9,
127.5, 128.4, 128.6, 129.4, 133.0, 135.8, 138.2, 138.3,
146.2, 147.9, 151.0, 156.5. MS (DCI/H2O), m/z (%): 512 (9)
[C28H30N7OS]C. Anal. calcd for C28H29N7OS (511.64): C,
65.73; H, 5.71; N, 19.16; O, 3.13; S, 6.27. Found: C, 65.42;
H, 6.08; N, 18.95; S, 6.42.
4.4.14. N-{[5-Methyl-2-(1-naphthyl)-1,3,4-thiazol-3(2H)-
yl](piperidin-1-yl)methylene}-4-(4-chlorobenzyl)-5-
methyl-4H-1,2,4-triazol-3-amine (8p), (SV A). Yield
90%; mp 161 8C. IR (KBr) nZ1574 cmK1 (C]N, exo-
1
cyclic). H NMR (CDCl3): dZ1.28 (s, 6H, CH2(pip)), 2.07
4.4.18. 5-Benzyl-3-butyl-2,6-dimethyl-9-(4-methylphe-
nyl)-3H,5H,9H-di[1,2,4]-triazolo[1,5-a:10,50-d][1,3,5]tri-
azin-8-ium iodide (9c). Yield 75%; (determined by 1H
(s, 3H, CH3), 2.24 (s, 3H, CH3), 3.27 (m, 4H, CH2(pip)),
6.51–6.75 (m, 4H, CHph), 7.40–7.89 (m, 7H, CHnaph), 7.67
(s, 1H, sp3CH). 13C NMR (CDCl3): dZ11.5, 17.1, 24.3,
25.7, 44.4, 49.9, 70.1, 122.3, 123.0, 125.4, 125.9, 126.6,
128.0, 128.3, 128.6, 128.9, 129.0, 133.1, 133.8, 124.2,
135.4, 147.5, 147.9, 153.2, 155.2. MS (DCI/H2O), m/z (%):
544 (16) [C29H31ClN7S]C. Anal. calcd for C29H30ClN7S
(544.11): C, 64.02; H, 5.56; Cl, 6.52; N, 18.02; S, 5.89.
Found: C, 63.93; H, 5.99; Cl, 6.90; N, 17.86; S, 5.62.
1
NMR analysis of the mixture 8c/9c), mp 248 8C. H NMR
(CDCl3): dZ0.99 (t, 3H, CH3), 1.41 (m, 2H, CH2), 1.78 (m,
2H, CH2), 2.34 (s, 3H, CH3), 2.37 (s, 3H, CH3), 2.43 (s, 3H,
CH3), 4.06 (t, 2H, CH2), 5.32 (dd, 2H, CH2(benzyl)), 7.27–
7.42 (m, 9H, CHph), 7.49 (s, 1H, sp3CHtriazinium). 13C NMR
(CDCl3): dZ11.6, 12.1, 13.6, 19.9, 21.4, 44.0, 47.5, 77.2,
128.0, 128.2, 128.9, 129.3, 129.6, 130.2, 133.3, 133.3,
141.8, 149.9, 150.4, 150.7, 150.9. MS (DCI/H2O), m/z (%):
428 (41) [C25H30N7]C. Anal. calcd for C25H30IN7 (555.46):
C, 54.06; H, 5.44; I, 22.85; N, 17.65. Found: C, 54.04; H,
5.64; I, 22.97; N, 17.78.
4.4.15. N-Butyl-2-(1-naphthyl)-N0-[4-(4-chlorobenzyl)-5-
methyl-4H-1,2,4-triazol-3-yl]-5-methyl-1,3,4-thiadia-
zole-3(2H)-carboximidamide (8q), (SV A). Yield 23%;
(simultaneous with 34% zwitterion 7q and 43% NNN 9q,
separated by column chromatography); mp 117 8C. IR
(KBr) nZ1604 cmK1 (C]N, exocyclic). 1H NMR
(CDCl3): dZ0.92 (t, 3H, CH3), 1.40 (m, 2H, CH2), 1.67
(m, 2H, CH2), 1.94 (s, 3H, CH3), 2.16 (s, 2H, CH3), 3.65 (m,
2H, CH2), 3.89–4.28 (dd, 2H, CH2), 6.18–6.90 (m, 4H,
CHph), 7.19 (s, 1H, sp3CH), 7.28–7.93 (m, 7H, CHnaph), 8.95
(s, br, 1H, NH). 13C NMR (CDCl3): dZ11.1, 13.9, 17.0,
20.2, 32.7, 43.8, 45.2, 69.8, 121.9, 122.8, 125.7, 126.4,
127.2, 128.4, 128.6, 129.0, 129.1, 129.3, 132.7, 133.7,
134.2, 136.4, 146.1, 147.3, 153.4, 156.9. MS (DCI/H2O),
m/z (%): 532 (10) [C28H31ClN7S]C. Anal. calcd for
C28H30ClN7S (532.10): C, 63.20; H, 5.68; Cl, 6.66; N,
18.43; S, 6.03. Found: C, 62.95; H; 5.98; Cl, 6.76; N, 18.68;
S, 6.42.
4.4.19. 5-Benzyl-3,9-di-(4-methylphenyl)-2,6-dimethyl-
3H,5H,9H-di[1,2,4]-triazolo[1,5-a:10,50-d][1,3,5]triazin-
8-ium iodide (9e), (modified reaction condition: 40 h at
60 8C, only 53% conversion). Yield 8%; mp 139 8C. IR
1
(KBr) nZ1587 cmK1. H NMR (CDCl3): dZ2.26 (s, 3H,
CH3), 2.28 (s, 3H, CH3), 2.41 (s, 3H, CH3), 2.46 (s, 3H,
CH3), 5.16 (s, 2H, CH2), 7.32–7.58 (13H, CHph), 7.71 (s,
1H, sp3CHtriazinium). 13C NMR (CDCl3): dZ11.9, 12.0,
21.4, 21.5, 47.2, 77.8, 126.9, 127.7, 127.8, 127.9, 128.5,
128.8, 129.2, 129.8, 130.2, 130.7, 133.1, 141.1, 141.8,
149.8, 150.2, 151.4. MS (DCI/H2O), m/z (%): 462 (44)
[C28H28N7]C. Anal. calcd for C28H28IN7 (589.48): C,
57.05; H, 4.79; I, 21.53; N, 16.63. Found: C, 56.99; H,
5.06; I, 22.19; N, 17.05.
4.4.16. N-Benzyl-2-(2-hydroxyphenyl)-N0-(4-butyl-5-
ethyl-4H-1,2,4-triazol-3-yl)-5-ethyl-1,3,4-thiadiazole-
3(2H)-carboximidamide (8r), (SV B). Yield 41%; (deter-
mined by 1H NMR analysis of the mixture 8r/9r); mp
166 8C; crystals for X-ray from aqueous MeOH. IR (KBr)
4.4.20. 3-Butyl-5-(4-chlorobenzyl)-2,6-dimethyl-9-(4-
methylphenyl)-3H,5H,9H-di[1,2,4]-triazolo[1,5-a:10,50-d]-
[1,3,5]triazin-8-ium iodide (9h). Yield 88% (determined
by 1H NMR analysis of the mixture 8h/9h); mp 175 8C; IR
1
(KBr) nZ1560 cmK1. H NMR (CDCl3): dZ0.98 (t, 3H,
1
nZ1626 cmK1 (C]N, exocyclic). H NMR (CDCl3): dZ
CH3), 1.43 (m, 2H, CH2), 1.83 (m, 2H, CH2), 1.83 (m, 2H,
CH2), 2.37 (s, 3H, CH3), 2.40 (s, 3H, CH3), 2.45 (s, 3H,
CH3), 5.37 (s, 2H, CH2), 7.29–7.47 (m 8H, CHph), 7.52 (s,
1H, sp3CHtriazinium). 13C NMR (CDCl3): dZ11.5, 12.1,
13.6, 19.9, 21.5, 30.7, 44.0, 46.8, 77.3, 128.2, 129.5, 130.2,
131.8, 2!134.9, 141.9, 149.8, 150.3, 150.7, 150.9. MS
(FAB/dmab), m/z (%): 462 (100) [C25H29ClN7]C. Anal.
calcd for C25H29 ClIN7 (589.90): C, 50.90; H, 4.96; Cl, 6.01;
I, 21.51; N, 16.62. Found C, 50.53; H, 4.79; Cl/I, 26.08; N,
16.91.
0.75 (t, 3H, CH3), 1.07 (m, 2H, CH2), 1.19–1.37 (m, 8H, 2!
CH3, 1!CH2), 2.49–2.65 (m, 4H, CH2), 3.49–3.56 (m, 2H,
CH2), 4.73–4.92 (dd, 2H, CH2), 6.22–7.32 (m, 9H, CHph)
7.51 (s, 1H, sp3CH), 9.21 (s br, 1H, NH), 10.50 (s br, 1H,
OH). 13C NMR (CDCl3): dZ11.3, 11.9, 13.8, 18.8, 19.8,
24.7, 31.5, 41.9, 48.7, 66.9, 116.3, 119.3, 126.0, 127.0,
127.3, 127.4, 128.4, 129.0 139.3, 151.9, 153.1, 153.9, 154.0,
156.4. MS (DCI/H2O), m/z (%): 492 (42) [C26H34N7OS]C.
Anal. calcd for C26H33N7OS (491.65): C, 63.52; H, 6.77; N,