REACTIONS OF (+)- -FENCHENE AND ( )-CAMPHENE WITH ACETONE
373
(
1
16), 80.1 (19), 69 (10), 55 (10), 43 (21). Found M:
Jendo-6, endo-5 = 6.5, Jendo-6, anti-10 = 3), 2.33 d.d (2 -H,
94.16681. C H O. Calculated M: 194.16706.
1
3
22
J = 12.5, J2 , 3 = 6.5), 3.95 d.d.d (endo-5-H, J = 6.5, 3,
Jendo-5, anti-10 = 1), 5.22 d.d (3=H, J = 9, 6.5), 7.15
7.30 m (5H, Harom).
Reaction of -fenchene (VIII) with acetone.
A solution of -fenchene (VIII) in acetone was added
dropwise to 150 mg of -zeolite wetted with approp-
riate solvent (Table 1). The mixture was stirred for
1
H NMR spectrum of compound XI, , ppm (J,
12
11
Hz): 0.96 s (C H ), 1.01 s (C H ), 1.04 m (endo-
3
3
2
0 h at room temperature, the products were extracted
9
-H), 1.52 d (exo-9-H, Jexo-9, endo-9 = 12), 1.46 1.64 m
2H, 10-H), 1.65 d.d.d (exo-6-H, Jexo-6, endo-6 = 13,
Jexo-6, 7 = 3.5, Jexo-6, endo-5 = 3), 1.79 br.s (7-H),
into diethyl ether, the extract was evaporated, and
the residue was subjected to column chromatography.
The results are summarized in Table 1.
(
1
6
.84 d.d (2-H, J2, 2 = 12.5, J2, 3 = 6), 2.10 d.d.d (endo-
-H, J = 13, Jendo-6, endo-5 = 6.5, Jendo-6, anti-10 = 3),
1
H NMR spectrum of compound IX, , ppm (J,
Hz): 0.77 br.d (endo-6-H, J
= 12), 0.90 s
endo-6, exo-6
10
2.22 d.d (2 -H, J = 12.5, J2 , 3 = 9), 3.75 d.d.d (endo-
5-H, J = 6.5, 3, Jendo-5, anti-10 = 1), 5.04 d.d (3-H, J =
9, 6), 7.15 7.35 m (5H, Harom).
9
8
(C H ), 0.98 s (C H ), 1.01 s (C H ), 1.14 d (exo-
3 3 3
6
-H, J = 12), 1.15 d.d.d (exo-3-H, Jexo-3, endo-3 = 14,
1
Jexo-3, 4 = 4.5, Jexo-3, endo-2 = 3.5), 1.34 1.40 m (2H,
Compound XII. H NMR spectrum, , ppm (J,
1
1
12
7
-H), 1.59 br.d (4-H, J = 4.5), 2.17 d.d.m (endo-3-H,
Hz): 1.05 s (C H , C H ), 1.09 d.d.d (anti-10-H,
3 3
J = 14, Jendo-3, endo-2 = 7), 3.32 br.d.d (endo-2-H,
J = 7, 3.5).
Janti-10, syn-10 = 10, Janti-10, endo-5 = 1.5, Janti-10, 7
=
1
.5), 1.25 m (endo-8-H), 1.45 d.d.d.d (exo-8-H,
Reaction of -fenchene (VIII) with benzalde-
hyde. Benzaldehyde, 200 mg, was added to a mixture
of 400 mg of -zeolite and 10 ml of CH Cl , and
a solution of 150 mg of -fenchene and 200 mg of
benzaldehyde in 3 ml of CH Cl was then added
dropwise. The mixture was stirred for 40 min, the
products were extracted into diethyl ether, the extract
was evaporated, and the products were separated by
repeated column chromatography on silica gel. We
isolated 46 mg of a mixture of 8,8-dimethyl-3 ( )-
Jexo-8, endo-8 = 13, Jexo-8, exo-9 = 13, Jexo-8, 7 = 4.5,
Jexo-8, endo-9 = 3.5), 1.63 1.74 m (2H, 9-H), 1.76 d.m
(7-H, J = 4.5), 1.80 d.d (2-H, J2, 2 = 12.5, J2, 3 = 9),
2
2
1
.97 d.m (syn-10-H, J = 10), 2.24 d.d (2 -H, J = 12.5,
J2 , 3 = 6.5), 3.44 d (endo-5-H, Jendo-5, anti-10 = 1.5),
.16 d.d (3-H, J = 9, 6.5), 7.17 quint and 7.26 d (5H,
Harom, AB system). Mass spectrum, m/z (I , %):
2
2
5
4
rel
+
2
1
42.1 (37) [M] , 213 (39), 151 (20), 138.1 (47),
36.1 (46), 123.1 (27), 121.1 (21), 109.1 (51), 105
(100), 95 (37), 93 (19), 91 (41), 80 (30.51) 77 (37),
1
,5
3
( )-phenyl-exo-4-oxatricyclo[5.2.1.0 ]decanes X
69 (20), 67 (19), 55 (16), 43.1 (14), 41 (32), 39 (10),
2
0
80
and XI at a ratio of 7:3 (overall yield 17%), [ ]5
=
2
8 (37). Found M: 242.16685. C H O. Calculated
1
7
22
+
5 (c = 1.5) (found M: 242.16734; C H O; calcu-
17 22
M: 242.16706.
lated M: 242.16706); 11 mg (4%) of 6,6-dimethyl-3-
1
,5
phenyl-exo-4-oxatricyclo[5.2.1.0 ]decane (XII); and
1 mg of a mixture containing (according to the GC
REFERENCES
4
MS data), 12% of -fenchene, 23% of -fenchene,
and 40% of -fenchene dimerization products (total
of 8 substances).
1
.
Tatarova, L.E., Yarovaya, O.I., Volcho, K.P., Korcha-
gina, D.V., Salakhutdinov, N.F., Ione, K.G., and
Barkhash, V.A., Russ. J. Org. Chem., 1995, vol. 31,
no. 7, pp. 908 920.
1
H NMR spectrum of compound X, , ppm (J, Hz):
1
2
0
.95 s (C H ), 0.99 d.d (endo-9-H, J
= 12,
3
endo-9, exo-9
2. Lipmaa, E., Pehk, T., Paasivirta, J., Belikova, N., and
Plate, A., Org. Magn. Reson., 1975, vol. 7, no. 9,
pp. 426 432.
1
1
Jendo-9, syn-10 = 3), 1.04 s (C H ), 1.52 d (exo-9-H,
3
J = 12), 1.53 m (exo-6-H, Jexo-6, endo-6 = 13, Jexo-6, 7
=
4
, Jexo-6, endo-5 = 3), 1.54 m (anti-10-H), 1.63 d.d.d
3.
Schneider, H.-J. and Weigand, E.F., Tetrahedron,
1975, vol. 31, no. 17, pp. 2125 2133.
(
syn-10-H, Jsyn-10, anti-10 = 10, Jsyn-10, endo-9 = 3,
Jsyn-10, 7 = 1.2), 1.77 d.d (2-H, J2, 2 = 12.5, J2, 3 = 9),
4.
US Patent no. 3308069, 1967; Chem. Abstr., 1967,
1
.83 br.d (7-H, J = 4), 2.14 d.d.d (endo-6-H, J = 13,
vol. 67, no. 6, p. 26245.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 3 2002