15.15 (-CH3, 2nd rotamer); m/z (FAB) 860 (100%, M + H+);
rotamer), 4.93 (1H, d, J 11.1, -CHACHBPh, 1st rotamer), 4.90
(1H, d, J 11.1, -CHACHBPh, 1st rotamer), 4.89 (1H, d, J 11.2,
-CHACHBPh, 1st rotamer), 4.88 (1H, d, J 11.2, -CHACHBPh,
1st rotamer), 4.76 (3H, s, J 11.0, -CHACHBPh, 2nd rotamer),
4.74 (1H, d, J 11.0, -CHACHBPh, 2nd rotamer), 3.76 (3H, s,
-OCH3, 1st rotamer), 3.67 (3H, s, -OCH3, 1st rotamer), 3.62
(3H, s, -OCH3, 1st rotamer), 3.55 (9H, s, -OCH3, 2nd rotamer),
3.36 (6H + 6H, m, -N–CH-, 1st and 2nd rotamers), 1.87 −
1
2
CHN requires for C51H66N6O6· EtOAc: C 70.42%, H 7.75%, N
9.30%; found: C 69.19%, H 8.43%, N 9.13%.
(2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-Hexaaza-2,3:12,
13:22,23-tributano-7,17,27-trimethoxy-8ꢀ,18ꢀ,28ꢀ-tripropoxy-
6,9:16,19:26,29-trietheno-2H,3H,12H,13H,22H,23H-
hexahydro[30]annulene 20b
1
1.28 (24H + 24H, m, -CH2-, 1st and 2nd rotamers); H-NMR
A
solution of 2-ethoxy-5-methoxyterephthalaldehyde 19b
st
=
(500 MHz, d8-toluene) dH: 9.02 (1H, s, -CH N-, 1 rotamer),
(120 mg, 0.54 mmol) in anhydrous CH2Cl2 (3 ml) was added
to a solution of (1R,2R)-cyclohexane-1,2-diamine 7 (0.061 g,
0.54 mmol) in anhydrous CH2Cl2 (3 ml) at 0 ◦C. The mixture was
stirred at room temperature for 3 h and the solvent evaporated.
The residue was recrystallised from ethyl acetate to give the
title product 2◦0b (74 mg, 15.20%) as mixture of rotamers (1 :
st
st
=
=
9.02 (1H, s, -CH N-, 1 rotamer), 8.99 (1H, s, -CH N-, 1 ro-
st
=
=
tamer), 8.97 (1H, s, -CH N-, 1 rotamer), 8.96 (1H, s, -CH N-,
1st rotamer), 8.94 (1H, s, -CH N-, 1 rotamer), 8.90 (3H, s,
st
=
-CH N-, 2 rotamer), 8.89 (3H, s, -CH N-, 2nd rotamer), 7.93
(1H, s, -Ar, 1st rotamer), 7.91 (1H, s, -Ar, 1st rotamer), 7.85
(1H, s, -Ar, 1st rotamer), 7.84 (3H, s, -Ar, 2nd rotamer), 7.82
(3H, s, -Ar, 2nd rotamer), 7.79 (1H, s, -Ar, 1st rotamer), 7.77
(1H, s, -Ar, 1st rotamer), 7.74 (1H, s, -Ar, 1st rotamer), 7.25–6.67
(15H + 15H, m, -C6H5, 1st and 2nd rotamers), 4.75 (3H, d, J 11.9,
-OCHAHBPh, 2nd rotamer), 4.71 (3H, d, J 11.9, -OCHAHBPh, 2nd
rotamer), 4.64 (1H, d, J 11.7, -OCHACHBPh, 1st rotamer), 4.59
(1H, d, J 11.7, -OCHACHBPh, 1st rotamer), 4.57 (1H, d, J 10.9,
-OCHACHBPh, 1st rotamer), 4.54 (1H, d, J 10.9, -OCHACHBPh,
1st rotamer), 4.47 (1H, d, J 11.6, -OCHACHBPh, 1st rotamer),
4.37 (1H, d, J 11.6, -OCHACHBPh, 1st rotamer), 3.54 (9H, s,
-OCH3, 2nd rotamer), 3.43 (3H, s, -OCH3, 1st rotamer), 3.33
(3H, s, -OCH3, 1st rotamer), 3.27 (3H, s, -OCH3, 1st rotamer),
2.21–0.64 (24H + 24H, m, -CH2-, 6H + 6H, m, -CH-N, m,
1st and 2nd rotamers); 13C-NMR (67.5 MHz, CDCl3) dC: 157.15
nd
=
=
1); mp >320 C; [a]D25 −200.1 (c 0.01, CHCl3, 1 dm); IR mmax
1
(Nujol)/cm−1 1633 (-CH N-); H-NMR (500 MHz, CDCl3)
=
st
=
=
dH: 8.62 (1H, s, -CH N-, 1 rotamer), 8.58 (1H, s, -CH N-,
1st rotamer), 8.57 (1H, s, -CH N-, 1 rotamer), 8.56 (1H, s,
st
=
st
st
=
=
-CH N-, 1 rotamer), 8.55 (1H, s, -CH N-, 1 rotamer),
st
nd
=
=
8.55(1H, s, -CH N-, 1 rotamer), 8.51 (3H, s, -CH N-, 2
nd
=
rotamer), 8.51 (3H, s, -CH N-, 2 rotamer), 7.29–7.27 (6H +
6H, m, 1st and 2nd rotamers), 3.89 (6H, m, -OCH2CH2CH3, 1st
rotamer), 3.86 (6H, m, -OCH2CH2CH3, 2nd rotamer), 3.73 (9H, s,
-OCH3, 1st rotamer), 3.70 (9H, s, -OCH3, 2nd rotamer), 3.36
(6H + 6H, m, -N-CH-, 1st and 2nd rotamers), 1.85–1.45 (48H +
12H, m, -CH2-, -CH2CH2CH3, 1st and 2nd rotamers), 0.95 (9H, t,
J 7.3, -CH3, 1st rotamer), 0.89 (9H, t, J 7.3, -CH3, 2nd rotamer);
13
st
=
C-NMR (67.5 MHz, CDCl3) dC: 157.20 (-CH N-, 1 rotamer),
st
nd
=
=
(-CH N-, 1 rotamer), 156.64 (-CH N-, 2 rotamer), 154.09
(1st rotamer), 154.03 (2nd rotamer), 152.94 (1st rotamer), 152.84
(20nd rotamer), 137.61 (1st rotamer), 136.87 (2nd rotamer), 129.17
(1st rotamer), 129.07 (2nd rotamer), 128.64 (1st rotamer), 128.59
(2nd rotamer), 128.51 (1st rotamer), 128.27 (2nd rotamer), 128.16
(1st rotamer), 128.11 (2nd rotamer), 112.18 (1st rotamer), 111.50
(2nd rotamer), 110.66 (1st rotamer), 110.56 (2nd rotamer), 74.86
(-OCH2Ph or CH-N-, 1st rotamer), 74.61 (-OCH2Ph or CH–N-,
2nd rotamer), 72.01 (-OCH2Ph or -CH–N-, 1st rotamer), 71.60
(-OCH2Ph or -CH-N-, 2nd rotamer), 56.61 (-CH2-, 1st rotamer),
56.41 (-CH2-, 2nd rotamer), 32.34 (-CH2-, 1st rotamer), 33.17
(-CH2-, 2nd rotamer), 24.98 (-CH3, 1st rotamer), 24.95 (-CH3,
2nd rotamer); m/z (FAB) 1045 (100%, M+); CHN requires for
C66H72N6O6·EtOAc: C 74.20%, H 7.06%, N 7.41%; found: C
74.63%, H 7.10%, N 7.71%.
157.08 (-CH N-, 2 rotamer), 153.73 (1st rotamer), 153.65
(2nd rotamer), 153.32 (1st rotamer), 153.29 (2nd rotamer), 128.38
(1st rotamer), 128.16 (2nd rotamer), 127.97 (1st rotamer), 127.92
(2nd rotamer), 111.73 (1st rotamer), 111.42 (2nd rotamer), 110.67
(1st rotamer), 110.13 (2nd rotamer), 74.61 (-OCH2CH2CH3 or
-CH-N-, 1st rotamer), 74.28 (-OCH2CH2CH3 or -CH-N-, 2nd
rotamer), 71.05 (-OCH2CH2CH3 or -CH-N-, 1st rotamer), 70.91
(-OCH2CH2CH3 or -CH-N-, 2nd rotamer), 56.29 (-OCH3, 1st
rotamer), 56.16 (-OCH3, 2nd rotamer), 33.03 (-CH2-, 1st rotamer),
32.90 (-CH2-, 2nd rotamer), 25.07 (-OCH2CH2CH3, 1st rotamer),
24.65 (-OCH2CH2CH3, 2nd rotamer), 22.76 (-CH2-, 1st rotamer),
22.73 (-CH2-, 2nd rotamer), 11.08 (-CH3, 1st rotamer), 10.72 (-
CH3, 2nd rotamer); m/z (FAB) 902 (100%, M + H+); CHN
requires for C54H72N6O6·EtOAc: C 70.43%, H 8.08%, N 8.49%;
found: C 70.73%, H 8.10%, N 8.61%.
nd
=
(2R,3R,12R,13R,22R,23R)-1,4,11,14,21,24-Hexaaza-2,3:12,
13:22,23-tributano-7,17,27-tribenzyloxy-8ꢀ,18ꢀ,28ꢀ-trimethoxy-
6,9:16,19:26,29-trietheno-2H,3H,12H,13H,22H,23H-
hexahydro[30]annulene 20c
(2R,3R,12R,13R,22R,23R-1,4,11,14,21,24-Hexaaza-2,3:12,
13:22,23-tributano-7,17,27-tri(2ꢀ-methoxyethoxy)-8ꢀ,18ꢀ,28ꢀ-
trimethoxy-6,9:16,19:26,29-trietheno-2H,3H,12H,13H,22H,
23H)-hexahydro[30]annulene 20d
A solution of 2-benzyloxy-5-methoxyterephthalaldehyde 19c
(120 mg, 0.54 mmol) in anhydrous CH2Cl2 (3 ml) was added
to a solution of (1R,2R)-cyclohexane-1,2-diamine 7 (0.061 g,
0.54 mmol) in anhydrous CH2Cl2 (3 ml) at 0 ◦C. The mixture was
stirred at room temperature for 3 h and the solvent evaporated.
The residue was recrystallised from ethyl acetate–petroleum
ether (40–60◦) (1 : 1) to give the title product 20c (38 mg,
A
solution of 2-methoxy-5-(2ꢀ-methoxyethoxy)terephth-
alaldehyde 19d (120 mg, 0.42 mmol) in anhydrous CH2Cl2
(3 ml) was added to a solution of (1R,2R)-cyclohexane-1,2-
diamine 7 (0.048 g, 0.42 mmol) in anhydrous CH2Cl2 (3 ml)
at 0 ◦C. The mixture was stirred at room temperature for 3 h
and the solvent evaporated. The residue was recrystallised from
ethyl acetate to give the title product 20d (20 mg, 5.0%), as
◦
◦
12.5%), as a mixture of rotamers; mp 225 C; [a]2D5 −217.19
mixture of rotamers (3 : 1); mp 190 C; [a]2D5 −500.1 (c 0.01,
(c 0.02, CHCl3, 1 dm); IR mmax (Nujol)/cm−1 1631 (-CH N-);
CHCl3, 1 dm); IR mmax (Nujol)/cm−1 1635 (-CH N-); H-NMR
1
=
=
1
st
nd
=
=
H-NMR (500 MHz, CDCl3) dH: 8.65 (1H, s, -CH N-1
(500 MHz, CDCl3) dH: 8.612 (3H, s, -CH N-, 2 rotamer),
st
st
=
=
=
rotamer), 8.62 (1H, s, -CH N-, 1 rotamer), 8.61 (1H, s,
-CH N-, 1 rotamer), 8.59 (1H, s, -CH N-, 1 rotamer), 8.59
(1H, s, -CH N-, 1 rotamer), 8.59(1H, s, -CH N-, 1 rotamer),
8.54 (3H, s, -CH N-, 2 rotamer), 8.54 (3H, s, -CH N-, 2
8.610 (1H, s, -CH N-, 1 rotamer), 8.58 (3H, s, -CH N-,
st
st
st
2nd rotamer), 8.57 (1H, s, -CH N-, 1 rotamer), 8.55 (1H, s,
=
=
=
st
st
st
st
=
=
=
=
-CH N-, 1 rotamer), 8.53 (1H, s, -CH N-, 1 rotamer),
8.51 (1H, s, -CH N-, 1 rotamer), 8.48 (1H, s, -CH N-, 1
nd
nd
st
st
=
=
=
=
rotamer), 7.49 (1H, s, 1st rotamer), 7.47 (1H, s, Ar, 1st rotamer),
7.46 (1H, s, Ar, 1st rotamer), 7.43 (1H, s, Ar, 1st rotamer), 7.42
(1H, s, Ar, 1st rotamer), 7.41 (1H, s, Ar, 1st rotamer), 7.38–7.31
(15H + 15H, m, -C6H5, 1st and 2nd rotamers), 7.21 (3H, s, Ar,
2nd rotamer), 7.19 (3H, s, Ar, 2nd rotamer), 5.02 (1H, d, J 11.3,
-CHACHBPh, 1st rotamer), 4.98 (1H, d, J 11.3, -CHACHBPh, 1st
rotamer), 7.30 (6H + 6H, m, 1st and 2nd rotamers), 4.03 (6H +
6H, m, -OCH2-CH2OCH3, 1st and 2nd rotamers), 3.73 (6H +
6H, m, -OCH2-CH2OCH3, 1st and 2nd rotamers), 3.37 (6H +
6H, m, -N-CH-, 1st and 2nd rotamers), 3.31 (9H + 9H, s, -OCH3,
1st and 2nd rotamer), 1.88 − 1.18 (24H + 24H, m, -CH2-1st
and 2nd rotamer); 13C-NMR (67.5 MHz, CDCl3)§ dC: 157.15
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 5 2 4 – 5 3 7
5 3 5