29.25, 29.3, 29.5, 29.6, 29.7, 31.2, 31.8, 31.9, 34.3, 37.6, 39.7
(CH2), 57.9 (C–NH), 60.1 (OCH2), 173.2, 173.5 (CO, amide),
173.8 (CO, ester) ppm. MS (ESI-TOF, pos.): m/z = 983.9 [M
+ Na]+. C58H112N4O6 (961.55): calcd C 72.45, H 11.74, N
5.83; found C 72.54, H 11.70, N 5.91%.
CQO, amide), 1540 (s), 1467 (m), 1391 (m), 1366 (s), 1155 (s),
850 (w), 724 (w). 1H NMR (400 MHz, CDCl3): d = 0.88 (t, 9
H, CH3), 1.25 (s, 90 H, CH2), 1.44 (m, 33 H, t-Bu, CH2), 2.15,
2.29 (m, 24 H, CH2), 3.20 (q, 6 H, CH2), 5.81 (t, 3 H, NHCH2),
7.10 (s, 1 H, CONH), 7.85 (d, 2 H, Ar–H), 7.92 (d, 2 H, Ar–H),
8.24 (s, 1 H, CONH) ppm. 13C NMR (100 MHz, CDCl3): d =
14.0 (CH3), 22.6, 26.9 (CH2), 28.0 [C(CH3)3], 29.5, 29.6, 29.7,
29.9, 30.2, 31.1, 31.6, 31.9, 39.7, 58.0 (CH2), 58.5 (C–NH),
80.7 [C(CH3)3], 127.1, 127.3, 137.4, 137.5 (C–Ar), 166.0,
166.5, 173.0, 173.1 (CO, amide, ester) ppm. MS (ESI-TOF,
pos.): m/z = 1569.4 [M + Na]+. C94H171N5O11 (1547.42):
calcd C 72.96, H 11.14, N 4.53; found C 73.06, H 11.18,
N 4.65%.
N - [Tris(2-dodecylaminocarbonyl-ethyl)methyl]-N0-[tris(2-tert-
butoxycarbonyl-ethyl)methyl]terephthaldiamide (16a). Reac-
tion mixture: 1 (3.24 g, 3.61 mmol), DCC (0.75 g, 3.61 mmol),
1-HOBt (0.49 g, 3.61 mmol), 22 (1.50 g, 3.61 mmol), CH2Cl2
(100 mL). Elution protocol: CH2Cl2–ethyl acetate (1 : 1),
CH2Cl2–ethyl acetate–MeOH (7 : 2 : 1), in this sequence.
Yield: 2.8 g (60%) of white plates; mp 115–117 1C. IR (KBr):
n = 3301 cmꢁ1 (br, NH), 2957 (s), 2929 (s), 2856 (s), 1730
(s, CQO, ester), 1643 (s, CQO, amide), 1541 (s), 1466 (m),
N - [Tris(2-dodecylaminocarbonyl-ethyl)methyl]-N0-[tris(2-tert-
butoxycarbonyl-ethyl)methyl]decanediamide (17). Reaction
mixture: 4 (1.71 g, 1.83 mmol), DCC (0.38 g, 1.83 mmol), 1-
HOBt (0.25 g, 1.83 mmol), 22 (0.76 g, 1.83 mmol), THF (75
1
1396 (m), 1367 (s), 1154 (s), 848 (w), 722 (w). H NMR (400
MHz, CDCl3): d = 0.88 (t, 9 H, CH3), 1.25 (s, 54 H, CH2),
1.44 (s, 33 H, t-Bu, CH2), 2.15, 2.29 (m, 24 H, CH2), 3.19 (q, 6
H, CH2), 5.93 (t, 3 H, CH2NH), 7.13 (s, 1 H, C–NH), 7.84 (d, 2
H, Ar–H), 7.92 (d, 2 H, Ar–H), 8.25 (s, 1 H, C–NH) ppm. 13
C
mL). Elution protocol: CH2Cl2–ethyl acetate (1
: 1),
CH2Cl2–ethyl acetate–MeOH (7 : 2 : 1), in this sequence.
Yield: 1.85 g (76%) of a white powder; mp 59–62 1C. IR
(KBr): n = 3296 cmꢁ1 (br, NH), 2958 (s), 2924 (s), 2851 (s),
1732 (s, CQO, ester), 1641 (s, CQO, amide), 1547 (s), 1466
(m), 1391 (m), 1365 (s), 1154 (s), 722 (w). 1H NMR (400 MHz,
CDCl3): d = 0.81 (t, 9 H, CH3), 1.19 (s, 62 H, CH2), 1.36 (m,
33 H, t-Bu, CH2), 1.49 (m, 4 H, CH2), 1.91, 2.04, 2.14 (m, 28
H, CH2), 3.09 (m, 6 H, CH2), 6.24 (s, 1 H, C–NH), 6.83 (t, br,
3 H, CH2NH), 7.37 (s, 1 H, C–NH) ppm. 13C NMR (100
MHz, CDCl3): d = 14.0 (CH3), 22.7, 25.7, 25.9, 27.1 (CH2),
28.1 [C(CH3)3], 29.0, 29.1, 29.4, 29.5, 29.7, 29.9, 30.0, 30.9,
31.5, 31.9, 37.3, 37.4, 39.8 (CH2), 57.2, 57.9 (C–NH), 80.5
[C(CH3)3], 172.9, 173.0, 173.5, 173.6 (CO, amide, ester) ppm.
NMR (100 MHz, CDCl3): d = 14.07 (CH3), 22.6, 26.9 (CH2),
28.1 [C(CH3)3], 29.3, 29.5, 29.6, 29.9, 30.2, 31.2, 31.8, 31.9
(CH2), 39.8, 58.0 (CH2), 58.5 (C–NH), 80.8 [C(CH3)3], 127.1,
127.3, 137.3, 137.5 (C–Ar), 165.9, 166.4, 173.05, 173.1 (CO,
amide, ester) ppm. MS (ESI-TOF, pos.): m/z = 670.0 [M +
Na]2+. C76H135N5O11 (1294.94): calcd C 70.49, H 10.51, N
5.41; found C 70.39, H 10.56, N 5.47%.
N-[Tris(2-hexadecylaminocarbonyl-ethyl)methyl]-N0-[tris(2-
tert-butoxycarbonyl-ethyl)methyl]terephthaldiamide
(16b).
Reaction mixture: 2 (5.73 g, 5.38 mmol), DCC (1.11 g, 5.38
mmol), 1-HOBt (0.73 g, 5.38 mmol), 22 (2.23 g, 5.38 mmol),
CH2Cl2 (200 mL). Elution protocol: CH2Cl2–ethyl acetate (1
: 1), CH2Cl2–ethyl acetate–MeOH (7 : 2 : 1), in this sequence.
Yield: 2.95 g (56%) of a white powder; mp 92–94 1C. IR
(KBr): n = 3303 cmꢁ1 (br, NH), 2958 (s), 2924 (s), 2851 (s),
1729 (s, CQO, ester), 1645 (s, CQO, amide), 1542 (s), 1466
MS (ESI-TOF, pos.): m/z
= 1353.1 [M +
Na]+.
C78H147N5O11 (1331.05): calcd C 70.39, H 11.13, N 5.26;
found C 70.22, H 11.10, N 4.96%.
1
(m), 1391 (m), 1365 (s), 1155 (s), 847 (w), 721 (w). H NMR
N -[Tris(2-dodecylaminocarbonyl-ethyl)methyl]-N0-{[N,N0,N00-
tris[tris(2-tert-butoxycarbonyl-ethyl)methyl]aminocarbonyl-
ethyl]methyl}terephthaldiamide (18). Reaction mixture: 1 (0.75
g, 0.84 mmol), DCC (0.17 g, 0.84 mmol), 1-HOBt (0.11 g, 0.84
mmol), 20 (1.21 g, 0.84 mmol), CHCl3 (100 mL). Elution
protocol: CH2Cl2–ethyl acetate (1 : 1), CH2Cl2–ethyl aceta-
te–MeOH (7 : 2 : 1), in this sequence. Yield: 1.43 g (73%) of a
white powder; mp 55–58 1C. IR (KBr): n = 2975 cmꢁ1 (m),
2929 (s), 2856 (m), 1734 (s, CQO, ester), 1648 (s, CQO,
amide), 1539 (s), 1458 (m), 1393 (m), 1368 (s), 1154 (s), 721
(w). 1H NMR (400 MHz, CDCl3): d = 0.88 (t, 9 H, CH3), 1.25
(s, 54 H, CH2), 1.44 (m, 87 H, t-Bu, CH2), 1.95, 2.06, 2.19, 2.28
(m, 60 H, CH2), 3.20 (q, 6 H, CH2), 6.00 (t, 3 H, CH2NH), 6.10
(s, 3 H, C–NH), 7.41 (s, 1 H, C–NH), 7.86 (d, 2 H, Ar–H), 7.98
(d, 2 H, Ar–H), 8.72 (s, 1 H, C–NH) ppm. 13C NMR (100
MHz, CDCl3): d = 14.1 (CH3), 22.6, 27.0 (CH2), 28.1
[C(CH3)3], 29.3, 29.5, 29.6, 29.8, 29.9, 31.2, 31.5, 31.7, 31.9,
39.8 (CH2), 57.6, 58.1, 58.7 (C–NH), 80.6 [C(CH3)3], 127.2,
127.5, 137.2, 137.4 (C–Ar), 166.2, 166.5, 172.6, 172.8, 172.9
(CO, amide, ester) ppm. MS (ESI-TOF, pos.): m/z = 2340.9
[M + Na]+. C130H228N8O26 (2319.28): calcd C 67.32, H 9.91,
N 4.83; found C 67.10, H 9.71, N 4.85%.
(400 MHz, CDCl3): d = 0.88 (t, 9 H, CH3), 1.25 (s, 78 H,
CH2), 1.44 (s, 33 H, t-Bu, CH2), 2.15, 2.29 (m, 24 H, CH2),
3.19 (q, 6 H, CH2), 5.92 (t, 3 H, NHCH2), 7.12 (s, 1 H,
CONH), 7.84 (d, 2 H, Ar–H), 7.92 (d, 2 H, Ar–H), 8.24 (s, 1
H, CONH) ppm. 13C NMR (100 MHz, CDCl3): d = 14.1
(CH3), 22.7, 27.0 (CH2), 28.1 [C(CH3)3], 29.3, 29.35, 29.5,
29.6, 29.65, 29.7, 30.0, 30.2, 31.2, 31.8, 31.9 (CH2), 39.8, 58.0
(CH2), 58.5 (C–NH), 80.8 [C(CH3)3], 127.1, 127.3, 137.3,
137.5 (C–Ar), 165.9, 166.4, 173.05, 173.1 (CO, amide, ester)
ppm. MS (ESI-TOF, pos.): m/z = 754.6 [M + Na]2+
.
C88H159N5O11 (1463.26): calcd C 72.23, H 10.95, N 4.79;
found C 72.15, H 10.96, N 4.75%.
N-[Tris(2-octadecylaminocarbonyl-ethyl)methyl]-N0-[tris(2-tert-
butoxycarbonyl-ethyl)methyl]terephthaldiamide (16c). Reaction
mixture: 3 (2.00 g, 1.74 mmol), DCC (0.38 g, 1.83 mmol),
1-HOBt (0.25 g, 1.83 mmol), 22 (0.76 g, 1.83 mmol), CH2Cl2
(80 mL). Elution protocol: CH2Cl2–ethyl acetate (1 : 1),
CH2Cl2–ethyl acetate–MeOH (7 : 2 : 1), CH2Cl2–ethyl acet-
ate–MeOH (20 : 2 : 1), in this sequence. Yield: 1.35 g (50%) of
a white powder; mp 93–95 1C. IR (KBr): n = 3302 cmꢁ1 (br,
NH), 2957 (s), 2924 (s), 2851 (s), 1730 (s, CQO, ester), 1641 (s,
ꢀc
This journal is the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2006
1830 | New J. Chem., 2006, 30, 1820–1833