ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 3, p. 477. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © B.F. Kukharev, V.K. Stankevich, G.R. Klimenko, V.V. Bayandin, V.A. Kukhareva, 2008, published in Zhurnal Organicheskoi
Khimii, 2008, Vol. 44, No. 3, p. 477.
SHORT
COMMUNICATIONS
Oxidation of 1-Oxa-5-azaspiro[5.5]undecane with Cyclohexanone
B. F. Kukharev, V. K. Stankevich, G. R. Klimenko, V. V. Bayandin, and V. A. Kukhareva
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russiae-mail:
Received December 18, 2007
DOI: 10.1134/S1070428008030305
We previously reported that oxidation of five-mem-
bered cyclic N,O-acetals (oxazolidines) with carbonyl
compounds leads to the formation of pyrroles [1]. In
the present communication we describe the oxidation
of 1-oxa-5-azaspiro[5.5]undecane (I) with cyclohexa-
none to produce 5,6,7,8-tetrahydroquinoline (II) as
an example of synthesis of pyridine derivatives via
oxidation of perhydro-1,3-oxazines having no substit-
uent on the nitrogen atom with carbonyl compounds.
oxazine I) gives imino aldehyde A which undergoes
intramolecular condensation (like crotonization) to
2,3,5,6,7,8-hexahydroquinoline B, and the latter is
oxidized with the second cyclohexanone molecule to
quinoline II.
A mixture of 31 g (0.2 mol) of compound I, 39.2 g
(0.4 mol) of cyclohexanone, and 4.48 g (0.08 mol) of
powdered potassium hydroxide was heated for 5 h
under reflux. The mixture was cooled, 25.2 ml
(0.21 mol) of 36% hydrochloric acid was added, and
the aqueous phase was separated, extracted with di-
ethyl ether (3×50 ml), made alkaline by addition of
potassium hydroxide, and extracted with benzene. The
benzene extract was subjected to distillation to isolate
4.2 g (16%) of 5,6,7,8-tetrahydroquinoline II with
bp 89–93°C (10 mm), d420 = 1.0314, nD20 = 1.5428;
published data [2]: bp 92–95°C (12 mm), d420 = 1.0304,
N
OH
O
NH
I
III
O
N
O
nD20 = 1.5435. H NMR spectrum, δ, ppm (J, Hz):
1
1.74 m (4H, 6-H, 7-H), 2.68 t (2H, 5-H), 2.80 t (2H,
8-H, J5,6 = 6.0, J7,8 = 6.0), 7.0 d.d (1H, 3-H, J3,4 = 8.0),
7.33 t (1H, 4-H), 8.24 d (1H, 2-H, J2,3 = 5.0). Found,
%: C 81.33; H 8.26; N 10.41. C9H11N. Calculated, %:
C 81.16; H 8.32; N 10.52.
–cyclo-C6H11OH
–H2O
N
A
B
O
REFERENCES
–cyclo-C6H11OH
N
1. Kukharev, B.F., Stankevich, V.K., and Kukhareva, V.A.,
II
Khim. Geterotsikl. Soedin., 1984, p. 700.
Presumably, as in the oxidation of oxazolidines
with carbonyl compounds, initial oxidation of imino
alcohol III (an open-chain tautomer of perhydro-1,3-
2. Svoistva organicheskikh soedinenii. Spravochnik (Prop-
erties of Organic Compounds), Potekhin, A.A., Ed.,
Leningrad: Khimiya, 1984.
477
Kukharev
