Efficient method for the microwave synthesis of 4-styrylquinolines

Full text of DOI:10.1007/s10593-010-0420-6

Chemistry of Heterocyclic Compounds, Vol. 45, No. 10, 2009
EFFICIENT METHOD FOR THE MICROWAVE
SYNTHESIS OF 4-STYRYLQUINOLINES
V. M. Lee1, T. N. Gavrishova1*, and M. F. Budyka1
Keywords: 4-styrylquinoline, microwave irradiation.
The traditional methods for the preparation of 4-styrylquinolines require prolonged heating of the
reagents and lead to a mixture of products, low yield of the desired styrylquinolines, and laborious procedures
for the separation and purification of these products. Furthermore, the isolation of 4-styrylquinolines is
complicated by photocyclization to give benzo[f]phenanthridines [1]. In previous work [2], the condensation of
quinaldine with aromatic aldehydes in the presence of acetic anhydride for the synthesis of 2-styrylquinoline
derivatives was carried out using microwave irradiation, which permitted shortening of the reaction time and a
reduction in the amount of side products formed.
In the present work, we have shown that the rate of condensation of lepidine 1 with various aromatic
aldehydes is also enhanced by the action of microwave irradiation but the reaction is best carried out in the
absence of solvent using catalytic amounts of ZnCl2. The proposed method permits us to obtain various
4-styrylquinolines with yield up to 70%, to reduce the reaction time to 5-15 min, and to avoid laborious
procedures for product isolation.
R
Me
R
ZnCl2
+
microwave irradiation
600 W, 5–15 min
N
1
CHO
1–2–ZnCl2, 1:2:0.45
N
2a–e
3a–e
60–70%
2, 3 a R = 4-NO2, b R = 4-Me2N, c R = 4-OH, d R = 2-OH, e R = 4-F
4-(4-Nitrostyryl)quinoline (3a) was obtained in 69% yield as yellow crystals with mp 229-231°C
(ethanol–chloroform) (mp 227-229°C [3]).
_______
* To whom correspondence should be addressed, e-mail: tngavr@icp.ac.ru.
1Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka 142432, Moscow
Region, Russia.
__________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1589-1590, October, 2009.
Original article submitted September 3, 2009.
0009-3122/09/4510-1279©2009 Springer Science+Business Media, Inc.
1279

4-(4-Dimethylaminostyryl)quinoline (3b) was obtained in 60% yield as orange crystals with mp 139°C
(hexane) (mp 139-140°C [4]).
4-(4-Hydroxystyryl)quinoline (3c) was obtained in 61% yield as yellow crystals with mp 244-246°C
(dec.) (ethanol) (mp 248-249°C [5]).
4-(2-Hydroxystyryl)quinoline (3d) was obtained in 66% yield as light-yellow crystals with mp 215°C
(dec.) (ethanol) (mp 215°C [5]).
4-(4-Fluorostyryl)quinoline (3e) was obtained in 58% yield as white crystals with mp 103°C (aqueous
acetone). IR spectrum, ν, cm-1: 3050, 3035, 1590, 1510, 833, 758 (Ar), 1220 (CF), 1633 (C=C), 968
1
(out-of-plane δ trans HC=CH). H NMR spectrum, δ, ppm (J, Hz): 7.13 (2H, t, JHF = 8.6, H-o); 7.33 (1H, d,
J = 16.1, CH=CH); 7.55-7.85 (6H, m, 2H-m, CH=CH, H-3, H-6, H-7); 8.22 (2H, d, J = 8.6, H-5, H-8); 8.91 (1H,
d, J = 4.9, H-2). Mass spectrum, m/z: 250.102 [M+H]+. Calculated: M 249.09. Found, %: C 81.96; H 4.79;
N 5.63. C17H12FN. Calculated, %: C 81.91; H 4.85; N 5.62.
IR spectrum was recorded on a Spectrum BX-2 spectrometer in KBr pellet.
1H NMR spectrum taken on a Bruker DPX 200 spectrometer at 200 MHz in CDCl3 with TMS as the
internal standard.
Mass spectrum was obtained on a custom-made ESI-TOF spectrometer.
This work was carried out with the financial support of the Russian Foundation for Basic Research
(Grant No. 07-03-00891).
REFERENCES
1.
M. F. Budyka, N. I. Potashova, T. N. Gavrishova, and V. M. Lee, J. Photochem. Photobiol., A: Chem.,
203, 100 (2009).
2.
3.
4.
5.
F.-M. Li, L.-Y. Wang, S.-K. Wang, and Z.-X. Zhang, Chin. J. Org. Chem., 24, 50 (2004).
R. S. Tipson and A. F. Walton, J. Am. Chem. Soc., 70, 893 (1948).
M. A. Clapp and R. S. Tipson, J. Am. Chem. Soc., 68, 1333 (1946).
B. Heymann and W. Koenigs, Ber., 21, 2172 (1888).
1280