SYNTHETIC APPROACH TO PREPARATION OF POLYCYCLIC COMPOUNDS...: I.
1129
with water, saturated solution of NaHCO3, and again
with water. The solution obtained was dried with
MgSO4, filtered, and evaporated. The residue was
purified by column chromatography [eluent ethyl
acetate petroleum ether (bp 40 60 C), 1: 2.5]. We
isolated 0.31 g of compound IV as colorless crystals.
1.37 g (7.1 mmol) of N-benzoyl- -alanine in 40 ml
of anhydrous THF at stirring under argon atmosphere
was added 1.6 g (7.8 mmol) of dicyclohexylcarbodi-
imide and 0.1 g of diethylaminopyridine. Further
procedure was the same as in the synthesis of
(N-benzoyl- -alanyloxy)adamantan-4-one (II). After
chromatographic purification [eluent ethyl acetate
petroleum ether (bp 40 60 C), 1: 3] we obtained
1.87 g of compound VII as colorless crystals.
(b) To solution of 0.3 g (1.1 mmol) of compound
VI and 0.14 g (0.7 mmol) of N-benzoyl- -alanine in
20 ml of THF at stirring under argon atmosphere was
added 0.15 g (0.7 mmol) of dicyclohexylcarbodiimide
and 0.02 g of diethylaminopyridine. Further proce-
dure is the same as in the synthesis of 1-(N-benzoyl-
(N-Benzoyl- -alanyloxy)adamantane (VIII). To
a solution of 1 g (6.6 mmol) of adamantanol and
0.84 g (4.4 mmol) of N-benzoyl- -alanine in 20 ml
of anhydrous THF at stirring under argon atmosphere
was added 1.03 g (4.9 mmol) of dicyclohexylcarbodi-
imide and 0.05 g of diethylaminopyridine. Further
procedure was the same as in the synthesis of
(N-benzoyl- -alanyloxy)adamantan-4-one (II). After
chromatographic purification [eluent ethyl acetate
petroleum ether (bp 40 60 C), 1: 3] we obtained
1.2 g of compound VIII as colorless crystals.
-alanyloxy)adamantan-4-one
(II).
After
the
chromatographic purification [eluent ethyl acetate
petroleum ether (bp 40 60 C), 1: 2.5] we obtained
0.22 g of compound IV as colorless crystals.
1,4-Dihydroxyadamantane (V). To 50 ml of
ethyl ether at room temperature while stirring was
added by portions 1.3 g (34 mmol) of LiAlH4 , and
to this mixture was added 2.6 g (16 mmol) of com-
pound I. The reaction mixture was stirred for 4 h at
room temperature, then it was evaporated, 2 ml of
water was added, and the mixture was dried in a
vacuum. The solid residue was treated with chloro-
form in a Soxhlet extractor for 4 h. The extract was
dried on MgSO4, filtered, and evaporated. We
obtained 2.5 g (93%) of compound V as colorless
crystals, mp 328 C (publ. bp 327 331 C [11]).
REFERENCES
1. Medicinal Chemistry: Principles and Practice,
King, F.D., Ed., Cambridge: Royal Soc. Chem., 1994,
pp. 207 209.
2. Zefirova, O.N. and Zefirov, N.S., Zh. Org. Khim.,
2000, vol. 36, no. 9, pp. 1273 1300.
3. Zhu, Q., Guo, Z., Huang, N., Wang, M., and
Chu, F., J. Med. Chem., 1997, vol. 40, no. 26,
pp. 4319 4328.
4. Geluk, H.W., Synthesis, 1972, no. 7, pp. 374 375.
5. Csanady, G. and Medzihradszky, K., Org. Prep.
Proced. Int., 1988, vol. 20, no. 2, pp. 180 184.
6. Mercle, L., Dubois, J., Place, E., Thoret, S., Gue-
ritte, F., Guenard, D., Poupat, C., Ahond, A., and
Potier, P., J. Org. Chem., 2001, vol. 66, no. 15,
pp. 5058 5065.
4-Benzoyloxy-1-hydroxyadamantane (VI). To
1 g (6 mmol) of compound V in 8 ml of pyridine at
0 C while stirring was added dropwise 0.67 g
(4.8 mmol) of benzoyl chloride. The reaction mixture
was stirred at 0 C for 3 h, then it was evaporated in
a rotary evaporator. To the residue 10 ml of water
was added, and the mixture was extracted with ethyl
acetate (3 20 ml). The combined extracts were
washed with 0.5% HCl, water, saturated solution of
NaHCO3, and again with water. The solution
obtained was dried with MgSO4, filtered, and
evaporated. After the chromatographic purification
[eluent ethyl acetate petroleum ether (bp 40 60 C),
1: 4] we isolated 0.4 g (31%) of compound VI as
colorless crystals, mp 62 C.
7. Faulkner, D. and McKervey, M.A., J. Chem. Soc.
(C), 1971, no. 23, pp. 3906 3910.
8. Duddeck, H., OMR., 1975, vol. 7, pp. 151 153.
9. Henkel, J.G. and Spektor, J.H., J. Org. Chem.,
1983, vol. 48, no. 21, pp. 3657 3661.
10. Meijer, E.W. and Wynberg, H., J. Am. Chem. Soc.,
1982, vol. 104, no. 4, pp. 1145 1146.
(N-Benzoyl- -alanyloxy)cyclohexane (VII). To a
solution of 1.4 g (14 mmol) of cyclohexanol and
11. Geluk, H.W. and Schlatmann, J.L.A., Tetrahedron,
1968, vol. 24, no. 15, pp. 5369 5377.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002