SYNTHESIS OF 1,3-DIMETHYLADAMANTANE BY SKELETAL REARRANGEMENT
1277
3
,6 2,7
a high-pressure microreactor, the reactor was tightly
closed and heated for 12 h at 160°C. When the reaction
was complete, the ampule was cooled to 20°C and
opened, and the mixture was extracted with methylene
chloride (3×5 ml). The solvent was distilled off from
the extract, and the residue was distilled under reduced
pressure. Yield 7.2 g (60%), colorless oily substance,
[6.2.1.1 .0 ]dodecane (II), 0.96 g of Y-zeolite
(Na/H 0.97), and 1 ml of hexane. The ampule was
sealed and placed into a high-pressure microreactor,
and the reactor was tightly closed and heated for 10 h
at 300°C. When the reaction was complete, the ampule
was cooled to room temperature and opened, the
mixture was filtered, and the solvent was distilled off
from the filtrate. The residue was distilled under
reduced pressure. Yield 60%.
–
1
bp 55–60°C (0.2 mm). IR spectrum, ν, cm : 1583
1
(
C=C), 890 (C=C). H NMR spectrum, δ, ppm: 0.906–
0
1
2
6
3
5
.983 m (2H, 11-H), 1.13–1.17 m (4H, 9-H, 10-H),
.28–1.47 m (4H, 2-H, 7-H), 1.57–1.69 m (2H, 12-H),
.17–2.39 m (2H, 1-H, 8-H), 2.79–2.85 m (2H, 3-H,
b. A 20-ml glass ampule was charged with 3 g of
2aR,5aα,8aR,8bα)-decahydroacenaphthene (VII), 3 g
(
of Y-zeolite (Na/H 97%), and 1.5 ml of hexane. The
ampule was sealed and placed into a high-pressure
microreactor, and the reactor was tightly closed and
heated for 10 h at 300°C. The mixture was then treated
1
3
9
10
-H). C NMR spectrum, δ , ppm: 31.86 (C , C ),
C
1
8
11
12
3
6
3.74 (C , C ), 37.83 (C ), 46.63 (C ), 48.61 (C , C ),
3.74 (C , C ), 135.21 (C , C ). Found, %: C 89.83;
2
7
4
5
H 10.17. C H . Calculated, %: C 89.94; H 10.06.
–1
1
2
16
as described in a. Yield 65%. IR spectrum, ν, cm :
3
,6 2,7
1
Tetracyclo[6.2.1.1 .0 ]dodecane (II). A high-
pressure hydrogenation reactor was charged with 5 g
of GM-3-supported nickel catalyst, 7.2 g of tetracyclo-
dodec-4-ene (III), and 45 ml of hexane. The reactor
was tightly closed and hydrogen was supplied at
a pressure of 100 atm for 3 h at 20°C. When the reac-
tion was complete, the reactor was opened, the mixture
was filtered, and the solvent was distilled off from the
2890 (CH ), 1449 (CH ). H NMR spectrum, δ, ppm:
3
2
0
1
.79–0.81 m (6H, CH ), 1.90–1.92 m (2H, CH ), 1.39–
3
2
1
3
.58 m (10H, CH ), 2.26–2.32 m (2H, CH ). C NMR
2
2
5
8
1
3
spectrum, δ , ppm: 29.50 (C , C ), 30.70 (C , C ),
C
7
2
4
8
10
3
(
(
1.15 (CH ), 36.30 (C ), 44.00 (C , C , C , C ), 51.95
3
2
+
C ). Mass spectrum, m/z (I , %): 164 (16) [M] , 149
100) [M – 15] . Found, %: C 87.73; H 12.27. C H .
rel
+
1
2
20
Calculated, %: C 87.79; H 12.33. M 164.1565.
1
filtrate. Yield 95%. H NMR spectrum, δ, ppm: 0.94–
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. NK 13-03-12027/13) and by the scholarship of
the President of the Russian Federation for young
scientists and post-graduate students (grant no. SP-
1
9
2
.00 m (4H, 11-H, 12-H), 1.41–1.53 m (8H, 4-H, 5-H,
-H, 10-H), 1.67–2.1 m (4H, 1-H, 3-H, 6-H, 8-H),
1
3
.23–2.30 m (2H, 2-H, 7-H). C NMR spectrum, δ ,
C
4
5
9
10
1
3
6
8
ppm: 24.38 (C , C , C , C ), 31.24 (C , C , C , C ),
4
H 11.27. C H . Calculated, %: C 88.82; H 11.18.
11
12
2
7
1.24 (C , C ), 50.07 (C , C ). Found, %: C 88.73;
4
426.2013.4).
1
2
18
(
2aR,5aα,8aR,8bα)-Dodecahydroacenaphthene
REFERENCES
(
VII, perhydroacenaphthene). GM-3-supported
nickel catalyst, 5 g, was added in a stream of helium to
a solution of 10 g (0.061 mol) of isomeric octahydro-
acenaphthenes VIIIa and VIIIb in 40 ml of hexane,
the mixture was transferred to a high-pressure hydro-
genation reactor, the reactor was tightly closed, and the
mixture was stirred for 10 h at 20°C under a hydrogen
pressure of 5–7 atm. When the reaction was complete,
the reactor was opened, the mixture was filtered, and
the solvent was distilled off from the filtrate. Yield
1
2
. Bagrii, E.I., Adamantany (Adamantanes), Moscow:
Nauka, 1989.
. Fort, R.C., Jr., Adamantane: The Chemistry of Diamond
Molecules, New York: Marcel Dekker, 1976, p. 385.
3
4
. McKervey, M.A., Tetrahedron, 1980, vol. 36, p. 971.
. Cupas, C.A., Schleyer, P.v.R., and Trecker, D.J., J. Am.
Chem. Soc., 1965, vol. 87, p. 917.
5
. Khazipova, A.N., Pavlova, I.N., Grigor’eva, N.G., Kute-
pov, B.I., Pavlov, M.L., and Basimova, R.A., Khim.
Tekhnol., 2012, vol. 1, p. 5.
1
3
9
.5 g (95%), colorless oily substance. C NMR spec-
3
6
4
5
trum, δ , ppm: 19.62 (C , C ), 27.20 (C , C ), 28.24
C
6
7
. Neiland, O.Ya., Organicheskaya khimiya (Organic Chem-
istry), Moscow: Vysshaya shkola, 1990.
2
7
12
9
10
1
8
(
C , C ), 29.57 (C ), 32.63 (C , C ), 38.84 (C , C ),
1
1
4
0.82 (C ). Mass spectrum, m/z (I , %): 164 (24)
rel
. Minachev, Kh.M., Garanin, V.I., Isakova, T.A., and
Kharlamov, V.V., Izv. Akad. Nauk SSSR, Ser. Khim.,
+
+
+
[M] , 136 (26) [M – 28] , 121 (100) [M – 43] . Found,
%
: C 87.68; H 12.24. C H . Calculated, %: C 87.73;
12 20
1
969, no. 2, p. 481.
H 12.27. M 164.1565.
8
. Minachev, Kh.M., Garanin, V.I., Isakova, T.A., and
Kharlamov, V.V., Izv. Akad. Nauk SSSR, Ser. Khim.,
1969, no. 8, p. 1737.
1
,3-Dimethyladamantane (I). a. A 20-ml glass
ampule was charged with 0.8 g (5 mmol) of tetracyclo-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 9 2013