1972
K. Rad-Moghadam, L. Youseftabar-Miri
LETTER
(5) (a) Breslow, R.; Rideout, D. C. J. Am. Chem. Soc. 1980, 102,
7816. (b) Lindström, U. M. Chem. Rev. 2002, 102, 2751.
(c) Herrerias, C. I.; Yao, X.; Li, Z.; Li, C. Chem. Rev. 2007,
107, 2546.
(6) (a) Suarez, M.; Verdecia, Y.; Illescas, B.; Martinez-Alvarez,
R.; Avarez, A.; Ochoa, E.; Seoane, C.; Kayali, N.; Martin, N.
Tetrahedron 2003, 59, 9179. (b) Shan, R.; Velazquez, C.;
Knaus, E. E. J. Med. Chem. 2004, 47, 254.
(7) (a) Sausins, A.; Duburs, G. Heterocycles 1988, 27, 269.
(b) Godfraind, T.; Miller, R.; Wibo, M. Pharmacol. Rev.
1986, 38, 321.
(8) Zhorov, B. V.; Folkman, E. V.; Ananthanarayanan, V. S.
Arch. Biochem. Biophys. 2001, 393, 22.
d, J = 8.4 Hz), 10.52 (1 H, s, NH), 11.42 (1 H, s, NH). 13
C
NMR (100.6 MHz, DMSO-d6): d = 51.4 (Cspiro), 102.7 (C-
12a), 110.4 (C-11a), 119.0, 120.7, 120.8, 121.5, 122.5,
124.0, 125.1, 125.7, 126.3, 127.2, 127.6, 128.8, 131.1,
132.1, 132.3, 133.6, 134.2, 136.7, 138.8, 143.2, 148.6 (C-
6a), 157.0 (C-7a), 180.4 (amidic C=O), 189.6 (C=O). MS
(EI, 70 eV): m/z (%) = 445 (48) [M+], 443 (100) [M+ – 2],
417 (60) [M+ – C=O], 400(89), 399 (75) [417 – H2O], 369
(76). Anal. Calcd for C27H15N3O4: C, 72.80; H, 3.39; N, 9.43.
Found: C, 72.76; H, 3.42; N, 9.37.
Spiro[1H-indeno[1,2-b]benzo[f]quinolin-13,3-indoline]-
7,13-dihydro-5¢-methoxy-12,2¢-dione (4c)
Orange powder (0.335 g, 78%); mp 306–308 °C. IR (KBr):
3237, 1703, 1684, 1532, 1187, 1175 cm–1. 1H NMR (400.13
MHz, DMSO-d6): d = 3.56 (3 H, s, OCH3), 6.56 (1 H, d,
J = 2.4 Hz, 4¢-H), 6.67 (1 H, d, J = 8.8 Hz, 1-H), 6.79 (1 H,
dd, J = 8.4, 2.0 Hz, 6¢-H), 6.89 (1 H, d, J = 8.8 Hz, 7¢-H),
7.26 (1 H, d, J = 6.8 Hz), 7.41 (1 H, t, J = 7.2 Hz), 7.54 (1 H,
d, J = 8.0 Hz), 7.55 (1 H, t, J = 6.4 Hz), 7.61 (1 H, t, J = 7.6
Hz), 7.72 (1 H, t, J = 7.2 Hz), 7.88 (1 H, d, J = 8.0 Hz), 8.17
(1 H, d, J = 7.2 Hz), 8.76 (1 H, d, J = 8.4 Hz), 10.35 (1 H, s,
NH), 10.48 (1 H, s, NH). 13C NMR (100.6 MHz, DMSO-d6):
d = 51.8 (Cspiro), 55.8 (OCH3), 102.8 (C-12a), 110.4 (C-11a),
111.7, 113.7, 120.5, 120.6, 121.1, 122.4, 123.9, 125.2,
125.4, 127.0, 127.2, 128.7, 130.9, 131.8, 132.0, 133.4,
134.3, 135.3, 136.8, 139.6, 155.8 (C-6a), 156.6 (C-7a), 179.9
(amidic C=O), 189.6 (C=O). MS (EI, 70 eV): m/z (%) = 430
(98) [M+], 402 (100) [M+ – C=O], 385 (88). Anal. Calcd for
C28H18N2O3: C, 78.13; H, 4.21; N, 6.51. Found: C, 78.22; H,
4.33; N, 6.46.
(9) Sannigrahi, M. Tetrahedron 1999, 55, 9007.
(10) (a) Okita, T.; Isobe, M. Tetrahedron 1994, 50, 11143.
(b) Rosenmond, P.; Hosseini-Merescht, M.; Bub, C. Liebigs
Ann. Chem. 1994, 2, 151. (c) Kornet, M. J.; Thio, A. P. J.
Med. Chem. 1976, 19, 892.
(11) (a) Kornet, M. J.; Thio, A. P. J. Med. Chem. 1979, 19, 892.
(b) Hilton, S. T.; Ho, T. C.; Pljevaljcic, G.; Jones, K. Org.
Lett. 2000, 2, 2639.
(12) For selected reviews, see: (a) Wang, L. M.; Jiao, N.; Qiu, J.;
Yu, J. J.; Liu, J. Q.; Guo, F. L.; Liu, Y. Tetrahedron 2010,
66, 339. (b) Abdel-Rahman, A. H.; Keshk, E. M.; Hanna, M.
A.; El-Bady, Sh. M. Bioorg. Med. Chem. 2004, 12, 2483.
(c) Ahadi, S.; Ghahremanzadeh, R.; Mirzaei, P.; Bazgir, A.
Tetrahedron 2009, 65, 9316.
(13) General Procedure for the Synthesis of Spiro{1H-
indeno[1,2-b]benzo[f]quinolin-13,3¢-indoline}-7,13-
dihydro-12,2¢-dione Derivatives 4a–e
To a stirred mixture of 2H-indene-1,3-dione (1, 0.146 g, 1
mmol), naphthalen-2-amine 2 (0.143 g, 1 mmol), and an
isatin derivatives 3a–e (1 mmol) in a solution of H2O–EtOH
[6 mL, 5:1 (v/v)], was added a catalytic amount of PTSA
(monohydrate, 0.1 g). The mixture was stirred at 60 °C (oil
bath) for about 15 min (as monitored by TLC). After
completion, the reaction mixture was filtered and the
obtained precipitate washed with hot EtOH (95.5%).
(14) Spiro{1H-indeno[1,2-b]benzo[f]quinolin-13,3¢-indoline}-
7,13-dihydro-12,2¢-dione (4a)
Spiro{1H-indeno[1,2-b]benzo[f]quinolin-13,3¢-indoline}-
7,13-dihydro-1¢-benzyl-12,2¢-dione (4e)
Orange powder (0.387 g, 79%); mp 310 °C (decomp.). IR
(KBr): 3235, 1686, 1622, 1604, 1526, 1362 cm–1. 1H NMR
(400.13 MHz, DMSO-d6): d = 5.00 (1 H, d, J = 16.0 Hz),
5.13 (1 H, d, J = 16.0 Hz), 6.58 (1 H, d, J = 8.8 Hz, 1-H),
6.91–6.96 (2 H, m), 7.05 (1 H, d, J = 7.2 Hz, 7¢-H), 7.21 (1
H, t, J = 7.6 Hz), 7.27–7.45 (6 H, m), 7.51–7.59 (3 H, m),
7.64 (1 H, t, J = 7.6 Hz), 7.75 (1 H, t, J = 7.6 Hz), 7.89 (1 H,
d, J = 8.4 Hz), 8.22 (1 H, d, J = 7.2 Hz), 8.79 (1 H, d, J = 8.4
Hz), 10.47 (1 H, s, NH). MS (EI, 70 eV): m/z (%) = 490 (34)
[M+], 461 (4) [M+ – HCO], 399 (100) [M+ – benzyl], 371
(86) [399 – C=O]. Anal. Calcd for C34H22N2O2: C, 83.25; H,
4.52; N, 5.71. Found: C, 83.12; H, 4.59; N, 5.58.
Red powder (0.340 g, 85%); mp 298–300 °C. IR (KBr):
3470, 3210, 3050, 1688, 1672, 1618 cm–1. 1H NMR (400.13
MHz, DMSO-d6): d = 6.67 (1 H, d, J = 8.4 Hz, 1-H), 6.86 (1
H, t, J = 7.2Hz, 4¢-H), 6.96 (2 H, t, J = 8.0 Hz, 5¢-H and 6¢-
H), 7.21 (1 H, t, J = 7.6 Hz, 7¢-H), 7.26 (1 H, d, J = 6.8 Hz),
7.41 (1 H, t, J = 7.2 Hz), 7.54 (1 H, d, J = 8.8 Hz), 7.55 (1 H,
t, J = 8.0 Hz), 7.62 (1 H, t, J = 7.2 Hz), 7.73 (1 H, t, J = 6.8
Hz), 7.88 (1 H, d, J = 8.0 Hz), 8.18 (1 H, d, J = 7.2 Hz), 8.76
(1 H, d, J = 8.4 Hz), 10.36 (1 H, s, NH), 10.65 (1 H, s, NH).
13C NMR (100.6 MHz, DMSO-d6): d = 51.3 (Cspiro), 104.0
(C-12a), 110.0 (C-11a), 120.5, 120.6, 121.1, 122.3, 122.7,
123.9, 125.1, 125.2, 125.4, 127.0, 127.3, 128.7, 128.8,
130.9, 131.8, 132.0, 133.3, 134.2, 136.8, 138.4, 141.9 (C-
6a), 156.5 (C-7a), 180.0 (amidic C=O), 189.6 (C=O). MS
(EI, 70 eV): m/z (%) = 400(56) [M+], 384 (14), 371 (100),
355 (95). Anal. Calcd for C27H16N2O2: C, 80.99; H, 4.03; N,
7.00. Found: C, 81.03; H, 4.21; N, 6.89.
Due to the very low solubility of compounds 4d and 4e we
were unable to obtain their 13C NMR spectra.
(15) Spiro{1H-indeno[1,2-b]benzo[f]quinolin-13,1¢(2¢H)-
acenaphthylene}-7,13-dihydro-12,2¢-dione (9)
Brick red powder (0.352 g, 81%); mp 284–286 °C. IR
(KBr): 3295, 1702, 1684, 1620, 1586, 1525 cm–1. 1H NMR
(400.13 MHz, DMSO-d6): d = 6.27 (1 H, d, J = 8.8 Hz, 1-H),
7.17 (1 H, d, J = 6.8 Hz), 7.34 (1 H, d, J = 6.8 Hz), 7.38–7.40
(2 H, m), 7.57 (1 H, t, J = 7.2 Hz), 7.62 (1 H, t, J = 8.6 Hz),
7.64 (1 H, t, J = 8.4 Hz), 7.74–7.91 (3 H, m), 8.02 (1 H, d,
J = 8.4 Hz), 8.12 (1 H, d, J = 6.8 Hz), 8.22 (1 H, d, J = 7.6
Hz), 8.41 (1 H, d, J = 8.4 Hz), 8.82 (1 H, d, J = 8.8 Hz),
10.45 (1 H, s, NH). 13C NMR (100.6 MHz, DMSO-d6): d =
57.2 (Cspiro), 105.3 (C-12a), 120.6 (C-11a), 121.2, 121.9,
122.4, 123.18, 123.22, 124.0, 125.1, 125.2, 125.6, 127.1,
127.3, 128.7, 129.4, 129.9, 130.4, 131.0, 132.0, 132.1,
132.5, 132.7, 133.3, 134.1, 136.7, 136.8, 141.9 (C-6a), 158.7
(C-7a), 189.9 (C=O), 209.8 (C=O). MS (EI, 70 eV): m/z (%)
= 435 (82) [M+], 407 (78) [M+ – C=O], 406 (100) [M+ –
HC=O]. Anal. Calcd for C31H17NO2: C, 85.50; H, 3.93; N,
3.22. Found: C, 85.61; H, 4.11; N, 3.14.
Spiro{1H-indeno[1,2-b]benzo[f]quinolin-13,3¢-indoline}-
7,13-dihydro-5¢-nitro-12,2¢-dione (4b)
Red powder (0.360, 81%); mp 304 °C (decomp.). IR (KBr):
3470, 3240, 1706, 1620, 1527, 1330 cm–1. 1H NMR (400.13
MHz, DMSO-d6): d = 6.69 (1 H, d, J = 8.8 Hz, 1-H), 7.21 (1
H, d, J = 8.8 Hz, 7¢-H), 7.28 (1 H, d, J = 7.2 Hz), 7.43 (1 H,
t, J = 7.2 Hz), 7.57 (1 H, t, J = 7.2 Hz), 7.58 (1 H, d, J = 8.8
Hz), 7.65 (1 H, t, J = 7.6 Hz), 7.76 (1 H, t, J = 7.2 Hz), 7.86
(1 H, d, J = 2.0 Hz, 4¢-H), 7.91 (1 H, d, J = 8.0 Hz), 8.22 (1
H, dd, J = 8.8, 2.4 Hz), 8.23 (1 H, d, J = 8.4 Hz), 8.82 (1 H,
Synlett 2010, No. 13, 1969–1973 © Thieme Stuttgart · New York