10
R. Danac et al.
125.8 (2 £ Ar-CH), 125.9 (2 £ Ar-CH), 126.1 (2 £ Ar-
CH), 126.8 (2 £ Ar-CH), 128.2 (2 £ Ar-Cq), 130.5
(2 £ Ar-Cq), 133.8 (2 £ Ar-Cq), 144.2 (2 £ Ar-Cq),
144.3 (2 £ Ar-Cq), 149.7 (2 £ Ar-Cq-OCOR), 149.8
(2 £ Ar-Cq-OH), 166.0 (2 £ CvO); IR (KBr, cm21):
3492, 2960, 1773, 1482, 1202, 1143; MS (ESIþ): 823
(M þ Naþ); anal. calcd. for C48H58Cl2O6: C, 71.90; H,
7.29. Found: C, 71.85; H, 7.27.
(2 £ CvO); IR (KBr, cm21): 3568, 2952, 2866, 1740,
1458, 1224, 1209, 754; MS (ESIþ): 1012 (M þ Hþ), 1035
(M þ Naþ); anal. calcd. for C66H68N4O6: C, 78.23; H,
6.76; N, 5.53. Found: C, 78.18; H, 6.83; N, 5.55.
5,11,17,23-Tetra-tert-butyl-25,27-bis-[2-(pyrid-20-
yl)pyridin-5-carbonyloxy]-26,28-dihydroxy-calix[4]arene
11
Compound 11 was obtained as pale yellow crystals in 77%
1
yield (0.24 g), mp 284–2878C; H NMR (CDCl3): d 1.07
5,11,17,23-Tetra-tert-butyl-25,27-bis[4-[1-
(ethoxycarbonyl)-3-(4-methylbenzoyl) indolizin-7-yl]-1-
(2-acetyloxy)pyridinium]-26,28-dihydroxy-calix[4]arene
dibromide 7
(s, 18H, t Bu-H), 1.10 (s, 18H, t Bu-H), 3.58 (d, 4H,
ArCH2Ar, J ¼ 14.4 Hz), 3.92 (d, 4H, ArCH2Ar,
J ¼ 14.4 Hz), 4.95 (s, 2H, OH), 6.98 (s, 4H, Ar-H), 7.01
(s, 4H, Ar-H), 7.27 (m, 2H, H-50, CDCl3 overlapped
signal), 7.50 (dt, 2H, H-40, J ¼ 7.6 and 0.8 Hz), 8.43 (d,
2H, H-30, J ¼ 8.0 Hz), 8.55 (ad, 2H, H-60, J ¼ 4.4 Hz),
8.66 (dd, 2H, H-3, J ¼ 8.4 and 1.6 Hz), 8.74 (d, 2H, H-4,
J ¼ 8.4 Hz), 9.47 (as, 2H, H-6); 13C NMR (CDCl3): 31.1
(6 £ CH3), 31.4 (6 £ CH3), 33.8 (2 £ C(CH3)3), 34.1
(2 £ C(CH3)3), 34.2 (4 £ ArCH2Ar), 121.3 (2 £ C-4),
122.3 (2 £ C-30), 124.3 (2 £ C-50), 124.6 (2 £ C-5), 125.7
(4 £ Ar-CH), 126.5 (4 £ Ar-CH), 127.5 (4 £ Ar-Cq),
132.1 (4 £ Ar-Cq), 136.9 (2 £ C-40), 138.8 (2 £ Ar-Cq),
144.7 (2 £ Ar-Cq), 143.5 (2 £ C2), 149.2 (2 £ C60), 150.5
(2 £ Ar-C-OH), 151.3 (2 £ C6), 155.0 (2 £ C20), 160.2
(2 £ Ar-Cq-OCOR), 163.8 (2 £ CvO). IR (KBr, cm21):
3533, 2959, 1728, 1591, 1480, 1177, 1117, 757; MS
(ESIþ): 1012 (M þ Hþ), 1035 (M þ Naþ); anal. calcd. for
C66H68N4O6: C, 78.23; H, 6.76; N, 5.53. Found: C, 78.18;
H, 6.82; N, 5.55.
Compound 7 was obtained as yellow powder in 69% yield
1
(0.86 g), mp 280–2828C; H NMR (CDCl3): d 1.12 (s,
18H, t Bu-H), 1.18 (s, 18H, t Bu-H), 1.42 (t, 6H,
2 £ CH2CH3, J ¼ 7.2 Hz), 2.47 (s, 6H, 2 £ CH3), 3.42
(d, 4H, ArCH2Ar, J ¼ 13.2 Hz), 4.38 (d, 4H, ArCH2Ar,
J ¼ 13.2 Hz), 4.42 (q, 4H, 2 £ CH2CH3, J ¼ 7.2 Hz), 6.96
(s, 4H, Ar-H), 7.05 (s, 4H, Ar-H), 7.11 (s, 4H, 2 £ CH2N),
7.35 (ad, 6H, 2 £ H-300, 2 £ H-500, 2 £ H-60), 7.63 (s, 2H,
OH), 7.76 (d, 4H, 2 £ H-200, 2 £ H-1600, J ¼ 7.6 Hz), 7.90
(s, 2H, 2 £ H-20), 8.25 (as, 4H, 2 £ H-2, 2 £ H-6), 8.87 (as,
2 £ H-80), 9.78 (as, 4H, 2 £ H-3, 2 £ H-5), 10.02 (d, 2H,
2 £ H-50, J ¼ 7.2 Hz); 13C NMR (CDCl3): 14.6, 21.7,
31.4, 31.2, 31.8, 32.6, 33.8, 34.0, 34.3, 60.7, 109.7, 112.1,
119.9, 124.0, 125.5, 128.9, 129.3, 129.9, 130.6, 132.0,
136.3, 138.0, 143.0, 144.4, 147.2, 163.4 (2 £ COOEt),
185.8 (2 £ CvO); IR (KBr, cm21): 3186, 2958, 1758,
1701, 1618, 1202; anal. calcd. for C96H98N4O12: C, 69.47;
H, 5.95; N, 3.38. Found: C, 69.39; H, 5.97; N, 3.35.
3-(4-Methylbenzoyl)-7-(pyridine-4-yl)indolizine-1-
carboxylic acid 12
5,11,17,23-Tetra-tert-butyl-25,27-bis-[2-(pyrid-20-
yl)pyridin-4-carbonyloxy]-26,28-dihydroxy-calix[4]arene
10
Compound 12 was obtained as yellow solid in 90% yield
(0.67 g), mp 284–2868C; IR (KBr, cm21): 3427 (bb),
2922, 1698, 1606, 1213.
Compound 10 was obtained as pale pink crystals in 70%
1
yield (0.22 g), mp 305–3078C; H NMR (CDCl3): d 1.02
(s, 18H, t Bu-H), 1.17 (s, 18H, t Bu-H), 3.54 (d, 4H,
ArCH2Ar, J ¼ 14.4 Hz), 3.97 (d, 4H, ArCH2Ar,
J ¼ 14.4 Hz), 5.09 (s, 2H, OH), 6.94 (s, 4H, Ar-H), 7.04
(s, 4H, Ar-H), 7.26 (m, 2H, H-50, CDCl3 overlapped
signal), 7.80 (dt, 2H, H-40, J ¼ 7.6 and 1.6 Hz), 8.03 (dd,
2H, H-5, J ¼ 4.8 and 1.2 Hz), 8.40 (d, 2H, H-30,
J ¼ 8.0 Hz), 8.59 (d, 2H, H-60, J ¼ 4.4 Hz), 8.72 (d, 2H,
H-6, J ¼ 4.8 Hz), 9.47 (s, 2H, H-3); 13C NMR (CDCl3):
31.0 (6 £ CH3), 31.5 (6 £ CH3), 33.3 (4 £ CH2), 33.9
(2 £ C(CH3)3), 34.1 (2 £ C(CH3)3), 121.3 (2 £ C-3),
121.4 (2 £ C-30), 122.7 (2 £ C-5), 124.2 (2 £ C-50),
125.7 (4 £ Ar-CH), 126.3 (4 £ Ar-CH), 127.8 (4 £ Ar-
Cq), 131.7 (4 £ Ar-Cq), 136.9 (2 £ C-40), 137.7 (2 £ Ar-
Cq), 142.9 (2 £ Ar-Cq), 143.1 (2 £ C2), 149.2 (2 £ C4),
149.4 (2 £ C60), 150.3 (2 £ C6), 150.4 (2 £ Ar-C-OH),
154.9 (2 £ C20), 157.8 (2 £ Ar-Cq-OCOR), 163.8
5,11,17,23-Tetra-tert-butyl-25,27-bis-[3-(4-
methylbenzoyl)-7-(pyridin-4-yl)indolizine-1-
carbonyloxy]-26,28-dihydroxy-calix[4]arene 14
Compound 14 was obtained as yellow powder in 50%
1
yield (0.20 g), mp .3608C; H NMR (CDCl3): d 0.94 (s,
18H, t Bu-H), 1.35 (s, 18H, t Bu-H), 2.15 (s, 6H, 2 £ CH3)
3.31 (d, 2H, ArCH2Ar, J ¼ 12.4 Hz), 3.62 (d, 2H,
ArCH2Ar, J ¼ 10.4 Hz), 4.04 (d, 2H, ArCH2Ar,
J ¼ 12.4 Hz), 4.28 (d, 2H, ArCH2Ar, J ¼ 10.4 Hz), 6.17
(s, 2H, OH), 6.42 (as, 4H, 2 £ H-300, 2 £ H-500), 6.80 (bs,
2H, Ar-H), 6.88 (bs, 2H, Ar-H), 7.12 (bs, 2H, Ar-H), 7.24
(bs, 2H, Ar-H), 7.37 (d, 4H, 2 £ H-200, 2 £ H-600,
J ¼ 5.6 Hz), 7.56 (as, 2H, 2 £ H-6), 7.76 (as, 4H, H-30,
H-50), 8.17 (s, 2H, 2 £ H-2), 8.83 (ad, 6H, 2 £ H-20, 2 £ H-
60, 2 £ H-8), 10.17 (as, 2H, 2 £ H-5); 13C NMR (CDCl3):