10904
M. Szarmach et al. / Tetrahedron 69 (2013) 10893e10905
4.2.4.1. Compound 1a. cis isomer of compound 1 (pale yellow
J¼7.8 and 1.5 Hz); 7.83 (2H, d, J¼8.8 Hz). 13C NMR (CDCl3): 69.8, 70.1,
71.0, 71.4, 90.9, 106.1, 109.9, 118.8, 122.8, 122.9, 126.1, 131.2, 140.2,
144.8, 153.7, 155.0, 159.5. FT-IR (film): 3063, 2923, 2866, 1598, 1574,
1479, 1446, 1282, 1174, 1120, 1054, 1015, 842, 757, 734 cmꢀ1. HRMS
(EI): [M]þ¼612.2225, calculated for C33H32N4O8 612.2220.
solid). Mp 121e122 ꢁC. 1H NMR (CDCl3): 3.79e3.88 (2H, m);
3.93e4.10 (6H, m); 6.66e6.72 (2H, m); 6.77 (1H, d, J¼8.3 Hz); 6.87
(1H, d, J¼8.3 Hz); 6.89 (1H, t, J¼7.8 Hz); 7.02e7.05 (1H, m); 7.24 (1H,
dt, J¼7.3 and 1.5 Hz); 7.34 (1H, dd, J¼7.8 Hz and 1.5 Hz). FT-IR (film):
3069, 2924, 2868, 1601, 1586, 1492, 1460, 1444, 1285, 1257, 1143,
1085, 1052, 921, 750 cmꢀ1. This compound, left in the solution for
4.2.5.2. Compound 26. Brown/orange solid was obtained with
the yield of 70%. Mp 82e85 ꢁC. 1H NMR (CDCl3), trans, trans isomer:
3.76 (8H, s); 3.91e3.99 (8H, m); 4.22e4.30 (8H, m); 5.82 (2H, s);
6.77 (2H, s); 6.87 (2H, dd, J¼8.8 and 2 Hz); 7.02e7.08 (4H, m); 7.33
a
few days, quantitatively transforms into the sub-
stratedcompound
1 being a stable trans isomer of azoxy
compound.
(2H, t, J¼7.4 Hz); 7.66 (2H, d, J¼7.3 Hz); 7.77 (2H, d, J¼8.8 Hz). 13
C
NMR (CDCl3): 69.2, 69.4, 69.46, 69.53, 70.5, 70.7, 90.9, 103.0, 108.2,
114.4, 121.2, 123.9, 125.8, 130.9, 139.2, 143.8, 152.8, 154.8, 159.6. FT-
IR (film): 3046, 2931, 2875, 1596, 1496, 1444, 1283, 1253, 1175, 1132,
4.2.4.2. Compound 2a. cis isomer of compound 2 (pale yellow
solid). Mp 111e113 ꢁC. 1H NMR (CDCl3): 3.71e3.83 (2H, m);
3.89e3.97 (4H, m); 4.0e4.32 (6H, m); 6.57 (1H, dd, J¼7.8 and
1.9 Hz); 6.63 (1H, t, J¼7.3 Hz); 6.72 (1H, d, J¼8.3 Hz); 6.87 (1H, d,
J¼7.8 Hz); 6.98 (1H, t, J¼7.8 Hz); 7.02e7.08 (1H, m); 7.26e7.29 (1H,
m (þCHCl3)); 7.55 (1H, dd, J¼7.8 and 1.4 Hz). FT-IR (film): 3071,
2924, 2870, 1602, 1586, 1492, 1463, 1442, 1287, 1254, 1122, 1083,
1051, 933, 749 cmꢀ1. This compound, left in the solution for a few
days, quantitatively transforms into the substratedcompound 2
being a stable trans isomer of azoxy compound.
1116, 1050, 1018, 938, 850, 757, 732 cmꢀ1
. HRMS (EI):
[M]þ¼700.2725, calculated for C37H40N4O10 700.2744.
4.2.5.3. Compound 27. Orange oil was obtained with the yield of
66%. 1H NMR (CDCl3), trans, trans isomer: 1.26 (6H, t, J¼7.3 Hz); 2.67
(4H, t, J¼7.3 Hz); 3.73e3.77 (8H, m); 3.93e3.99 (8H, m); 4.23e4.28
(8H, m); 5.81 (2H, s); 6.76 (2H, s); 6.81e6.85 (4H, m); 6.89 (2H, d,
J¼8.3 Hz); 7.62 (2H, d, J¼7.8 Hz); 7.73 (2H, d, J¼9 Hz). 13C NMR
(CDCl3): 15.6, 29.3, 29.9, 69.4, 70.5, 70.6, 90.9, 103.0, 108.2, 114.0,
114.3, 120.5, 120.8, 123.9, 124.3, 125.6, 130.9, 139.1, 148.1, 152.9,
154.6, 159.3. FT-IR (film): 3052, 2960, 2928, 2872, 1599, 1496, 1454,
1429, 1283, 1255, 1177, 1115, 1054, 1019, 943, 833, 732 cmꢀ1. HRMS
(ESI): [MþH]þ¼757.3428, calculated for C41H49N4O10 757.3449.
4.2.5.4. Compound 28. Bright pink/red solid was obtained with
the yield of 56%. Mp 91e93 ꢁC. 1H NMR (CDCl3), trans, trans isomer:
0.88 (6H, t, J¼6.8 Hz); 1.23e1.35 (48H, m); 1.63 (4H, t, J¼6.8 Hz);
2.62 (4H, t, J¼7.5 Hz); 3.90e3.94 (8H, m); 4.24e4.27 (8H, m); 5.80
(2H, s); 6.81 (2H, d, J¼2.4 Hz); 6.89e6.93 (4H, m); 6.95 (2H, d,
J¼7.8 Hz); 7.68 (2H, d, J¼8.3 Hz); 7.81 (2H, d, J¼8.8 Hz). 13C NMR
(CDCl3): 14.4, 22.9, 29.5, 29.6, 29.7, 29.8, 29.90, 29.94, 31.4, 32.2,
36.3, 69.8, 70.1, 70.9, 71.4, 91.0, 106.1, 109.8, 118.7, 122.8, 123.0, 126.1,
140.3, 142.8, 147.2, 153.8, 154.7, 159.2. FT-IR (film): 2916, 2855, 1603,
1565,1464,1377,1285,1176,1131,1037,1016, 967, 874, 849, 823, 737,
4.2.4.3. Compound 23. Brown/yellow oil: 1H NMR (acetone-d):
3.83e3.90 (4H, m); 4.22 (2H, t, J¼4.2 Hz); 4.32 (2H, t, J¼4.4 Hz);
6.67 (1H, d, J¼8.3 Hz); 6.77 (1H, d, J¼7.8 Hz); 7.19 (1H, t, J¼7.6 Hz);
7.22 (1H, d, J¼8.3 Hz); 7.35 (1H, t, J¼8.3 Hz); 7.42 (1H, dt, J¼7.8 and
1.4 Hz); 7.78 (1H, dd, J¼7.8 and 2 Hz); 12.66 (w1H, s). 13C NMR
(acetone-d): 69.2, 69.72, 69.75, 69.79, 73.85, 73.9, 111.1, 112.2, 112.3,
116.4, 116.5, 121.6, 128.97, 129.0, 131.3, 134.4, 134.5, 141.6, 151.2,
153.6, 154.0, 159.5. FT-IR (film): 3427, 3067, 1602, 1491, 1467, 1449,
1284, 1253, 1142, 1086, 1052, 923, 755 cmꢀ1. UVevis (acetonitrile):
l1¼328 nm, ε1¼1.40ꢂ104; l2¼359 nm, ε2¼1.30ꢂ104. HRMS (EI):
[M]þ¼300.1106, calculated for C16H16N2O4 300.1110.
4.2.4.4. Compound 24. Brown/yellow oil: 1H NMR (acetone-d):
3.62e3.67 (4H, m); 3.87e3.89 (2H, m); 3.94 (2H, t, J¼5.4 Hz); 4.23
(2H, t, J¼5.4 Hz); 4.29e4.31 (2H, m); 6.55 (1H, d, J¼8.3 Hz); 6.67
(1H, dd, J¼8.3 and 3.4 Hz); 7.16 (1H, t, J¼7.5 Hz); 7.26 (1H, d,
J¼8.3 Hz); 7.33 (1H, t, J¼8.3 Hz); 7.41 (1H, dt, J¼7.8 and 2 Hz); 7.63
(1H, d, J¼7.8 Hz); 13.4 (1H, s). 1H NMR (DMSO-d6): 3.58 (4H, s);
3.76e3.79 (2H, m); 3.82 (2H, t, J¼4.7 Hz); 4.15e4.18 (2H, m); 4.20
(2H, t, J¼4.7 Hz); 6.56 (1H, d, J¼8.3 Hz); 6.64 (1H, d, J¼8.3 Hz); 7.09
(1H, t, J¼7.6 Hz); 7.24 (1H, d, J¼8.3 Hz); 7.27 (1H, t, J¼8.4 Hz); 7.41
(1H, dt, J¼7.8 and 1.9 Hz); 7.62 (1H, dd, J¼7.8 and 1.5 Hz); 12.08 (1H,
s). 13C NMR (acetone-d): 69.2, 69.4, 69.6, 69.76, 69.84, 71.6, 103.8,
104.0, 110.1, 110.3, 115.0, 121.4, 127.7, 127.8, 130.9, 134.5, 134.6, 141.2,
151.1, 154.8, 158.6. FT-IR (film): 3399, 3063, 2926, 2874, 1599, 1490,
1454, 1279, 1246, 1134, 1093, 1078, 942, 786, 756, 733 cmꢀ1. UVevis
721 cmꢀ1
.
HRMS (ESI): [MþH]þ¼1033.6992, calculated for
C63H93N4O8 1033.6993.
4.2.5.5. Compound 29. Bright orange/brown solid was obtained
with the yield of 51%. Mp 85e87 ꢁC. 1H NMR (CDCl3), trans, trans
isomer: 0.87 (6H, t, J¼6.9 Hz); 1.22e1.34 (48H, m); 1.60e1.67 (4H,
m); 2.62 (4H, t, J¼7.8 Hz); 3.76 (8H, s); 3.94e3.98 (8H, m);
4.23e4.27 (8H, m); 5.80 (2H, s); 6.75 (2H, s); 6.81e6.84 (4H, m);
6.87 (2H, d, J¼8.3 Hz); 7.61 (2H, d, J¼7.8 Hz); 7.73 (2H, d, J¼8.8 Hz).
13C NMR (CDCl3): 14.4, 22.9, 29.5, 29.6, 29.76, 29.85, 29.92, 29.94,
31.5, 32.2, 36.4, 69.3, 69.4, 69.7, 70.6, 70.7, 91.0, 103.0, 108.2, 114.6,
121.4, 124.1, 125.5, 139.3, 141.7, 146.8, 152.8, 154.6, 159.3. FT-IR
(film): 2923, 2853, 1600, 1495, 1453, 1428, 1282, 1255, 1177, 1123,
1052, 1020, 825, 723 cmꢀ1. HRMS (ESI): [MþH]þ¼1121.7522, cal-
culated for C67H101N4O10 1121.7518.
(acetonitrile):
l1¼364
nm,
ε1¼1.50ꢂ104.
HRMS
(ESI):
[MþH]þ¼345.1449, calculated for C18H21N2O5 345.1450.
4.2.5.6. Compound 30. Orange solid was obtained with the yield
of 64%. Mp 91e93 ꢁC. 1H NMR (CDCl3), trans, trans isomer:
0.83e0.90 (12H, m); 1.20e1.37 (40H, m); 1.54e1.68 (8H, m);
2.57e2.65 (8H, m); 3.87e3.94 (8H, m); 4.20e4.22 (4H, m);
4.27e4.29 (4H, m); 5.85 (2H, s); 6.99 (2H, s); 6.99 (2H, d, J¼8.3 Hz);
4.2.5. Bis(azobenzocrown(ether)s. General procedure p-Hydroxy-
azobenzocrown (0.2 mmol), bromochloroethane (0.2 mmol), po-
tassium carbonate (0.4 mmol), and DMF (2 mL) were stirred and
heated at 65 ꢁC for 30 h. After cooling down the mixture, ca. 20 mL
of water was added. The product was extracted with chloroform
and purified by column chromatography using chloroform and
acetone mixture (finally 1:2). The fractions containing the product
(three stereoisomers eluted separately) were combined and evap-
orated. The product was crystallized from methanol.
7.12 (2H, dd, J¼8.3 and 2 Hz); 7.57 (2H, d, J¼2 Hz); 7.65 (2H, s). 13
C
NMR (CDCl3): 14.4, 22.9, 29.5, 29.6, 29.7, 29.8, 29.9, 30.1, 30.4, 31.7,
32.1, 32.2, 35.4, 69.9, 70.0, 70.9, 71.9, 91.2, 105.0, 117.6, 124.1, 124.3,
126.8, 130.8, 137.1, 139.9, 144.3, 150.1, 153.7, 157.4. FT-IR (film): 2924,
2855, 1608, 1569, 1492, 1455, 1357, 1282, 1257, 1175, 1142, 1083,
1054, 1007, 932, 905, 845, 736 cmꢀ1
.
HRMS (ESI):
[MþH]þ¼1061.7312, calculated for C65H97N4O8 1061.7306.
4.2.5.1. Compound 25. Red/orange solid was obtained with the
yield of 72%. Mp 155e156 ꢁC. 1H NMR (CDCl3), trans, trans isomer:
3.91e3.93 (8H, m); 4.26e4.27 (8H, m); 5.82 (2H, s); 6.83 (2H, d,
J¼2.4 Hz); 6.92 (2H, dd, J¼8.8 and 2.4 Hz); 7.12 (2H, d, J¼7.8 Hz);
7.15 (2H, t, J¼7.8 Hz); 7.34 (2H, dt, J¼8.8 and 1.5 Hz); 7.75 (2H, dd,
4.2.5.7. Compound 31. Red oil was obtained with the yield of
56%. 1H NMR (CDCl3), trans, trans isomer: 0.82e0.92 (12H, m);
1.15e1.38 (72H, m); 1.57e1.65 (8H, m); 2.60 (8H, t, J¼7.8 Hz);
3.70e3.77 (8H, m); 3.91e3.99 (8H, m), 4.20e4.30 (8H, m); 5.85
(2H, s); 6.92e6.96 (4H, m); 7.12 (2H, d, J¼8.3 Hz); 7.47 (2H, s); 7.61