Nov-Dec 2001
The Effect of Twin-tailed Sidearms on Sodium
1399
N,N-Didodecyl-2-chloroacetamide (9).
PhCH <N18N>(CH ) <N18N>(CH ) <N18N>CH Ph (12)
2 2 12 2 12 2
was prepared as reported in reference 26.
To a solution of N,N-didodecyl amine (0.707 g, 2.0 mmol),
Dansyl<N18N>(CH ) <N18N>(CH ) <N18N>Dansyl (13)
was prepared as reported in reference 24.
Et N (0.606 g, 6.0 mmol) and DMAP (20 mg) in CH Cl
2 12
2 12
3
2
2
(20 mL) pre-cooled to 5 °C was added chloroacetyl chloride
(0.249 mg, 2.2 mmol). After 20 minutes, the reaction mixture
was allowed to come to room temperature, and was stirred for 18
Acknowledgements.
We thank the NIH (GM-36262) and the NSF (CHE-9805840)
for grants that supported this work.
hours. The brown solution was washed with aqueous NaHCO
3
(10%, 10 mL), the organic layer dried over MgSO and
4
1
evaporated to dryness (0.52 g, 60% yield). H-NMR: δ 0.88
(t, J = 6.9 Hz, 6H), 1.26 (bs, 42H), 1.56 (m, 4H), 3.20-3.35
(m, 4H), 4.01 (s, 2H); C-NMR: δ 14.0, 22.5, 26.7, 26.8, 27.2,
REFERENCES AND NOTES
13
29.0, 29.2, 29.3, 29.4, 29.5, 31.8, 41.2, 46.1, 48.2, 166.1.
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2-[16-(12-{16-[12-(16-Didodecylcarbamoylmethyl-1,4,10,13-
tetraoxa-7,16-diaza-cyclooctadec-7-yl)-dodecanoyl]-1,4,10,13-
tetraoxa-7,16-diaza-cyclooctadec-7-yl}-12-oxo-dodecyl)-
1,4,10,13-tetraoxa-7,16-diaza-cyclooctadec-7-yl]-N,N-didodecyl-
acetamide ((C
H ) NCOCH <N18N>(CH ) CO<N18N>CO-
12 25 2 2 2 11
(CH ) <N18N>CH CON(C H ) , 10).
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2 11
2
12 25 2
To a solution of chloroacetamide 9 ( 0.083 g , 0.192 mmol) in
acetonitrile (20 mL) was added tris(macrocyclic) diamide 8
(0.100, 0.087 mmol), KI (20 mg), and Na CO (0.055 g,
0.55 mmol). The reaction mixture was heated to reflux for
48 hours. The solvent was removed under reduced pressure and
the residue purified by column chromatography (SiO , 20%
2
3
2
1
MeOH-CHCl ). Yellow oil (30 mg, 20%). H-NMR: δ 0.88
3
(t, J = 6.6 Hz, 6H), 1.26 (bs, 104H), 1.42- 1.59 (m, 16H), 2.32
(t, J = 7.5 Hz, 4H), 2.68-2.75 (m, 16H), 2.93 (t, J = 5.5 Hz, 4H),
3.27 (t, J = 7.5 Hz, 8H), 3.46 (bs, 4H), 3.63 (bs, 64H); C-NMR:
13
δ 14.0, 22.5, 23.5, 25.2, 26.7, 27.2, 27.7, 29.2, 29.3, 29.4, 29.5,
29.5, 31.8, 33.02, 46.7, 47.3, 48.7, 51.8, 53.8, 54.8, 56.6, 66.9,
67.4, 68.4, 69.0, 69.9, 70.3, 70.4, 70.7, 70.8, 170.8, 173.4.
+
2+
3+
FAS-MAS m/z: (M+Na) 1957.0, (M+2Na) 990.3, (M+3Na)
667.8, calcd for C N O , 1933.66.
H
112 220
8 16
2-[16-(12-{16-[12-(16-Didodecylcarbamoylmethyl-1,4,10,13-
tetraoxa-7,16-diaza-cyclooctadec-7-yl)-dodecyl]-1,4,10,13-
tetraoxa-7,16-diaza-cyclooctadec-7-yl}-dodecyl)-1,4,10,13-
tetraoxa-7,16-diaza-cyclooctadec-7-yl]-N,N-didodecylacetamide
((C
H ) N(CH ) <N18N>(CH ) <N18N>(CH ) <N18N>
12 25 2 2 2 2 12 2 12
(CH ) N (C
H ) , 11).
2 2
12 25 2
To a solution of tetraamide 10 (0.200 g, 0.103 mmol) in
THF (5 mL), BH •THF (3 mL, 2 M in THF) was added and the
3
resulting solution was stirred at room temperature for
72 hours. The reaction mixture was cooled to 5 °C, quenched
with ice-water, and the solvent removed in vacuo. The solid
residue was heated to reflux with 2 N HCl (4 mL) for 4 hours.
After cooling, the solution was brought to pH = 10
(2 N NaOH), extracted with CHCl (20 mL), dried over
3
MgSO , and evaporated in vacuo. The product was purified by
4
column chromatography (SiO , 10% MeOH-CHCl ) to afford
2
3
1
11 as a yellow oil (0.030 g, 16%). H-NMR: δ 0.88 (t, J =
6.6 Hz, 6H), 1.26 (bs, 104H), 1.42-1.59 (m, 22H), 2.49 (t, J =
7.0 Hz, 4H), 2.82 (t, J = 5.5 Hz, 16H), 2.91 (t, J = 5.4 Hz,
13
28H), 3.62 (bs, 24H), 3.74 (bs, 24H): C-NMR: 14.0, 22.6,
27.0, 27.2, 29.2, 29.4, 29.5, 31.8, 53.6, 70.5: FAS-MAS m/z
+
2+
(M+Na)
1901.8, (M+2Na)
N O , 1877.75.
962.4, calcd for
C
H
112 228
8 12