δ 7.96 (4H, d, J 7.2), 7.48 (2H, d, J 7.6), 7.41 (4H, dd, J 7.2 and
7.6), 2.98 (4H, t, J 7.2), 1.69 (4H, tt, J 6.9 and 7.2) and 1.46 (2H,
quintet, J 6.9). GC/MS (EI) m/z (rel. int.) 280 (Mϩ, 5), 262 (41),
161 (29), 133 (6), 120 (41), 105 (100), 77 (35).
3.00 (3H, t, J 7.6), 2.12 (2H, dt, J 6.6 and 7.3), 1.74 (2H, tt, J 7.6
and 7.6) and 1.50 (2H, tt, J 7.3 and 7.6). GC/MS (EI) m/z (rel.
int.) 188 (Mϩ, 20), 146 (24), 120 (60), 105 (100).
1
1-Phenyloct-7-en-1-one 3d. H NMR (CDCl3; Me4Si) δ 7.96
(2H, d, J 7.3), 7.56 (1H, d, J 7.6), 7.46 (2H, dd, J 7.3 and 7.6),
5.81 (1H, ddt, J 2.9, 3.6 and 7.0), 4.98 (2H, dd, J 3.0 and 3.6),
2.97 (2H, t, J 7.3), 2.07 (2H, dt, J 6.9 and 7.0), 1.78 (2H, tt, J 6.9
and 7.3) and 1.42 (4H, tt, J 6.9 and 6.9). GC/MS (EI) m/z (rel.
int.) 202 (Mϩ, 48), 184 (8), 173 (16), 146 (8), 133 (8), 120 (76),
105 (100).
1,8-Diphenyloctane-1,8-dione 1b. Anal. Found: C, 81.88; H,
7.29. Calcd for C20H22O2: C, 81.60; H, 7.53%. 1H NMR (CDCl3;
Me4Si) δ 7.95 (4H, d, J 6.9), 7.54 (2H, d, J 7.3), 7.46 (4H, dd,
J 7.3 and 6.9), 2.98 (4H, t, J 7.3), 1.66 (4H, tt, J 5.0 and 7.3) and
1.44 (4H, quintet, J 5.0). GC/MS (EI) m/z (rel. int.) 294 (Mϩ,
12), 276 (7), 156 (33), 120 (38), 105 (100), 77 (29).
1
1-Phenylnon-8-en-1-one 3e. H NMR (CDCl3; Me4Si) δ 7.95
1,9-Diphenylnonane-1,9-dione 1c. Anal. Found: C, 81.73; H,
7.68. Calcd for C21H24O2: C, 81.78; H, 7.84%. 1H NMR (CDCl3;
Me4Si) δ 7.96 (4H, d, J 7.9), 7.54 (2H, d, J 6.4), 7.48 (4H, dd,
J 6.4 and 7.9), 2.97 (4H, t, J 6.6), 1.73 (4H, tt, J 6.6 and 6.9),
1.57 (2H, quintet, J 6.6) and 1.40 (4H, quintet, J 6.6). GC/MS
(EI) m/z (rel. int.) 308 (Mϩ, 11), 290 (44), 189 (41), 133 (19), 120
(48), 105 (100), 77 (33).
(2H, d, J 7.2), 7.52 (2H, dd, J 6.2 and 7.2), 7.46 (1H, d, J 6.2),
5.77 (1H, ddt, J 3.3, 3.6 and 6.6), 5.01 (1H, d, J 3.6), 4.95 (1H,
d, J 3.3), 2.95 (2H, t, J 7.2), 2.02 (2H, dt, J 6.6 and 7.2), 1.74
(2H, tt, J 7.2 and 7.2) and 1.41 (8H, tt, J 7.2 and 7.2). GC/MS
(EI) m/z (rel. int.) 230 (Mϩ, 71), 187 (18), 173 (9), 159 (23), 146
(52), 133 (13), 120 (100), 105 (92), 77 (30).
1
1-Phenylhex-4-en-1-one 4b. H NMR (CDCl3; Me4Si) δ 7.97
1,10-Diphenyldecane-1,10-dione 1d. Anal. Found: C, 81.78;
H, 8.25. Calcd for C22H26O2: C, 81.95; H, 8.13%. H NMR
1
(2H, d, J 5.0), 7.55 (1H, d, J 4.6), 7.46 (2H, dd, J 4.6 and 5.0),
5.53 (1H, dt, J 5.6 and 6.2), 5.43 (1H, dq, J 2.6 and 5.6), 2.98
(2H, t, J 7.3), 2.50 (2H, dt, J 6.3 and 7.3) and 1.65 (3H, d, J 5.3).
GC/MS (EI) m/z (rel. int.) 174 (Mϩ, 4), 120 (8), 105 (100).
(CDCl3; Me4Si) δ 7.96 (4H, d, J 8.3), 7.55 (2H, d, J 6.9), 7.45
(4H, dd, J 6.9 and 8.3), 2.96 (4H, t, J 7.3), 1.71 (4H, tt, J 6.9 and
7.3), 1.57 (4H, quintet, J 6.9) and 1.36 (4H, quintet, J 6.9). GC/
MS (EI) m/z (rel. int.) 322 (Mϩ, 7), 304 (48), 203 (40), 133 (11),
120 (48), 105 (100), 77 (33).
1-Phenyl-2-vinylcyclobutan-1-ol 5b. 1H NMR (CDCl3; Me4Si)
δ 7.38 (2H, d, J 6.9), 7.31 (1H, d, J 6.9), 7.19 (2H, dd, J 6.9 and
6.9), 5.40 (1H, ddd, J 2.6, 7.3 and 7.6), 4.78 (2H, dd, J 7.3 and
7.6), 2.64 (1H, dt, J 2.6 and 9.2), 2.18 (2H, t, J 9.9) and 1.53
(2H, dt, J 9.2 and 9.9). GC/MS (EI) m/z (rel. int.) 174 (Mϩ, 8),
145 (10), 120 (100), 105 (96).
1,12-Diphenyldodecane-1,12-dione 1e. Anal. Found: C, 82.41;
1
H, 8.59. Calcd for C24H30O2: C, 82.24; H, 8.63%. H NMR
(CDCl3; Me4Si) δ 7.96 (4H, d, J 7.2), 7.46 (2H, d, J 7.9), 7.44
(4H, dd, J 7.2 and 7.9), 2.96 (4H, t, J 7.4), 1.71 (4H, tt, J 6.9 and
7.4), 1.58 (4H, quintet, J 6.9) and 1.32 (8H, quintet, J 6.9). GC/
MS (EI) m/z (rel. int.) 350 (Mϩ, 46), 332 (11), 314 (16), 244 (12),
231 (46), 133 (14), 120 (59), 105 (100), 77 (28).
2-Allyl-1-phenylcyclobutan-1-ol 5c. 1H NMR (CDCl3; Me4Si)
δ 7.47 (2H, d, J 5.3), 7.38 (1H, d, J 6.7), 7.31 (2H, dd, J 5.3 and
6.7), 5.79 (1H, ddt, J 3.3, 3.4 and 6.9), 5.02 (2H, dd, J 3.3 and
3.4), 2.72 (1H, tt, J 7.3 and 8.2), 2.48 (2H, t, J 3.0), 2.29 (2H, dd,
J 6.9 and 7.3) and 1.89 (2H, dt, J 3.0 and 8.2). GC/MS (EI) m/z
(rel. int.) 188 (Mϩ, 4), 160 (32), 146 (24), 120 (100).
General photolysis procedure for isolation of products
A 200 cm3 acetonitrile solution of 1 (1.0 × 10Ϫ2 mol dmϪ3) was
charged in a doughnut type cell 10 mm thick (quartz), and
argon was bubbled through the solution to purge off dissolved
air. After irradiation with a medium-pressure Hg lamp (350 W)
at ambient temperature, the reaction mixtures were analyzed by
GLC or GC/MS. The products 2 and 7 were identified by com-
parison of the retention times with those of the purchased
authentic samples using 2% Silicone OV-17 on Chrom and 10%
polyethylene glycol 20M on Uniport B columns, respectively.
The reaction products 3–6 were isolated with column chrom-
atography on silica gel, and the isolated products were identified
1
2-But-3-enyl-1-phenylcyclobutan-1-ol 5d. H NMR (CDCl3;
Me4Si) δ 7.44 (2H, d, J 6.9), 7.35 (1H, d, J 7.3), 7.24 (2H, dd,
J 6.9 and 7.3), 5.79 (1H, ddt, J 3.0, 3.6 and 6.4), 4.93 (2H, dd,
J 3.0 and 3.6), 2.67 (1H, tt, J 6.3 and 8.6), 2.29 (1H, dt, J 6.3
and 6.6), 2.00 (2H, t, J 2.3), 1.83 (2H, dt, J 6.4 and 6.6) and 1.69
(2H, tt, J 2.3 and 8.6). GC/MS (EI) m/z (rel. int.) 202 (Mϩ, 12),
174 (48), 133 (28), 120 (100), 105 (28).
1
2-Hex-5-enyl-1-phenylcyclobutan-1-ol 5e. H NMR (CDCl3;
1
with H NMR spectroscopy. The product yields were deter-
Me4Si) δ 7.46 (2H, d, J 7.5), 7.26 (1H, d, J 6.9), 7.12 (2H, dd,
J 6.9 and 7.5), 5.75 (1H, ddt, J 3.3, 3.6 and 6.9), 4.89 (2H, dd,
J 3.3 and 3.6), 2.67 (1H, tt, J 6.3 and 8.8), 2.44 (2H, t, J 2.5),
1.85 (2H, dt, J 2.5 and 6.3), 1.92 (2H, dt, J 5.3 and 6.9), 1.27
(2H, dt, J 8.5 and 8.8) and 1.25 (4H, tt, J 5.3 and 8.5). GC/MS
(EI) m/z (rel. int.) 230 (Mϩ, 15), 202 (18), 159 (18), 146 (28), 120
(100), 105 (34).
mined by GLC using eicosane as an internal standard.
Product analyses
1-Phenylpent-4-en-1-one 3a. 1H NMR (CDCl3; Me4Si) δ 7.96
(2H, d, J 6.9), 7.57 (1H, d, J 7.2), 7.44 (2H, dd, J 7.2 and 6.9),
5.85 (1H, ddt, J 2.9, 3.6 and 6.6), 5.12 (1H, d, J 2.9), 5.04 (1H,
d, J 3.6), 3.07 (2H, t, J 7.2) and 2.51 (2H, dt, J 6.6 and 7.2). GC/
MS (EI) m/z (rel. int.) 160 (Mϩ, 68), 145 (48), 131 (30), 105
(100), 77 (30).
1
1-Phenylcyclohex-3-en-1-ol 6b. H NMR (CDCl3; Me4Si) δ
8.04 (2H, d, J 7.3), 7.56 (1H, d, J 7.3), 7.49 (2H, dd, J 7.3 and
7.3), 7.34 (2H, t, J 5.3), 7.25 (2H, d, J 6.9), 5.79 (2H, dt, J 6.3
and 5.3), 2.28 (1H, dt, J 6.3 and 6.9) and 2.05 (1H, dt, J 6.3 and
5.3). GC/MS (EI) m/z (rel. int.) 174 (Mϩ, 28), 120 (100), 105
(56), 92 (8).
1
1-Phenylhex-5-en-1-one 3b. H NMR (CDCl3; Me4Si) δ 7.96
(2H, d, J 6.9), 7.57 (1H, d, J 7.6), 7.40 (2H, dd, J 6.9 and 7.6),
5.83 (1H, ddt, J 3.3, 3.6 and 6.8), 5.08 (1H, d, J 3.6), 4.98 (1H,
d, J 3.3), 3.0 (2H, t, J 7.6), 2.16 (2H, dt, J 6.8 and 7.3) and 1.85
(2H, tt, J 7.3 and 7.6). GC/MS (EI) m/z (rel. int.) 174 (Mϩ, 45),
133 (6), 120 (75), 105 (100).
Measurement of quantum yield
The quantum yields were measured as follows: A 3 cm3 meth-
anol solution of the substrate (1.0 × 10Ϫ2 mol dmϪ3) saturated
with argon gas in a quartz cell (10 mm × 10 mm) was irradiated
using a low-pressure Hg lamp (60 W). Photolysis was carried
out to less than 10% conversion. Actinometry was carried out
1-Phenylhept-6-en-1-one 3c. 1H NMR (CDCl3; Me4Si) δ 7.95
(2H, d, J 6.9), 7.57 (1H, d, J 7.3), 7.46 (2H, dd, J 6.9 and 7.3),
5.82 (1H, ddt, J 3.0, 3.6 and 6.6), 4.99 (2H, dd, J 3.0 and 3.6),
J. Chem. Soc., Perkin Trans. 1, 2000, 415–420
419