E. Wagner-Wysiecka et al. / Tetrahedron 59 (2003) 4415–4420
4419
1456; 1364; 1263; 1132. UV–Vis (acetonitrile):
l1¼247 nm, 11¼5.90£103; l2¼314 nm, 12¼7.39£103;
l3¼396 nm, 13¼7.55£103; l4¼518 nm, 14¼6.70£103.
HRMS (EI): Mþ 489.2757; C28H35N5O3 requires 489.2740.
up to high excess of cation to crown ether and finally
the limiting spectra were obtained. The dependence of
the absorbance on metal salt concentration was
described well by equation (A02A)/(A2Ai)¼K[Mþ]15
where A0 and Ai are the absorbancies at zero and
infinite salt concentration, respectively. Data taken at
least at three different wavelengths were fitted to the
above equation.
4.1.5. Compound 3. Yield 27%, red solid, mp 105–1088C.
1
Rf,0.7. H NMR dH (d6-acetone, 500 MHz): 10.80 (1H, s,
NH); 7.66 (2H, d, J¼1.8 Hz, ArH); 7.26 (2H, dd,
J1¼2.6 Hz, J2¼8.4 Hz, ArH); 7.08 (2H, s, ArH); 7.05
(2H, d, J¼8.4 Hz, ArH); 4.34–4.38 (4H, m, ArOCH2);
3.97–4.20 (4H, m, CH2OCH2); 3.62 (4H, t, J¼7.0 Hz,
ArCH2CH2); 3.36 (6H, s, OCH3); 2.88 (4H, t, J¼7.0 Hz,
ArCH2CH2). IR nmax (film): 3433; 2924; 2871; 2360;
2341; 1573; 1498; 1454; 1374; 1233; 1158; 1112; 1065;
1029; 805; 669. UV–Vis (acetonitrile): l1¼250 nm,
11¼8.51£104; l2¼314 nm, 12¼1.10£105; l3¼388 nm,
13¼1.08£105; l4¼518 nm, 14¼2.40£105. HRMS (EI):
Mþ 493.2301; C26H31N5O5 requires 493.2325.
4.3. Membrane preparation and emf measurements
The membrane components [5 mg of crown ether, 50 mg
PVC, 0.1 mL 2-nitrophenyl octyl ether and 1 mg potassium
tetrakis(4-chlorophenyl)borate] were dissolved in 1 mL
freshly distilled THF and poured into a 2 cm diameter
glass ring. After solvent evaporation, the membranes were
incorporated into Ag/AgCl electrode bodies. 0.01 M NaCl
was used as internal electrolyte. Selectivity coefficients
were determined by separate solution method (SSM) at
1022 M activity of metal chlorides.13
4.1.6. Compound 4. Yield 41%, red solid, mp 156–1578C.
Rf,0.8. 1H NMR; dH (CDCl3, 200 MHz): 12.6 (1H, s, NH);
7.54–7.82 (2H, m, ArH); 7.26–7.39 (2H, m, ArH); 6.97–
7.06 (6H, m, ArH); 4.33–4.26 (4H, m, ArOCH2); 3.91–3.97
(4H, m, ArOCH2CH2); 3.82 (4H, s, OCH2CH2O). IR nmax
(film): 3589; 3496; 3010; 2918; 1587; 1486; 1450; 1388;
1277; 1249; 1161; 1110; 1056; 950; 843; 752; 667; 613;
596; 555; 483. UV–Vis (acetonitrile): l1¼250 nm,
11¼6.53£103; l2¼311 nm, 12¼7.10£103; l3¼372 nm,
13¼7.46£103; l4¼494 nm, 14¼2.40£104. HRMS (EI):
Mþ 421.1737; C22H23N5O4 requires 421.1750.
4.4. Supplementary data
Supplementary data are deposited with the Cambridge
Crystallographic Data Centre as a supplementary publication
numbers CCDC 203525 (CCDC, 12 Union Road, Cam-
bridge, CB2 1EZ, UK; e-mail; deposit@ccdc.cam.ac.uk).
Acknowledgements
4.1.7. Compound 5. Yield 42%, red solid, mp 228–2328C.
Rf,0.5. 1H NMR; dH (CDCl3, 200 MHz): 8.1 (1H, s, ArH);
7.85 (1H, d, J¼8.1 Hz, ArH); 7.60 (1H, d, J¼8.3 Hz, ArH);
7.38–7.51 (2H, m, ArH); 7.00–7.20 (4H, m, ArH); 4.35–
Financial support from the Polish State Committee for
Scientific Research, Grant No. 3TO9A13716 is kindly
˙
acknowledged. The authors thank Jolanta Zochowska
4.50 (4H, m, ArOCH2); 3.80–4.10 (4H, m, CH2OCH2). 13
C
and Iwona Stenka for remarkable experimental help.
The X-ray measurements were undertaken in the
Crystallographic Unit of the Physical Chemistry Lab.
at the Chemistry Department of the University of
Warsaw. We are grateful to Dr V. Ch. Kravtsov from
Institute of Applied Physics, Academy of Sciences of
Moldova, Kishinev for final refinement of the X-ray
structure.
NMR; dC (CDCl3; 125 MHz): 71.17; 71.24; 116.07; 116.55;
117.71; 117.85; 122.95; 133.76; 135.36; 142.47; 142.70;
146.16; 155.18; 157.60; 158.37. IR nmax (film): 3567; 3513;
3435; 2928; 2878; 1589; 1530; 1486; 1448; 1281; 1234;
1159; 1112; 1064; 1039; 940; 754; 670; 604; 557; 480; 426.
UV–Vis (acetonitrile): l1¼241 nm, 11¼8.97£103;
l2¼317 nm, 12¼1.01£104; l3¼376 nm, 13¼1.38£104;
l4¼469 nm, 14¼1.95£103; l5¼486 nm, 15¼1.95£104.
HRMS (EI): Mþ 378.1446; C19H18N6O3 requires 378.1440.
4.1.8. Compound 6. Yield 30%, red solid, mp 2238C.
Rf,0.6. 1H NMR; dH (CDCl3, 200 MHz): 11.4 (1H, s, NH);
8.10 (1H, s, ArH); 8.0 (1H, d, J¼2.4 Hz, ArH); 7.85 (1H, d,
J¼2.2 Hz, ArH); 7.62–7.48 (2H, m, ArH); 7.18–7.06 (4H,
m, ArH); 4.46–4.34 (4H, m, ArOCH2); 4.08–3.94 (4H, m,
CH2OCH2); 1.4 (18H, s, Ar-t-Bu). IR nmax (film): 3572;
3517; 3427; 2960; 1499; 1460; 1363; 1264; 1232; 1188;
1124; 1065; 812; 754. UV–Vis (acetonitrile): l1¼330 nm,
11¼4.61£103; l2¼382 nm, 12¼5.99£103; l3¼490 nm,
13¼6.98£103. HRMS (EI): Mþ 490.2684; C27H34N6O3
requires 490.2692.
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