45
Swansburg et al.
1H NMR δ: 7.29–7.16 (m, 5H), 6.20 (s, 1H), 3.32 (s, 3H), 2.69
(s, 1H), 2.27 (s, 1H), 1.89–1.72 (m, 10H); 13C NMR δ: 148.59
(s), 137.94 (s), 128.61 (d), 128.05 (d), 125.90 (d), 118.37 (C11,
d), 71.80 (C5, s), 48.07 (q), 42.23 (C6, t), 41.99 (C3, d), 41.45
(C9, t), 40.65 (C4, t), 38.80 (C8, t), 37.92 (C10, t), 33.23 (C7,
d), 30.53 (C1, d); MS m/z: 255 (M + 1, 19), 254 (M, 100), 167
(13), 162 (12), 134 (12), 119 (26), 109 (20), 105 (11), 91 (14),
86 (34), 84 (50), 71 (11), 56 (19), 46 (10), 40 (10). Anal. calcd.
for C18H22O: C 84.99, H 8.72; found: C 84.79, H 8.54.
(100, M – CH2CN), 91 (11); HRMS calcd. for C18H21N:
251.167; found: 251.66. X-ray structure, Fig. 3.4
Methyl 1-phenyl-2-(2-tricyclo[3.3.1.13,7]decanyl)ethyl ether,
11
This ether was not isolated from the photoreaction of 3 but was
prepared as follows.
1-Phenyl-2-(2-tricyclo[3.3.1.13,7]decanyl)ethanol
A solution of alkene 22 (0.10 g, 4.46 × 10–4 mol) in THF
(15 mL) was cooled to 0°C in an ice–water bath with stirring.
Borane (1.0 M solution in THF, 2.5 mL, 0.0025 mol) was
added dropwise and the resulting solution was warmed to room
temperature and stirred for several hours. The reaction was
then opened to the air, and water (1 mL), followed by aqueous
sodium hydroxide (3 M, 2 mL), was added dropwise. Vigorous
bubbling was observed. Hydrogen peroxide (30% solution,
2 mL) was added dropwise, after which the solution was left to
stir for 5 min at 0°C, then for 20 min at room temperature.
Water (10 mL) and ether (20 mL) were added to the reaction
flask and the resulting mixture was left to stir for several min-
utes. The solution was transferred to a separatory funnel leav-
ing a white solid behind, and was extracted three times with
ether. The combined ether extracts were dried over anhydrous
magnesium sulfate and the solvent removed under vacuum.
Purification by column chromatography (95:5 hexane:ethyl
acetate) gave the desired alcohol (0.10 g, 91% yield); 1H NMR
δ: 7.41–7.22 (m, 5H), 4.84 (d, 1H, J = 10.4 Hz), 2.32 (s, 1H),
2.08 (d, 1H, J = 12.8 Hz), 1.93–1.49 (m, 11H), 1.44 (d, 1H,
J = 10.7 Hz), 1.20 (s, 1H); 13C NMR δ: 144.05, 128.45, 127.67,
126.73, 74.69, 51.43, 39.06, 38.81, 38.25, 32.24, 31.66, 28.89,
28.19, 28.01, 27.84.
Photochemistry
Either a 200 or 450 W Hanovia medium-pressure mercury
lamp was used as the light source for photoreactions. Mixtures
of acetonitrile and methanol were used as solvent in every
case. Acetonitrile was purified by a four-step procedure: distil-
lation from sodium hydride, distillation from phosphorus pen-
toxide, passage through basic alumina, and distillation from
calcium hydride after 24 h reflux under nitrogen. Methanol
was distilled from sodium prior to use. Dicyanobenzene
(DCB) and 1,4-dicyanonaphthalene were available in our
laboratory. DCB and the desired alkene were dissolved in ace-
tonitrile–methanol in an immersion well (300 or 420 mL)
equipped with a Pyrex filter. The solution was purged with
nitrogen for 15 min prior to the irradiation. A positive pressure
of nitrogen and magnetic stirring were maintained for the du-
ration of the reaction. After the photolysis the solvent was
removed under vacuum and the photoproducts were separated
by column chromatography on silica gel and identified by
spectroscopic methods.
Photoproducts
1
The ether 11 was prepared from the above alcohol by the
same procedure as 5-methoxy-2-adamantone, above: 1H NMR
δ: 7.34–7.25 (m, 5H), 4.31 (d, 1H, J = 10.4 Hz), 3.16 (s, 3H),
2.35 (s, 1H), 2.05 (d, 1H, J = 12.8 Hz), 1.94–1.53 (m, 11H),
1.44 (d, 1H, J = 10.4 Hz); 13C NMR δ: 141.49, 128.27, 127.55,
127.47, 84.26, 56.76, 50.88, 39.14, 38.82, 38.34, 31.96, 30.09,
29.42, 28.32, 28.16, 27.95; GC–MS m/z: 122 (16), 121 (100),
91 (23), 79 (12), 77 (24).
4-tert-Butyl-1-diphenylmethylcyclohexene, 8: H NMR δ:
7.29–7.13 (m, 10H), 5.21 (s, 1H), 4.64 (s, 1H), 2.01–1.98 (m,
2H), 1.87–1.76 (m, 2H), 1.31–.122 (m, 2H), 1.04–0.99 (m,
1H), 0.85 (s, 9H); 13C NMR δ: 143.05 (s), 143.02 (s), 139.70
(s), 129.35 (d), 129.29 (d), 128.17 (d), 128.14 (d), 126.14 (d),
126.08 (d), 125.74 (d), 58.48 (s), 44.18 (s), 32.26, 30.38, 27.27
(q), 27.11, 24.51; GC–MS m/z: 305 (15, M + 1), 304 (M, 61),
206 (13), 205 (14), 180 (31), 168 (15), 167 (100), 166 (13),
165 (31), 141 (10), 129 (19), 128 (13), 117 (11), 115 (15), 91
(51), 57 (47).
Methyl 2-phenylmethyl-2-tricyclo[3.3.1.13,7]decanyl ether, 12: Re-
crystallized from ethanol, mp 101–103°C; 1H NMR δ:
7.31–7.19 (m, 5H), 3.34 (s, 3H), 3.00 (s, 2H), 2.12–2.00 (m,
4H), 1.91–1.69 (m, 8H), 1.46 (d, 2H); 13C NMR δ: 137.92,
130.19, 128.02, 125.97, 79.57, 47.34 (C2), 38.42 (C6), 35.21
(C4,C9), 34.53 (C1,C3), 33.63 (C8,C10), 32.80 (C11), 27.70
(C7), 27.29 (C5); MS (70 eV) m/z: 165 (100, M – C7H7), 91
(19); MS (20 eV) m/z: 256 (M, 1), 166 (12), 165 (100), 91 (19),
81 (10), 79 (11); CIMS (iso-C4H10) m/z: 257 (4), 226 (18), 225
(100), 185 (10), 165 (37).
2-Phenylmethyl-2-tricyclo[3.3.1.13,7]decanenitrile, 9:
Re-
crystallized from ethanol–water, mp 105–106.5°C; 1H NMR
δ: 7.32–7.24 (m, 5H), 3.08 (s, 3H), 2.24 (d, 2H, J = 13.4 Hz),
2.16 (d, 2H, J = 14.0 Hz), 1.92 (s, 4H), 1.83 (s, 1H), 1.76 (s,
4H), 1.70 (s, 1H); 13C NMR δ: 135.80, 130.20, 128.26, 127.14,
123.81, 46.31, 40.09, 38.05, 35.35, 33.15, 31.05, 26.96, 26.81;
MS m/z: 252 (M + 1, 11), 251 (M, 67), 91 (100). Anal. calcd.
for C18H21N: C 86.01, H 8.42; found: C 86.14, H 8.42. X-ray
structure, Fig. 2.4
2-(4-Methoxyphenylmethyl)-2-tricyclo[3.3.1.13,7]decanenitrile, 13:
mp 96–98°C; H NMR δ: 7.27 (d, 2H, J = 8.5 Hz), 6.86 (d,
1
2-Phenyl-2-(2-tricyclo[3.3.1.13,7]decanyl)ethanenitrile, 10: Re-
crystallized from ethanol–water, mp 140.5–142°C; H NMR
δ: 7.44–7.21 (m, 5H), 3.73 (s, 2H), 2.58 (s, 2H), 2.10 (s, 1H),
2.05 (s, 2H), 1.98 (s, 1H), 1.90 (s, 2H), 1.86 (s, 2H), 1.72 (s,
4H), 1.64 (s, 2H); 13C NMR δ: 144.23 (s), 128.72 (d), 126.59
(d), 126.11 (d), 117.88 (s), 44.91 (s), 38.32 (t), 32.84 (t), 30.50
(t), 27.55 (d), 26.95 (d); MS m/z: 251 (M, 6), 212 (17), 211
1
2H, J = 8.5 Hz), 3.79 (s, 3H), 3.03 (s, 2H), 2.24 (d, 2H, J =
12.8 Hz), 2.15 (s, 2H, J = 13.4 Hz), 1.92 (s, 4H), 1.83 (s, 1H),
1.76 (s, 4H), 1.69 (s, 1H); 13C NMR δ: 158.72, 131.18, 127.80,
123.98, 113.66, 55.19, 46.51, 39.24, 38.07, 35.39, 33.09,
31.04, 27.00, 26.85; MS m/z: 281 (M, 100), 121 (100); HRMS
calcd. for C19H23NO: 281.178; found: 281.180.
© 1998 NRC Canada