5698
K. Rad-Moghadam, L. Youseftabar-Miri / Tetrahedron 67 (2011) 5693e5699
(37), 295 (17), 71 (47), 43 (100). Anal. Calcd for C17H14N4O6: C,
55.14; H, 3.81; N, 15.13%. Found: C, 55.10; H, 3.86; N, 15.17%.
(d,1H, J 16 Hz, 8-HB), 2.15 (d,1H, J 16 Hz, 8-HA), 2.48 (d,1H, J 17.6 Hz, 6-
HB), 2.58 (d,1H, J 17.6 Hz, 6-HA), 3.69e3.72 (m, 2H, OCH2CH3), 6.67 (d,
1H, J 7.6 Hz, 70-H), 6.76 (t,1H, J 7.2 Hz, 50-H), 6.83 (d,1H, J 7.2 Hz, 40-H),
7.04 (t, 1H, J 7.2 Hz, 60-H), 7.86 (s, 2H, NH2), 10.14 (s, 1H, NH).
4.1.12. Ethyl 20-amino-5-nitro-30-cyano-60-propyl-2-oxo-spiro[indo-
line-3,40-pyran]-50-carboxylate (4l). White powder. Yield (0.36 g,
92%). Mp: 238e240 ꢀC. IR (KBr), nmax: 3392, 3303, 3200, 2992, 2200,
4.1.17. Ethyl 2-amino-20,5-dioxo-5,6-dihydro-spiro[pyrano[3,2-c]qui-
noline-4,30-indoline]-3-carboxylate (4q). Yellow powder. Yield
(0.35 g, 88%). Mp >300 ꢀC. IR (KBr), nmax: 3300, 3200, 2950,1720,1690,
1722, 1675, 1620, 1595, 1521, 1338 cmꢂ1 1H NMR (400.13 MHz,
.
DMSO-d6) d: 0.85 (t, 3H, J 7.2 Hz, CH3), 0.96 (t, 3H, J 7.2 Hz, CH3), 1.63
(br sextet, 2H, CH2CH2CH3), 2.65e2.80 (m, 2H, CH2CH2CH3),
3.79e3.87 (m, 2H, OeCH2CH3), 7.04 (d,1H, J 8.6 Hz, 7-H), 7.38 (s, 2H,
NH2), 7.96 (d, 1H, J 2.4 Hz, 4-H), 8.20 (dd, 1H, J 8.6 and 2.4 Hz, 6-H),
1670, 1620, 1365 cmꢂ1.1H NMR (400.13 MHz, DMSO-d6)
d: 0.84 (t, 3H, J
7.2 Hz, OCH2CH3), 3.70e3.82 (m, 2H, OCH2CH3), 6.71 (d,1H, J 7.6 Hz, 70-
H), 6.75 (t, 1H, J 7.2 Hz, 50-H), 6.87 (d, 1H, J 7.2 Hz, 40-H), 7.07 (t, 1H, J
7.6 Hz, 60-H), 7.30 (t,1H, J7.2 Hz, 9-H), 7.31 (d,1H, J8.0 Hz, 7-H),7.59(dt,
1H, J 7.8 and 1.4 Hz, 8-H), 8.02 (d, 1H, J 7.6 Hz, 10-H), 8.05 (s, 2H, NH2),
11.20 (s,1H, NH).13C NMR (100.61 MHz, DMSO-d6)
d: 13.5 (CH3),13.8
(CH3), 20.6 (CH2CH2CH3), 33.6 (CH2CH2CH3), 49.7 (Cspiro), 55.4
(CeC^N), 61.1 (OeCH2CH3), 103.9 (CeCO2Et), 110.1 (C^N), 117.6 (C-
3a), 119.3, 126.6, 136.2 (3CH), 142.9 (C-7a), 149.1 (C-5), 159.7, 163.5,
164.5 (C]O ester), 179.5 (C]O amide). MS (EI, 70 eV) m/z (%): 400
(Mþ, 80), 295 (37),105 (100). Anal. Calcd for C19H18N4O6: C, 57.28; H,
4.55; N, 14.06%. Found: C, 57.25; H, 4.59; N, 14.17%.
10.27 (s,1H, NH),11.53 (s,1H, NH). 13C NMR (100.61 MHz, DMSO-d6)
d:
13.6 (CH3), 48.2 (Cspiro), 59.4 (OeCH2), 76.4 (C-4a), 108.6, 110.0, 112.0,
115.5, 121.0, 122.4, 122.6, 123.2, 127.8, 132.0, 136.1, 138.1, 145.0, 151.6,
159.7, 159.8, 168.1 (C]O), 180.1 (C]O). MS (EI) m/z (%): 403 (Mþ, 3),
381 (100), 330 (MþꢂCO2Et,14), 253 (45). Anal. Calcd for C22H17N3O5:C,
65.50; H, 4.25; N, 10.42%. Found: C, 65.51; H, 4.33; N, 10.37%.
4.1.13. Ethyl 20-amino-5-methoxy-30-cyano-60-methyl-2-oxo-spiro
[indoline-3,40-pyran]-50-carboxylate (4m). White powder. Yield
(0.33 g, 94%). Mp: 214e216 ꢀC. IR (KBr), nmax: 3445, 3296, 3172, 2200,
4.1.18. Ethyl 2-amino-6-methyl-20,5-dioxo-5,6-dihydro-spiro[pyrano
[3,2-c]quinoline-4,30-indoline]-3-carboxylate (4r). White powder.
Yield (0.37 g, 90%). Mp >300 ꢀC. IR (KBr), nmax: 3305, 3197, 2996,
1716, 1700, 1681, 1621, 1600, 1494 cmꢂ1 1H NMR (400.13 MHz,
.
DMSO-d6)
d
: 0.81 (t, 3H, J 7.0 Hz, OCH2CH3), 2.32 (s, 3H, 60-CH3), 3.68
1715, 1685, 1623, 1524, 1465, 1360, 1287 cmꢂ1 1H NMR
.
(s, 3H, OCH3), 3.74e3.84 (m, 2H, OeCH2CH3), 6.68 (d, 1H, J 2.4 Hz, 4-
H), 6.71 (d,1H, J 8.4 Hz, 7-H), 6.75 (dd,1H, J 8.4 and 2.4 Hz, 6-H), 7.14
(400.13 MHz, DMSO-d6) d: 0.87 (t, 3H, J 7.2 Hz, OCH2CH3), 3.45 (s,
3H, 6-CH3), 3.71e3.83 (m, 2H, OCH2CH3), 6.72 (d, 1H, J 7.6 Hz, 70-H),
6.74 (t, 1H, J 7.6 Hz, 50-H), 3.86 (d, 1H, J 6.8 Hz, 40-H), 7.07 (dt, 1H, J
7.6 and 1.2 Hz, 60-H), 7.41 (t,1H, J 7.4 Hz, 9-H), 7.53 (d,1H, J 8.4 Hz, 7-
H), 7.71 (dt, 1H, J 8.0 and 1.2 Hz, 8-H), 8.08 (s, 2H, NH2), 8.15 (dd, 1H,
J 8.0 and 1.2 Hz, 10-H), 10.29 (s, 1H, NH).
(s, 2H, NH2), 10.22 (s, 1H, NH). 13C NMR (100.61 MHz, DMSO-d6)
d:
13.5 (OeCH2CH3), 19.1 (60-CH3), 49.9 (Cspiro), 55.9 (OCH3), 57.1
(CeC^N), 60.7 (OeCH2CH3), 105.0 (CeCO2Et), 110.2, 110.7, 113.6,
118.0 (C-3a),135.9,136.3,155.5,159.1,159.4,165.0 (C]O ester),179.0
(C]O amide). MS (EI, 70eV) m/z (%): 355 (Mþ,13), 282 (28), 225 (33),
210 (41), 177 (54), 149 (85), 106 (100). Anal. Calcd for C18H17N3O5: C,
60.84; H, 4.82; N, 11.83%. Found: C, 60.83; H, 4.89; N, 11.75%.
4.1.19. 2-Amino-50-methoxy-20,5-dioxo-5,6-dihydro-spiro[pyrano
[3,2-c]quinoline-4,30-indoline]-3-carbonitrile (4s). Yellow powder.
Yield (0.34 g, 89%). Mp >300 ꢀC. IR (KBr), nmax: 3530, 3402, 3300,
4.1.14. Ethyl 20-amino-5-methoxy-30-cyano-60-propyl-2-oxo-spiro[indo-
line-3,40-pyran]-50-carboxylate (4n). White powder. Yield (0.35 g,
92%). Mp: 230e232 ꢀC. IR (KBr), nmax: 3400, 3300, 3200, 2960,
2200, 1722, 1668,1600,1485 cmꢂ1. 1H NMR (400.13 MHz, DMSO-d6)
3155, 2198, 1707, 1670, 1620, 1588, 1486, 1360 cmꢂ1 1H NMR
.
(400.13 MHz, DMSO-d6) d
: 3.63(s, 3H, OCH3), 6.69(br s,1H, 40-H), 6.74
(m, 2H, 60-H and 70-H), 7.33 (t,1H, J 7.6 Hz, 9-H), 7.36 (d,1H, J 7.6 Hz, 7-
H), 7.45(s, 2H, NH2),7.62(dt,1H, J7.6 and 1.4 Hz), 7.95 (dd, 1H, J8.0and
1.2 Hz, 10-H), 10.35 (s, 1H, NH), 11.72 (s, 1H, NH). 13C NMR
d: 0.82 (t, 3H, J 7.2 Hz, CH3), 0.95 (t, 3H, J 7.2 Hz, CH3), 1.63 (br sextet,
2H, CH2CH2CH3), 2.61e2.71 (m, 2H, CH2CH2CH3), 3.68 (s, 3H, OCH3),
3.74e3.83 (m, 2H, OCH2CH3), 6.61 (d, 1H, J 2.4 Hz, 4-H), 6.71 (d, 1H, J
8.4 Hz, 7-H), 6.76 (dd, 1H, J 8.4 and 2.4 Hz, 6-H), 7.14 (s, 2H, NH2),
(100.61 MHz, DMSO-d6) d: 48.7 (Cspiro), 55.8 (OCH3), 57.7 (CeC^N),
107.4, 110.0, 110.7, 112.1, 113.6, 115.8, 118.0, 122.5, 122.6, 132.2, 136.0,
136.2, 138.3, 152.9 (C-50),155.5(C-4b),159.4,159.9(C-2and C-5),178.3
(C]O oxindoline). MS (EI) m/z (%): 381 (MþꢂNH2, 4), 370 (6), 368 (5),
342 (18), 305 (100), 277 (57), 250 (39). Anal. Calcd for C21H14N4O4: C,
65.28; H, 3.65; N, 14.50%. Found: C, 65.25; H, 3.65; 14.61%.
10.22 (s, 1H, NH). 13C NMR (100.61 MHz, DMSO-d6)
d: 13.5 (CH3),
13.7 (CH3), 20.6 (CH2CH2CH3), 33.3 (CH2CH2CH3), 49.9 (Cspiro), 55.9
(OCH3), 56.9 (CeCN), 60.7 (OeCH2CH3), 105.5 (CeCO2Et), 110.2,
110.7, 113.5, 118.0 (C-3a), 135.9, 136.2, 155.5 (C-5), 159.6, 161.6 (C-20
and C-60), 164.9 (C]O ester), 178.9 (C]O amide). MS (EI, 70 eV) m/z
(%): 383 (Mþ, 16), 328 (14), 310 (32), 57 (58), 43 (100). Anal. Calcd
for C20H21N3O5: C, 62.65; H, 5.52; N, 10.96%. Found: C, 62.60; H,
5.58; N, 10.87%.
4.1.20. Ethyl 2-amino-50-methoxy-6-methyl-20,5-dioxo-5,6-dihydro-
spiro[pyrano[3,2-c]quinoline-4,30-indoline]-3-carboxylate
(4t). Yellow powder. Yield (0.40 g, 90%). Mp >300 ꢀC. IR (KBr), nmax
:
3350, 3280, 2965, 1705, 1685, 1645, 1593, 1484, 1358, 1282 cmꢂ1. 1H
NMR (400.13 MHz, DMSO-d6) : 0.88 (t, 3H, J 6.8 Hz, OCH2CH3), 3.46
d
4.1.15. Ethyl 2-amino-20,5-dioxo-5,6,7,8-tetrahydro-spiro[chromene-
4,30-indoline]-3-carboxylate (4o). White powder. Yield (0.31 g,
93%). Mp: 252e254 ꢀC. IR (KBr), nmax: 3374, 3230, 3180, 1718, 1708,
(s, 3H, NeCH3), 3.58 (s, 3H, OeCH3), 3.78 (m, 2H, OCH2CH3), 6.50 (d,
1H, J 2.2 Hz, 40-H), 6.62 (d, 1H, J 8.0 Hz, 70-H), 6.65 (dd, 1H, J 8.4 and
2.2 Hz, 60-H), 7.40 (t, 1H, J 8.0 Hz, 9-H), 7.53 (d, 1H, J 8.4 Hz, 7-H),
7.72 (dt, 1H, J 7.8 and 1.6 Hz, 8-H), 8.07 (s, 2H, NH2), 8.15 (dd, 1H, J
8.0 and 1.2 Hz, 10-H), 10.12 (s, 1H, NH). 13C NMR (100.61 MHz,
1685, 1650, 1618, 1590 cmꢂ1 1H NMR (400.13 MHz, DMSO-d6)
. d:
0.79 (t, 3H, J 7.2 Hz, OCH2CH3), 1.80e1.92 (m, 2H, CH2), 2.10e2.26
(m, 2H, CH2), 2.64 (t, 2H, J 6.4 Hz, CH2), 3.64e3.75 (m, 2H,
OCH2CH3), 6.66 (d, 1H, J 7.6 Hz, 70-H), 6.76 (dt, 1H, J 7.2 and 0.8 Hz,
50-H), 6.85 (d, 1H, J 6.8 Hz, 40-H), 7.04 (dt, 1H, J 7.6 and 1.2 Hz, 60-H),
7.85 (s, 2H, NH2), 10.14 (s, 1H, NH).
DMSO-d6)
d: 13.6 (OCH2CH3), 29.6 (NeCH3), 49.0 (Cspiro), 55.7
(OCH3), 59.4 (OCH2CH3), 76.5 (CeC^N), 108.6, 109.4, 110.5, 112.1,
112.7, 115.2, 122.6, 123.1, 132.4, 137.3, 138.8, 139.0, 150.8 (C-50), 154.8
(C-4b), 159.1, 159.6 (C-2 and C-5), 168.1 (C]O ester), 179.9 (C]O
oxindoline). MS (EI) m/z (%): 447 (Mþ, 26), 374 (MþꢂCO2Et, 59), 317
(100), 249 (84). Anal. Calcd for C24H21N3O6: C, 64.42; H, 4.73; N,
9.39%. Found: C, 64.37; H, 4.77; N, 9.43%.
4.1.16. Ethyl 2-amino-7,7-dimethyl-20,5-dioxo-5,6,7,8-tetrahydro-spiro
[chromene-4,30-indoline]-3-carboxylate (4p). White powder. Yield
(0.35 g, 91%). Mp: 255e257 ꢀC. IR (KBr), nmax: 3360, 3230, 3190, 1713,
1682, 1664, 1610, 1520 cmꢂ1. 1H NMR (400.13 MHz, DMSO-d6)
d: 0.80
4.1.21. 2-Amino-50-nitro-20,5-dioxo-5,6-dihydro-spiro[pyrano[3,2-c]
quinoline-4,30-indoline]-3-carbonitrile (4u). Yellow powder. Yield
(t, 3H, J 7.2 Hz, OCH2CH3), 0.95 (s, 3H, 7-CH3), 1.02 (s, 3H, 7-CH3), 2.01