48
R. Ghahremanzadeh, T. Amanpour, and A. Bazgir
Vol 47
100-Amino-1,2-dihydro-1-methyl-5-nitro-2,70-dioxospiro[3H-
indole-3,80(7H,8H)-phenaleno[1,2-b]pyran]-90-carbonitrile (4e).
Yellow powder (97%); mp >300ꢀC dec. IR (potassium bro-
mide): 3311, 3198, 2197, 1730, 1666 cmꢁ1. 1H NMR (dimethyl
sulfoxide-d6): dH 3.36 (s, 3H, NCH3), 7.36–8.48 (m, 11H, HAAr
and NH2). 13C NMR (dimethyl sulfoxide-d6): dC 27.4, 47.9,
55.8, 109.0, 112.1, 117.5, 119.7, 121.1, 125.5, 126.4, 127.1,
127.3, 127.9, 128.2, 130.7, 131.9, 134.5, 135.1, 136.5, 153.5,
150.1, 156.2, 159.7, 177.9, 181.2. MS (70 eV, electron impact)
m/z: 450 (Mþ). Anal. Calcd for C25H14N4O5: C, 66.67; H, 3.13;
N, 12.44%. Found: C, 66.61; H, 3.17; N, 12.49%.
Scheme 4
recorded using an FTIR apparatus. Elemental analyses were
performed using a Heracus CHN-O-Rapid analyzer.
100-Amino-1,2-dihydro-1-ethyl-5-nitro-2,70-dioxospiro[3H-
indole-3,80(7H,8H)-phenaleno[1,2-b]pyran]-90-carbonitrile
(4f). Yellow powder (88%); mp >300ꢀC dec. IR (potassium
Typical procedure for the preparation of spirooxindoles
4a–i, 7a–c, and 9. A mixture of malononitrile (1 mmol), isa-
tins (1 mmol), 3-hydroxy-1H-phenalen-1-one or 4-hydroxy-6-
methyl-2H-pyran-2-one (1 mmol), p-TSA (0.1 g) was refluxed
in water (5 mL) for 24 h (TLC). After completion of reaction,
the reaction mixture was filtered and the precipitate washed
with ethanol to afford the pure product.
bromide): 3435, 3322, 2207, 1719, 1667 cmꢁ1
.
1H NMR (di-
3
methyl sulfoxide-d6): dH 1.30 (t, 3H, JHH ¼ 6.9 Hz, CH3),
3.87–4.01 (m, 2H, NCH2), 7.39–8.45 (m, 11H, HAAr and
NH2). 13C NMR (dimethyl sulfoxide-d6): dC 12.7, 47.8, 56.0,
109.0, 112.0, 117.4, 119.8, 121.0, 125.5, 126.4, 127.0, 127.1,
127.2, 127.8, 128.1, 130.6, 131.9, 134.4, 135.3, 136.4, 143.3,
149.2, 156.2, 159.6, 177.4, 181.2. MS (70 eV, electron impact)
m/z: 464 (Mþ). Anal. Calcd for C26H16N4O5: C, 67.24; H,
3.47; N, 12.06%. Found: C, 67.30; H, 3.42; N, 12.13%.
100-Amino-1,2-dihydro-2,70-dioxospiro[3H-indole-3,80(7H,8H)-
phenaleno[1,2-b]pyran]-90-carbonitrile (4a). Yellow powder
(93%); mp >300ꢀC dec. IR (potassium bromide): 3403, 3015,
2200, 1730, 1669 cmꢁ1. H NMR (dimethyl sulfoxide-d6): dH
1
6.87–8.41 (m, 12H, HAAr and NH2), 10.63 (s, 1H, NH). 13C
NMR (dimethyl sulfoxide-d6): dC 48.2, 57.7, 109.8, 113.4,
117.8, 121.0, 122.2, 123.9, 125.4, 127.3, 127.7, 127.9, 128.8,
130.4, 131.9, 134.1, 134.9, 136.1, 142.7, 155.3, 156.2, 178.5,
181.0. MS (70 eV, electron impact) m/z: 391 (Mþ). Anal.
Calcd for C24H13N3O3: C, 73.65; H, 3.35; N, 10.74%. Found:
C, 73.60; H, 3.39; N, 10.80%.
100-Amino-5-bromo-1,2-dihydro-2,70-dioxospiro[3H-indole-
3,80(7H,8H)-phenaleno[1,2-b]pyran]-90-carbonitrile (4g). Yellow
powder (94%); mp 310ꢀC dec. IR (potassium bromide): 3322,
3198, 2199, 1724, 1665 cmꢁ1 1H NMR (dimethyl sulfoxide-
.
d6): dH 6.86–8.40 (m, 11H, HAAr and NH2), 10.77 (s, 1H,
NH). 13C NMR (dimethyl sulfoxide-d6): dC 48.5, 57.0, 111.6,
112.7, 113.9, 117.8, 121.1, 125.4, 126.9, 127.2, 127.8, 130.4,
131.5, 131.8, 134.1, 136.1, 137.3, 142.1, 155.7, 159.3, 178.2,
181.1. MS (70 eV, electron impact) m/z: 471 (Mþ þ2), 469
(Mþ). Anal. Calcd for C24H12BrN3O3: C, 61.30; H, 2.57; N,
8.94%. Found: C, 61.25; H, 2.52; N, 8.87%.
100-Amino-1,2-dihydro-1-methyl-2,70-dioxospiro[3H-indole-
3,80(7H,8H)-phenaleno[1,2-b]pyran]-90-carbonitrile (4b). Yellow
powder (75%); mp >300ꢀC dec. IR (potassium bromide):
3347, 3111, 2200, 1724, 1663 cmꢁ1. H NMR (dimethyl sulf-
1
oxide-d6): dH 3.25 (s, 3H, NCH3), 6.95–8.48 (m, 12H, HAAr
and NH2). 13C NMR (dimethyl sulfoxide-d6): dC 31.7, 52.7,
62.2, 113.5, 118.1, 122.4, 125.8, 127.8, 128.4, 130.2, 132.1,
132.7, 133.8, 135.3, 136.7, 138.8, 139.0, 141.1, 149.0, 160.2,
164.1, 181.8, 185.8. MS (70 eV, electron impact) m/z: 405
(Mþ). Anal. Calcd for C25H15N3O3: C, 74.07; H, 3.73; N,
10.36%. Found: C, 74.01; H, 3.67; N, 10.28%.
100-Amino-5-bromo-1,2-dihydro-1-methyl-2,70-dioxospiro[3H-
indole-3,80(7H,8H)-phenaleno[1,2-b]pyran]-90-carbonitrile (4h).
Yellow powder (91%); mp >300ꢀC dec. IR (potassium bro-
mide): 3378, 3306, 3142, 2207, 1716, 1676 cmꢁ1 1H NMR
.
(dimethyl sulfoxide-d6): dH 3.35 (s, 3H, NCH3), 7.11–8.46 (m,
11H, HAAr and NH2). 13C NMR (dimethyl sulfoxide-d6): dC
27.1, 48.0, 56.6, 110.7, 112.6, 114.8, 117.7, 121.1, 125.5,
126.7, 127.2, 127.3, 127.9, 128.0, 130.6, 131.7, 131.9, 134.3,
136.3, 136.4, 143.6, 155.8, 159.4, 176.8, 181.1. MS (70 eV,
electron impact) m/z: 485 (Mþ þ2), 483 (Mþ). Anal. Calcd
for C25H14BrN3O3: C, 62.00; H, 2.91; N, 8.68%. Found: C,
61.96; H, 2.96; N, 8.60%.
100-Amino-1,2-dihydro-1-ethyl-2,70-dioxospiro[3H-indole-
3,80(7H,8H)-phenaleno[1,2-b]pyran]-90-carbonitrile (4c). Yellow
powder (83%); mp >300ꢀC dec. IR (potassium bromide):
3312, 2993, 2192, 17.9, 1664 cmꢁ1 1H NMR (dimethyl sulf-
.
oxide-d6): dH 1.24 (bs, 3H, CH3), 4.05 (bs, 2H, NCH2), 6.93–
8.42 (m, 12H, HAAr and NH2). MS (70 eV, electron impact)
m/z: 419 (Mþ). Anal. Calcd for C26H17N3O3: C, 74.45; H,
4.09; N, 10.02%. Found: C, 74.40; H, 4.05; N, 10.09%.
Due to very low solubility of the product 4c, we cannot
report the 13C NMR data for this product.
100-Amino-5-bromo-1,2-dihydro-1-ethyl-2,70-dioxospiro[3H-
indole-3,80(7H,8H)-phenaleno[1,2-b]pyran]-90-carbonitrile (4i).
Yellow powder (89%); mp >300ꢀC dec. IR (potassium bro-
mide): 3265, 2962, 2192, 1698, 1665 cmꢁ1.1H NMR (dimethyl
3
100-Amino-1,2-dihydro-5-nitro-2,70-dioxospiro[3H-indole-
3,80(7H,8H)-phenaleno[1,2-b]pyran]-90-carbonitrile (4d). Yellow
powder (90%); mp >300ꢀC dec. IR (potassium bromide):
sulfoxide-d6): dH 1.25 (t, 3H, JHH ¼ 6.9 Hz, CH3), 3.74–3.90
(m, 2H, NCH2), 7.10–8.47 (m, 11H, HAAr and NH2). 13C
NMR (dimethyl sulfoxide-d6): dC 110.0, 111.6, 112.0, 120.1,
120.8. 121.1, 121.8, 122.4, 126.0, 127.1, 127.6, 127.8, 129.5,
131.5, 133.1, 134.6, 138.7, 139.8, 140.7, 146.8, 149.7, 153.4.
MS (70 eV, electron impact) m/z: 499 (Mþ þ2), 497 (Mþ).
Anal. Calcd for C26H16BrN3O3: C, 62.67; H, 3.24; N, 8.43%.
Found: C, 62.61; H, 3.20; N, 8.50%.
3328, 3018, 2197, 1714, 1666 cmꢁ1. H NMR (dimethyl sulf-
1
oxide-d6): dH 7.11–8.46 (m, 11H, HAAr and NH2), 11.41 (s,
1H, NH). 13C NMR (dimethyl sulfoxide-d6): dC 48.4, 56.2,
109.9, 112.2, 117.6, 120.0, 121.1, 125.5, 126.3, 127.2, 127.3,
127.9, 128.1, 130.6, 131.9, 134.3, 135.9, 136.4, 143.0, 149.3,
156.1, 159.6, 179.2, 181.2. MS (70 eV, electron impact) m/z:
436 (Mþ). Anal. Calcd for C24H12N4O5: C, 66.06; H, 2.77; N,
12.84%. Found: C, 66.12; H, 2.82; N, 12.75%.
20-Amino-1,2-dihydro-70-methyl-2,50-dioxospiro[3H-indoline-
3,40(4H,5H)-pyrano[4,3-b]pyran]-30-carbonitrile (7a). Brown
powder (54%); mp 265ꢀC dec. IR (potassium bromide): 3337,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet