Reaction of 1,3-dehydroadamantane with camphor and isocamphanone

Full text of DOI:10.1134/S1070428009120215

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 12, pp. 1864–1865. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © G.M. Butov, V.M. Mokhov, G.Yu. Parshin, R.U. Kunaev, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 12,
pp. 1865–1866.
SHORT
COMMUNICATIONS
Reaction of 1,3-Dehydroadamantane with Camphor
and Isocamphanone
G. M. Butova, V. M. Mokhovb, G. Yu. Parshina, and R. U. Kunaeva
a Volzhsk Polytechnical Institute, ul. Engel’sa 42a, Volzhskii, Volgograd oblast, 404121 Russia
e-mail: vht@volpi.ru
b Volgograd State Technical University, Volgograd, Russia
Received November 6, 2006
DOI: 10.1134/S1070428009120215
In continuation of our previous studies [1–3] on the
chemical behavior of 1,3-dehydroadamantane (I) to-
ward carbonyl compounds, we examined its reactions
with bicyclic ketones: 1,7,7-trimethylbicyclo[2.2.1]-
heptan-2-one (II, DL-camphor) and 5,5,6-trimethyl-
bicyclo[2.2.1]heptan-2-one (VI, isocamphanone). The
reaction mixtures were analyzed by gas chromatog-
raphy–mass spectrometry. The reaction of 1,3-dehy-
droadamantane (I) with camphor (II) gave approxi-
mately equal amounts of two stereoisomeric addition
products at the C3 atom of II (endo-III, exo-III;
m/z 286 [M]+); the chromatogram contained two peaks
with close retention times and identical mass spectra.
In addition, 1,1′-biadamantane (IV, m/z 270 [M]+) and
camphor dimer (V, m/z 301 [M]+) were identified as
by-products.
was compound VIIb formed as a result of addition of I
at the C3 atom of VI. Also, addition product VIIa at
the C1 tertiary carbon atom (m/z 286 [M]+, ~5%),
1,1-biadamantane (IV, recombination product of
1-adamantyl radicals), and isocamphanone dimer VIII
were formed.
Thus, high reactivity of 1,3-dehydroadamantane en-
sures formation of addition products with trimethylbi-
cyclo[2.2.1]heptan-2-one derivatives in one step with
high yields under fairly mild conditions.
Possible biological activity of some adducts was
analyzed using Mikrokosm software. It was found that
compounds III and VIIb may be interesting as poten-
tial drugs [4] possessing analgesic, narcotic, and car-
diotonic activity.
In the reaction of 1,3-dehydroadamantane (I) with
isocamphanone (VI) the major product (yield ~80%)
The structure of the isolated compounds was con-
firmed by the IR, 1H NMR, and GC–MS data.
Me
Me
Me
O
Me
Me
Me
Me
Me
+
+
+
Me
Me
O
Me
Me
O
O
I
II
III (endo, exo)
IV
V
Me
Me
Me
Me
O
Me
Me
Me
Me
Me
O
Me
O
Me
Me
I
+
+
+ IV +
O
Me
Me
O
Me
VI
VIIa
VIIb
VIII
1864

REACTION OF 1,3-DEHYDROADAMANTANE WITH CAMPHOR AND ISOCAMPHANONE
1865
1
endo/exo-3-(1-Adamantyl)-1,7,7-trimethylbi-
cyclo[2.2.1]heptan-2-one (III). A solution of 1.34 g
(0.01 mol) of freshly sublimed 1,3-dehydroadamantane
(I) in 20 ml of anhydrous diethyl ether was added
dropwise at room temperature under dry argon to
1.52 g (0.01 mol) of 1,7,7-trimethylbicyclo[2.2.1]hep-
tan-2-one (II). The mixture was stirred, the solvent
was distilled off, and the residue was heated to 100°C
and kept for 5 h at that temperature without stirring.
Volatile substances were removed. Yield 2.91 g (80%),
colorless crystals, mp 115–118°C (from EtOH).
1H NMR spectrum (DMSO-d6), δ, ppm: 0.7–0.9 m
(9H, CH3), 1.0–2.3 m (21H). Mass spectrum, m/z
(Irel, %): 286 (17) [M] +, 258 (2), 135 (100) [Ad] +.
The H NMR spectra were recorded on a Varian
Mercury-300 spectrometer. The mass spectra were ob-
tained on a Hewlett–Packard GC–MS system con-
sisting of an HP 5890 Series II gas chromatograph
coupled with an HP 5972 mass-selective detector. The
IR spectra were measured on a UR-20 spectrometer.
This study was performed under financial support
by the Federal Education Agency of the Russian
Federation, program “Development of Scientific Po-
tential of Higher School 2005” (subprogram no. 3,
section 3, project no. 4507).
REFERENCES
3-(1-Adamantyl)-5,5,6-trimethylbicyclo[2.2.1]-
heptan-2-one (VIIb). The reaction was carried out as
described above using 1.52 g (0.01 mol) of 5,5,6-tri-
methylbicyclo[2.2.1]heptan-2-one and 1.34 g
(0.01 mol) of freshly sublimed 1,3-dehydroadamantane
(I). Yield 2.28 g (80%), colorless crystals, mp 98–
101°C. IR spectrum, ν, cm–1: 3460, 2886, 2840, 1750
(C=O), 1450, 1417, 1350, 1061. Mass spectrum, m/z
(Irel, %): 286 (7.5) [M]+, 271 (1), 135 (100) [Ad] +.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 12 2009