156 JOURNAL OF CHEMICAL RESEARCH 2009
6'-Amino-5 -bromo- 5'-cyano-3' -methyl-l '-phenylspiro {indo line-
6'-Amino-5 -bromo-5 '-cyano-3' -phenylspiro{indoline-3, 4 '(1HJ-
pyrano[2,3-c}pyrazol}-2-one (4k): M.p. 258-259°C. IR (em-'): 3397
(NH2), 3142 (NH), 2188 (CN), 1714 (CO). 'H NMR 8: 6.70 (d, lH,
J= 8.5 Hz, ArH), 6.85 (m, 2H,ArH), 7.18-7.35 (m, 7H,ArH, NH2), 10.66
(s, lH, CONH), 12.95 (s, lH, N-NH), Anal. Calcd for C20H12BrNs02:
C, 55.32; H, 2.79; N, 16.13. Found: C, 55.21; H, 2.66; N, 16.20%.
6'-Amino- 5'-cyano-5 -nitro-3 '-phenylspiro {indoline-3, 4'(1 HJ-
pyrano[2,3-c}pyrazol}-2-one (41): M.p. 212-213°C. IR (em-'): 3325
(NH2), 2194 (CN), 1726 (CO). 'H NMR 8: 6.84 (d, 2H, J= 7.5 Hz,
ArH), 6.91 (d, lH, J= 7.5 Hz, ArH), 7.19 (m, 2H, ArH), 7.27 (m, 2H,
ArH), 7.46 (s, 2H, NH2), 7.90 (s, lH, CONH) , 8.10 (m, lH, ArH),
13.00 (s, 1H, N-NH). Anal. Calcd for C2oH12N604: C, 60.00; H,
3.02; N, 20.99. Found: C, 60.12; H, 3.08; N, 20.87%.
3,4'(1HJ-pyrano[2,3-c}pyrazol}-2-one
(4c): M.p. 198°C IR (em-'):
3370 (NH2), 3187 (NH), 2205 (CN), 1705 (CO). 'H NMR 8: 1.59
(s, 3H, CH3), 6.91 (d, lH, J = 8 Hz, ArH), 7.35 (t,lH, J = 7 Hz,
ArH), 7.46 (m, 2H, ArH), 7.52 (m, 2H, ArH), 7.64 (s, 2H, NH2),
7.78(d, 2H, J = 7.5 Hz, ArH), 10.90 (s, lH, CONH). Anal. Calcd
for C2,H'4BrNs02: C, 56.27; H, 3.15; N, 15.62. Found: C, 56.07; H,
3.21; N, 15.55%.
6'-Amino-5 '-cyano-3 '-methyl-5-nitro-l '-phenylspiro[indoline-
3,4'(1HJ-pyrano[2,3-c} pyrazol}-2-one (4d): M.p. 219-220°C, lit.
m.p. 226-228°C.2S IR (em-'): 3377 (NH2), 3189 (NH), 2206 (CN),
1711 (CO). 'H NMR 8: 1.59 (s, 3H, CH3), 7.17 (d, lH, J= 8.5 Hz,
ArH), 7.36 (m, lH, ArH), 7.52 (m, 2H, ArH), 7.73 (s, 2H, NH2), 7.79
(m, 2H, ArH), 8.22 (d, lH, J= 2.5 Hz, ArH), 8.28 (dd, lH, J,: 1.7, J2:
8.5 Hz, ArH), 11.48 (s, lH, CONH). Anal. Calcd for C2,H'4N604: C,
60.87; H, 3.41; N, 20.28. Found: C, 60.74; H, 3.50; N, 20.27%.
6'-Amino-5'-cyano-3 '-methylspiro[indoline-3,4 '(1HJ-pyrano[2, 3-c)
pyrazol}-2-one(4e): M.p. 279-280°C, lit. m.p. 275°C.24 IR (em-'):
3293(NH2), 3175(NH), 2196(CN), 1700(CO). 'H NMR 8: 1.53
(s, 3H, CH3), 6.90 (d, lH, J= 8.5 Hz, ArH), 7.02 (m, 2H, ArH), 7.24
(s, 2H, NH2), 7.25 (m, lH, ArH), 10.60 (s, lH, CONH), 12.29 (s, lH,
N-NH). Anal. Calcd for C,sHllNs02: C, 61.43; H, 3.78; N, 23.88.
Found: C, 61.33; H, 3.75; N, 23.90%. X-ray: CCDC No. 716904.
Formula: C'S Hll Ns O2, Mr = 293.29, Volume = 694.26(14) A3,
Z= 2, Wavelength = 0.71073 A, u= 0.099 mm-'. Unit cell parameters:
Thanks are due to the National Natural Science Foundation
of China (No. 20872088) and the Foundations of Educations
Commission
of Shanghai Municipality
(Nos. J50102 and
08ZZ44) for financial support.
Received 13 December 2008; accepted 6 January 2009
Published online: 6 April 2009
References
a, 7.5256(9); b, 9.3635(11); c, 10.8897(13)
~ 105.5700(10), Y 107.3650(10). Space group: P-1.
a
94.7820(10),
1
2
3
4
5
6
7
8
9
R.J. Suodberg, The chemistry olindoles, Academic: New York, 1996.
6 '-Amino- 5-chloro- 5'-cyano-3 '-methylspiro {indoline-3, 4'(1HJ-
pyrano[2,3-c}pyrazol}-2-one (4f): M.p. 239-240°C, lit. m.p. 230-
232 °C.2SIR (em-'): 3346 (NH2), 3136 (NH), 2182 (CN), 1714 (CO).
'H NMR 8: 1.58 (s, 3H, CH3), 6.92 (d, lH, J= 8 Hz, ArH), 7.14 (d,
lH, J = 2.5 Hz, ArH), 7.29 (s, 2H, NH2), 7.30 (dd, lH, J,: 2.5, J2:
8 Hz, ArH), 10.76 (s, lH, CONH), 12.35 (s, lH, N-NH). Anal.
Calcdd for C,sHIOC1Ns02: C, 54.97; H, 3.08; N, 21.37. Found: C,
54.96; H, 3.10; N, 21.34%.
6 '-Amino- 5-bromo- 5'-cyano-3 '-methylspiro {indo line- 3,4'(1 HJ-
pyrano[2,3-c}pyrazol}-2-one (4g): M.p. 282-283 DC.IR (em-'): 3347
(NH2), 3139 (NH), 2182 (CN), 1713 (CO). 'H NMR 8: 1.58 (s, 3H,
CH3), 6.88 (d, lH, J = 8 Hz, ArH), 7.24 (d, lH, J = 2 Hz, ArH),
7.32 (s, 2H, NH2), 7.43 (dd, lH, J,: 2, J2: 8 Hz, ArH), 10.77 (s, lH,
CONH), 12.35 (s, 1H, N-NH). Anal. Calcd for C,sHIOBrNs02: C,
48.41; H, 2.71; N, 18.82. Found: C, 48.40; H, 2.80; N, 18.66%.
10 A. Dandia, R. Sing, S. Khaturia, C. Merienne, G. Morgant and A. Loupy,
11 M.M. Khafagy, A.H.F.A. El-Wahas, FA Eid and A.M. El-Agrody,
12 T.H. Kang, K. MatslUOoto, Y. Murakami, H. Takayama, M. Kitajima,
14 P. Rosenmond, M. Hosseini-Mereseht and C. Bub, Leibigs Ann. Chem.,
1994,2,151.
6'-Amino-5 '-cyano-3 '-methyl-5-nitrospiro[indoline-3,
4 '(1 HJ-
pyrano[2,3-c}pyrazol}-2-one (4h): M.p. 270-271 °c IR (em-'): 3323
(NH2), 2194 (CN), 1731 (CO). 'H NMR 8: 1.58 (s, 3H, CH3), 7.14 (d,
lH,J= 8.5 Hz, ArH), 7.43 (s, 2H, NH2), 7.92 (d, lH, J= 2 Hz, ArH),
8.23 (dd, lH, J,: 2, J2: 8.5 Hz, ArH), 11.37 (s, lH, CONH), 12.41
(s, lH, N-NH). Anal. Calcd for C,sHION604: C, 53.26; H, 2.98; N,
24.84. Found: C, 53.02; H, 2.79; N, 24.88%.
6'-Amino-5'-cyano-3 '-phenylspiro[indoline-3,4 '(1HJ-pyrano[2, 3-c)
pyrazol}-2-one (4i): M.p. 219-220°C. IR (em-'): 3308 (NH2), 3120
(NH), 2186 (CN), 1705 (CO). 'H NMR 8: 6.74 (d, lH, J = 3 Hz,
ArH), 6.80 (d, 2H, J= 8.5 Hz, ArH), 6.89 (m, lH,ArH), 7.03 (m, lH,
ArH), 7.16 (m, 3H,ArH), 7.23 (m, lH,ArH), 7.26 (s, 2H, NH2), 10.49
(s, lH, CONH), 12.89 (s, lH, N-NH). Anal. Calcd for C2oH13Ns02:
C, 67.60; H, 3.69; N, 19.71. Found: C, 67.55; H, 3.63; N, 19.77%.
6 '-Amino- 5-chloro- 5'-cyano-3 '-phenylspiro {indoline-3, 4'(1HJ-
pyrano[2,3-c}pyrazol}-2-one (4j): M.p. 247-249°C. IR (em-'): 3295
(NH2), 3126 (NH), 2187 (CN), 1713 (CO). 'H NMR 8: 6.74 (d, lH,
J= 8.5 Hz, ArH), 6.85 (m, 2H, ArH), 7.13 (d, lH, J= 2.5 Hz, ArH),
7.20 (m, 3H, ArH), 7.27 (m, lH, ArH), 7.35 (s, 2H, NH2) 10.66 (s,
lH, CONH) , 12.95 (s, lH, N-NH). Anal. Calcd for C20H12C1Ns02:
C, 61.63; H, 3.10; N, 17.97. Found: C, 61.61; H, 3.08; N, 17.88%.
16 W.G. Rajeswatan, T.B. Labroo and T.A. Cohen,
17 W.N. Chan, J.M. Evans, M.S. Hadley, H.J. Herdon, J.C. Jerman,
H.K.A. Morgan, T.O. Stean, M. Thompson, N. Upton and A.K. Yong,
19 W. Kemnitzer, J. Drewe, S. Jiang, H. Zhang, Y. Wang, J. Zhao, S. Jia,
J. Herieh, D. Labreque, R. Storer, K. Meeroviteh, D. Bouffard, R. Rei.
S.R. Denis, K. Mccroyitch, D. Bouffard, R. Rei, R. Denis, C. Blais,
S. Lamothe, G. Attardo, H. Gourdeau, B. Tseng, S. Kasibhatla and
21 D. Anshu, A. Kapil, S. Meha and S. Rekha, Heterocyclic Commun., 2003,
9,415.
22 R.G. Redkin, L.A. Shemehuk, Y.P. Chemykh, O.Y. Shishkin and
24 F.F.A. El-Latif, A.E. Gohar, M.N.-K., A.M. Fshmy and M.Z.A. Badr,
25 D. Anshu, A. Kapil, S. Meha and S. Rekha, Heterocycl. Commun., 2003,
9,415.