29.27, 29.32, 29.36, 29.42, 29.45, 30.0, 31.6, 31.7, 68.8, 73.6,
74.6, 83.5, 106.1, 124.9, 126.8, 128.7, 130.9, 141.5, 150.5, 151.0,
157.9. IR (neat) n/cm21: 2917, 2850, 1724, 1582, 1468, 1350,
1135, 1073. Anal. Calc. for C63H116BrNO7S (1111.58 g mol21):
C 68.07, H 10.52, N 1.26, S 2.88; Found: C 68.15, H 10.65, N
1.08, S 2.64%.
156H), 1.43 (s, 18H), 1.84 (m, 12H), 3.83 (d, J 5 6.1 Hz, 4H),
4.03 (t, J 5 6.5 Hz, 6H), 4.06 (t, J 5 6.6 Hz, 6H), 4.36 (d,
J 5 5.2 Hz, 4H), 5.61 (dt, J 5 15.4 and 6.1 Hz, 2H), 5.78 (dt,
J 5 15.4 and 5.5 Hz, 2H), 6.93 (d, J 5 8.5 Hz, 1H), 6.94 (d, J 5
8.5 Hz, 2H), 7.36 (d, J 5 2.2 Hz, 1H), 7.39 (d, J 5 2.2 Hz, 2H),
7.45 (dd, J 5 8.5 and 2.2 Hz, 3H). 13C NMR (62.5 MHz,
CDCl3): d 13.8, 22.4, 25.70, 25.74, 27.6, 28.76, 28.84, 28.9,
29.0, 29.09, 29.12, 29.2, 29.39, 29.44, 31.7, 47.4, 47.8, 68.9,
69.0, 69.3, 69.4, 83.8, 111.7, 112.3, 112.8, 120.7, 121.6, 128.0,
129.8, 131.2, 131.3, 148.2, 148.8, 150.5, 152.4, 153.1. IR (neat)
n/cm21: 2915, 2849, 1727, 1262, 1136. Anal. Calc. for
C132H237N3O16S3 (2218.53 g mol21): C 71.46, H 10.77, N
1.89, S 4.34; Found: C 71.32, H 11.22, N 1.81, S 3.63%.
Synthesis of (E,E)-1,6,11-tris(arylsulfonyl)-1,11-bis(tert-
butyloxycarbonyl)-1,6,11-triazaundeca-3,8-dienes, 7a–d
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris{[4-(hexade-
cyloxy)phenyl]sulfonyl}-1,6,11-triazaundeca-3,8-diene, 7a.
General procedure. A stirred mixture of sulfonamide 4a
(0.38 g, 0.95 mmol), bromosulfomanide 6a (1.20 g, 1.9 mmol),
anhydrous potassium carbonate (0.79 g, 5.7 mmol) and
acetonitrile (30 mL) was heated under reflux for 14 h. The
salts were filtered off and the filtrate was evaporated. The
residue was chromatographed on silica gel with hexanes–
diethyl ether (9 : 1) to afford 7a (1.22 g, 86% yield) as a
colourless oil. 1H NMR (250 MHz, CDCl3): d 0.91 (t,
J 5 6.5 Hz, 9H), 1.18–1.60 (complex absorption, 78H), 1.37
(s, 18H), 1.82 (m, 6H), 3.83 (d, J 5 5.9 Hz, 4H), 4.03 (t,
J 5 6.5 Hz, 6H), 4.39 (d, J 5 5.6 Hz, 4H), 5.60 (dt, J 5 15.4
and 5.9 Hz, 2H), 5.76 (dt, J 5 15.4 and 5.6 Hz, 2H), 6.97 (d,
J 5 8.9 Hz, 2H), 6.98 (d, J 5 8.9 Hz, 4H), 7.75 (d, J 5 8.9 Hz,
2H), 7.84 (d, J 5 8.9 Hz, 4H). 13C NMR (62.5 MHz, CDCl3): d
13.8, 22.4, 25.7, 27.7, 28.8, 29.1, 29.4, 31.7, 47.3, 47.7, 68.3,
83.9, 114.0, 114.5, 127.9, 129.0, 129.7, 130.0, 131.05, 131.10,
150.5, 162.2, 162.8. IR (neat) n/cm21: 2923, 2854, 1729,
1596, 1357, 1259, 1158. Anal. Calc. for C84H141N3O13S3
(1497.25 g mol21): C 67.39, H 9.49, N 2.81, S 6.42; Found:
C 67.31, H 9.39, N 2.78, S 6.14%.
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris{[2,3,4-tri-
(hexadecyloxy)phenyl]sulfonyl}-1,6,11-triazaundeca-3,8-diene,
7d. This compound was obtained in the same way as 7a, using
mixtures of acetonitrile–tetrahydrofuran (9 : 1) as solvents.
Silica gel chromatography was performed with hexanes–
1
diethyl ether (9.5 : 0.5). Yield 81%. Mp 30–33 uC. H NMR
(250 MHz, CDCl3): d 0.91 (t, J 5 6.6 Hz, 27H), 1.20–1.60
(complex absorption, 252H), 1.80 (m, 18H), 3.95 (apparent t,
J 5 6.6 Hz, 8H), 4.03 (apparent t, J 5 5.8 Hz, 8H), 4.18
(complex absorption, 6H), 4.39 (apparent d, J 5 4.9 Hz, 4H),
5.65 (dt, J 5 15.2 and 6.1 Hz, 2H), 5.80 (dt, J 5 15.1 and
5.4 Hz, 2H), 6.67 (d, J 5 9.0 Hz, 1H), 6.68 (d, J 5 9.0 Hz, 2H),
7.58 (d, J 5 9.0 Hz, 1H), 7.68 (d, J 5 9.0 Hz, 2H). 13C NMR
(62.5 MHz, CDCl3): d 13.8, 22.4, 25.56, 25.62, 25.8, 25.9, 26.0,
27.6, 28.9, 29.0, 29.1, 29.2, 29.3, 29.4, 29.45, 29.48, 29.9, 30.0,
30.3, 31.7, 47.48, 47.53, 47.9, 48.0, 68.8, 73.6, 74.5, 74.6, 83.1,
106.0, 125.4, 126.5, 126.7, 127.8, 130.2, 141.3, 142.3, 150.5,
151.0, 151.2, 157.0, 157.7. IR (neat) n/cm21: 2916, 2849, 1725,
1580, 1467, 1137, 1087. Anal. Calc. for C180H333N3O19S3
(2939.82 g mol21): C 73.54, H 11.42, N 1.43, S 3.27; Found: C
73.39, H 11.40, N 1.41, S 3.15%.
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris{[3,4-di-
(dodecyloxy)phenyl]sulfonyl}-1,6,11-triazaundeca-3,8-diene, 7b.
This compound was obtained in the same way as 7a. Silica gel
chromatography was performed with hexanes–ethyl acetate
(9.7 : 0.3). Yield 54%. Colourless oil. 1H NMR (250 MHz,
CDCl3): d 0.89 (t, J 5 6.6 Hz, 18H), 1.20–1.55 (complex
absorption, 108H), 1.35 (s, 18H), 1.84 (m, 12H), 3.82 (d,
J 5 5.9 Hz, 4H), 4.02 (t, J 5 6.4 Hz, 6H), 4.05 (t, J 5 6.5 Hz,
6H), 4.36 (d, J 5 5.2 Hz, 4H), 5.60 (dt, J 5 15.4 and 6.1 Hz,
2H), 5.77 (dt, J 5 15.4 and 5.6 Hz, 2H), 6.92 (d, J 5 8.6 Hz,
1H), 6.93 (d, J 5 8.6 Hz, 2H), 7.36 (d, J 5 2.2 Hz, 1H), 7.39 (d,
J 5 2.2 Hz, 2H), 7.44 (dd, J 5 8.6 and 2.2 Hz, 3H). 13C NMR
(62.5 MHz, CDCl3): d 13.8, 22.4, 25.66, 25.69, 27.6, 28.7, 28.8,
28.9, 29.1, 29.2, 29.3, 29.4, 31.6, 47.4, 47.7, 68.86, 68.91, 69.2,
69.3, 83.7, 111.6, 112.2, 112.7, 120.6, 121.6, 127.9, 129.8, 131.1,
131.2, 148.1, 148.8, 150.4, 152.4, 153.0. IR (neat) n/cm21: 2921,
2852, 1728, 1587, 1260, 1136, 718. Anal. Calc. for
C108H189N3O16S3 (1881.89 g mol21): C 68.93, H 10.12, N
2.23, S 5.11; Found: C 68.89, H 9.86, N 2.19, S 4.99%.
Synthesis of (E,E)-1,6,11-tris(arylsulfonyl)-1,6,11-triazaundeca-
3,8-dienes 1a–d
(E,E)-1,6,11-Tris{[4-(hexadecyloxy)phenyl]sulfonyl}-1,6,11-
triazaundeca-3,8-diene, 1a. General procedure. Trifluoroacetic
acid (10 mL) was added to a solution of 7a (0.57 g, 0.38 mmol)
in dichloromethane (10 mL). The mixture was stirred at room
temperature for 4 h and evaporated to dryness. The residue
was partitioned between dichloromethane and water. The
organic layer was dried with anhydrous Na2SO4 and evapo-
rated to afford practically pure 1a (0.45 g, 91% yield) as a
white solid. A sample for elemental analysis was purified by
digestion in CHCl3–hexanes (1 : 1). Mp 109–111 uC. 1H NMR
(250 MHz, CDCl3): d 0.90 (t, J 5 6.6 Hz, 9H), 1.18–1.57
(complex absorption, 78H), 1.79 (m, 6H), 3.50 (br m, 4H),
3.69 (d, J 5 6.8 Hz, 4H), 4.02 (t, J 5 6.5 Hz, 4H), 4.04 (t,
J 5 6.4 Hz, 2H), 4.83 (br t, J 5 6.8 Hz, 2H, NH), 5.56 (br m,
4H), 6.97 (d, J 5 8.9 Hz, 6H), 7.70 (d, J 5 8.9 Hz, 2H), 7.79
(d, J 5 8.9 Hz, 4H). 13C NMR (62.5 MHz, CDCl3, 54 uC): d
14.4, 23.0, 26.3, 29.5, 29.67, 29.7, 29.90, 29.93, 30.0, 32.3, 44.7,
49.4, 69.0, 115.17, 115.20, 128.8, 129.6, 129.7, 130.1, 131.7,
131.8, 163.1. IR (neat) n/cm21: 3301, 3275, 2918, 2851, 1599,
1329, 1156. Anal. Calc. for C74H125N3O9S3 (1297.01 g mol21):
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris{[3,4-di(hex-
adecyloxy)phenyl]sulfonyl}-1,6,11-triazaundeca-3,8-diene, 7c.
This compound was obtained in the same way as 7a. Silica
gel chromatography was performed with hexanes–ethyl acetate
(9.9 : 0.1). Yield 19%. Mp 47 uC. 1H NMR (250 MHz, CDCl3):
d 0.90 (t, J 5 6.5 Hz, 18H), 1.20–1.60 (complex absorption,
2216 | J. Mater. Chem., 2005, 15, 2210–2219
This journal is ß The Royal Society of Chemistry 2005