ZEFIROVA et al.
1288
(first 1:5 and then 1:1) as eluent. Yield 0.13 g (93%),
4,4-Dimethyladamantan-1-ol (III). A solution of
colorless crystals, mp 115–117°C, [α]D23 = –16.1° (c =
0.01, CH2Cl2). IR spectrum, ν, cm–1: 3280–3320 (OH,
NH), 1720 (C=O, ester), 1645 (C=O, amide), 1610,
1.5 g (4.3 mmol) of 50% m-chloroperoxybenzoic acid
in 30 ml of 1,2-dichloroethane was added to 400 mg
(2.4 mmol) of 2,2-dimethyladamantane (II), and the
mixture was heated for 24 h at 65°C. It was then
cooled to room temperature and diluted with 25 ml of
1,2-dichloroethane, and 8 ml of a 1 N solution of
sodium hydroxide was added. The organic phase was
washed with 10 ml of a 1 N solution of sodium hy-
droxide and water (2×10 ml), dried over Na2SO4, and
evaporated on a rotary evaporator. The residue was
subjected to column chromatography on silica gel
using ethyl acetate–petroleum ether (bp 40–60°C)
(first 1:9 and then 1:5) as eluent to isolate 190 mg of
initial compound II and 210 mg (49%) of product III
as colorless crystals with mp 98–100°C. IR spectrum,
ν, cm–1: 3350 (OH), 1465, 1380, 1369. 1H NMR spec-
trum (CDCl3), δ, ppm: 0.87 s and 0.88 s (3H each,
CH3), 1.12 s (1H, OH), 1.28–1.66 m (8H), 2.02 m
(2H), 2.11 m (2H), 2.13 m (1H). 13C NMR spectrum
(CDCl3), δC, ppm: 26.70 and 28.70 (CH3), 32.36,
33.45, 35.33, 39.59, 41.74, 46.21, 67.25 (C1). Mass
spectrum, m/z (Irel, %): 180 [M]+ (37), 166 (25), 123
(85), 109 (100), 95 (55), 81 (32), 55 (35), 43 (35).
1
1580, 1560. H NMR spectrum (CDCl3), δ, ppm:
1.03 s and 1.09 s (3H each, CH3), 1.12–2.08 m (13H,
CH and CH2 in adamantane, OH), 2.50 (1H, CH, ada-
mantane), 4.54 d (1H, CHOH), 5.78 d.d (1H, CHN),
13
7.16 d (1H, NH), 7.29–7.81 m (10H, Harom). C NMR
spectrum (CDCl3), δC, ppm: 26.60 and 27.95 (CH3),
30.17, 31.85, 34.54, 36.60, 36.72, 40.14, 42.90, 54.74
(CHN), 73.52 (CHOH), 84.23 (C1), 126.96–138.96
(Carom), 166.90 (CONH), 171.82 (COO). Found, %:
C 75.33; H 7.86; N 3.50. C28H33NO4. Calculated, %:
C 75.14; H 7.43; N 3.13.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 04-03-32937).
REFERENCES
1. Zefirova, O.N., Selyunina, E.V., Averina, N.V.,
Zyk, N.V., and Zefirov, N.S., Russ. J. Org. Chem., 2002,
vol. 38, p. 1125.
2. Zefirova, O.N., Selyunina, E.V., Nuriev, V.N.,
Zyk, N.V., and Zefirov, N.S., Russ. J. Org. Chem., 2003,
vol. 39, p. 831.
3. Averina, N.V., Borisova, G.S., Zefirova, O.N., Selyu-
nina, E.V., Zyk, N.V., and Zefirov, N.S., Russ. J. Org.
Chem., 2004, vol. 40, p. 497.
4. Zefirova, O.N., Nurieva, E.V., Chekhlov, A.N., Aldo-
shin, S.M., Nesterenko, P.N., Zyk, N.V., and Zefi-
rov, N.S., Russ. J. Org. Chem., 2004, vol. 40, p. 502.
5. Averina, N.V., Zefirova, O.N., Zefirov, N.S., Chekh-
lov, A.N., Shilov, G.V., and Aldoshin, S.M., Russ. J.
Org. Chem., 2004, vol. 40, p. 1437.
6. Selyunina, E.V., Zefirova, O.N., Zyk, N.V., and Zefi-
rov, N.S., Vestn. Mosk. Gos. Univ., Ser. 2: Khim., 2002,
vol. 43, p. 237.
7. Mikhailov, B.M., Smirnov, V.N., Smirnova, O.D., Pro-
kof’ev, E.I., and Shashkov, A.S., Izv. Akad. Nauk SSSR,
Ser. Khim., 1979, p. 2340.
tert-Butyl (4S,5R)-2,2-dimethyl-5-(4,4-dimethyl-
1-adamantylcarbonyloxy)-4-phenyloxazolidine-3-
carboxylate (V) was synthesized according to the
procedure described in [6] from 0.15 g (0.8 mmol)
of 4,4-dimethyladamantan-1-ol (III) and 0.27 g
(0.84 mmol) of tert-butyl (4S,5R)-5-carboxy-2,2-di-
methyl-4-phenyloxazolidine-3-carboxylate (IV) in dry
methylene chloride. The product was isolated by col-
umn chromatography on silica gel using ethyl acetate–
petroleum ether (bp 40–70°C) (1:10) as eluent. Yield
1
0.2 g (53%), colorless liquid. H NMR spectrum
(CDCl3), δ, ppm: 1.03 s and 1.09 s (3H each, CH3),
1.12 s (9H, t-Bu), 1.28–2.08 m (12H, CH, CH2, and
CH3 in adamantane), 2.50 m (1H, CH, adamantane),
4.50 d (1H, OCHCHN), 4.96 s (1H, OCHCHN), 7.17–
7.36 m (5H, Ph).
4,4-Dimethyl-1-adamantyl (2R,3S)-3-benzoyl-
amino-2-hydroxy-3-phenylpropionate (VI) was syn-
thesized according to the procedure described in [6]
from 0.15 g (0.31 mmol) of ester V in 10 ml of 85%
formic acid. Intermediate product was treated with
0.05 g (0.35 mmol) of benzoyl chloride. The product
was isolated by column chromatography on silica gel
using ethyl acetate–petroleum ether (bp 40–70°C)
8. Reetz, M.T., Westermann, J., and Steinbach, R.,
J. Chem. Soc., Chem. Commun., 1981, p. 237.
9. Noller, C.R., Organic Syntheses, Blatt, A.H., Ed., New
York: Wiley, 1943, collect. vol. 2, p. 184.
10. Robert, C.K. and Philip, J.C.T., J. Am. Chem. Soc.,
1954, vol. 76, p. 2262.
11. Takaishi, N., Fujikura, Y., and Inamoto, Y., Synthesis,
1983, p. 293.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005