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1256
Pd/C catalyst was added. The course of reaction was
followed using the gas measuring tube with hydrogen. The
consumption of hydrogen reached 48 ml (107% of theory)
after 1 h and the reaction mixture was filtered through a fine
analytical filter to remove the catalyst. The filtrate was
evaporated to dryness and the residue was triturated with
20 ml of tert-butyl(methyl)ether. Solid was collected by
filtration and dried in vacuum to yield 231 mg (84%) of title
product as a white powder, which was used immediately in
the next step. 1H NMR (CDCl3CCD3OD, 300 MHz) d
(ppm): 1.28 (s, 18H, But), 3.52 (s, 6H, –O–CH3), 3.70 (s,
6H, –O–CH3), 7.47 (s, 4H, H-arom), 8.16 (s, 4H, H-arom).
IR (CHCl3) cmK1: 3418, 1479, 1426, 1326.
over MgSO4 and evaporated to dryness. The crude product
was purified using preparative TLC (20!20 cm) on silica
gel (CHCl3/MeOHZ99:1) to yield 100 mg (51%) of title
compound as a white solid with mp 298 8C (decomp.)
(CHCl3/acetone). 1H NMR (300 MHz, CDCl3/CD3CNZ4:1
v/v) d (ppm): 1.30 (s, 9H, But), 1.32 (s, 18H, But), 2.34 (s,
3H, CH3-tolyl), 3.98 (s, 3H, –OCH3), 4.05 (s, 3H, –OCH3),
4.12 (s, 6H, –OCH3), 7.05 (br s, 1H, NH), 7.07 (d,
2H, JZ7.5 Hz, H-arom-tolyl), 7.18 (d, 2H, JZ7.5 Hz,
H-arom-tolyl), 7.62 (br s, 1H, NH), 8.23 (s, 2H, H-arom),
8.25 (s, 2H, H-arom), 8.39 (s, 4H, H-arom). 13C NMR
(125 MHz) d (ppm): 20.53, 29.50, 29.41, 30.73, 34.71,
34.80, 66.59, 66.66, 66.87, 119.38, 125.20, 129.38, 132.60,
132.66, 133.74, 135.44, 135.48, 135.63, 135.70, 135.81,
136.36, 146.92, 147.01, 149.81, 152.28, 153.82, 153.95.
IR (KBr) cmK1: 3421, 1632, 1479, 1426. MS (ESI) (MeCN)
m/zZ1019 (MCNa)C. EA calcd for C48H56N2O13S4: C,
57.81; H, 5.66, N, 2.81, S, 12.86. Found C, 57.36; H,
5.37; N, 2.72.
3.1.2. Synthesis of 15-amino-11,17,23-tri-tert-butyl-
25,26,27,28-tetramethoxytetrasulfonylcalix[4]arene 7.
Mononitrotetrasulfonylcalix[4]arene 5 (100 mg; 0.112 mmol)
was suspended in 20 ml of ethyl acetate and 10% Pd/C
(70 mg) was added. The flask was purged several times with
hydrogen and the content was intensively stirred for 3.5 h
under balloon with hydrogen. The reaction mixture was
filtered through the short pad of diatomaceous earth to
remove the catalyst. The filtrate was evaporated to dryness
to yield 84 mg (87%) of title product as a white solid, which
was used immediately in the next step. 1H NMR (CDCl3C
CD3OD, 300 MHz) d (ppm): 1.32 (s, 18H, But), 1.36 (s, 9H,
But), 3.90 (s, 3H, –OCH3), 4.03 (s, 6H, –OCH3), 4.05 (s, 3H,
–OCH3), 7.48 (s, 2H, H-arom), 8.22 (d, JZ2.75 Hz,
H-arom), 8.26 (d, JZ2.75 Hz, H-arom), 8.29 (s, 2H,
H-arom). IR (CHCl3) cmK1: 2965, 1479, 1427, 1325.
Acknowledgements
This research was partially supported by the Grant Agency
of the Czech Republic (GA 203/03/0926). The authors are
grateful to Dr. Dvorakova (Central laboratory, ICT, Prague)
for the measurement of NMR spectra.
3.1.3. Synthesis of 5,17-di-tert-butyl-25,26,27,28-tetra-
methoxy-11,23-bis(p-tolylureido)tetrasulfonylcalix[4]-
arene 8. Diaminocalix[4]arene (95.8 mg; 0.116 mmol) was
suspended in 2 ml of dry DCM and 35 ml of p-tolyl
isocyanate (37 mg; 0.280 mmol) was added. The suspension
gradually dissolved and within 5 min a clear reaction
solution was obtained. The reaction mixture was stirred for
an additional 5 h and evaporated, the residue dissolved in
chloroform and washed with dilute hydrochloric acid. The
organic layer was separated, dried over anhydrous MgSO4
and after filtration evaporated to dryness. The crude product
was purified using preparative TLC on silica gel to yield
67 mg of title compound as a white powder (57%) with mp
277 8C (decomp.) (CHCl3/acetone). 1H NMR (CDCl3/
CD3CNZ4:1 v/v, 300 MHz) d (ppm): 1.30 (s, 18H, t-Bu),
2.28 (s, 6H, CH3-tolyl), 4.03 (s, 6H, OCH3), 4.13 (s, 6H,
OCH3), 7.07 (br s, 8H, H-arom-tolyl), 8.18 (s, 8H, H-arom),
8.29 (s, H-arom). 13C NMR (125 MHz) d (ppm): 20.86,
30.93, 34.98, 67.23, 67.79, 120.91, 129.61, 129.96, 132.90,
134.02, 134.32, 135.59, 135.99, 137.28, 147.25, 153.05,
154.03, 155.00. IR (KBr) nmax cmK1: 3404, 1651, 1469,
1425. MS (ESI) (MeCN) m/zZ1111 (MCNa)C. EA calcd
for C52H56N4O14S4: C, 57.34; H, 5.18, N, 5.14, S, 11.77.
Found C, 56.86; H, 5.07; N, 5.02.
References and notes
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