Russian Journal of Organic Chemistry, Vol. 38, No. 3, 2002, p. 456. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 3, 2002, p. 477.
Original Russian Text Copyright 2002 by Shmyreva, Ponomareva.
SHORT
COMMUNICATIONS
Quinonimine Formation in the Reaction
of 6-Hydroxy-2,2,4-trimethyl-1,2-dihydroquinoline
with 1-Chloro-2,3-epoxypropane
Zh. V. Shmyreva and L. F. Ponomareva
Voronezh State University, Universitetskaya pl. 1, Voronezh, 394693 Russia
e-mail: office@main.vsu.ru
Received March 23, 2001
We have revealed an anomalous reaction of 6-hy-
droxy-2,2,4-trimethyl-1,2-dihydroquinoline (I) with
1-chloro-2,3-epoxypropane (II). Instead of expected
O-alkylation, which is typical of reactions of II with
phenols [1], oxidation of quinoline I occurred to give
2,2,4-trimethyl-2,6-dihydroquinolin-6-one (III):
b. A mixture of equimolar amounts (0.03 mol) of
compounds I and II, 1 g of anhydrous potassium
carbonate, and 20 ml of acetone was refluxed until
compound I disappeared according to the TLC data
(Silufol plates, development with iodine vapor or by
heating). The mixture was poured into water, the
product was extracted into benzene, and the extract
was treated as described above in a. Yield 50%,
mp 66 67 C; published data [2, 3]: mp 67 C. IR
1
spectrum, , cm : 1620, 1660; no NH or OH absorp-
1
tion was observed. H NMR spectrum, , ppm: 1.35 s
(6H, CH3), 1.99 s (3H, CH3), 6.25 s (1H, CH), 6.58 s
(1H, CH), 7.18 s (1H, CH).
The IR spectrum was recorded on a UR-20 spec-
1
trometer in mineral oil. The H NMR spectrum was
No analogous reactions were found in the literature.
The structure of product III was confirmed by the
1H NMR and IR spectra and elemental analysis.
Quinoline III was previously synthesized by oxida-
tion of 2,2,4-trimethyl-1,2-dihydroquinoline with
potassium nitrosodisulfonate [2] and silver oxide in
20% yield [3]. The discovered reaction provides
a more convenient method for preparation of quinon-
imine III, for it ensures a greater yield of the product.
obtained on a Bruker AC-300 instrument (300 MHz)
in DMSO-d6 with TMS as internal reference.
REFERENCES
1. Malinovskii, M.S., Okisi olefinov i ikh proizvodnye
(Olefin Oxides and Their Derivatives), Moscow:
Goskhimizdat, 1961, pp. 152 173.
2,2,4-Trimethyl-2,6-dihydroquinoline (III).
a. A mixture of 1.85 g (0.2 mol) of 1-chloro-2,3-
epoxypropane, 0.5 g (0.03 mol) of 6-hydroxy-2,2,4-
trimethyl-1,2-dihydroquinoline (I), 50 ml of 50%
aqueous sodium hydroxide, 100 ml of benzene, and
0.1 g of tetrabutylammonium iodide was stirred for
1 h at 50 60 C [4]. The organic phase was separated,
washed with water until neutral reaction, dried, and
passed through a column charged with Al2O3 using
benzene as eluent. The eluate was evaporated, and the
residue was recrystallized from hexane. Yield 50%.
2. Teuber, H.J. and Glosauer, A.S., Chem. Ber., 1965,
vol. 98, no. 9, pp. 2943 2953.
3. Ivanov, Yu.A., Zaichenko, I.L., Rykov, S.V., Grand-
berg, O.Ya., Dubinskii, A.A., Pirozhkov, S.D., Rozan-
tsev, E.G., Pokrovskaya, I.E., and Shapiro, A.B., Izv.
Akad. Nauk SSSR, Ser. Khim., 1979, no. 8, pp. 1800
1807.
4. Yanovskaya, L.A. and Yufit, S.S., Organicheskii
sintez v dvukhfaznykh sistemakh (Organic Synthesis
in Two-Phase Systems), Moscow: Khimiya, 1982,
pp. 60 65.
1070-4280/02/3803-0456$27.00 2002 MAIK Nauka/Interperiodica
Shmyreva
