4054
V. K. Rai et al.
PAPER
2-(4-Chlorophenyl)-5-(hydroxymethyl)-4-phenyl-4,5,6,7-tet-
rahydro-3H-imidazo[4,5-b]pyridine-6,7-diol (4e)
Colorless solid; mp 121–123 °C.
J3H,4H = 9.2 Hz, J2H,3H = 9.8 Hz, 1 H, 3-H), 3.89 (dd, J1¢Ha,1¢Hb = 10.1
Hz, J1¢Hb,2H = 2.8 Hz, 1 H, 1¢-Hb), 4.41 (d, J3H,4H = 9.2 Hz, 1 H, 4-
H), 6.57–6.71 (m, 3 H, ArH), 7.19–7.51 (m, 7 H, ArH).
13C NMR (100 MHz, DMSO-d6): d = 59.2, 60.7, 71.2, 79.3, 115.7,
IR (KBr): 3383, 3316, 3045, 2975, 1631, 1605, 1540, 1451 cm–1.
118.4, 126.8, 127.5, 128.3, 129.0, 129.5, 130.3, 131.1, 132.3, 133.5.
1H NMR (400 MHz, DMSO-d6 + D2O): d = 3.02 (ddd, J2H,3H = 9.6
Hz, J1¢Ha,2H = 5.4 Hz, J1¢Hb,2H = 2.9 Hz, 1 H, 2-H), 3.49 (dd,
J1¢Ha,1¢Hb = 10.5 Hz, J1¢Ha,2H = 5.4 Hz, 1 H, 1¢-Ha), 3.58 (dd,
J3H,4H = 9.2 Hz, J2H,3H = 9.6 Hz, 1 H, 3-H), 3.83 (dd, J1¢Ha,1¢Hb = 10.5
Hz, J1¢Hb,2H = 2.9 Hz, 1 H, 1¢-Hb), 4.46 (d, J3H,4H = 9.2 Hz, 1 H, 4-
H), 6.61–6.78 (m, 3 H, ArH), 7.21–7.59 (m, 4 H, ArH) 7.78–7.85
(m, 2 H, ArH).
13C NMR (100 MHz, DMSO-d6): d = 59.5, 60.8, 70.8, 79.1, 115.3,
119.0, 125.3, 126.1, 126.8, 127.5, 128.8, 129.5, 130.1, 132.5, 133.8.
MS (FAB): m/z = 372 [M + H+], 374 [M + H+ + 2].
MS (FAB): m/z = 338 [M + H+].
Anal. Calcd for C19H19N3O3: C, 67.64; H, 5.68; N, 12.46. Found: C,
67.35; H, 5.79; N, 12.61.
4-Benzyl-5-(hydroxymethyl)-2-phenyl-4,5,6,7-tetrahydro-3H-
imidazo[4,5-b]pyridine-6,7-diol (4b)
Colorless solid; mp 142–145 °C.
IR (KBr): 3383, 3318, 3037, 2975, 1633, 1595, 1551, 1456 cm–1.
1H NMR (400 MHz, DMSO-d6 + D2O): d = 2.91 (ddd, J2H,3H = 9.8
Hz, J1¢Ha,2H = 5.3 Hz, J1¢Hb,2H = 2.9 Hz, 1 H, 2-H), 3.48 (dd,
J1¢Ha,1¢Hb = 10.2 Hz, J1¢Ha,2H = 5.3 Hz, 1 H, 1¢-Ha), 3.66 (dd,
J3H,4H = 9.2 Hz, J2H,3H = 9.8 Hz, 1 H, 3-H), 3.85 (dd, J1¢Ha,1¢Hb = 10.2
Hz, J1¢Hb,2H = 2.9 Hz, 1 H, 1¢-Hb), 4.23 (s, 2 H, CH2), 4.45 (d,
J3H,4H = 9.2 Hz, 1 H, 4-H), 7.06–7.45 (m, 10 H, ArH,).
13C NMR (100 MHz, DMSO-d6): d = 52.7, 59.7, 61.2, 69.8, 80.3,
115.8, 116.2, 127.1, 127.9, 128.8, 129.6, 130.3, 131.2, 131.9, 132.5,
133.3.
Anal. Calcd for C19H18ClN3O3: C, 61.38; H, 4.88; N, 11.30. Found:
C, 61.62; H, 4.59; N, 11.45.
4-Benzyl-2-(4-chlorophenyl)-5-(hydroxymethyl)-4,5,6,7-tet-
rahydro-3H-imidazo[4,5-b]pyridine-6,7-diol (4f)
Colorless solid; mp 141–143 °C.
IR (KBr): 3385, 3325, 3044, 2965, 1632, 1593, 1554, 1451 cm–1.
1H NMR (400 MHz, DMSO-d6 + D2O): d = 2.91 (ddd, J2H,3H = 9.8
Hz, J1¢Ha,2H = 5.4 Hz, J1¢Hb,2H = 2.7 Hz, 1 H, 2-H), 3.49 (dd,
J1¢Ha,1¢Hb = 10.0 Hz, J1¢Ha,2H = 5.4 Hz, 1 H, 1¢-Ha), 3.64 (dd,
J3H,4H = 9.2 Hz, J2H,3H = 9.8 Hz, 1 H, 3-H), 3.92 (dd, J1¢Ha,1¢Hb = 10.0
Hz, J1¢Hb,2H = 2.7 Hz, 1 H, 1¢-Hb), 4.23 (s, 2 H, CH2), 4.43 (d,
J3H,4H = 9.2 Hz, 1 H, 4-H), 7.04 (d, J = 8.6 Hz, 2 H, ArH, 4-ClC6H4),
7.08–7.21 (m, 5 H, ArH) 7.41 (d, J = 8.6 Hz, 2 H, ArH, 4-ClC6H4).
13C NMR (100 MHz, DMSO-d6): d = 52.1, 59.5, 60.3, 71.6, 79.6,
125.3, 126.1, 127.6, 128.5, 129.3, 130.1, 130.8, 131.7, 132.6, 133.5,
134.3.
MS (FAB): m/z = 352 [M + H+].
Anal. Calcd for C20H21N3O3: C, 68.36; H, 6.02; N, 11.96. Found: C,
68.59; H, 5.86; N, 12.11.
5-(Hydroxymethyl)-2-methyl-4-phenyl-4,5,6,7-tetrahydro-3H-
imidazo[4,5-b]pyridine-6,7-diol (4c)
Colorless solid; mp 120–121 °C.
IR (KBr): 3379, 3321, 3041, 2968, 1631, 1602, 1549, 1458 cm–1.
1H NMR (400 MHz, DMSO-d6 + D2O): d = 2.31 (s, 3 H, CH3), 2.99
(ddd, J2H,3H = 9.9 Hz, J1¢Ha,2H = 5.3 Hz, J1¢Hb,2H = 2.7 Hz, 1 H, 2-H),
3.41 (dd, J1¢Ha,1¢Hb = 10.1 Hz, J1¢Ha,2H = 5.3 Hz, 1 H, 1¢-Ha), 3.56 (dd,
J3H,4H = 9.2 Hz, J2H,3H = 9.9 Hz, 1 H, 3-H), 3.86 (dd, J1¢Ha,1¢Hb = 10.1
Hz, J1¢Hb,2H = 2.7 Hz, 1 H, 1¢-Hb), 4.43 (d, J3H,4H = 9.2 Hz, 1 H, 4-
H), 6.71–7.11 (m, 5 H, ArH).
MS (FAB): m/z = 386 [M + H+], 388 [M + H+ + 2].
Anal. Calcd for C20H20ClN3O3: C, 62.26; H, 5.22; N, 10.89. Found:
C, 61.97; H, 5.05; N, 11.26.
5-(1,2-Dihydroxyethyl)-2,4-diphenyl-4,5,6,7-tetrahydro-3H-im-
idazo[4,5-b]pyridine-6,7-diol (5a)
Colorless solid; mp 148–150 °C.
IR (KBr): 3385, 3315, 3042, 2970, 1635, 1599, 1546, 1457 cm–1.
13C NMR (100 MHz, DMSO-d6): d = 20.1, 59.6, 61.2, 70.7, 79.8,
116.7, 118.1, 128.1, 129.1, 130.9, 132.6, 134.1.
MS (FAB): m/z = 276 [M + H+].
1H NMR (400 MHz, DMSO-d6 + D2O): d = 2.93 (dd, J2H,3H = 9.1
Hz, J1¢H,2H = 6.2 Hz, 1 H, 2-H), 3.49 (dd, J1¢H,2¢Ha = 5.7 Hz,
J2¢Ha,2¢Hb = 11.3 Hz, 1 H, 2¢-Ha), 3.58 (ddd, J1¢H,2H = 6.2 Hz,
J1¢H,2¢Ha = 5.7 Hz, J1¢H,2¢Hb = 2.5 Hz, 1 H, 1¢-H), 3.65 (dd, J2H,3H = 9.1
Hz, J3H,4H = 9.5 Hz, 1 H, 3-H), 3.86 (dd, J1¢H,2¢Hb = 2.5 Hz,
J2¢Ha,2¢Hb = 11.3 Hz, 1 H, 2¢-Hb), 4.51 (d, J3H,4H = 9.5 Hz, 1 H, 4-H),
6.59–6.68 (m, 3 H, ArH), 7.08–7.49 (m, 7 H, ArH).
13C NMR (100 MHz, DMSO-d6): d = 61.9, 63.3, 65.9, 67.5, 78.2,
115.1, 118.5, 125.5, 126.2, 126.9, 127.7, 128.5, 129.3, 130.1, 132.9,
134.1.
Anal. Calcd for C14H17N3O3: C, 61.08; H, 6.22; N, 15.26. Found: C,
61.35; H, 6.51; N, 15.04.
4-Benzyl-5-(hydroxymethyl)-2-methyl-4,5,6,7-tetrahydro-3H-
imidazo[4,5-b]pyridine-6,7-diol (4d)
Colorless solid; mp 127–128 °C.
IR (KBr): 3380, 3320, 3036, 2974, 1628, 1597, 1552, 1459 cm–1.
1H NMR (400 MHz, DMSO-d6 + D2O): d = 2.38 (s, 3 H, CH3), 2.97
(ddd, J2H,3H = 9.9 Hz, J1¢Ha,2H = 5.4 Hz, J1¢Hb,2H = 2.7 Hz, 1 H, 2-H),
3.46 (dd, J1¢Ha,1¢Hb = 10.1 Hz, J1¢Ha,2H = 5.4 Hz, 1 H, 1¢-Ha), 3.58 (dd,
J3H,4H = 9.1 Hz, J2H,3H = 9.9 Hz, 1 H, 3-H), 3.91 (dd, J1¢Ha,1¢Hb = 10.1
Hz, J1¢Hb,2H = 2.7 Hz, 1 H, 1¢-Hb), 4.26 (s, 2 H, CH2), 4.41 (d,
J3H,4H = 9.1 Hz, 1 H, 4-H), 7.05–7.31 (m, 5 H, ArH).
MS (FAB): m/z = 368 [M + H+].
Anal. Calcd for C20H21N3O4: C, 65.38; H, 5.76; N, 11.44. Found: C,
65.75; H, 5.51; N, 11.72.
13C NMR (100 MHz, DMSO-d6): d = 19.8, 52.4, 59.2, 60.7, 71.2,
4-Benzyl-5-(1,2-dihydroxyethyl)-2-phenyl-4,5,6,7-tetrahydro-
3H-imidazo[4,5-b]pyridine-6,7-diol (5b)
Colorless solid; mp 158–161 °C.
79.3, 126.1, 127.8, 129.6, 130.3, 131.1, 131.8, 133.9.
MS (FAB): m/z = 290 [M + H+].
IR (KBr): 3389, 3319, 3038, 2977, 1641, 1591, 1540, 1463 cm–1.
Anal. Calcd for C15H19N3O3: C, 62.27; H, 6.62; N, 14.52. Found: C,
61.90; H, 6.43; N, 14.74.
1H NMR (400 MHz, DMSO-d6 + D2O): d = 2.88 (dd, J2H,3H = 9.2
Hz, J1¢H,2H = 6.2 Hz, 1 H, 2-H), 3.51 (dd, J1¢H,2¢Ha = 5.6 Hz,
J2¢Ha,2¢Hb = 11.3 Hz, 1 H, 2¢-Ha), 3.54 (ddd, J1¢H,2H = 6.2 Hz,
J1¢H,2¢Ha = 5.6 Hz, J1¢H,2¢Hb = 2.6 Hz, 1 H, 1¢-H), 3.63 (dd, J2H,3H = 9.2
Synthesis 2010, No. 23, 4051–4056 © Thieme Stuttgart · New York