On the Functionalization of [2.2](1,4)Phenanthrenoparacyclophane
FULL PAPER
131.57, 131.90, 132.11, 134.18 (d, C-4,-5,-8,-9,-11,-12,-16,-17,-19,
-20), 122.17 (s, C-5a), 132.15, 132.65, 136.65, 136.77, 137.93, 138.81
and 1 hidden signal (s, C-3,-3a,-9a,-9b,-10,-15,-18), 151.56 (s, C-
(92 mg, 0.21 mmol) and boron tribromide (500 mg, 2.00 mmol) af-
ter work-up and purification (see above) 64 mg (93%) of 29b were
obtained, colorless needles (hexane), m.p. 146–148 °C. 1H NMR
6) ppm. IR (KBr): ν = 3490 cm–1 (vs), 3420 (vs), 2920 (m), 1600 (400 MHz): δ = 2.78 (mc, 1 H), 2.86–3.04 (m, 3 H), 3.17 (mc, 1 H),
˜
(vs), 1565 (m), 1520 (m), 1445 (vs), 1350 (m), 1265 (vs), 1230 (m), 3.31 (mc, 1 H), 3.80 (mc, 1 H), 4.25 (mc, 1 H, 1-,2-,13-,14-H), 5.18
1115 (s), 920 (m), 810 (vs), 760 (s), 715 (s). UV (acetonitrile): λmax (s, 1 H, OH), 5.27 (dd, Jo = 7.9, Jm = 1.3 Hz, 1 H, 20-H), 5.87 (dd,
(lgε) = 378 nm (2.90), 362 (3.04), 328 (3.96), 308 (sh, 4.08), 285 (sh,
4.31), 278 (4.36), 251 (4.18), 211 (sh, 4.59), 207 (4.60). MS: m/z (%)
= 324 (25) [M+], 219 (100), 205 (21), 189 (15). C24H20O (324.44):
calcd. C 88.84, H 6.23; found C 88.84, H 6.17.
Jo = 7.8, Jm = 1.3 Hz, 1 H, 19-H), 6.52 (mc, 2 H, 16-,17-H), 6.73
(d, Jo = 7.4 Hz, 1 H, 12-H), 6.87 (d, Jo = 7.4 Hz, 1 H, 11-H), 7.07
(dd, Jo = 8.5, Jm = 2.5 Hz, 1 H, 7-H), 7.49 (d, J = 8.9 Hz, 1 H, 4-
H), 7.63 (d, J = 8.9 Hz, 1 H, 5-H), 7.75 (d, Jo = 8.5 Hz, 1 H, 6-H),
7.87 (d, Jm = 2.5 Hz, 1 H, 9-H) ppm. 13C NMR (100 MHz): δ =
33.50, 34.33, 34.69, 38.22 (t, C-1,-2,-13,-14), 111.87, 115.92 (d, C-
7,-9), 121.76, 125.69, 128.38, 128.90, 129.90, 131.62, 131.87, 132.07,
133.88 (d, C-4,-5,-6,-11,-12,-16,-17,-19,-20), 127.10, 132.12, 134.37,
136.39, 136.74, 137.92, 138.67, 1 C unresolved (s, C-3,-3a,-5a,-9a,
8-Hydroxy[2.2](1,4)phenanthrenoparacyclophane (29b). a) trans-4-
(4-Methoxystyryl)[2.2]paracyclophane (27b): By methods described
in the literature 4-methoxybenzaldehyde (23b) was reduced to ben-
zyl alcohol 24b,[28] and this was converted via the bromide 25b[29]
to the phosphonate 26b.[30] A solution of 26b (2.32 g, 9.00 mmol)
in anhydrous THF (100 mL) was cooled to 0 °C under nitrogen.
After the addition of n-butyllithium (10 mmol, THF; color change
to yellow) solid 4-formyl[2.2]paracyclophane (20) (1.90 g,
8.04 mmol) was added in portions. Work-up as above for 27a pro-
vided 1.7 g (62%) of 27b, colorless needles (ethanol), m.p. 160–
-9b,-10,-15,-18), 153.10 (s, C-8) ppm. IR (KBr): ν = 3480 cm–1 (vs),
˜
2920 (m), 1610 (vs), 1520 (m), 1450 (m), 1350 (m), 1200 (vs), 1175
(vs), 940 (m), 835 (vs), 800 (m), 715 (vs). UV (acetonitrile): λmax
(lgε) = 382 nm (3.18), 363 (3.08), 317 (sh, 3.91), 282 (4.49), 241 (sh,
4.21), 218 (sh, 4.51), 205 (4.65). MS: m/z (%) = 324 (22) [M+], 219
(100), 205 (24), 202 (15), 189 (14), 104 (6). C24H20O (324.44): calcd.
C 88.84, H 6.23; found C 88.95, H 6.27.
1
161 °C. H NMR (400 MHz): δ = 2.74–3.20 (m, 7 H), 3.56 (mc, 1
H, 1-,2-,9-,10-H), 3.82 (s, 3 H, OCH3), 6.61 (s, 1 H, 5-H), 6.39–
6.56 (m, 5 H), 6.70 (dd, Jo = 7.8, Jm = 1.6 Hz, 1 H, 7-,8-,12-,
13-,15-,16-H), 6.93 (mc, 2 H, 21-,22-H), 6.82 (d, J = 16.1 Hz, 1 H),
7.04 (d, J = 16.1 Hz, 1 H, 17-,18-H), 7.50 (mc, 2 H, 20-,24-H) ppm.
13C NMR (100 MHz): δ = 33.99, 34.83, 35.24, 35.47 (t, C-1,-2,-9,
-10), 55.35 (q, OCH3), 114.19 (d, 2 C, C-21,-23), 124.92, 127.66 (2
C), 128.67, 129.72, 129.99, 131.38, 131.70, 132.98 (2 C), 134.89
(d, C-5,-7,-8,-12,-13,-15,-16,-17,-18,-20,-24), 130.75, 137.68, 138.05,
139.29 (2 C), 139.83 (s, C-3,-4,-6,-11,-14,-19), 159.22 (s, C-22) ppm.
6,9-Dimethoxy[2.2](1,4)phenanthrenoparacyclophane (28c). a) trans-
4-(2,5-Dimethoxystyryl)[2.2]paracyclophane (27c): By methods de-
scribed in the literature 2,5-(dimethoxy)benzaldehyde (23c) was re-
duced to benzyl alcohol 24c,[31] and this was converted via the bro-
mide 25c[32] to the phosphonate 26c.[33] According to the procedure
described above for 27a and 27b 26c (2.10 g, 5.82 mmol) was cou-
pled with 20 (1.54 g, 6.52 mmol) to provide after work-up and puri-
fication (see above) 1.54 g (71%) of 27c, colorless prisms (ethanol),
m.p. 161–162 °C. 1H NMR (400 MHz): δ = 2.77–3.18 (m, 7 H),
3.57 (mc, 1 H, 1-,2-,9-,10-H), 3.84 (s, 3 H, OCH3), 3.87 (s, 3 H,
OCH3), 6.68 (d, Jm = 1.4 Hz, 1 H, 5-H), 6.42–6.50 (m, 4 H), 6.53
(dd, Jo = 7.8, Jm = 1.7 Hz, 1 H), 6.74 (dd, Jo = 7.8, Jm = 1.7 Hz, 1
H, 7-,8-,12-,13-,15-,16-H), 6.80 (dd, Jo = 8.9, Jm = 2.9 Hz, 1 H, 22-
H), 6.86 (d, Jo = 8.9 Hz, 1 H, 21-H), 7.15 (d, J = 16.4 Hz, 1 H),
7.21 (d, J = 16.4 Hz, 1 H, 17-,18-H), 7.20 (d, Jm = 2.9 Hz, 1 H, 24-
H) ppm. 13C NMR (100 MHz): δ = 34.07, 34.92, 35.31, 35.57 (t,
C-1,-2,-9,-10), 55.92 (q, OCH3), 56.59 (q, OCH3), 112.55, 112.76,
113.21 (d, C-21,-22,-24), 124.29, 128.10, 129.84, 130.53, 131.71,
131.84, 132.97, 133.06, 134.88 (d, C-5,-7,-8,-12,-13,-15,-16,-17,-18),
138.07, 138.33, 139.31, 139.33, 139.87, 1 quat. C not observed (s,
C-3,-4,-6,-11,-12,-19), 151.84, 154.08 (s, C-20,-23) ppm. IR (KBr):
IR (KBr): ν = 3020 cm–1 (w), 2920 (m), 1605 (m), 1580 (m), 1510
˜
(vs), 1450 (m), 1290 (m), 1255 (s), 1170 (s), 850 (m). UV (acetoni-
trile): λmax (lgε) = 324 nm (4.24), 308 (sh, 4.19), 259 (4.06), 211
(4.45), 199 (4.51). MS: m/z (%) = 340 (40) [M+], 235 (100), 221
(27), 205 (16), 178 (12), 125 (12), 97 (21). C25H24O (340.49): calcd.
C 88.18, H 7.12; found C 88.18, H 7.16.
b) 8-Methoxy[2.2](1,4)phenanthrenoparacyclophane (28b): The pho-
tocyclization of 27b was carried out as described above for the 21
Ǟ 22 interconversion using 27b (408 mg, 1.20 mmol), iodine
(108 mg) and biacetyl (0.4 mL) in toluene (250 mL). After 30 min
irradiation and work-up (see above) 111 mg (27%) of 28b was iso-
lated; colorless leaflets (ethanol), m.p. 197–198 °C. 1H NMR
(400 MHz): δ = 2.79, (mc, 1 H), 2.91–3.05 (m, 3 H), 3.17 (mc, 1 H),
3.37 (mc, 1 H), 3.82 (mc, 1 H), 4.33 (mc, 1 H, 1-,2-,13-,14-H), 3.96
ν = 3000 cm–1 (w), 2940 (m), 2920 (m), 1600 (w), 1500 (vs), 1465
˜
(m), 1280 (m), 1240 (m), 1220 (vs), 1050 (s), 1025 (m), 970 (s). UV
(acetonitrile): λmax (lgε) = 346 nm (4.21), 306 (sh, 4.08), 248 (sh,
4.10), 215 (4.51), 201 (sh, 4.43). MS: m/z (%) = 370 (43) [M+], 265
(100), 251 (19), 235 (26), 104 (5). C26H26O2 (370.52): calcd. C 84.28,
H 7.09; found C 84.18, H 7.15.
(s, 3 H, OCH3), 5.25 (d, Jo = 7.9 Hz, 1 H, 20-H), 5.87 (d, Jo
=
7.9 Hz, 1 H, 19-H), 6.52 (mc, 2 H, 16-,17-H), 6.74 (d, Jo = 7.4 Hz,
1 H, 12-H), 6.91 (d, Jo = 7.4 Hz, 1 H, 11-H), 7.19 (dd, Jo = 8.6, Jm
= 2.5 Hz, 1 H, 7-H), 7.51 (d, J = 8.9 Hz, 1 H, 4-H), 7.65 (d, J =
8.9 Hz, 1 H, 5-H), 7.79 (d, Jo = 8.6 Hz, 1 H, 6-H), 7.91 (d, Jm
=
2.5 Hz, 1 H, 9-H) ppm. 13C NMR (100 MHz): δ = 33.50, 34.33,
34.68, 38.15 (t, C-1,-2,-13,-14), 55.47 (q, OCH3), 109.12, 116.07
(d, C-7,-9), 121.77, 125.65, 128.29, 128.83, 129.53, 131.64, 131.77,
131.94, 133.95 (d, C-4,-5,-6,-11,-12,-16,-17,-19,-20), 127.03, 131.91,
132.35, 134.37, 136.14, 136.85, 137.89, 138.57 (s, C-3,-3a,-5a,-9a,
b) 6,9-Dimethoxy[2.2](1,4)phenanthrenoparacyclophane (28c): By
the procedure described above for 28a and 28b, 27c (542 mg,
1.46 mmol) was photocyclized in the presence of iodine (116 mg)
and biacetyl (0.4 mL) in toluene (250 mL). After 1 h irradiation
and work-up and purification (see above) 170 mg (32%) of 28c
were obtained, colorless needles (ethanol), m.p. 184–185 °C. 1H
NMR (400 MHz): δ = 2.61 (mc, 1 H), 2.86–3.04 (m, 3 H), 3.16–
3.29 (m, 2 H), 3.50 (mc, 1 H), 3.81 (mc, 1 H), 3.82 (s, 3 H, OCH3),
4.02 (s, 3 H, OCH3), 5.34 (mc, 1 H, 20-H), 5.82 (dd, Jo = 7.9, Jm
= 1.5 Hz, 1 H, 19-H), 6.58 (dd, Jo = 8.0, Jm = 1.5 Hz, 1 H, 16-H),
6.66 (dd, Jo = 8.0, Jm = 1.5 Hz, 1 H, 17-H), 6.70 (d, Jo = 7.5 Hz,
1 H, 12-H), 6.80 (d, Jo = 7.5 Hz, 1 H, 11-H), 6.89 (mc, 2 H, 7-,8-
H), 7.64 (d, J = 9.2 Hz, 1 H, 4-H), 8.15 (d, J = 9.2 Hz, 1 H, 5-
H) ppm. 13C NMR (100 MHz): δ = 34.14, 34.82, 35.57, 37.03 (t,
-9b,-10,-15,-18), 157.31 (s, C-8) ppm. IR (KBr): ν = 3000 cm–1 (w),
˜
2940 (m), 2920 (m), 1610 (vs), 1515 (m), 1460 (s), 1435 (s), 1220
(vs), 1040 (s), 860 (m), 840 (vs), 795 (m), 720 (s). UV (acetonitrile):
λmax (lgε) = 381 nm (3.11), 362 (3.04), 318 (sh, 3.90), 283 (4.50),
242 (sh, 4.22), 219 (sh, 4.49), 206 (4.64). MS: m/z (%) = 338 (37)
[M+], 233 (100), 219 (17), 203 (62), 202 (34), 189 (20). C25H24O
(338.47): calcd. C 88.71, H 6.56; found C 88.79, H 6.60.
c) 8-Hydroxy[2.2](1,4)phenanthrenoparacyclophane (29b): The ether
cleavage was performed as described above for 29a; from 28b
Eur. J. Org. Chem. 2007, 1891–1904
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