Photochemistry
FULL PAPER
747 cmÀ1; elemental analysis calcd (%) for C11H14O2: C 74.97, H 8.39;
found: C 75.0, H 8.4.
13.0 (CH3), 37.5 (CH2), 55.5 (CH3), 110.1 (CH), 111.4 (CH), 119.0 (CH),
125.8, 126.4 (CH), 139.4, 146.0, 157.7 ppm; MS: m/z (%): 160 (100) [M+],
145 (50), 129 (25), 115 (65), 102 (10), 91 (20), 77 (5), 63 (15), 51 (15), 40
(10); IR (neat, for the mixture): n˜ =2948, 1611, 1487, 1257, 1164, 1037,
975 cmÀ1. The spectroscopic data ofcompound 25 were in accordance
with the literature.[51]
In TFE: The reaction was carried out in the presence ofCs 2CO3. After
17 h of irradiation, purification of the raw photolyzate afforded 13
(22 mg, 9% yield) and 2,3-dihydro-3-[2-(2,2,2-trifluoroethoxy]propan-2-
yl)benzofuran (17; 124 mg 32% yield, colorless oil). Data for 17:
1H NMR (CDCl3): d=1.15 (s, 3H), 1.25 (s, 3H), 3.60 (dd, J=4.7, 9 Hz,
1H), 3.75–3.90 (m, 2H), 4.50–4.65 (m, 2H), 6.80–6.95 (m, 2H), 7.15–7.25
(m, 1H), 7.35 ppm (d, J=7.4 Hz, 1H); 13C NMR (CDCl3): d=21.1
(CH3), 21.5 (CH3), 51.3 (CH), 60.2 (q, J=34 Hz), 72.8 (CH2), 78.8, 109.5
(CH), 120.1 (CH), 124.1 (q, J=276 Hz, CF3), 126.1 (CH), 126.7, 128.7
(CH), 160.7 ppm; IR (neat): n˜ =3425, 2114, 1651, 1485, 1460, 1387, 1371,
1280, 1234, 1160, 1110, 1017, 969, 750 cmÀ1; elemental analysis calcd (%)
for C14H18F3O2: C 61.08, H 6.59; found: C 61.0, H 6.6.
In TFE: The reaction was carried out in the presence ofTEA. After 16 h
of irradiation, purification of the raw photolyzate afforded a mixture of
20 (18 mg, 6% yield), 2-(2,2,2-trifluoroethoxy)-1,2,3,4-tetrahydro-6-me-
thoxynaphthalene (27; 70 mg 17% yield), and 1-(2,2,2-trifluoroethoxy)-
1,2,3,4-tetrahydro-6-methoxynaphthalene (28; 78 mg, 20% yield). Further
purification of the fractions containing product 27 afforded
a pure
sample ofsuch compound. Data of r 27: 1H NMR (CDCl3): d=1.80–1.95
(m, 1H), 2.05–2.15 (m, 1H), 2.75–2.85 (m, 2H), 2.95 (m, 1H), 3.15 (dd,
J=5, 16 Hz, 1H), 3.80 (s, 3H), 3.85–4.00 (m, 3H), 6.65 (d, J=2.7 Hz,
1H), 6.75 (dd, J=2.7, 8.4 Hz, 1H), 7.00 ppm (d, J=8.4 Hz, 1H);
13C NMR (CDCl3): d=27.1 (CH2), 27.9 (CH2), 34.3 (CH2), 55.1 (CH3),
65.8 (q, J=34 Hz), 77.3 (CH), 112.2 (CH), 113.1 (CH), 124.6 (q, J=
274 Hz, CF3), 125.9, 130.1 (CH), 136.6, 157.8 ppm; IR (neat): n˜ =2933,
1610, 1505, 1465, 1277, 1236, 1158, 1125, 1039, 968 cmÀ1; elemental analy-
sis calcd (%) for C14H18F3O2: C 61.08, H 6.59; found: C 61.2, H 6.4. Data
In cyclohexane: After 16 h of irradiation, purification of the raw photoly-
zate afforded a complex mixture (14 mg) containing 13 (5%), 3-isoprop-
yl-2,3-dihydrobenzofuran (18;[46] 8%) and (3-methyl-but-2-enyl)phenyl
ether (19;[47] 3%) in an approximate 1.5:2.5:1 ratio as evidenced by 1H
and 13C NMR spectroscopy and GC/MS analysis, which are in accordance
with the literature.[46–47] Data for 18: MS: m/z (%): 162 (33) [M+], 119
(56), 91 (100), 65 (13); data for 19: MS: m/z (%): 162 (11) [M+], 94
(100), 66 (26).
1
for 28: H NMR (CDCl3, from the mixture): d=1.80–1.95 (m, 1H), 2.00–
2.15 (m, 1H), 2.60–3.10 (m, 4H), 3.80 (s, 3H), 3.85–4.00 (m, 2H), 4.60 (t,
J=4.4 Hz, 1H), 6.65 (m, 1H), 6.80 (dd, J=2.7, 8.4 Hz, 1H), 7.30 ppm (d,
J=8 Hz, 1H); 13C NMR (CDCl3, from the mixture): d=18.2 (CH2), 27.9
(CH2), 29.2 (CH2), 55.1 (CH3), 66.0 (q, J=34 Hz), 76.9 (CH), 112.1 (CH),
113.4 (CH), 124.6 (q, J=175 Hz, CF3), 125,9, 130.1 (CH), 136.6,
159.2 ppm; IR (neat, for the mixture): n˜ =2933, 1610, 1501, 1465, 1277,
Photochemical reactions of 3-(but-3-enyl)-4-chloroanisole (3)
In ethyl acetate: After 20 h of irradiation, purification (C6H12 as the
eluant) of the raw photolyzate afforded a mixture (124 mg) containing 2-
chloro-1,2,3,4-tetrahydro-6-methoxynaphthalene (20; 62 mg 22% yield,
see below) and 1-chloromethyl-5-methoxyindane (21;[48] 62 mg 22%
yield). Data for 21: 1H NMR (CDCl3, from the mixture): d=1.95–2.20
(m, 1H), 2.25–2.45 (m, 1H), 2.80–3.10 (m, 2H), 3.45–3.60 (m, 2H), 3.75–
3.90 (m, 4H), 6.70–6.80 (m, 2H; ArH), 7.20 ppm (d, J=8.2 Hz, 1H);
13C NMR (CDCl3, from the mixture): d=30.4 (CH2), 31.0 (CH2), 46.6
(CH), 48.5 (CH2), 55.3 (CH3), 110.0 (CH), 112.2 (CH), 124.5 (CH), 135.4,
146.0, 159.4 ppm; IR (neat, for the mixture): n˜ =2948, 1609, 1504, 1260,
1252, 1157, 1123, 1038, 968 cmÀ1
.
In cyclohexane: After 16 h of irradiation, purification (C6H12 as the
eluant) of the raw photolyzate afforded of a mixture (124 mg) containing
20 (56 mg, 22% yield) and 21 (34 mg, 22% yield).
Photochemical reactions of 3-allyloxy-4-chloroanisole (4)
1236, 1036 cmÀ1
.
In ethyl acetate: After 16 h of irradiation, purification (C6H12 as the
eluant) of the raw photolyzate afforded 3-chloromethyl-2,3-dihydro-6-
methoxybenzofuran (29; 149 mg, 50% yield, colorless oil) and 6-me-
thoxy-3-methylbenzofuran (30; 7 mg, 3% yield, see below). Data for 29:
1H NMR (CDCl3): d=3.50–3.60 (m, 1H), 3.65–3.80 (m, 2H), 3.80 (s,
3H), 4.50–4.60 (m, 1H), 4.65–4.75 (m, 1H), 6.40–6.50 (m, 2H), 7.10 ppm
(d, J=8.1 Hz, 1H); 13C NMR (CDCl3): d=43.9 (CH), 46.3 (CH2), 55.0
(CH3), 75.3 (CH2), 96.0 (CH), 106.0 (CH), 118.5, 124.3 (CH), 160.9,
In water/acetonitrile 1:3: The reaction was carried out in the presence of
Cs2CO3. After 24 h of irradiation, purification (from cyclohexane/ethyl
acetate 99:1 to 7:3 as the eluant) of the raw photolyzate afforded 20
(44 mg, 15% yield, colorless oil), 7-methoxy-1,2-dihydro-naphthalene
(22; 31 mg, 13% yield, colorless oil), and 6-methoxy-1,2,3,4-tetrahydro-2-
naphthol (23; 48 mg 18% yield, colorless oil). Data for 20: 1H NMR
(CDCl3): d=2.05–2.20 (m, 1H), 2.25–2.40 (m, 1H), 2.80–3.10 (m, 3H),
3.30 (dd, J=4.8, 15 Hz, 1H), 3.80 (s, 3H), 4.40–4.50 (m, 1H), 6.65 (d, J=
2.5 Hz, 1H), 6.70–6.75 (m, 1H), 7.10 ppm (d, J=8.4 Hz, 1H); 13C NMR
(CDCl3): d=28.8 (CH2), 33.7 (CH2), 39.9 (CH2), 56.5 (CH3), 58.1 (CH),
113.8 (CH), 114.6 (CH), 127.0, 131.2 (CH), 137.1, 159.3 ppm; IR (neat):
n˜ =2931, 1611, 1507, 1458, 1263, 1154, 1128, 1040, 876 cmÀ1; elemental
analysis calcd (%) for C11H13ClO: C 67.18, H 6.66; found: C 67.0, H 6.6.
The spectroscopic data ofcompounds 22[49] (elemental analysis calcd (%)
for C11H12O: C 82.46, H 7.55; found: C 82.3, H 7.6.) and 23[50] (elemental
analysis calcd (%) for C11H14O2: C 74.13, H 7.92; found: C 74.2, H 8.0.)
were in accordance with the literature.
161.2 ppm; IR (neat): n˜ =2957, 1621, 1598, 1498, 1283, 1198, 1147 cmÀ1
;
elemental analysis calcd (%) for C10H11ClO2: C 60.46, H 5.58; found: C
60.4, H 5.5.
In methylene chloride: Atfer 32 h ofirradiation (77% ofconsumption of
4), purification of the raw photolyzate yielded 29 (115 mg, 50% yield)
and 30 (36 mg, 19% yield, colorless oil). Both yields were calculated on
consumed 4. The spectroscopic data ofcompound 30 were in accordance
with the literature.[52] elemental analysis calcd (%) for C10H10O2: C 74.06,
H 6.21; found: C 74.1, H 6.3.
In acetonitrile: The reaction was carried out in the presence ofCs 2CO3.
After 22 h of irradiation purification of the raw photolyzate yielded 29
(92 mg 31% yield) and 4-methoxyphenol (31; 23% yield) which was de-
termined by GC analysis.
In methanol: The reaction was carried out in the presence ofTEA. After
16 h of irradiation, purification of the raw photolyzate afforded 1,2,3,4-
tetrahydro-2,6-dimethoxynaphthalene (24; 102 mg, 35% yield, colorless
oil), and a mixture of5-methoxy-1-methylindane ( 25; 32 mg, 13% yield)
and 5-methoxy-1-methyl-1-indene (26; 10 mg, 4% yield). Data for 24:
1H NMR (CDCl3): d=1.75–1.90 (m, 1H), 2.00–2.15 (m, 1H), 2.75–3.10
(m, 4H), 3.45 (s, 3H), 3.60–3.70 (m, 1H), 3.80 (s, 3H), 6.65 (d, J=2.7 Hz,
1H), 6.70 (dd, J=2.7, 8.3 Hz, 1H), 7.00 ppm (d, J=8.3 Hz, 1H);
13C NMR (CDCl3): d=27.2 (CH2), 27.6 (CH2), 34.2 (CH2), 55.1 (CH3),
55.7 (CH3), 75.9 (CH), 112.1 (CH), 113.1 (CH), 126.4, 130.2 (CH), 137.0,
157.6 ppm; MS: m/z (%): 192 (100) [M+], 160 (75), 145 (20), 134 (80),
104 (15), 91 (20), 77 (10), 65 (10), 51 (10); IR (neat): n˜ =2938, 1610,
1514, 1467, 1278, 1236, 1155, 1136, 1040, 967 cmÀ1; elemental analysis
calcd (%) for C12H16O2: C 74.97, H 8.39; found: C 74.9, H 8.3. Data for
In water/acetonitrile 1:3: Atfer 40 h ofirradiation (73% ofconsumption
of 4), purification of the raw photolyzate yielded 29 (83 mg, 38% yield)
and 30 (17 mg, 10% yield, colorless oil). Both yields were calculated on
consumed 4.
In methanol: After 9 h of irradiation purification of the raw photolyzate
yielded 29 (30 mg, 10% yield) and 31 (78% yield), which was determined
by GC analysis.
In TFE: The reaction was carried out in the presence ofCs 2CO3. After
42 h ofirradiation puriifcation ofthe raw photolyzate yielded 29 (18 mg,
6% yield) as the only isolated product.
1
26: H NMR (CDCl3, from the mixture): d=2.15 (d, J=1.6 Hz, 3H), 3.35
In TFE in the presence of benzene: The reaction was carried out in the
presence ofCs 2CO3. Atfer 42 h ofirradiation in the presence ofbenzene
(1m), purification of the raw photolyzate yielded 2-allyloxy-4-methoxybi-
(brs, 2H), 3.90 (s, 3H), 6.10 (d, J=1.6 Hz, 1H), 6.60–6.95 (m, 2H),
7.25 ppm (d, J=8.2 Hz, 1H); 13C NMR (CDCl3, from the mixture): d=
Chem. Eur. J. 2006, 12, 3905 – 3915
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3913