Synthesis of 2-[2-(2-aminophenyl)ethyl]-6-R-quinnoline-4-carboxylic acids from 2-[2-(2-nitrophenyl)ethenyl]-6-R-quinoline-4-carboxylic Acids

Full text of DOI:10.1134/S1070428010090307

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 9, pp. 1425−1426. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.G. Kashaev, A.V. Zimichev, Yu.N. Klimochkin, M.N. Zemtsova, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46,
No. 9, pp. 1420−1421.
SHORT
COMMUNICATIONS
Synthesis
of 2-[2-(2-Aminophenyl)ethyl]-6-R-quinnoline-4-carboxylic Acids
from 2-[2-(2-Nitrophenyl)ethenyl]-6-R- quinoline-4-carboxylic
Acids
A. G. Kashaev, A. V. Zimichev, Yu. N. Klimochkin, and M. N. Zemtsova
Samara State Technical University, Samara, 443100Russia;
e-mail: plov-chor@mail.ru
Received April 30, 2010
DOI: 10.1134/S1070428010090307
The reduction of the ethylene bond in vinylquinolines
was described [1] by prolonged boiling of the appropriate
vinilogs in THF applying as reducer indium in acetic
acid.
I–III which by treatment with hydrazine hydrate in alco-
holic medium were converted into 2-[2-(2-aminophenyl)
ethenyl]-6-R-quinoline-4-carboxylic acids IV–VI [2, 3].
In this study we demonstrated that the increase in the
reaction time over 6 h under the same conditions resulted
alongside the nitro group reduction in the nitrostyrenes
I–III also in the hydrogenation of the ethylene bond with
the formation of compounds VII–IX.
In extension of the search on biologically active com-
pounds among 6-substituted 4-quinolinecarboxylic acids
and their derivatives we formerly synthesized 2-[2-(2-ni-
trophenyl)ethenyl]-6-R-quinoline-4-carboxylic acids
COOH
R
N
H2N
COOH
IV_VI
R
N
O2N
I_III
COOH
R
N
H2N
VII_IX
1425

KASHAEV et al.
1426
2-[2-(2-Aminophenyl)ethyl]quinoline-4-carboxylic
C 74.49; H 5.92; N 9.14.
acid (VII). To a solution of 3 mmol of compound I in
25 ml of ethanol while vigorous stirring at 70°C was
added 20 ml of hydrazine hydrate. The reaction mixture
was heated at reflux for 19 h, filtered, and the solvent
was evaporated. Yield 0.65 g (75%), red crystals,
2-[2-(2-Aminophenyl)ethyl]-6-methoxyquinoline-
4-carboxylic acid (IX) was obtained from compound
III. Yield 0.79 g (82%), beige crystals, mp 243–244°C
(from 2-propanol). H NMR spectrum, δ, ppm: 2.91 t
(2H, CH2CH2, J 7.3 Hz), 3.17 t (2H, CH2CH2 J 7.3 Hz),
3.88 s (3H, OMe), 3.89 s (2H, NH2), 6.45 t (1H, H4phenyl
,
1
1
mp 228–230°C (from 2-propanol). H NMR spectrum,
J 7.3 Hz), 6.62 d (1H, H5phenyl, J 7.3 Hz), 6.87 t (1H,
H3phenyl, J 7.3 Hz), 6.93 d (1H, H2phenyl, J 7.3 Hz), 7.42 t
(1H, H7quinoline, J 7.34 Hz), 7.89 s (1H, H3quinoline), 7.96 s
(1H, H5quinoline), 8.07 d (1H, H8quinoline, J 7.34 Hz). Found,
%: C 70.78; H 5.60; N 8.67. C19H18N2O3. Calculated, %:
C 70.79; H 5.63; N 8.69.
δ, ppm: 2.96 t (2H, CH2CH2, J 7.3 Hz), 3.21 t (2H,
CH2CH2, J 7.3 Hz), 3.93 s (2H, NH2), 6.47 t (1H,
H4phenyl, J 7.3 Hz), 6.63 d (1H, H5phenyl, J 7.3 Hz), 6.88 t
(1H, H3phenyl, J 7.3 Hz), 6.95 d (1H, H2phenyl, J 7.3 Hz),
7.61 t (1H, H7quinoline, J 7.3 Hz), 7.77 t (1H, H6quinoline
J 7.3 Hz), 7.90 s (1H, H3quinoline), 8.05 d (1H, H5quinoline
,
,
1H NMR spectra were registered on a spectrometer
Bruker AC-300 (300 MHz) in DMSO-d6, internal refer-
ence TMS. Elemental analysis was performed on an ana-
lyzer Euro Vector EA 3000. The reaction progress was
monitored and the homogeneity of compounds obtained
was checked by TLC on Silufol UV-254 plates, eluent
CCl4–acetone, 6 : 1.
J 8.1 Hz), 8.60 d (1H, H8quinoline, J 7.3 Hz). Found, %:
C 73.93; H 5.51; N 9.58. C18H16N2O2. Calculated, %:
C 73.95; H 5.52; N 9.58.
Compounds VIII and IX were similarly obtained.
2-[2-(2-Aminophenyl)ethyl]-6-methylquinoline-4-
carboxylic acid (VIII) was obtained from compound
II. Yield 0.64 g (71%), red crystals, mp 294–297°C
1
(from 2-propanol). H NMR spectrum, δ, ppm: 2.51 s
REFERENCES
(3H, Me), 2.93 t (2H, CH2CH2, J 7.3 Hz), 3.19 t (2H,
CH2CH2, J 7.3 Hz), 4.02 s (2H, NH2), 6.49 t (1H, H4phe-
nyl, J 7.3 Hz), 6.67 d (1H, H5phenyl, J 7.3 Hz), 6.89 t (1H,
H3phenyl, J 7.3 Hz), 6.96 d (1H, H2phenyl, J 7.3 Hz), 7.61 t
(1H, H7quinoline, J 7.3 Hz), 7.84 s (1H, H3quinoline), 7.94 s
(1H, H5quinoline), 8.32 d (1H, H8quinoline, J 7.3 Hz). Found,
%: C 74.45; H 5.90; N 9.13. C19H18N2O2. Calculated, %:
1. Pitts, M.R., Harrison, J.R., and Moody, Ch. J., J. Chem. Soc.
Perkin Trans. 1, 2001, p. 955.
2. Kashaev, A.G. and Zimichev, A.V., Bashkirskii Khim. Zh.,
2008, vol. 15, no. 4, p. 45.
3. Kashaev, A.G. and Zimichev, A.V., Izv. Vuzov, Ser. Khim. i
Khim. Tekhnol., 2009, vol. 52, p. 113.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 9 2010