938
VYGLAZOV et al.
limonene and converted it to a tertiary amine by the
EXPERIMENTAL
procedure in [16]. The amine was oxidized by the
procedure in [17], and the resulting N-oxide was de-
composed by the procedure in [18]. Yield 52% per
taken alcohol. The conditions of preparation of
tosylate, amine, and N-oxide, as well as of decomposi-
1
The H NMR spectra were recorded on a Tesla BS-
567A spectrometer in deuterochloroform against
internal HMDS. Gas chromatography was performed
on a Khrom-5 chromatograph with a flame ionization
detector, column 2000 3 mm, carrier Chromaton
N-AW-DMCS (fraction 0.125 0.160), liquid phase
Reoplex-400, temperature programming from 100 to
180 C (4 deg/min), carrier gas nitrogen.
1
tion of the latter excluded their isomerization. H
NMR spectrum, , ppm: 0.99 d (3H, CCH3, J 7.5 Hz),
1.68 s (3H, =CCH3), 2.02 2.12 m (2H, >CH2), 2.49
2.60 (2H, methine protons on C1 and C4), 4.85 s and
4.96 s (2H, isopropenyl methylene protons), 4.80
5.03 m (2H, semicyclic methylene group), 5.46 d and
5.55 d (2H, vinyl protons, J 4 Hz).
Allyl ethers were obtained by the procedure in [1].
Standard experimental procedure. Ground KOH,
0.5 mol, was vigorously stirred in 3 mol of DMSO at
100 C. After cooling to 70 C, allyl ether, 0.1 mol,
was added dropwise. The mixture was then heated to
120 C, stirred at that temperature for 4 h, cooled, and
diluted ten times with water. The organic layer was
separated, and the reaction products were extracted
from the aqueous layer with water with diethyl ether
(2 50 ml). The organic layer was combined with the
ether extracts, washed to neutral, and dried with
MgSO4. The solvent was removed, and the reaction
product was distilled at reduced pressure.
ACKNOWLEDGMENTS
The authors express their gratitude to V.M. Zelen-
kovskii for help in quantum-chemical calculations.
REFERENCES
1. Manukov, E.N., Vyglazov, O.G., Zmushko, L.S.,
Bazhina, G.N., Urbanovich, T.R., and Rachin-
skii, A.A., Izv. Akad. Nauk BSSR, Ser. Khim. Nauk,
1991, no. 6, p. 77.
The physicochemical and spectral properties of the
products were consistent with published data: XII [6],
XIV [13], XVII [9], XVIII [14].
2. Temnikova, T.I. and Semenova, S.N., Molekulyarnye
peregruppirovki v organicheskoi khimii (Molecular
Rearrangements in Organic Chemistry), Leningrad:
Khimiya, 1983, p. 47.
The mixture of isomeric aldehydes XXIV and
XXV was separated by column chromatography on
alumina, eluent hexane diethyl ether with increasing
fraction of the latter. Exo isomer XXIV was isolated
98% pure. The spectral properties of endo isomer
XXV were studied using a fraction containing 43% of
this isomer.
3. Trofimov, B.A., Zh. Org. Khim., 1986, vol. 22, no. 9,
p. 1991.
4. Wu, Yun-Dong, Houk, K.N., and Marshall, J.A.,
J. Org. Chem., 1990, vol. 55, no. 5, p. 1421.
5. Margot, C., Matsuda, H., and Schlosser, M., Tetra-
hedron, 1990, vol. 46, no. 7, p. 2425.
2-(3,3-Dimethylbicyclo[2.2.1]hept-2-exo-yl)pent-
4-enal (XXIV). H NMR spectrum, , ppm: 0.98 s
1
6. Margot, C., Rizzolio, M., and Schlosser, M., Tetra-
hedron, 1990, vol. 46, no. 7, p. 2411.
and 1.02 s (6H, 2CH3), 1.56 d and 1.92 d (2H, iso-
camphane C7H2, J 9 Hz), 1.86 d (1H, isocamphane
endo-HC2, J 7.5 Hz), 2.05 2.45 m (5H, isocamphane
bridging protons, aldehyde C2H and C3H2), 5.02 d.d
(1H, =C5H, J5,5 2, J4,5 10.5 Hz), 5.20 d.d (1H, =C5H,
J5,5 2, J4,5 16 Hz), 5.98 d.d (1H, CH=C, J4,5 10.5,
J4,5 16 Hz), 9.32 (1H, CHO).
7. Buinova, E.N., Urbanovich, T.R., Udarov, B.G., and
Izotova, L.V., Khim. Prir. Soedin., 1982, no. 5,
p. 587.
8. Gilchrist, T.L. and Storr, R.C., Organic Reactions and
Orbital Symmetry, Cambridge: Cambridge Univ.,
1972.
2-(3,3-Dimethylbicyclo[2.2.1]hept-2-endo-yl)-
pent-4-enal (XXV). 1H NMR spectrum, , ppm:
0.97 s and 1.00 s (6H, 2CH3), 1.52 d and 1.73 d (2H,
isocamphane C7H2, J 9.5 Hz), 2.19 2.24 m (1H, iso-
camphane exo-HC2), 2.11 2.58 m (5H, isocamphane
bridging fragments, aldehyde C2H and C3H2), 5.06
5.18 m (2H, =C5H2), 5.92 d.d (1H, CH=C, J4,5 10,
J4,5 17 Hz), 9.28 (1H, CHO).
9. Manukov, E.N., Vyglazov, O.G., Chuiko, V.A., and
Shingel’, I.A., Zh. Org. Khim., 1985, vol. 21, no. 10,
p. 2089.
10. Ciganec, E., J. Am. Chem. Soc., 1971, vol. 93, no. 9,
p. 2207.
11. Stewart, J.J.P., J. Comput. Chem., 1989, vol. 10, no. 2,
p. 209; Stewart, J.J.P., J. Comput. Chem., 1989,
vol. 10, no. 2, p. 221.
6-Methylene-p-menta-2,8-diene (XVI). By the
procedure in [15] we obtained 6-(tosyloxymethyl)iso-
12. Hi, Young Yoo and Houk, K.N., J. Am. Chem. Soc.,
1997, vol. 119, no. 12, p. 2877.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 6 2003