H. Akdas et al. / Tetrahedron Letters 43 (2002) 8975–8979
8979
15. M. W. Hosseini, A. De Cian, see Feature Article in
Chem. Commun. 1998, 727–733.
C48H64O8S4, CH3OH: C, 63.33; H, 7.38; S13.8. Found: C,
63.13; H, 7.00; S, 13.95%; H NMR (200 MHz, CDCl3,
1
16. X-Ray studies: For compound 8, data were measured at
294 K on a Enraf–Nonius CAD4 diffractometer with
graphite-monochromated Mo-Ka radiation. For the
other two compounds 9 and 14, data were measured at
173 K on a kappa CCD diffractometer with graphite-
monochromated Mo-Ka radiation. All structures were
solved by direct methods using OpenMoleN 2.2 and
refined anisotropically using absorption corrected data.
Atomic coordinates, bond lengths and angles and thermal
parameters have been deposited at the Cambridge Crys-
tallographic Data Centre.
25°C): l (ppm): 1.10 (s, 36H, CH3); 4.00 (m, 8H, CH2);
4.30 (m, 8H, CH2); 4.97 (t, 6.6 Hz, 4H, OH); 7.35 (s, 8H,
Ar); 13C NMR (50 MHz, CDCl3, 25°C): l (ppm): 31.17
(CH3); 34.29 (C(CH3)3); 61.60; 79.22 (CH2); 129.76;
134.69; 147.27; 158.34 (arom.).
20. Akdas, H.; Jaunky, W.; Graf, E.; Hosseini, M. W.; De
Cian, A.; Fischer, J. Tetrahedron Lett. 2000, 41, 3601–
3606.
21. Compound 6: mp 310°C (decomp.). Anal. calcd for
C52H68O4Br4S4.(CH3)CO: C, 52.30; H, 5.91; S, 10.15.
Found: C, 52.72; H, 5.93; S, 10.45%; 1H NMR (200
MHz, CDCl3, 25°C): l (ppm): 1.34 (s, 36H, CH3); 1.54 (t,
J=7.3 Hz; 8H; CH2); 3.07 (t, J=7.1 Hz, 8H, CH2); 3.97
(t, J=6.8 Hz, 8H, CH2), 7.35 (s, 8H, Ar); 13C NMR (50
MHz, CDCl3, 25°C): l (ppm): 30.46 (CH2); 31.42 (CH3);
32.28 (CH2); 34.48 (CCH3); 67.06 (OCH2); 127.28;
128.19; 146.49; 156.32 (arom.).
17. Compound 8: A mixture of p-tert-butylthiacalix[4]arene 2
(0.5 g, 0.70 mmol), 1,2-dibromoethane (1.0 ml, 11 mmol),
K2CO3 (1.5 g, 11 mmol) in dry dimethylformamide (50
ml) was heated under argon to 80°C overnight. After
cooling at rt, the mixture was poured onto ice and the
yellow solid obtained was washed with water (100 ml).
The solid was redissolved in CH2Cl2 (50 ml), dried on
MgSO4 and evaporated to dryness. Upon purification by
column chromatography (SiO2, hexane/CH2Cl2 1:1) the
pure compound 8 was obtained as a white solid (120 mg,
22% yield). Mp 310°C (decomp.). Anal. calcd for
C44H52O4S4: C, 68.36; H, 6.78. Found: C, 68.27; H,
22. Compound 9: mp 290°C (decomp.). Anal. calcd for
C44H52S8, 0.5 CH2Cl2: C, 60.75; H, 6.07. Found: C,
1
60.56; H, 6.61%; H NMR (200 MHz, CDCl3, 25°C): l
(ppm): 1.34 (s, 36H, CH3); 1.65 (m, 4H, CH2); 2.65 (m,
4H, CH2); 7.77 (d, 2.2 Hz, 4H, arom.); 7.90 (d, 2.2 Hz,
4H, arom.); 13C NMR (50 MHz, CDCl3, 25°C): l (ppm):
29.7 (OCH2CH2); 31.2 (CH3); 32.8 (OCH2CH2); 34.7
(C(CH3)); 135.1, 135.5, 138.8, 139.8, 143.1, 150.8 (arom.).
Compound 13: 1H NMR (200 MHz, CDCl3, 25°C): l
(ppm): 1.25 (s, 36H, CH3); 2.06 (s, 12H, SCH3); 2.58 (m,
8H, CH2); 3.09 (m, 8H, CH2), 7.75 (s, 8H, Ar); 13C NMR
(50 MHz, CDCl3, 25°C): l (ppm): 15.5 (SCH3); 30.9
(CCH3); 34.3 (CH2); 34.5 (CCH3); 35.2 (CH2); 135.0;
140.1; 142.6; 149.9 (arom.).
1
6.78%. H NMR (300 MHz, CDCl3, 25°C): l (ppm): 0.86
(s, 18H, CH3); 1.38 (s, 18H, CH3); 4.24 (d, J=12 Hz, 2H,
CH2); 4.34 (d, J=11 Hz, 2H, CH2); 5.11 (t, J=11 Hz,
2H, CH2); 5.58 (t, J=12 Hz, 2H, CH2); 6.62 (d, J=2.6
Hz, 2H, arom.); 6.96 (d, J=2.6 Hz, 2H, arom.); 7.59 (d,
J=2.3 Hz, 2H, arom.); 7.72 (d, J=2.3 Hz, 2H, arom.);
13C NMR (50 MHz, CDCl3, 25°C): l (ppm): 30.8 (CH3);
31.3 (CH3); 33.8 (C(CH3)); 34.5 (C(CH3)); 67.3 (OCH2
CH2); 72.4 (OCH2 CH2); 125.4; 129.9; 130.3; 130.9; 131.3;
132.5; 134.8; 146.8; 156.5 (arom.).
23. Compound 7: mp 265°C (decomp.). Anal. calcd for
C52H68Br4S8: C, 49.21; H, 5.4; S, 19.54. Found: C, 49.64;
18. Lhotak, P.; Dudic, M.; Stibor, I.; Petrickova, H.; Sykora,
J.; Hodacova, J. Chem. Commun. 2001, 731–732.
1
H, 5.38; S, 20.21%; H NMR (200 MHz, CDCl3, 25°C):
19. Compound 10: 1H NMR (200 MHz, CDCl3, 25°C): l
(ppm): 1.06 (s, 36H, CH3); 2.43 (s, 12H, CH3 (Tos)); 4.31
(t, 3.3 Hz, 8H, CH2); 4.47 (t, 3.4 Hz, 8H, CH2); 7.20 (s,
8H, Ar); 7.33 (d, 8H, Ar (Tos)); 7.79 (d, 8H, Ar (Tos)).
Compound 11: mp 330°C (decomp.). Anal. calcd for
l (ppm):1.32 (s, 36H, CH3); 1.89 (m, J=6.38 Hz; 8H;
CH2); 3.06 (t, J=6.4 Hz, 8H, CH2); 3.71 (t, J=6.8, 8H,
CH2), 7.69 (s, 8H, Ar); 13C NMR (50 MHz, CDCl3,
25°C): l (ppm):30.9 (CH2); 31.0 (CH3); 31.8, 33.2 (CH2)
34.4 (CCH3); 133.5, 138.7, 142.52, 151.0 (arom.).