1054
I. Kock, B. Clement
SHORT PAPER
IR (KBr): 3166, 3060, 2358, 1654, 1610, 1558, 1490 cm–1.
13C NMR (75 MHz, DMSO-d6): d = 120.6 (C-11), 120.7 (C-10b),
122.6 (C-7), 124.2 (C-1), 126.5 (C-10a), 127.0 (C-2), 127.5 (C-3),
127.68 (C-9), 127.75 (C-12), 127.80 (C-4), 128.8 (C-10), 131.3 (C-
4a), 131.4 (C-8), 132.1 (C-6a), 132.9 (C-12a), 140.5 (C-4b), 152.3
(C-6).
1H NMR (300 MHz, DMSO-d6): d = 7.63–7.71 (m, 3 H, ArH), 7.81
(d, J = 8.8 Hz, 1 H, ArH), 7.92 (t, J = 7.6 Hz, 1 H, ArH), 8.01–8.04
(m, 1 H, ArH), 8.42 (d, J = 7.5 Hz, 1 H, ArH), 8.49 (d, J = 8.8 Hz,
1 H, ArH), 8.63 (d, J = 8.2 Hz, 1 H, Ar-H), 8.90–8.93 (m, 1 H,
ArH), 11.90 (br s, 1 H, =NH).
MS (EI): m/z (%) = 229 (M+, 100), 228 (M+ – 1, 25), 114.5 (M2+,
21).
13C NMR (75 MHz, DMSO-d6): d = 113.2, 120.7, 122.2 (2 C),
122.6, 123.1, 125.5, 126.5, 127.3, 127.5, 127.7, 128.3, 132.3, 133.1,
133.4, 134.8, 161.6.
Acknowledgment
MS (EI): m/z (%) = 245 (M+, 100), 122.5 (M2+, 5).
We acknowledge the excellent experimental assistance of M. Kö-
nig. We are grateful to Dr. U. Girreser for NMR and MS spectral ex-
periments. This work was supported by the Fonds der Chemischen
Industrie.
5,6-Dihydrobenzo[c]phenanthridin-6-thione (7)
A mixture of 6 (0.74 g, 3 mmol), phosphorus pentasulfide (0.89 g,
4 mmol), and pyridine (10 mL) was heated under reflux for 2 h. The
resulting mixture was quenched with ice water (50 mL). The aque-
ous layer was extracted with CH2Cl2 (3 × 50 mL). The organic layer
was dried (MgSO4), the solvent was removed in vacuo and the res-
idue was crystallized from DMF–H2O (1:1) to give 0.7 g of 7 (89%),
mp 279 °C. Compound 7 decomposed in solution. The decomposi-
tion products were not investigated.
References
(1) Simeon, S.; Rios, J. L.; Villar, A. Pharmazie 1989, 44, 593.
(2) Clement, B.; Weide, M.; Wolschendorf, U.; Kock, I. Angew.
Chem. Int. Ed. 2005, 44, 635; Angew. Chem. 2005, 117, 641.
(3) Graebe, C. Justus Liebigs Ann. Chem. 1904, 335, 122.
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(5) Ritchie, E. J. Proc. R. Soc. N. S. W. 1944, 78, 173.
(6) Badger, G. M.; Seidler, J. H. J. Chem. Soc. 1954, 2329.
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J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1968, 6,
422.
IR (KBr): 3234, 3048, 2922, 1628, 1610, 1572, 1526, 1498, 1450,
1430 cm–1.
1H NMR (300 MHz, DMSO-d6): d = 7.70–7.78 (m, 3 H, ArH),
7.96–8.01 (m, 2 H, ArH), 8.06–8.09 (m, 1 H, ArH), 8.60 (d, J = 9.0
Hz, 1 H, ArH), 8.73 (d, J = 7.9 Hz, 1 H, ArH), 9.04 (d, J = 7.5 Hz,
1 H, ArH), 9.19–9.22 (m, 1 H, ArH), 13.26 (br s, 1 H, =NH).
13C NMR (75 MHz, DMSO-d6): d = 117.0, 120.4, 121.6, 122.6,
123.3, 125.1, 127.0, 127.8, 128.3, 128.5*, 130.4, 130.8, 131.8,
133.2, 133.5 183.8; * two overlapping signals.
MS (EI): m/z (%) = 261 (M+, 100), 260 (M+ – 1, 13), 130.5 (M2+,
11).
(11) Bhargava, S. S.; Saharia, G. S. Indian J. Chem., Sect. B: Org.
Chem. Incl. Med. Chem. 1972, 10, 919.
(12) Ninomiya, I.; Naito, T.; Kiguchi, T.; Mori, T. J. Chem. Soc.
Perkin Trans. 1 1973, 1696.
HRMS: m/z calcd for C17H11NS, 261.06122; found, 261.06110.
HRMS: m/z calcd for C1613CH11NS, 262.06458; found, 262.06460.
(13) Boyer, J. H.; Patel, J. R. J. Chem. Soc. Perkin Trans. 1 1979,
1070.
Benzo[c]phenanthridine (8)
A mixture of 7 (0.5 g, 1.9 mmol) and Raney nickel (1.8 g, moistened
with water) in DMF (5 mL) and EtOH (5 mL) was heated under re-
flux for 1 h. The resulting mixture was filtered and the filtrate acid-
ified with HCl. The solvent was removed in vacuo, the resulting
residue was dissolved in H2O (5 mL) and alkalized with NH3. The
precipitate was collected and crystallized from MeOH–H2O (1:1).
Further purification was achieved by precipitation of 8 as the hydro-
chloride following by releasing of the free base to give 195 mg
(44%) of 8; mp 130 °C (Lit.20 130–133 °C).
(14) Beugelmans, R.; Chastanet, J.; Ginsburg, H.; Quintero-
Cortes, L.; Roussi, G. J. Org. Chem. 1985, 50, 4933.
(15) Kessar, S. V.; Gupta, Y. P.; Balakrishnan, P.; Sawal, K. K.;
Mohammed, T.; Dutt, M. J. Org. Chem. 1988, 53, 1708.
(16) Grimshaw, J.; Hewitt, S. A. J. Chem. Soc., Perkin Trans. 1
1990, 2995.
(17) Keene, B. R. T.; Tissington, P. Adv. Heterocycl. Chem.
1971, 13, 315.
(18) Taylor, E. C.; Martin, A. E. J. Am. Chem. Soc. 1952, 74,
6295.
IR (KBr): 1618, 1600, 1582, 1512, 1477 cm–1.
1H NMR (300 MHz, DMSO-d6): d = 7.73–7.83 (m, 2 H, H-2, H-3),
7.86 (t, J = 7.5 Hz, 1 H, H-9), 8.03 (t, J = 7.9 Hz, 1 H, H-8), 8.13 (d,
J = 7.2 Hz, 1H, H-4), 8.19 (d, J = 9.0 Hz, 1 H, H-12), 8.35 (d,
J = 8.0 Hz, 1 H, H-10,), 8.83 (d, J = 9.0 Hz, 1 H, H-11,), 8.95 (d,
J = 8.3 Hz, 1 H, H-7), 9.33 (d, J = 8.8 Hz, 1 H, H-1), 9.61 (s, 1 H,
H-6).
(19) Chatterjea, J. N.; Bhakta, S. C.; Chattopadahyay, A. K. J.
Indian Chem. Soc. 1974, 51, 757.
(20) Boyer, J. H.; Patel, J. R. J. Chem. Soc., Chem. Commun.
1977, 855.
Synthesis 2005, No. 7, 1052–1054 © Thieme Stuttgart · New York