Reaction of [3.3.1]propellanes with diaryl diselenides

Full text of DOI:10.1134/S1070428010060266

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 6, pp. 929–930. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © G.M. Butov, V.M. Mokhov, Yu.P. Tsapkova, R.L. Antipin, A.Yu. Gavrilova, N.V. Zyk, 2010, published in Zhurnal Organicheskoi
Khimii, 2010, Vol. 46, No. 6, pp. 928–929.
SHORT
COMMUNICATIONS
Reaction of [3.3.1]Propellanes with Diaryl Diselenides
G. M. Butova, V. M. Mokhova, Yu. P. Tsapkovaa, R. L. Antipinb,
A. Yu. Gavrilovab, and N. V. Zykb
a Volgograd State Technical University, Volgograd, Russia
b Faculty of Chemistry, Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
e-mail: gavrilova@org.chem.msu.ru
Received May 18, 2009
DOI: 10.1134/S1070428010060266
Selenium-containing compounds play an important
role in both synthetic chemistry and biological proc-
esses [1]. However, published data on the synthesis of
selenium-containing adamantane derivatives remain so
far few in number. An example is the reaction of
adamantylideneadamantane with benzeneselenenyl
chloride [2].
essary condition ensuring sufficient purity of the re-
sulting 1,3-bis(arylselanyl)adamantanes is stoichiomet-
ric ratio of compounds I and II. Excess dehydroada-
mantane favors formation of a considerable amount of
side polymerization products, whereas excess diaryl
diselenide contaminates the target product.
General procedure for the synthesis of 1,3-bis-
(arylselanyl)adamantanes. A solution of freshly sub-
limed 1,3-dehydroadamantane (Ia) or 5,7-dimethyl-
1,3-dehydroadamantane (Ib) in anhydrous diethyl
ether was added at room temperature under dry nitro-
gen to a solution of an equimolar amount of diaryl
diselenide IIa or IIb in anhydrous diethyl ether.
A weak exothermic effect was observed during the
addition. The mixture was then heated for 0.5–1 h
under reflux, the solvent was distilled off, and the resi-
due was kept for 2 h under reduced pressure (water-jet
pump) at 60–80°C. The structure of the products was
confirmed by the 1H NMR and GC–MS data.
While searching for methods of synthesis of new
selenium-containing adamantane derivatives, we used
as initial compounds two representatives of [3.3.1]pro-
pellanes, 1,3-dehydroadamantane (Ia) and 5,7-dimeth-
yl-1,3-dehydroadamantane (Ib), which are known to
be highly reactive in radical processes. Reactions of
diaryl diselenides with propellanes were studied previ-
ously only with [1.1.1]propellane as an example [3].
We found that 1,3-dehydroadamantane (Ia) and
5,7-dimethyl-1,3-dehydroadamantane (Ib) react with
diphenyl diselenide (IIa) and bis(4-chlorophenyl) di-
selenide (IIb) on heating in boiling diethyl ether to
give the corresponding 1,3-bis(arylselanyl)adaman-
tanes IIIa–IIId in high yields (81–86%).
1,3-Bis(phenylselanyl)adamantane (IIIa) was
synthesized from 1 g (3.2 mmol) of diphenyl disele-
nide (IIa) and 0.43 g (3.2 mmol) of 1,3-dehydroada-
1
The complete conversion of [3.3.1]propellanes Ia
and Ib was attained in 0.5–1 h; higher reaction tem-
perature and the use of higher boiling solvents is
undesirable, for the reaction rate is fairly high. A nec-
mantane (Ia). Yield 1.23 g (86%). H NMR spectrum,
δ, ppm: 1.42–2.10 m (14H, CH2, CH), 7.14–7.43 m
(10H, Harom). Mass spectrum, m/z (Irel, %): 448 (7)
[M]+, 291 (100), 235 (6), 157 (50), 133 (78).
R'
R
R
R
Se
Et2O
+
Se
R'
Se
R'
Se
R
R'
Ia, Ib
IIa, IIb
IIIa–IIId
I, R′ = H (a), Me (b); II, R = H (a), Cl (b); III, R = R′ = H (a); R = Cl, R′ = H (b); R = H, R′ = Me (c); R = Cl, R′ = Me (d).
929

BUTOV et al.
930
1,3-Bis(4-chlorophenylselanyl)adamantane (IIIb)
Mass spectrum, m/z (Irel, %): 544 (2) [M]+, 353 (81),
191 (29), 161 (100). Found, %: C 53.70; H 5.01.
C24H26Cl2Se2. Calculated, %: C 53.04; H 4.79.
was synthesized from 1 g (2.62 mmol) of bis(4-chloro-
phenyl) diselenide (IIb) and 0.35 g (2.62 mmol) of
1,3-dehydroadamantane (Ia). Yield 1.12 g (83%),
1
The H NMR spectra were recorded on a Varian
1
mp 117–118°C. H NMR spectrum, δ, ppm: 1.53–
Mercury-300 spectrometer (300 MHz) at 28°C from
solutions in carbon tetrachloride. The chemical shifts
were determined relative to tetramethylsilane as
internal reference. The mass spectra were obtained on
a Hewlett–Packard HP 5972 mass-selective detector
(electron impact, 70 eV) coupled with an HP 5890
Series II gas chromatograph.
2.14 m (14H, CH2, CH), 7.18 d (4H, Harom), 7.34 m
(4H, Harom). Mass spectrum, m/z (Irel, %): 516 (3) [M]+,
325 (20), 191 (100), 133 (25).
5,7-Dimethyl-1,3-bis(phenylselanyl)adamantane
(IIIc) was synthesized from 1 g (3.2 mmol) of di-
phenyl diselenide (IIa) and 0.525 g (3.2 mmol) of
5,7-dimethyl-1,3-dehydroadamantane (Ib). Yield 1.31 g
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 08-03-00707-a) and by the Russian Academy of
Sciences (program “Theoretical and Experimental
Studies on the Nature of Chemical Bond and Chemical
Processes”).
1
(86%), mp 102–103°C. H NMR spectrum, δ, ppm:
0.74 s (6H, CH3), 1.00–2.02 m (12H, CH2), 7.14–
7.27 m (6H, Harom), 7.40–7.42 m (4H, Harom). Mass
spectrum, m/z (Irel, %): 476 (3) [M]+, 319 (65), 263 (5),
161 (100). Found, %: C 61.09; H 5.97. C24H28Se2. Cal-
culated, %: C 60.76; H 5.91.
1,3-Bis(4-chlorophenylselanyl)-5,7-dimethylada-
mantane (IIId) was synthesized from 1 g (2.62 mmol)
of bis(4-chlorophenyl) diselenide (IIb) and 0.43 g
(3.2 mmol) of 5,7-dimethyl-1,3-dehydroadamantane
REFERENCES
1. Nogueira, C.W., Zeni, G., and Rocha, J.B.T., Chem. Rev.,
2004, vol. 104, p. 6255.
2. Garratt, D.G., Tetrahedron Lett., 1978, vol. 19, p. 1915.
1
(Ib). Yield 1.15 g (81%), mp 145–147°C. H NMR
spectrum, δ, ppm: 0.76 s (6H, CH3), 1.03–1.75 m
3. Wiberg, K.B. and Waddell, S.T., J. Am. Chem. Soc., 1990,
(12H, CH2), 7.17 d (4H, Harom), 7.34 d (4H, Harom).
vol. 112, p. 2194.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010