132.92, 130.82, 126.20, 125.66, 124.96, 79.23, 78.96, 78.70, 73.20,
71.56, 71.42, 70.97, 69.25, 34.53, 34.16, 32.77, 31.90, 31.37.
ArCH2Ar, OCH2CH2O), 3.62–3.70 (2 H, m, OCH2CH2O), 3.54–
3.62 (2 H, m, OCH2CH2O), 3.36–3.46 (2 H, m, OCH2CH2O), 3.31
(2 H, d, J 12.2, ArCH2Ar), 3.25 (3 H, s, CH3SO2), 2.97 (3 H, s,
CH3SO2), 1.49 (2 H, s, anti-OCH2CO), 1.44 (9 H, s, C(CH3)3),
1.21 (9 H, s, C(CH3)3), 1.15 (18 H, s, C(CH3)3); dC 170.06, 166.23,
152.91, 151.63, 151.43, 147.05, 146.33, 145.72, 136.43, 134.16,
132.58, 131.96, 126.70, 126.46, 125.82, 125.74, 75.23, 72.23, 70.86,
70.55, 70.23, 68.30, 41.35, 41.19, 38.43, 34.19, 34.04, 34.01, 31.61,
31.23, 31.13, 30.74.
Cone 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-bis(N-trifluo-
romethanesulfonyl carbamoylmethoxy)calix[4]arene-crown-5 (3e).
Chromatography on silica gel with EtOAc as eluent, yield 57%,
white solid, mp 200–202 ◦C. Found: C, 58.57; H, 6.32; N,
2.40. C58H74O13N2S2F6 requires C, 58.77; H, 6.29; N, 2.36%.
mmax(film)/cm−1 2800–3200 (NH); 1754 (C O); dH 11.09 (2 H,
=
br s, NH), 7.10 (4 H, s, ArH), 6.53 (4 H, s, ArH), 5.27 (4 H, s,
OCH2CO), 4.26 (4 H, d, J 12.7, ArCH2Ar), 4.04–4.14 (4 H, m,
OCH2CH2O), 3.95–4.04 (4 H, m, OCH2CH2O), 3.89–3.95 (4H,
m, OCH2CH2O), 3.80–3.89 (4 H, m, OCH2CH2O), 3.26 (4 H, d, J
12.9, ArCH2Ar), 1.32 (18 H, s, C(CH3)3), 0.81 (18 H, s, C(CH3)3);
dC 167.35, 151.69, 150.70, 146.35, 145.44, 134.84, 131.81, 125.68,
124.99, 71.77, 71.40, 70.49, 70.26, 32.17, 31.61, 30.92.
Partial-cone 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-bis(N-
benzenesulfonyl carbamoylmethoxy)calix[4]arene-crown-5 (4c).
Recrystallization from CH2Cl2–MeOH, yield 67%, white solid,
mp 177–180 ◦C. Found: C, 68.28; H, 7.20; N, 2.37. C68H84O13N2S2
requires C, 67.97; H, 7.05; N, 2.33%. mmax(film)/cm−1 2800–3300
=
(NH); 1742, 1731 (C O); dH 10.99 (1 H, s, NH), 8.52 (1 H, s,
NH), 8.02–8.12 (2 H, m, ArH), 7.78–7.86 (2 H, m, ArH), 7.61
(1 H, t, J 7.4, ArH), 7.44–7.56 (3 H, m, ArH), 7.36 (2 H, t, J 7.9,
ArH), 7.17 (2 H, s, ArH), 7.07 (2 H, d, J 2.3, ArH), 6.86 (2 H,
d, J 2.2, ArH), 6.76 (2 H, s, ArH), 4.48 (2 H, s, syn-OCH2CO),
4.08 (2 H, d, J 12.2, ArCH2Ar), 3.85–3.94 (2 H, m, OCH2CH2O),
3.82 (4 H, s, ArCH2Ar), 3.70–3.80 (8 H, m, OCH2CH2O), 3.60–
3.68 (2 H, m, OCH2CH2O), 3.48–3.58 (2 H, m, OCH2CH2O),
3.30–3.40 (2 H, m, OCH2CH2O), 2.93 (2 H, d, J 12.3, ArCH2Ar),
1.42 (9 H, s, C(CH3)3), 1.27 (2 H, s, anti-OCH2CO), 1.09 (18 H,
s, C(CH3)3), 1.00 (9 H, s, C(CH3)3); dC 168.18, 164.39, 152.64,
152.05, 151.35, 146.91, 145.96, 145.67, 139.02, 138.49, 133.91,
133.61, 133.37, 132.26, 131.39, 128.75, 128.44, 128.39, 126.46,
126.31, 125.91, 125.68, 75.66, 72.25, 71.29, 70.47, 70.26, 68.21,
38.20, 34.17, 33.89, 33.88, 31.56, 31.13, 30.98, 30.35.
Partial-cone 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-bis-
(carboxymethoxy)-calix[4]arene-crown-5 (4a). A mixture of 7
(8.00 g, 9.91 mmol), THF (250 mL), and KH (2.50 g, 35%
dispersion in mineral oil, 21.80 mmol) was stirred under nitrogen at
room temperature for 1 h. Ethyl bromoacetate (4.98 g, 29.82 mmol)
in THF (50 mL) was added slowly. The reaction mixture was stirred
at room temperature for 12 h and quenched with a small amount
of water. The THF was evaporated in vacuo. To the residue was
added 95% EtOH (200 mL), NaOH (2.29 g, 57.25 mmol) and
H2O (50 mL) and the solution was refluxed for 24 h. The EtOH
was evaporated in vacuo and the resulting aqueous solution was
cooled in an ice-bath and acidified with 6 N HCl. The solution
was extracted with CH2Cl2 (2 × 100 mL). The combined organic
layers were washed with water (2 × 50 mL) and dried over MgSO4.
After evaporation of the CH2Cl2 in vacuo, the crude product was
recrystallized from CH2Cl2–MeOH to give 4a (8.23 g, 90%) as a
white solid (mp 189–192 ◦C). Found: C, 73.09; H, 7.84. C56H74O11
requires C, 72.85; H 8.08%; mmax(film)/cm−1 2500–3200 (CO2H),
Partial-cone 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-bis(N-
p-nitrobenzenesulfonyl carbamoylmethoxy)calix[4]arene-crown-5
(4d). Recrystallization fr◦om CH2Cl2–MeOH, yield 56%, light
yellow solid, mp 188–190 C. Found: C, 62.20; H, 6.47; N, 4.11.
C68H82O17N4S2·0.3CH2Cl2 requires C, 62.29; H, 6.32; N, 4.25%.
=
1782, 1731 (C O); dH 7.10–7.15 (6 H, m, ArH), 6.78 (2 H, d, J 2.3,
mmax(film)/cm−1 2800–3300 (NH); 1742, 1732 (C O); dH 11.28 (1 H,
=
ArH), 4.83 (2 H, s, syn-OCH2CO), 4.41 (2 H, d, J 12.4, ArCH2Ar),
3.95 (2 H, d, J 16.7, ArCH2Ar), 3.82–3.90 (6 H, m, OCH2CH2O),
3.72–3.78 (4 H, m, OCH2CH2O, ArCH2Ar), 3.51–3.66 (6 H, m,
OCH2CH2O), 3.44–3.51 (4 H, m, OCH2CH2O, anti-OCH2CO),
3.27 (2 H, d, J 12.4, ArCH2Ar), 1.45 (9 H, s, C(CH3)3), 1.26 (9 H,
s, C(CH3)3), 1.14 (18 H, s, C(CH3)3); dC 171.99, 168.08, 152.88,
151.18, 150.68, 146.49, 146.26, 134.63, 134.04, 133.13, 131.45,
126.90, 126.15, 125.41, 124.47, 71.76, 71.22, 70.68, 70.51, 70.43,
65.44, 38.94, 34.27, 34.08, 33.90, 31.78, 31.44, 31.10.
s, NH), 8.62 (1 H, s, NH), 8.29–8.35 (2 H, m, ArH), 8.23–8.29 (2 H,
m, ArH), 8.18–8.23 (2 H, m, ArH), 8.00–8.05 (2 H, m, ArH), 7.18
(2 H, s, ArH), 7.06 (2 H, d, J 2.3, ArH), 6.84 (2 H, d, J 2.3, ArH),
6.78 (2 H, s, ArH), 4.52 (2 H, s, syn-OCH2CO), 4.06 (2 H, d,
J 12.3, ArCH2Ar), 3.69–3.90 (14 H, m, ArCH2Ar, OCH2CH2O),
3.62–3.69 (2 H, m, OCH2CH2O), 3.50–3.62 (2 H, m, OCH2CH2O),
3.30–3.42 (2 H, m, OCH2CH2O), 2.95 (2 H, d, J 12.3, ArCH2Ar),
1.43 (9 H, s, C(CH3)3), 1.27 (2 H, s, anti-OCH2CO), 1.06 (18 H,
s, C(CH3)3), 1.01 (9 H, s, C(CH3)3); dC 168.39, 164.82, 152.65,
151.84, 151.29, 150.58, 150.50, 147.09, 146.23, 145.97, 144.41,
143.85, 136.38, 134.02, 132.23, 131.51, 129.97, 129.95, 126.61,
126.40, 125.82, 125.71, 123.89, 123.65, 75.42, 72.34, 70.93, 70.45,
70.22, 68.10, 38.27, 34.23, 33.93, 33.87, 31.60, 31.05, 30.97, 30.48.
General procedure for the preparation of partial-cone 5,11,17,23-
tetrakis(1,1-dimethylethyl)-25,27-bis[N-(X)-sulfonyl carbamoyl-
methoxy]calix[4]arene-crown-5 ligands 4b–e. The procedure was
the same as that for the cone conformers.
Partial-cone 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-bis(N-
methanesulfonyl carbamoylmethoxy)calix[4]arene-crown-5 (4b).
Recrystallization from CH2Cl2–MeOH, yield 88%, white
solid, mp 272–274 ◦C. Found: C, 63.65; H, 7.68; N, 2.49.
C58H80O13N2S2·0.2CH2Cl2 requires C, 63.87; H, 7.40; N, 2.56%.
Partial-cone 5,11,17,23-tetrakis(1,1-dimethylethyl)-25,27-bis(N-
trifluoromethanesulfonyl carbzmoylmethoxy)calix[4]arene-crown-5
(4e). Recrystallization from CH2Cl2–MeOH, yield 68%, white
solid, mp 180–183 ◦C. Found: C, 58.64; H, 6.47; N, 2.37.
C58H74O13N2S2F6 requires C, 58.77; H, 6.29; N, 2.36%. mmax(film)/
mmax(film)/cm−1 2800–3200 (NH); 1736 (C O); dH 10.88 (1 H, s,
cm−1 2800–3200 (NH); 1775 (C O); dH 11.54 (1 H, br s, NH), 8.69
=
=
NH), 8.41 (1 H, s, NH), 7.23 (2 H, d, J 2.3, ArH), 7.20 (2 H, s,
ArH), 6.99 (2 H, s, ArH), 6.92 (2 H, d, J 2.3, ArH), 4.67 (2 H, s, syn-
OCH2CO), 4.35 (2 H, d, J 12.2, ArCH2Ar), 3.72–3.94 (14 H, m,
(1 H, s, NH), 7.25 (2 H, d, J 2.9, ArH), 7.22 (2 H, s, ArH), 6.98
(2 H, s, ArH), 6.92 (2 H, d, J 2.2, ArH), 4.74 (2 H, s, syn-OCH2CO),
4.31 (2 H, d, J 12.2, ArCH2Ar), 3.72–3.94 (14 H, m, ArCH2Ar,
This journal is
The Royal Society of Chemistry 2006
Org. Biomol. Chem., 2006, 4, 1104–1114 | 1111
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