ACID-CATALYZED REARRANGEMENTS OF ( )-THUJOPSENE
373
mp 45 46 C), and 0.048 g of ketone XV, mp 64 C
in 1.2 ml of SO2FCl we addded at 117 C 0.02 g of
compound XVII in 0.2 ml of CH2Cl2. The mixture
was poured into 4 ml of methanol diethyl ether.
According to the GLC data, the product, 0.015 g, was
ketone XVIII. The same product was obtained from
epoxy derivative XVII when the reaction was carried
out at 75, 40, and 10 C, as well as with the system
5% SbF5 HSO3F at 20 and 50 C.
(published data [30]: mp 67 68 C).
4,7,11,11-Tetramethyltricyclo[5.4.0.01,3]undecan-
1
5-one (XIV). H NMR spectrum, , ppm (J, Hz):
0.39 d (2H, 2-H, J2, 3 = 8), 0.53 s (C14H3), 1.01 s
(C15H3), 1.03 d (C12H3, J12, 4 = 7), 1.05 s (C13H3),
1.19 m (8-Hax, 10-Hax), 1.20 t.d (3-H, J = 8, J3, 4 = 6),
1.30 d.d.d.d (8-Heq, J8-eq, 8-ax = 13.5, J8-eq, 9-ax = 3.5,
The authors are grateful to the Russian Foundation
for Basic Research (project no. 96-07-89187) for pro-
viding access to the Cambridge Structural Database.
J8-eq, 9-eq = 3, J8-eq, 10-eq = 2), 1.40 d.d.d.d (10-Heq,
J10-eq, 10-ax = 13.5, J10-eq, 9-ax = 3.5, J10-eq, 9-eq = 3, J =
2), 1.44 d.d.d.d (9-Heq, J9-eq, 9-ax = 13.5, J9-eq, 10-ax = 4,
REFERENCES
J = 3, 3), 1.58 d.d (6-Heq, J6-eq, 6-ax = 16.5, J6-eq, 4-eq
=
1.5), 1.68 d.d.d.d.d (9-Hax, J = 13.5, J9-ax, 8-ax = 13.5,
J9-ax, 10-ax = 13.5, J = 3.5, 3.5), 1.98 d (6-Hax, J =
16.5), 2.48 q.d.d (4-Heq, J = 7, 6, 1.5).
Reaction of -cedrene (XVI) with monoperoxy-
phthalic acid. Alkene XVI, 0.3 g (0.0015 mol), was
added to 3.4 ml of a solution of monoperoxyphthalic
acid (0.0022 mol) in ether. The mixture was kept for
4 days at 5 C and was treated as described above for
oxidation of compound I. We isolated 0.28 g of epoxy
derivative XVII.
1. Nagahama, S., Bull. Chem. Soc. Jpn., 1960, vol. 33,
p. 1467; Dauben, W.G. and Friedrich, L., Tetra-
hedron Lett., 1967, no. 18, pp. 1735 1740; Ito, S.,
Yatagai, M., and Endo, K., Tetrahedron Lett., 1971,
no. 16, pp. 1149 1152; Ito, S., Yatagai, M., Endo, K.,
and Kodama, M., Tetrahedron Lett., 1971, no. 16,
pp. 1153 1156.
2. Ito, S., Endo, K., Yoshida, T., Yatagai, M., and
Kodama, M., J. Chem. Soc., Chem. Commun., 1967,
p. 186; Ohta, Y. and Hirose, Y., Tetrahedron Lett.,
1968, no. 20, p. 2483.
3. Daeniker, H., Hochstefler, A., Kaiser, K., and
Kitchens, G., J. Org. Chem., 1972, vol. 37, no. 1,
pp. 1 5; Dauben, W., Friedrish, L., Oberhansli, P.,
and Aoyagy, E., J. Org. Chem., 1972, vol. 37, no. 1,
pp. 9 13; Dauben, W., Agric. Food Chem., 1974,
vol. 22, no. 2, pp. 156 162.
4. Gordeeva, E.V., Shcherbukhin, V.V., and Zefi-
rov, N.S., Tetrahedron Comput. Methodol., 1990,
vol. 3, no. 6B, pp. 429 443.
9 ,10 -Epoxy-2,2,6,10-tetramethyltricyclo-
3,7
20
580
[5.3.1.0 ]undecane (XVII). Yield 89%. [ ]
=
1
80.2 (CHCl3, c = 8.7). H NMR spectrum, , ppm
(J, Hz): 0.76 d (C14H3, J14, 6 = 7), 0.95 s (C13H3),
1.14 s (C12H3), 1.20 d.d.d (anti-11-H, Janti-11, syn-11
=
12, Janti-11, 1 = 4, Janti-11, 8-eq = 2.5), 1.24 d.d.d.d (5-H,
J5, 5 = 12, J5, 4 = 6, J5, 4 = 6, J5, 6 = 6), 1.36 s (C15H3),
1.37 d.d.d.d (4-H, J4, 4 = 12, J = 6, J4, 3 = 6, J4, 5 = 6),
1.54 d.d.d (8-Heq, J8-eq, 8-ax = 15, J8-eq, 9 = 4.5, J =
5. Ohloff, G. and Grierson, W., Croat. Chim. Acta.,
2.5), 1.55 m (4 -H), 1.57 q.d.d (6-H, J = 7, 6, J6, 5
=
1985, vol. 58, no. 4, pp. 491 509.
6), 1.63 br.d.d (endo-3-H, Jendo-3, 4 = 9, Jendo-3, 4 = 6),
1.74 d (syn-11-H, J = 12), 1.76 d.d.d.d (5 -H, J = 12,
6, 6, J5 , 4 = 1.5), 1.81 br.d (1-H, J = 4), 1.88 d (8-Hax,
6. Allen, F.H., Kennard, O., Watson, D.G., Bram-
mer, L., Orpen, A.G., and Taylor, R., J. Chem. Soc.,
Perkin Trans. 2, 1987, no. 12, pp. S1 S19.
J = 15), 2.95 d.d (9-H, J = 4.5, J9, 1 = 1).
7. Allen, F.H. and Kennard, O., Chem. Design Autom.
News, 1993, vol. 8, no. 1, pp. 31 37.
8. Nirmala, K.A. and Gowda, D.S.S., Acta Crystallogr.,
Sec. B, 1982, vol. 38, p. 839.
9. Molecular Mechanics, Burkert, U. and Allinger, N.L.,
Eds., Washington, DC: Am. Chem. Soc., 1982.
Translated under the title Molekulyarnaya mekhani-
ka, Moscow: Mir, 1986, p. 106.
10. Polovinka, M.P., Shal’ko, A.A., Korchagina, D.V.,
Gatilov, Yu.V., Shcherbukhin, V.V., Zenko-
vets, G.A., and Barkhash, V.A., Russ. J. Org. Chem.,
2000, vol. 36, no. 1, pp. 40 54.
Isomerization of epoxy derivative XVII over
TiO2/SO24 . To 0.05 g of TiO2/SO24 in 1 ml of
CH2Cl2 we added a solution of 0.05 g of compound
XVII in 1 ml of CH2Cl2, and the mixture was stirred
for 15 min at room temperature. After appropriate
treatment, we isolated 0.05 g of a crude product con-
taining 95% (GLC) of ketone XVIII. The product was
purified by column chromatography on Al2O3. Yield
0.043 g (86%). Following a similar procedure, ketone
XVIII was synthesized from compound XVII in the
presence of HB-2 -zeolite, askanite bentonite clay,
and solid superacid ZrO2/SO24 .
11. Nomura, M., Fujihara, Y., Otubo, E., Inoue, T.,
Yamada, A., and Hotta, K., Yukagaku, 1992, vol. 41,
no. 3, pp. 237 242.
Reaction of compound XVII with the system
HSO3F SO2FCl. To a solution of 0.25 g of HSO3F
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 3 2001