176
J Incl Phenom Macrocycl Chem (2011) 71:169–178
4.26 (t, J = 4.9 Hz, 8H, OCH2), 3.94 (t, J = 4.9 Hz, 8H,
CH8O), 3.60 (q, J = 4.8 Hz, 8H, –CH2CH3), 3.36 (d,
J = 13.8 Hz, 4H, ArCH2Ar), 1.26 (t, J = 4.8 Hz, 12H,
–CH2CH3); 13C NMR (CDCl3, d): 156.44, 146.57, 135.18,
132.40, 128.16, 127.84, 126.86, 126.47, 124.61, 73.47,
69.52, 66.40, 30.77, 15.30.
CH2CH3), 3.32 (d, J = 13.6 Hz, 4H, ArCH2Ar), 3.98–3.94
(m, 8H, –CH2–), 1.24 (t, J = 4.9 Hz, 6H, –CH3), 1.21 (t,
J = 4.9 Hz, 12H, –CH3).
Synthesis of 5,17-bis(40,50-diphenylimidazolyl)-25,26,
27,28-tetrakis(hexadecyloxy)calix[4]arene 7e
Synthesis of 5,11,17-tris(40,50-diphenylimidazolyl)-
To a solution of 5e (0.25 g, 0.17 mmol) in acetic acid
(30 mL), benzil (0.45 g, 2.1 mmol) and ammonium acetate
(1.4 g, 17.5 mmol) were added and the resultant solution
was refluxed for 3 h. After the work-up as described earlier,
a light cream colored solid was obtained and was identified
as 5,17-bis(40,50-diphenylimidazolyl)-25,26,27,28-tetrakis
(hexadecyloxy) calix[4]arene 7e. Yield (0.31 g, 83%): UV
(kmax, CHCl3): 300 nm. Anal. calcd. for C122H172O4N4: C,
83.37; H, 9.79; N, 3.19; found: C, 83.20; H, 9.85; N, 2.79.
Molecular mass (vapour pressure osmometry): 2206 (calcd.
2192). IR (mmax, KBr): 3305, 3092, 2917, 2850, 1588, 1385,
25,26,27,28-tetrakis(2-ethoxyethoxy) calix[4]arene 7c
To a solution of 5,11,17-triformyl-5,26,27,28-tetrakis(2-
ethoxyethoxy)calix[4]arene 5c (0.2 g, 0.25 mmol) in acetic
acid (30 mL), benzil (0.32 g, 1.5 mmol) and ammonium
acetate (0.6 g, 7.5 mmol) were added and the resultant
solution was refluxed for 3 h. After the work-up as
described in the above procedure, a light cream colored
solid was obtained and was identified as 5,11,17-tris(40,50-
diphenylimidazolyl)-25,26,27,28-tetrakis(2-ethoxyeth-
oxy)calix[4]arene 7c (0.29 g, 85%); m.p. [250 °C; Anal.
calcd. for C89H86O8N6: C, 78.18; H, 6.29; N, 8.19; found:
C, 77.98; H, 6.02; N, 8.68. Molecular mass (vapour pres-
sure osmometry): 1360 (calcd. 1366). IR (mmax, KBr); 3302,
3055, 2428, 1645, 1594, 1481, 1453, 1411, 1408, 1104,
1
1261, 1163, 1079, 804, 762 cm-1; H-NMR (CDCl3, d):
7.48–7.45 (m, 8H, ArH), 7.37–7.34 (m, 12H, ArH), 7.78 (s,
4H, ArH), 7.18–7.06 (m, 6H, ArH), 4.30 (d, J = 13.8 Hz,
4H, ArCH2Ar), 4.23–4.12 (m, 8H, -CH2), 3.51 (d,
J = 13.8 Hz, 4H, ArCH2Ar), 2.21–1.31 (m, 128H, –CH2),
1.16 (t, J = 7.3 Hz, 12H, –CH3).
1
765 cm-1; UV(kmax, CHCl3): 301 nm; H-NMR (CDCl3,
d): 7.41–6.98 (m, 30H, ArH), 7.72 (s, 6H, ArH), 7.15–6.92
(m, 3H, ArH), 4.68 (d, J = 13.6 Hz, 2H, ArCH2Ar), 4.52
(d, J = 13.6 Hz, 2H, ArCH2Ar), 4.4–4.21 (m, 6H,
–OCH2), 4.16 (t, J = 5.3 Hz, 2H, –CH2), 4.02–3.9 (m, 8H,
–CH2), 3.28 (d, J = 13.6 Hz, 2H, ArCH2Ar) and 3.12(d,
J = 13.6 Hz, 2H, ArCH2Ar), 1.29–1.17 (m, 12H, –CH3).
Synthesis of 5,11,17,23,29,35,41,47-octakis
(40,50-diphenylimidazolyl)-49,50,51,52, 53,54,55,
56-octamethoxycalix[8]arene 7f
To a solution of 5f (0.2 g, 0.24 mmol) in acetic acid
(30 mL), benzil (0.66 g, 3.1 mmol) and ammonium acetate
(1.5 g, 19.5 mmol) were added and the resultant solution
was refluxed for 3 h. After the work-up as described ear-
lier, a light cream colored solid was obtained and was
identified as 5,11,17,23,29,35,41,47-octa(40,50-diphenylim-
idazolyl)-49,50,51,52,53,54,55,56-octamethoxycalix[8]arene
7f. Yield (0.485 g, 75%). UV (kmax, CHCl3): 299 nm.
Anal. calcd. for C184H144N16O8: C, 81.65; H, 5.32; N, 8.28;
found: C, 81.55; H, 5.53; N, 7.03; MS-FAB Mass(m/e):
1353 (M/2 ? H?). IR (mmax, KBr): 3308, 3056, 2929, 1604,
Synthesis of 5,17-bis(40,50-diphenylimidazolyl)-
25,26,27,28-tetrakis(2-ethoxyethoxy) calix[4]arene 7d
To a solution of 5,11,17-triformyl-5,26,27,28-tetrakis(2-
ethoxyethoxy)calix[4]arene 5c (0.2 g, 0.25 mmol) in acetic
acid (30 mL), benzil (0.32 g, 1.5 mmol) and ammonium
acetate (0.6 g, 7.5 mmol) were added and the resultant
solution was refluxed for 3 h. After the usual work-up as
described in the above procedure, a light cream colored
solid was obtained and was identified as 5,17-bis(40,50-
diphenylimidazolyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)-
calix[4]arene 7d. Yield (0.26 g, 87%); m.p. [250 °C. UV
(kmax, CHCl3): 298 nm. Anal. calcd. for C74H76O8N4: C,
77.35; H, 6.62; N, 4.88; found: C, 77.04; H, 6.53; N, 3.99.
Molecular mass (vapour pressure osmometry): 1160 (calcd.
1148). IR (mmax, KBr): 3310, 3058, 1650, 1595, 1505, 1481,
1598, 1503, 1479, 1246, 1116, 1008, 765, 696 cm-1; H-
1
NMR (CDCl3, d): 7.42–7.39 (m, 32H, ArH), 7.14–7.12 (m,
48H, ArH), 7.83 (s, 16H, ArH), 4.08 (s, 16H, ArCH2Ar),
3.55 (s, 24H, OCH3); 13C NMR (CDCl3, d): 156.6, 145.5,
136.8, 135.1, 134.1, 131.3, 128.4, 128.37, 127.9, 127.5,
126.9, 126.4, 125.9, 60.3, 30.1.
1415, 1316, 1242, 1181, 1104, 1009, 868, 764 cm-1
;
Synthesis of 5,11,17,23,29,35-hexakis
(40,50-diphenylimidazolyl)-37,38,39,40,
41,42-hexamethoxycalix[6]arene 7g
1H-NMR (CDCl3, d): 7.25–7.22 (m, 8H, ArH), 7.06–7.04
(m, 12H, ArH), 7.28 (s, 4H, ArH), 6.81–6.77 (m, 6H, ArH),
4.51 (d, J = 13.6 Hz, 4H, ArCH2Ar), 4.27 (t, J = 4.9 Hz,
4H, –CH2), 4.20 (t, J = 4.9 Hz, 4H, –CH2–), 3.63
(q, J = 4.9 Hz, 4H, CH2CH3), 3.60 (q, 4H, J = 4.9 Hz,
To a solution of 5g (0.45 g, 0.50 mmol) in acetic acid
(50 mL), benzil (1.50 g, 7.15 mmol) and ammonium
123