484
J. S. Yadav et al.
PAPER
13C NMR (proton decoupled, CDCl3): d = 18.6, 19.3 29.7, 43.2,
73.0, 122.3, 125.4, 126.8, 126.9, 127.8, 128.2, 129.3, 129.4, 129.6,
134.8, 135.7, 137.6, 139.7, 147.8, 166.8.
13C NMR (proton decoupled, 50 MHz, CDCl3): d = 22.5, 23.2, 26.5,
28.4, 28.9, 29.5, 29.7, 30.1, 38.2, 38.5, 40.9, 54.3, 72.5, 121.3,
121.6, 125.5, 127.6, 137.5, 139.8, 179.1.
EIMS: m/z = 340 (M+), 195, 103, 77, 65.
EIMS: m/z = 296 (M+).
Anal. Calcd for C20H28N2 (296.455): C, 81.03; H, 9.52; N, 9.45.
Found: C, 81.29; H, 9.73; N, 9.91.
2,2,4-Trimethyl-2,3-dihydro-8-chloro-1H-1,5-benzodiazepine
(3k)
Pale yellow solid; mp 90–92 °C.
IR (KBr): 3283, 1649, 1597 cm–1.
Acknowledgment
1H NMR (300 MHz, CDCl3): d = 1.27 (s, 6 H), 2.23 (s, 2 H), 2.26
(s, 3 H), 5.58–6.60 (s, 1 H), 6.86–6.90 (s, 1 H), 6.98–7.05 (s, 1 H).
BVS and SPK thank CSIR, New Delhi for the award of fellowships.
13C NMR (proton decoupled, 75 MHz, CDCl3): d = 29.2, 29.8, 30.0,
44.9, 67.0, 120.4, 120.8, 125.9, 127.8, 129.8, 139.1, 172.5.
References
EIMS: m/z = 222 (M+ 10), 207 (24), 167 (38), 142 (100), 114 (20),
80 (25), 41 (30).
(1) (a) Schutz, H. Benzodiazepines; Springer: Heidelberg,
1982. (b) Landquist, J. K. In Comprehensive Heterocyclic
Chemistry, Vol. 1; Katritzky, A. R.; Rees, C. W., Eds.;
Pergamon: Oxford, 1984, 166–170. (c) Fryer, R. I. Bicyclic
Diazapines, In The Chemistry of Heterocyclic Compounds,
Vol. 50; Taylor, E. C., Ed.; Wiley: New York, 1991, Chap.
II.
(2) Randall, L. O.; Kappel, B. Benzodiazepines; Garattini, S.;
Mussini, E.; Randall, L. O., Eds.; Raven Press: New York,
1973, 27.
2,2,4-Trimethyl-2,3-dihydro-8-nitro-1H-1,5-benzodiazepine
(3l)
Pale yellow solid; mp 113–114 °C.
IR (KBr): 3280, 1645, 1600 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.90 (s, 6 H), 2.95 (s, 3 H), 3.20
(s, 2 H), 7.15–7.20 (s, 1 H), 8.0–8.15 (m, 1 H), 8.75–8.80 (m, 1 H).
13C NMR (proton decoupled, 75 MHz, CDCl3): d = 29.9, 30.0, 30.2,
45.6, 60.8, 118.3, 121.2, 126.2, 132.4, 137.9, 145.2, 170.7.
(3) Haris, R. C.; Straley, J. M. U. S. Patent 1537757, 1968;
Chem. Abstr. 1970, 73, 100054w.
(4) De Baun, J. R.; Pallos, F. M.; Baker, D. R. U. S. Patent
3978227, 1976; Chem. Abstr. 1977, 86, 5498d.
(5) (a) Aversa, M. C.; Ferlazzo, A.; Gionnetto, P.; Kohnke, F. H.
Synthesis 1986, 230. (b) Essaber, M.; Baouid, A.; Hasnaoui,
A.; Benharref, A.; Lavergne, J. P. Synth. Commun. 1998, 28,
4097. (c) El-Sayed, A. M.; Abdel-Ghany, H.; El-Saghier, A.
M. M. Synth. Commun. 1999, 29, 3561. (d) Chimirri, A.;
Grasso, S.; Ottana, R.; Romeo, G.; Zappala, M. J.
Heterocycl. Chem. 1990, 27, 371.
(6) (a) Stahlhofen, P.; Ried, W. Chem. Ber. 1957, 90, 815.
(b) Reid, W.; Torinus, E. Chem. Ber. 1959, 92, 2902.
(c) Herbert, J. A. L.; Suschitzky, H. J. Chem. Soc., Perkin
Trans. 1 1974, 2657. (d) Kaupp, G.; Pogodda, U.;
Schmeyers, J. Chem. Ber. 1994, 127, 2249.
EIMS: m/z = 233 (M+ 30), 218 (100), 177 (48), 172 (48), 131 (30),
90 (40), 63 (45).
10-Spirocyclopentane-1,2,3,9,10,10a-hexahydrobenzo[b]cyclo-
penta[e][1,4]diazepine (4m)
Yellow solid; mp 137–138 °C.
IR (KBr): 3338, 1659, 1600 cm–1.
1H NMR (200 MHz, CDCl3): d = 1.30–1.90 (m, 12 H), 2.30–2.60
(m, 3 H), 4.50 (br s, NH, 1 H), 6.70–7.39 (m, 4 H).
13C NMR (proton decoupled, 50 MHz, CDCl3): d = 23.4, 24.1, 24.3,
28.7, 33.4, 38.5, 39.2, 54.4, 67.3, 118.6, 119.3, 126.9, 132.1, 139.2,
143.4, 178.0.
(7) (a) Balakrishna, M. S.; Kaboudin, B. Tetrahedron Lett.
2001, 42, 1127. (b) Curini, M.; Epifano, F.; Marcotullio, M.
C.; Rosati, O. Tetrahedron Lett. 2001, 42, 3193.
(c) Morales, H. R.; Bulbarela, A.; Contreras, R. Heterocycles
1986, 24, 135. (d) Kaboudin, B.; Navaee, K. Heterocycles
2001, 55, 1443.
(8) (a) Pozarentzi, M.; Stephanatou, J. S.; Tsoleridis, C. A.
Tetrahedron Lett. 2002, 43, 1755. (b) Reddy, B. M.;
Sreekanth, P. M. Tetrahedron Lett. 2003, 44, 4447.
(c) Jarikote, D. V.; Siddiqui, S. A.; Rajagopal, R.; Daniel, T.;
Lahoti, R. J.; Srinivasan, K. V. Tetrahedron Lett. 2003, 44,
1835.
(9) (a) Li, C. J.; Chan, T. H. Tetrahedron 1999, 55, 11149.
(b) Babu, G.; Perumal, P. T. Aldrichima Acta 2000, 33, 16.
(c) Ghosh, R. Indian J. Chem. 2001, 40B, 550.
(10) (a) Ceschi, M. A.; Felix, L. A.; Peppe, C. Tetrahedron Lett.
2000, 41, 9695. (b) Bandini, M.; Cozzi, P. G.; Giocomini,
M.; Melchiorre, P.; Selva, S.; Umani-Ronchi, A. J. Org.
Chem. 2002, 67, 3700.
EIMS: m/z = 240 (M+).
Anal. Calcd for C16H20N2 (240.347): C, 79.96; H, 8.39; N, 11.66.
Found: C, 79.54; H, 8.21; N, 11.47.
10-Spirocyclohexane-2,3,4,10,11,11a-hexahydro-1H-diben-
zo[b,e][1,4]diazepine (4n)
Pale yellow solid; mp 136–137 °C.
IR (KBr): 3290, 1640, 1600 cm–1.
1H NMR (200 MHz, CDCl3): d = 1.23–1.85 (m, 16 H), 2.30–2.70
(m, 3 H), 4.45 (br s, 1 H, NH), 6.65–7.35 (m, 4 H).
13C NMR (proton decoupled, 50 MHz, CDCl3): d = 21.6, 21.7, 23.2,
24.5, 25.3, 33.2, 34.4, 39.3, 40.5, 52.4, 63.1, 121.3, 121.5, 126.3,
129.6, 138.1, 142.6, 178.9.
EIMS: m/z = 268 (M+).
Anal. Calcd for C18H24N2 (268.401): C, 80.55; H, 9.01; N, 10.44.
Found: C, 80.26; H, 9.54; N, 10.31.
(11) (a) Yadav, J. S.; Reddy, B. V. S. Synthesis 2002, 511.
(b) Yadav, J. S.; Reddy, B. V. S.; Raju, A. K.; Rao, C. V.
Tetrahedron Lett. 2002, 43, 5437. (c) Yadav, J. S.; Reddy,
B. V. S.; Satheesh, G.; Prabhakar, A.; Kunwar, A. C.
Tetrahedron Lett. 2003, 44, 2221. (d) Yadav, J. S.; Reddy,
B. V. S.; Baishya, G. Synlett 2003, 396.
10-Spirocycloheptan-6,7,8,9,10,10a,11,12-octahydroben-
zo[b]cyclohepta[e] [1,4]diazepine (4o)
Pale yellow solid; mp 135–136 °C.
IR (KBr): 3320, 3275, 1630, 1600 cm–1
1H NMR (200 MHz, CDCl3): d = 0.90–1.95 (m, 20 H), 2.25–2.95
(m, 3 H), 3.60 (br s, NH, 1 H), 6.60–7.38 (m, 4 H).
Synthesis 2005, No. 3, 480–484 © Thieme Stuttgart · New York