9g. Yield 60%, colorless crystals, mp [300 ¡C; l
max
cm~1: 2963, 1464, 1438, 1250, 1083; d ([D ]DMSO): 2.87 (3
H, s), 3.02 (3 H, s), 2.80È3.40 (3 H, m), 3.21 (3 H, s), 3.24 (3 H,
s), 3.26 (3 H, s), 3.69 (1 H, dd, J 7.0, 11.0), 4.72 (1 H, dd, J 7.0,
11.0), 4.82 (1 H, dd, J 7.0, 11.0), 6.22 (1 H, d, J 8.0), 6.72 (1 H,
d, J 8.0), 7.31 (1 H, d, J 8.0), 7.36 (1 H, d, J 2.0), 7.40 (1 H, d, J
8.0), 7.42 (1 H, d, J 2.0).
(KBr)/
H
6
s), 7.30 (2 H, s), 7.57 (2 H, s); m/z: 381 (M`). Anal. calc. for
C
H
NS (381.6): C, 72.39; H, 7.13; N, 3.67; found: C,
Typical procedure for the preparation of 1. To a solution of
9b (1.2 g, 2.14 mmol) in THF (80 mL) was added with stirring
KOBut (0.72 g, 6.41 mmol) at room temperature. The mixture
was stirred for an additional 12 h. Then, 1 M hydrochloric
acid (50 mL) was added and extracted with CH Cl (200 mL).
23 27
2
72.19; H, 7.10; N, 3.72%.
8f. Yield 36%, colorless prisms (hexane), mp 123È126 ¡C;
l
(KBr)/cm~1: 2943, 2908, 1463, 1426, 1245, 1048; d
max
H
(CDCl ): 2.03 (3 H, s), 2.20 (3 H, s), 2.29 (1 H, dd, J 12.2, 12.2),
3
2 2
2.57 (1 H, dd, J 12.2, 12.2), 2.77 (1 H, dd, J 7.0, 12.2), 3.14 (3 H,
The combined extracts were washed with water (50 mL ] 2),
s), 3.51 (1 H, dd, J 7.0, 12.2), 3.69 (1 H, dd, J 7.0, 12.2), 4.14 (1
H, dd, J 7.0, 12.2), 5.87 (2 H, s), 6.79 (1 H, dd, J 2.0, 7.0), 6.88
(1 H, t, J 8.0), 6.03 (1 H, d, J 8.0), 7.14 (1 H, d, J 8.0), 7.29 (1 H,
dried over Na SO and the solvent was evaporated in vacuo
2
4
to leave a residue. The residue was chromatographed over
silica gel (Wako, C-300; 100 g) with 1 : 1 benzeneÈhexane, as
eluent to give 1b (430 mg, 77%). Compounds 1cÈ1g were syn-
thesized in the same manner as for 1b.
dd, J 2.0, 7.0); m/z: 328 (M`). Anal. calc. for C
(330.51): C, 69.05; H, 6.71; found: C, 69.26; H, 6.78%.
H
OS
19 22
2
8g. Yield 42%, colorless prisms (hexane), mp 121È123 ¡C;
5-tert-buty1[2.2]metaparacyclophane-1,9-diene (1b). Yield
l
(KBr)/cm~1: 2949, 1496, 1240, 1101, 1086; d (CDCl ):
77%, colorless oil; l
(NaCl)/cm~1: 2959, 1585, 1572, 1476,
max
H
3
max
2.03 (3 H, s), 2.22 (3 H, s), 2.28 (1 H, dd, J 12.2, 12.2), 2.53 (1 H,
dd, J 12.2, 12.2), 2.76 (1 H, dd, J 7.0, 12.2), 3.15 (3 H, s), 3.51 (1
H, dd, J 7.0, 12.2), 3.74 (1 H, dd, J 7.0, 12.2), 4.10 (1 H, dd, J
7.0, 12.2), 6.01 (2 H, d, J 2.0), 6.97 (1 H, d, J 2.0), 7.15 (1 H, d, J
8.0), 7.43 (1 H, d, J 2.0), 7.56 (1 H, d, J 8.0); m/z: 408, 410
1361; d (CDCl ): 1.25 (9 H, s), 4.24 (1 H, s), 6.66 (2 H, d, J
H
3
10.3), 6.79 (2 H, s), 6.86 (4 H, s), 7.18 (2 H, d, J 10.3); m/z: 260
(M`). Anal. calc. for C
found: C, 92.21; H, 7.84%.
H
(260.38): C, 92.26; H, 7.74;
20 20
5-tert-Butyl-8-methyl[2.2]metaparacyclophane-1,9-diene (1c).
(M`). Anal. calc. for C
found: C, 56.02; H, 5.12%.
H
OS Br (409.4): C, 55.74; H, 5.17;
Yield 80%, colorless oil; l (NaCl)/cm~1: 2962, 2866, 1463,
19 21
2
max
1392; d (CDCl ): 1.28 (9 H, s), 1.32 (3 H, s), 6.11 (2 H, s), 6.66
H
3
(2 H, s), 6.80 (2 H, d, J 9.8), 6.97 (2 H, d, J 9.8), 7.02 (2 H, s);
m/z: 274 (M`). Anal. calc. for C
8.08; found: C, 91.70; H, 8.26%.
5-tert-Butyl-8-methoxy[2.2]metaparacyclophane-1,9-diene
H
(274.41): C, 91.92; H,
21 22
Typical procedure for the preparation of sulfonium salts (9).
A solution of 8b (1.1 g, 3.1 mmol) in CH Cl (10 mL) was
2
2
added with stirring to a suspension of dimethoxymethylium
tetraÑuoroborate (18.1 g, 94 mmol) in CH Cl (25 mL) main-
(1d). Yield 77%, colorless oil; l (NaCl)/cm~1: 2958, 1483,
max
1360, 1244, 1021; d (CDCl ): 1.27 (9 H, s), 3.26 (3 H, s), 6.20
2
2
H
3
tained at [30 ¡C under nitrogen. The mixture was allowed to
warm to room temperature and was stirred for an additional 4
h. Then, ethyl acetate (150 mL) was added, the mixture was
stirred overnight, and the solvent was decanted. The resulting
crystalline precipitate was collected and dried, giving 9b (1.3 g,
94%). Compounds 9cÈ9g were synthesized in the same
manner as for 9b and compounds 9bÈ9g were used directly
without further puriÐcation.
(2 H, s), 6.63 (2 H, s), 6.68 (2 H, d, J 9.8), 7.06 (2 H, d, J 9.8),
7.13 (2 H, s); m/z: 290 (M`). Anal. calc. for C
C, 86.81; H, 7.64; found: C, 86.60; H, 7.76%.
H
O (290.41):
21 22
5-tert-Butyl-8-cyano[2.2]metaparacyclophane-1,9-diene (1e).
Yield 70%, colorless prisms (hexane), mp 87È90 ¡C; l
max
(KBr)/cm~1: 2958, 2281 (CN), 1437; d (CDCl ): 1.26 (9 H, s)
H
3
6.09 (2 H, s), 6.74 (2 H, d, J 10.0), 6.82 (2 H, s), 7.26 (2 H, d, J
10.0), 7.34 (2 H, s); m/z: 285 (M`). Anal. calc. for C
(285.39): C, 88.38; H, 6.71; N, 4.91; found: C, 88.31; H, 6.80;
N, 4.89%.
H
N
21 19
9b. Yield 94%, colorless crystals, mp 262È270 ¡C; l
max
(KBr)/cm~1: 2970, 1593, 1479, 1366, 1207, 1035;
d
H
([D ]DMSO): 1.31 (9 H, s), 2.76 (3 H, s), 3.02 (3 H, s), 3.20 (3
8-Methoxy[2.2]metaparacyclophane-1,9-diene (1f ). Yield
6
H, s), 3.22 (3 H, s), 2.40È3.40 (3 H, m), 3.71 (1 H, dd, J 7.0,
40%, colorless oil; l
max
1164; d (CDCl ): 3.22 (3 H, s), 6.22 (2 H, s), 6.61 (3 H, s), 6.64
(NaCl)/cm~1: 2954, 1438, 1363, 1226,
11.0), 4.38 (1 H, d, J 7.0, 11.0), 4.77 (1 H, dd, J 7.0, 11.0), 5.29
(1 H, s), 5.99 (2 H, s), 7.11 (2 H, s), 7.44 (2 H, d, J 8.0).
H
3
(2 H, d, J 9.8), 7.04 (2 H, d, J 9.8), 7.12 (2 H, s); m/z: 234 (M`).
9c. Yield 84%, colorless crystals, mp [300 ¡C; l
(KBr)/
Anal. calc. for C
87.40; H, 6.34%.
H
O (234.3): C, 87.15; H, 6.02; found: C,
max
17 14
cm~1: 2960, 2890, 1465, 1365, 1083, 1055; d ([D ]DMSO):
H
6
1.44 (9 H, s), 1.95 (3 H, s), 2.88 (6 H, s), 3.31 (6 H, s), 3.16 (2 H,
t, J 11.0), 3.75 (2 H, dd, J 7.0, 11.0), 3.92 (2 H, dd, J 7.0, 11.0),
6.06 (2 H, s), 7.26 (2 H, s), 7.36 (2 H, s).
5-Bromo-8-methoxy[2.2]metaparacyclophane-1,9-diene (1g).
Yield 60%, colorless oil; l (NaCl)/cm~1: 2949, 1496, 1240,
max
1101, 1086; d (CDCl ): 3.25 (3 H, s), 6.64 (2 H, s), 6.59 (2 H,
H
3
9d. Yield 74%, colorless crystals, mp [300 ¡C; l
(KBr)/
d, J 9.8), 6.78 (2 H, s), 7.11 (2 H, d, J 9.8), 7.14 (2 H, s); m/z:
max
cm~1: 2955, 2914, 1460, 1363, 1204, 1065; d ([D ]DMSO):
312, 314 (M`). Anal. calc. for C
4.18; found: C, 65.41; H, 4.35%.
H
OBr (313.20): C, 65.2; H,
H
6
17 13
1.41 (9 H, s), 2.94 (6 H, s), 3.07 (6 H, s), 3.22 (3 H, s), 3.02È3.20
(2 H, m), 3.64È3.80 (2 H, m), 4.84È4.95 (2 H, m), 6.08 (2 H, s),
7.22 (2 H, s), 7.43 (2 H, s).
9e. Yield 70%, colorless crystals, mp 275È278 ¡C; l
Typical procedure for the Lewis and protic acid catalyzed
transannular reaction of 1. To a solution of compound 1d (100
mg, 0.35 mmol) in methylene dichloride (20 mL) was added a
max
(KBr)/cm~1: 2948, 2223 (CN), 1498, 1456, 1369;
d
H
([D ]DMSO): 1.44 (9 H, s), 2.85 (6 H, s), 3.82 (6 H, s), 3.10È
6
5.00 (6 H, m), 5.99 (2 H, s), 7.53 (2 H, s), 7.57 (2 H, s).
solution of TiCl (0.17 mL, 1.5 mmol) or triÑuoromethane sul-
4
9f. Yield 85%, colorless crystals, mp [300 ¡C; l
(KBr)/
fonic acid in CH Cl (5 mL). After the reaction mixture had
max
2 2
cm~1: 2944, 1463, 1426, 1245, 1048; d ([D ]DMSO): 2.83 (3
been stirred for 1 min at 0 ¡C, it was poured into ice water and
extracted with CH Cl . The CH Cl solution was dried
(Na SO ) and evaporated under reduced pressure to leave a
H
6
H, s), 3.01 (3 H, s), 3.22 (3 H, s), 3.24 (3 H, s), 3.25 (3 H, s),
2.60È3.60 (3 H, m), 4.69 (1 H, dd, J 7.0, 11.0), 4.65 (1 H, dd, J
7.0, 11.0), 4.84 (1 H, dd, J 7.0, 11.0), 6.05 (1 H, d, J 8.0), 6.12 (1
H, d, J 8.0), 7.12 (1 H, t, J 7.2), 7.36 (2 H, d, J 7.2), 7.31 (1 H, d,
J 8.0), 7.39 (1 H, d, J 8.0).
2
2
2 2
2
4
residue. GLC analysis of the residue showed a single product,
10b. The residue was recrystallized from methanol to give 75.7
mg (95%) of 2-tert-butylpyrene (10b), using TiCl . Com-
4
726
New J. Chem., 2001, 25, 721È727