ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 1, p. 148. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © I.V. Aksenova, N.G. Saprykina, A.V. Aksenov, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 1, p. 149.
SHORT
COMMUNICATIONS
Synthesis of 1H-Benzo[de]cinnolines from Nitronaphthalenes
I. V. Aksenova, N. G. Saprykina, and A. V. Aksenov
Stavropol State University, ul. Pushkina 1a, Stavropol, 355009 Russia
e-mail: k-biochem-org@stavsu.ru
Received June 22, 2007
DOI: 10.1134/S1070428008010223
Lacy et al. previously reported on the synthesis of
1H-benzo[de]cinnolines II (1,2-diazaphenalenes) via
cyclization of 1-acetyl-, 1-benzoyl- [1], and 1-formyl-
8-hydroxynaphthalenes [2] by the action of hydrazine
hydrate. The present communication describes the syn-
thesis of the same compounds from more accessible
1-formyl-, 1-acetyl-, and 1-benzoyl-8-nitronaphtha-
lenes Ia–Ic [3]. Heating of compounds I with excess
hydrazine hydrate in boiling ethanol gave the corre-
sponding 1H-benzo[de]cinnolines IIa–IIc in 62–87%
yield. Presumably, the reaction involved nucleophilic
attack by hydrazine on the carbonyl carbon atom,
followed by intramolecular replacement of the nitro
group in the peri position.
3-H), 7.28 d (1H, 4-H, J4,5 = 7.4 Hz), 8.16 br.s (1H,
NH). Found, %: C 78.71; H 4.72; N 16.57. C11H8N2.
Calculated, %: C 78.55; H 4.79; N 16.66.
3-Methyl-1H-benzo[de]cinnoline (IIb). Yield
0.14 g (77%), mp 153_155°C (from benzene–petrole-
um ether); published data [1]: mp 153_155°C. 1H NMR
spectrum (CDCl3), δ, ppm: 2.16 s (3H, CH3), 6.21 d
(1H, 9-H, J8, 9 = 7.0 Hz), 6.65 d (1H, 7-H, J7, 8
=
6.3 Hz), 6.87 d (1H, 6-H, J5,6 = 8.1 Hz), 7.12 m (2H,
5-H, 8-H), 7.38 d (1H, 4-H, J4,5 = 7.5 Hz), 8.28 br.s
(1H, NH). Found, %: C 79.15; H 5.47; N 15.38.
C12H10N2. Calculated, %: C 79.10; H 5.53; N 15.37.
3-Phenyl-1H-benzo[de]cinnoline (IIc). Yield
0.212 g (87%), mp 206_208°C (from benzene–petrole-
um ether); published data [1]: mp 206_208°C. 1H NMR
R
O
N
R
NO2
HN
spectrum (CDCl3), δ, ppm: 6.23 d (1H, 9-H, J8,9
=
N2H4 ·H2O, EtOH
7.0 Hz), 6.74 d (1H, 7-H, J7,8 = 7.3 Hz), 6.92 d (1H,
6-H, J5,6 = 8.2 Hz), 7.12 m (2H, 5-H, 8-H), 7.31 d (1H,
4-H, J4, 5 = 7.6 Hz), 7.45 m (3H, m-H, p-H), 7.56 d
(2H, o-H, J = 6.9 Hz), 8.26 br.s (1H, NH). Found, %:
C 83.71; H 4.89; N 11.40. C17H12N2. Calculated, %:
C 83.58; H 4.95; N 11.47.
Ia–Ic
IIa–IIc
R = H (a), Me (b), Ph (c).
General procedure for the synthesis of 1H-benzo-
[de]cinnolines IIa–IIc. A mixture of 1 mmol of nitro-
naphthalene Ia–Ic and 1 ml of 88% hydrazine hydrate
in 10 ml of ethanol was heated for 6 h under reflux in
an argon atmosphere. The mixture was cooled and
poured into 20 ml of water, and the precipitate was
filtered off and dried.
1
The H NMR spectra were recorded on a Bruker
WP-200 spectrometer (200 MHz) using tetramethyl-
silane as intermal reference. The progress of reactions
and the purity of products were monitored by TLC on
Silufol UV-254 plates using ethyl acetate as eluent.
REFERENCES
1H-Benzo[de]cinnoline (IIa). Yield 0.104 g (62%),
mp 149_151°C (from benzene–petroleum ether); pub-
1. Lacy, Ph.H. and Smith, D.C.C., J. Chem. Soc. C, 1971,
lished data [2]: mp 148_151°C. H NMR spectrum
1
p. 747.
(CDCl3), δ, ppm: 6.12 d (1H, 9-H, J8, 9 = 7.0 Hz),
2. Lacy, Ph.H. and Smith, D.C.C., J. Chem. Soc., Perkin
Trans. 1, 1975, p. 419.
6.62 d (1H, 7-H, J7,8 = 6.2 Hz), 6.85 d (1H, 6-H, J5,6
=
8.8 Hz), 7.08 d.d (1H, 5-H, J4,5 = 7.4, J5,6 = 8.8 Hz),
7.19 d.d (1H, 8-H, J7,8 = 6.2, J8,9 = 7.0 Hz), 7.21 s (1H,
3. Spiteller, G. and Derkosch, J., Monatsh. Chem., 1959,
vol. 90, p. 634.
148
Aksenova
