1662
B. Insuasty, F. Orozco, A. García, J. Quiroga, R. Abonía, M. Nogueras, J. Cobo
Vol 45
54.8, 56.1, 57.3, 106.0, 113.5, 122.7, 122.8, 127.4, 131.7, 133.1,
135.7, 138.0, 147.7, 152.4, 153.6, 158.4, 158.5, 160.3, 198.2
ppm; Mass (m/z, %): 371 (M·+, 100), 342 (19), 328 (22), 264
(13), 250 (5), 236 (81). Anal. Calcd. For C21H17N5O2: C, 67.91;
H, 4.61; N, 18.86. Found: C, 67.83; H, 4.67; N, 18.77.
General procedure for synthesis of 9,11-diamino-6-aryl-
6,7-dihydroindeno[1,2-e]pyrimido[4,5-b][1,4]diazepin-5(5aH)-
ones (7a-f) and 8,10-diamino-6-aryl-6,7-dihydroindeno[1,2-
ppm; 13C NMR (DMSO-d6, 100 MHz): ꢁ 55.7, 56.5, 99.5, 121.0,
122.8, 128.4, 131.2, 131.4, 135.8, 137.4, 139.5, 147.7, 151.7,
154.9, 158.0, 162.3, 198.0 ppm; Mass (m/z, %): 434 (M·+, 83),
408 (9), 407 (14), 279 (43), 251 (100). Anal. Calcd. For
C20H15BrN6O: C, 55.19; H, 3.47; N, 19.31. Found: C, 55.23; H,
3.59; N, 19.27.
9,11-Diamino-6-phenyl-6,7-dihydroindeno[1,2-e]pyrimido-
[4,5-b][1,4]diazepin-5(5aH)-one (7d). Beige powder (65%); mp
309-311 ºC (d); FTIR (KBr) ꢀ 3442, 3303, 3158 (NH and NH2);
e]pyrimido[5,4-b][1,4]diazepin-5(5aH)-ones (8a-c).
A dry
1
mixture of tetraamine (1.53 mmol) and 2-arylidene-
5
1715 (C=O); 1665 (C=N and C=C) cm-1; H NMR (DMSO-d6,
indandiones 6a-f (1.53 mmol) was subjected to microwave
irradiation in open vessels at 80 °C with a maximum power of
300 W. The standard reaction time was estimated in 6 min by
TLC control. After cooling, the resulting mixture was triturated
with ethanol and the formed precipitate was collected by
filtration and purified by silica gel chromatography with
methylene chloride:methanol (20:1) as eluent to afford
compounds 7a-c in good yield and the regioisomers 8a-c in
lower yield. When the reaction was performed with arylidene
derivatives 6d-f, the resulting mixture was treated by addition of
dry ethanol under stirring, affording a precipitate which was
collected by filtration and washed with ethanol followed by
hexane to yield compounds 7d-f as single products.
9,11-Diamino-6-(4-nitrophenyl)-6,7-dihydroindeno[1,2-e]-
pyrimido[4,5-b][1,4]diazepin-5(5aH)-one (7a). Orange powder
(71%); mp 300-302 ºC (d); FTIR (KBr) ꢀ 3444, 3389, 3188 (NH
and NH2); 1717 (C=O); 1664 (C=N and C=C); 1518, 1349
(NO2) cm-1 ; 1H NMR (DMSO-d6, 400 MHz): ꢁ 3.95 (d, J = 4.00
Hz, 1H), 5.33 (dd, J = 4.02, J = 6.36, 1H), 6.02 (d, J = 8.00 Hz,
2H) , 7.14 (d, J = 8.00 Hz, 2H), 7.42 (t, J = 7.93 Hz, 1H), 7.44
(s, 2H, NH2), 7.60 (d, J = 7.65 Hz, 1H), 7.66 (t, J = 7.93 Hz,
1H), 8.02 (s, 2H, NH2), 8.18 (d, J = 7.65 Hz, 1H), 8.73 (d, J =
6.35 Hz, 1H, NH) ppm; 13C NMR (DMSO-d6, 100 MHz): ꢁ
55.5, 56.7, 101.7, 122.0, 122.7, 123.4, 127.5, 130.3, 135.8,
136.8, 146.7, 148.6, 148.9, 151.1, 155.2, 163.7, 167.0, 198.8
ppm; Mass (m/z, %): 401 (M·+, 20), 373 (2), 372 (4), 279 (7),
251 (58). Anal. Calcd. For C20H15N7O3: C, 59.85; H, 3.77; N,
24.03. Found: C, 59.78; H, 3.69; N, 23.92.
400 MHz): ꢁ 3.95 (d, J = 3.60, 1H), 5.40 (dd, J = 3.62, J = 6.43,
1H), 7.08 (d, J = 8.14 Hz, 2H) , 7.11-7.13 (m, 3H), 7.51 (t, J =
7.84 Hz, 1H), 7.54 (s, 2H, NH2), 7.61 (d, J = 7.65 Hz, 1H), 7.62
(t, J = 7.84 Hz, 1H), 7.70 (s, 2H, NH2), 8.29 (d, J = 7.65 Hz 1H),
8.71 (d, J = 6.45, 1H, NH) ppm; 13C NMR (DMSO-d6, 100
MHz): ꢁ 55.4, 56.0, 119.6, 120.5, 122.6, 123.6, 126.6, 127.8,
128.3, 128.5, 131.0, 133.5, 134.1, 136.2, 144.9, 162.2, 191.9
ppm; Mass (m/z, %): 356 (M·+, 100), 328 (10), 327 (19), 279 (4),
251 (3). Anal. Calcd. For C20H16N6O: C, 67.40; H, 4.53; N,
23.58. Found: C, 67.33; H, 4.57; N, 23.65.
9,11-Diamino-6-(4-methylphenyl)-6,7-dihydroindeno[1,2-e]-
pyrimido[4,5-b][1,4]diazepin-5(5aH)-one (7e). Beige powder
(84%); mp 272-274 ºC; FTIR (KBr) ꢀ 3443, 3347, 3166 (NH and
NH2); 1718 (C=O); 1660 (C=N and C=C) cm-1; 1H NMR (DMSO-
d6,400 MHz): ꢁ 2.09 (s, 3H), 4.01 (d, J = 3.51 Hz, 1H), 5.28 (dd, J
= 3.51 Hz, J = 6.34 Hz, 1H), 6.78 (d, J = 8.06 Hz, 2H) , 6.93 (d, J
= 8.06 Hz, 2H), 7.52 (t, J = 7.03 Hz, 1H), 7.54 (s, 2H, NH2), 7.61
(d, J = 7.65 Hz, 1H), 7.62 (t, J = 7.04 Hz, 1H), 7.70 (s, 2H, NH2),
8.29 (d, J = 7.65 Hz, 1H), 8.71 (d, J = 6.32 Hz, 1H, NH) ppm; 13
C
NMR (DMSO-d6, 100 MHz): ꢁ 55.9, 56.7, 99.4, 122.7, 126.1,
128.8, 131.3, 135.7, 136.9, 137.2, 137.5, 147.8, 151.4, 155.3,
198.1 ppm; Mass (m/z, %): 370 (M·+, 100), 342 (12), 341 (23), 280
(4), 251 (6). Anal. Calcd. For C21H18N6O: C, 68.09; H, 4.90; N,
22.69. Found: C, 67.98; H, 4.98; N, 22.73.
9,11-Diamino-6-(4-methoxyphenyl)-6,7-dihydroindeno[1,2-
e]pyrimido[4,5-b][1,4]diazepin-5(5aH)-one (7f). Beige powder
(80%); mp 332-333ºC (d); FTIR (KBr) ꢀ 3432, 3273, 3172 (NH
1
and NH2); 1719 (C=O); 1663 (C=N and C=C) cm-1; H NMR
(DMSO-d6, 400 MHz): ꢁ 3.67 (s, 3H), 3.90 (d, J = 3.11 Hz, 1H),
5.34 (dd, J = 3.11, J = 6.21, 1H), 6.66 (d, J = 8.47 Hz, 2H) , 6.86
(d, J = 8.47 Hz, 2H), 7.52 (t, J = 7.24 Hz, 1H), 7.63 (s, 2H,
NH2), 7.65 (d, J = 7.65 Hz, 1H), 7.70 (t, J = 7.26 Hz, 1H), 7.98
(s, 2H, NH2), 8.22 (d, J = 7.65 Hz, 1H), 8.51 (d, J = 6.20, 1H,
NH) ppm; 13C NMR (DMSO-d6, 100 MHz): ꢁ 55.5, 56.3, 113.2,
121.7, 122.0, 126.9, 130.6, 131.6, 134.8, 137.2, 151.9, 155.2,
158.3, 196.9 ppm; Mass (m/z, %): 386 (M·+, 100), 358 (10), 357
(19), 279 (18), 251 (87). Anal. Calcd. For C21H18N6O2: C, 65.27;
H, 4.70; N, 21.75. Found: C, 65.33; H, 4.63; N, 21.73.
9,11-Diamino-6-(4-chlorophenyl)-6,7-dihydroindeno[1,2-e]-
pyrimido[4,5-b][1,4]diazepin-5(5aH)-one (7b). Yellow powder
(92%); mp 305-307 ºC (d); FTIR (KBr) ꢀ 3443, 3260, 3170 (NH
1
and NH2); 1719 (C=O); 1665 (C=N and C=C) cm-1; H NMR
(DMSO-d6, 400 MHz): ꢁ 4.07 (d, J = 3.71 Hz, 1H), 5.33 (dd, J =
3.72 Hz, J = 6.21 Hz,1H), 6.91 (d, J = 8.69 Hz, 2H) , 7.22 (d, J
= 8.69 Hz, 2H), 7.54 (t, J = 7.85 Hz, 1H), 7.60 (s, 2H, NH2),
7.65 (d, J = 7.65 Hz, 1H), 7.73 (t, J = 7.85 Hz, 1H), 8.12 (s, 2H,
NH2), 8.36 (d, J = 7.65 Hz, 1H), 8.84 (d, J = 6.20 Hz, 1H, NH)
ppm; 13C NMR (DMSO-d6, 100 MHz): ꢁ 55.7, 56.5, 99.5, 122.8,
127.9, 128.1, 128.3, 131.5, 132.4, 135.8, 137.4, 139.1, 147.7,
151.6, 155.0, 198.0 ppm; Mass (m/z, %): 390 (M·+, 42), 362
8,10-Diamino-6-(4-nitrophenyl)-6,7-dihydroindeno[1,2-e]-
pyrimido[5,4-b][1,4]diazepin-5(5aH)-one (8a). Orange powder
(8 %); mp 231-233 ºC (d); FTIR (KBr) ꢀ 3442, 3332, 3189 (NH
and NH2); 1724 (C=O); 1661 (C=N and C=C); 1525, 1346
(14),
361 (22), 279 (29), 251 (78). Anal. Calcd. For
C20H15ClN6O: C, 61.46; H, 3.87; N, 21.50. Found: C, 61.58; H,
3.79; N, 21.61.
1
(NO2) cm-1; H NMR (DMSO-d6, 400 MHz): ꢁ 4.09 (d, J = 3.52
Hz,1H), 5.41 (dd, J = 3.52 Hz, J = 8.00 Hz, 1H), 6.94 (s, 2H,
NH2) , 7.48 (d, J = 8.89 Hz, 2H), 7.52 (t, J = 7.85 Hz, 1H), 7.64
(s, 2H, NH2), 7.71 (t, J = 7.85 Hz, 1H), 8.02 (d, J = 8.89 Hz,
2H), 8.28 (d, J = 9.10 Hz, 1H), 8.28 (d, J = 8.00 Hz, 1H, NH),
8.37 (d, J = 9.09 Hz, 1H) ppm; 13C NMR (DMSO-d6, 100 MHz):
ꢁ 55.8, 56.5, 122.5, 123.5, 124.3, 126.4, 127.6, 131.1, 135.9,
137.1, 146.8, 147.8 ppm; Mass (m/z, %): 401 (M·+, 20), 373 (2),
372 (4), 279 (7), 251 (58). Anal. Calcd. For C20H15N7O3: C,
59.85; H, 3.77; N, 24.03. Found: C, 59.92; H, 3.81; N, 24.10.
9,11-Diamino-6-(4-bromophenyl)-6,7-dihydroindeno[1,2-e]-
pyrimido[4,5-b][1,4]diazepin-5(5aH)-one (7c). Orange powder
(89%); mp 310-312 ºC (d); FTIR (KBr) ꢀ 3450, 3297, 3161 (NH
1
and NH2); 1719 (C=O); 1665 (C=N and C=C) cm-1; H NMR
(DMSO-d6, 400 MHz): ꢁ 4.06 (d, J = 3.51 Hz, 1H), 5.30 (dd, J =
3.52, J = 6.41 Hz, 1H), 7.11 (d, J = 9.10 Hz, 2H) , 7.36 (d, J =
9.13 Hz, 2H), 7.54 (t, J = 7.03 Hz, 1H), 7.58 (s, 2H, NH2), 7.66
(d, J = 7.65 Hz, 1H), 7.73 (t, J = 7.00 Hz, 1H), 8.10 (s, 2H,
NH2), 8.36 (d, J = 7.65 Hz, 1H), 8.83 (d, J = 6.41 Hz, 1H, NH)