Paper
NJC
(2H, m, OCH2), 3.28 (2H, d, J = 14.1 Hz, ArCH2Ar eq), 2.09–1.86 5,11,17-Triamino-23-tert-butyl-25,26,27,28-
(6H, m, OCH2CH2), 1.37–1.30 (11H, m, OCH2CH2 + But), 1.13– tetrapropoxycalix[4]arene (partial cone) 9
1.06 (9H, m, CH3), 0.67 (3H, t, J = 7.5 Hz, CH3). 13C{1H} NMR
A general procedure was applied to trinitro derivative 6 (0.25 g,
0.32 mmol), SnCl2ꢀ2H2O (1.08 g, 4.79 mmol). The product 9 was
isolated as a dark brown powder (0.22 g) in 98% yield, mp: 124–
(75 MHz, CDCl3, 296 K) d: 161.7, 161.3, 155.05, 144.7, 143.0,
142.4, 137.4, 134.0, 133.6, 132.0, 127.8, 126.0, 125.2, 123.4, 77.2,
75.2, 75.0, 36.4, 34.3, 31.8, 31.2, 24.0, 23.9, 21.8, 11.0, 10.7, 10.0;
TOF HRMS (ESI+): calcd for [C44H53N3O10 + Na]+: 806.3623.
Found: m/z (rel. int. %) 806.3627 (100) [M + Na]+.
1
126 1C. H NMR (300 MHz, CDCl3, 296 K) d: 7.16 (2H, s, ArH),
6.44 (2H, s, ArH), 6.41 (2H, d, J = 2.9 Hz, ArH), 5.79 (2H, d, J = 2.6
Hz, ArH), 3.99 (2H, d, J = 12.9 Hz, ArCH2Ar ax), 3.72–3.42 (10H,
m, 3 ꢃ OCH2 + 2 ꢃ ArCH2Ar), 3.30–3.25 (2H, m, OCH2), 2.83
(2H, d, J = 12.9 Hz, ArCH2Ar eq), 1.89–1.77 (6H, m, OCH2CH2),
1.37–1.32 (11H, m, OCH2CH2 + But), 1.08–0.98 (9H, m, CH3),
0.63 (3H, t, J = 7.5 Hz, CH3). 13C{1H} NMR (75 MHz, CDCl3, 298
K) d: 155.5, 149.7, 149.6, 143.4, 140.5, 140.0, 137.9, 133.9, 133.1,
133.0, 127.3, 118.3, 116.2, 116.0, 76.5, 74.9, 73.9, 36.9, 31.9,
31.2, 29.9, 24.3, 24.0, 21.5, 11.1, 10.8, 10.0; TOF HRMS (ESI+):
calcd for [C44H59N3O4 + H]+: 694.4578. Found: m/z (rel. int. %)
694.4582 (100) [M + H]+.
General procedure: reduction of nitro derivatives 4–6
The corresponding nitro derivatives 4–6 were dispersed in
ethanol (10 ml for 100 mg) and SnCl2ꢀ2H2O (5 equiv. for each
nitro group) was added. The mixture was heated to reflux
overnight and then poured into 1 M NH3 (aq.). Resulting
suspension was repeatedly extracted with CH2Cl2, combined
organic layers were washed with water, then with brine and
dried over MgSO4. Organic solvent was removed under reduced
pressure to give the pure products 7–9.
General procedure: synthesis of calixarene-based receptors
10–14
5,17-Diamino-25,26,27,28-tetrapropoxycalix[4]arene
(partial cone, syn-diamino) 7
The amino derivatives 7–9 were dissolved in anhydrous CH2Cl2
(30 ml for 0.100 g) under the atmosphere of dry nitrogen. The
corresponding isocyanate (2.50 equiv. for each amino group)
was added and the mixture was stirred overnight at room
temperature. The reaction was quenched by the addition of
methanol, then organic solvents were removed under reduced
pressure and the residue was purified. The purification method
is described below for each particular ligand.
A general procedure was applied to dinitro derivative 4 (0.43 g,
0.63 mmol), SnCl2ꢀ2H2O (1.42 g, 6.30 mmol). The product 7
was isolated as a brown powder (0.37 g) in 95% yield, mp:
176–179 1C. 1H NMR (300 MHz, CDCl3, 298 K) d: 7.20 (2H, d, J =
7.6 Hz, ArH), 7.05 (2H, d J = 7.3 Hz, ArH), 6.87 (1H, t, J = 7.0 Hz,
ArH), 6.83 (1H, t, J = 7.5 Hz, ArH), 6.45 (2H, d, J = 2.6 Hz, ArH),
5.61 (2H, d, J = 2.6 Hz, ArH), 4.04 (2H, d, J = 13.5 Hz, ArCH2Ar
ax), 3.75–3.45 (10H, m, 3 ꢃ OCH2 + 2 ꢃ ArCH2Ar), 3.29–3.23
(2H, m, OCH2), 2.96 (2H, d, J = 13.5 Hz, ArCH2Ar eq), 2.00–1.93
(2H, m, OCH2CH2), 1.89–1.77 (4H, m, OCH2CH2), 1.42–1.34
(2H, m, OCH2CH2), 1.14–1.07 (9H, m, 3 ꢃ CH3), 0.68 (3H, t, J =
7.6 Hz, CH3). 13C{1H} NMR (75 MHz, CDCl3, 296 K) d: 157.7,
149.5, 140.3, 137.4, 134.3, 134.1, 132.9, 130.5, 129.1, 122.0, 121.9,
118.1, 116.1, 76.4, 75.6, 74.8, 35.9, 31.0, 24.6, 24.0, 22.6, 11.2,
11.1, 9.6; TOF HRMS (ESI+): calcd for [C40H50N2O4 + H]+:
623.3843. Found: m/z (rel. int. %) 623.3847 (100) [M + H]+.
5,17-Bis[N0-(phenyl)ureido]-25,26,27,28-
tetrapropoxycalix[4]arene (partial cone) 10
A general procedure was applied to amino derivative 7 (0.15 g,
0.24 mmol) and phenyl isocyanate (143 mg, 0.13 ml,
1.20 mmol). The product 10 was isolated by column chromato-
graphy (30 g of Al2O3, eluent CH2Cl2/MeOH = 50 : 1, then
CH2Cl2/MeOH = 1 : 1, RF = 0.11) as a white powder (0.14 g) in
66% yield, mp: 163–166 1C. 1H NMR (300 MHz, DMSO-d6,
298 K) d: 8.36 (2H, s, NH), 8.05 (2H, s, NH), 7.32 (4H, d, J =
7.9 Hz, ArH), 7.22–7.12 (8H, m, ArH), 7.06 (2H, d, J = 2.1 Hz,
ArH), 6.91–6.82 (4H, m, ArH), 6.47 (2H, d, J = 2.3 Hz, ArH), 4.00
5,17-Diamino-11,23-di-tert-butyl-25,26,27,28-
tetrapropoxycalix[4]arene (partial cone, syn-diamino) 8
A general procedure was applied to dinitro derivative 5 (0.30 g,
0.38 mmol), SnCl2ꢀ2H2O (0.85 g, 3.77 mmol). The product 8
was isolated as a brown powder (0.27 g) in 97% yield, mp:
(2H, d, J = 12.6 Hz, ArCH2Ar ax), 3.76–3.57 (8H, m, OCH2
+
ArCH2Ar), 3.44–3.30 (4H, m, OCH2), 3.08 (2H, d, J = 13.5 Hz,
ArCH2Ar eq), 1.80–1.64 (6H, m, OCH2CH2), 1.43–1.23 (2H, m,
OCH2CH2), 1.03 (6H, t, J = 7.3 Hz, CH3), 0.74 (3H, t, J = 7.2 Hz,
CH3), 0.66 (3H, t, J = 7.6 Hz, CH3). 13C NMR (75 MHz, CDCl3, 296
K) d: 157.4, 154.2, 153.4, 139.0, 137.0, 135.3, 133.8, 133.5, 131.0,
130.5, 129.5, 129.1, 124.0, 123.2, 122.7, 122.6, 122.2, 119.6, 76.4,
75.6, 35.5, 31.0, 24.4, 24.0, 22.6, 11.2, 10.9, 9.5; TOF HRMS
(ESI+): calcd for [C54H60N4O6 + Na]+: 883.4405. Found: m/z
(rel. int. %) 883.4402 (100) [M + Na]+.
1
104–105 1C. H NMR (300 MHz, CDCl3, 298 K) d: 7.17 (2H, s,
ArH), 7.01 (2H, s, ArH), 6.42 (2H, d, J = 2.6 Hz, ArH), 5.70 (2H, d,
J = 2.9 Hz, ArH), 4.07 (2H, d, J = 13.2 Hz, ArCH2Ar ax), 3.75–3.63
(2H, m, OCH2), 3.58 (4H, d, J = 4.7 Hz, ArCH2Ar), 3.52–3.44 (2H,
m, OCH2), 3.36–3.30 (4H, m, OCH2), 2.94 (2H, d, J = 13.5 Hz,
ArCH2Ar eq), 1.89–1.75 (6H, m, OCH2CH2), 1.41–1.32 (20H, m,
OCH2CH2 + 2 ꢃ But), 1.12–1.02 (6H, m, CH3), 0.91 (3H, t, J = 7.5
Hz, CH3), 0.63 (3H, t, J = 7.6 Hz, CH3). 13C{1H} NMR (75 MHz,
CDCl3, 296 K) d: 155.4, 154.2, 149.9, 144.7, 143.5, 140.0, 136.4,
134.3, 133.3, 133.1, 127.4, 125.8, 118.3, 116.2, 76.5, 74.7, 73.9,
37.0, 36.5, 34.3, 34.2, 31.9, 24.2, 24.0, 21.6, 11.2, 10.6, 9.9; TOF
5,17-Bis[N0-(4-nitrophenyl)ureido]-25,26,27,28-
tetrapropoxycalix[4]arene (partial cone) 11
HRMS (ESI+): calcd for [C48H66N2O4 + H]+: 735.5095. Found: A general procedure was applied to amino derivative 7 (0.10 g,
m/z (rel. int. %) 735.5095 (100) [M + H]+.
0.16 mmol) and 4-nitrophenyl isocyanate (97% purity, 136 mg,
c
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2013
New J. Chem., 2013, 37, 220--227 225