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J Incl Phenom Macrocycl Chem (2012) 72:323–330
was added. The mixture was refluxed for half an hour and
triethylene glycol-p-ditosylate (0.88 g, 1.93 mmol) in THF
(5 mL) was added drop wise. The reaction mixture was
refluxed for 12 h and then cooled and worked up as men-
solution of triethylene glycol-p-ditosylate (1.09 g,
2.39 mmol) in THF (5 mL) was added drop wise. The
reaction was refluxed for 15 h and then cooled down and
worked up as above and purified by column chromatog-
1
tioned above to purify as 2a. Yield
:
(51.8%),
raphy as in 2a. Yield: (55.2%), m.p [ 210 °C, H-NMR
m.p [ 210 °C, IR (KBr): 1463 cm-1, 1H-NMR (CDCl3): d
0.9 (s, 18H, C[(CH3)3], 1.15 [s,18H, C[(CH3)3], 3.33 (d,
4H, ArCH2Ar), 3.36–4.38 (m, 16H, ArCH2Ar, OCH2-
CH2O, OCH2CH2), 6.9 (d, 4H, ArH), 7.72(d, 4H, ArH), 0.1
(s, 2H, OH), Anal Calcd. for C50H66O6: C, 78.40; H, 8.66.
Found: C, 77.89; H, 8.50. FAB-MS (m/z): 763.0 (M?),
found 763.0.
CDCl3: d 3.33 (d, ArCH2Ar), 3.53–5.16 (m, 24H,
ArCH2Ar, OCH2Ar, OCH2), 6.82 (s, 4H, ArH), 7.17 (d,
4H, ArH), 7.35 (d, 4H, ArH,), 7.78 (d, 4H, ArH). Anal
calcd. for C48H46O6: C, 80.16; H, 6.4. Found: C, 81.02; H,
6.61. FAB-MS (m/z): 718.8 (M?), found: 719.0.
Compound 2g
Compound 2d
A mixture of calix[4]arene, 1a (0.40 g, 0.94 mmol) and
K2CO3 (1.04 g, 7.54 mmol) was refluxed in CH3CN
(15 mL) for 25–30 min and a warm solution of trithylene
glycol-p-ditosylate, (0.86 g, 1.88 mmol) in CH3CN
(10 mL) was added drop wise and mixture was further
refluxed for 6 days, worked up and purified as described
for the compound 2c. Yield : (53.7%), m.p [ 210 °C IR
(KBr pallets): 3401 cm-1, 1H-NMR CDCl3: d 3.08 (d, 4H,
ArCH2Ar), 3.44-4.75 (m, 20H, ArCH2Ar, OCH2CH2O,
OCH2), 6.07 (m 2H, ArH), 6.34 (m, 2H, ArH), 6.60 (d, 4H,
ArH), 6.76 (d, 4H, ArH), 7.29 (d, 4H, ArHphenyl), 7.48 (d,
4H, ArHphenyl). Anal calcd. for C47H53O11S: C, 68.19; H,
6.41. Found: 67.82; H, 6.02. FAB-MS C47H53O11S (m/z):
828.0, found: 827.0.
The compound 2c (0.27 g, 0.25 mmol) was added to
SnCl2.2H2O (0.41 g, 1.99 mmol) in dry ethanol (15 mL)
and refluxed for 6 h. The content was poured into alkaline
water and the pH was adjusted till neutral. Extract the
product with CH2Cl2, evaporated the solvent and precipi-
tated the product with methanol. The product was purified
by column chromatography (SiO2, ethyl acetate: hexane:
1:1) Yield : (54%), m.p [ 210 °C, IR (KBr) 1467 cm-1
,
1H-NMR (CDCl3): d 0.97 (s, 18 H, Bu), 1.19 (s, 18 H,
But), 3.35 (d, 4H, ArCH2Ar), 3.6–5.1 (m, 28H, ArCH2Ar,
OCH2Ar, OCH2), 6.81 (s, 4H, ArH), 7.12 (s, 4H, ArH), 7.8
(d, 4H, ArH, 4-aminophenyl-H3,5), 8.1 (d, 4H, ArH,
4-aminophenyl-H2,6). Anal calcd. for C66H80N2O7: C,
77.95; H, 7.87; N, 2.75. Found: C, 77.84; H, 7.62; N, 2.58.
FAB-MS (m/z): 1013.3 (M?), found 1013.0.
t
Compound 2h
The calix[4]arene, 1e (0.50 g, 0.98 mmol) was dissolved in
THF/toluene (10:1, 25 mL) and NaH (0.05 g, 1.97 mmol)
was added. The mixture was refluxed for half an hour and a
solution of triethylene glycol-p-ditosylate (1.13 g,
2.46 mmol) in THF (5 mL) was added drop wise. The
reaction was refluxed for 14 h and then cooled down and
worked up as above and purified by column chromatog-
raphy as in 2a. Yield : (56%), m.p [ 210 °C, IR (KBr)
Compound 2e
The calix[4]arene, 1c (0.45 g, 1.06 mmol) and K2CO3
(1.17 g, 8.48 mmol) was dissolved in CH3CN (20 mL) and
refluxed for 25–30 min and a warm solution of pentaeth-
ylene glycol-p-ditosylate (1.16 g, 2.12 mmol) was added
dropwise and mixture was further refluxed for 8 days and
worked up and purified as described for the compound
2a.Yield : (54.9%), m.p [ 210 °C, IR (KBr pallets):
1
3345 cm-1, H-NMR CDCl3: d 2.55 (s, 3H, CH3), 4.38 (d,
4H, ArCH2Ar), 3.40–4.09 (m, 28H, ArCH2Ar, OCH2-
CH2O, OCH2), 6.41 (m, 2H, ArH), 6.61 (m, 2H, ArH), 6.82
(d, 4H, ArH), 6.92 (d, 4H, ArH), 7.04 (d, 2H, ArHOTs),
7.17 (d, 2H, ArHOTs), 8.1(s, H, OH). Anal calcd. for
C40H44O6: C, 77.36; H, 7.03. Found: 76.81; H, 6.98. FAB-
MS (m/z): 620.7 (M?), found 622.0.
1
3397 cm-1; H-NMR (CDCl3): d 0.95 (s, 18H, C[(CH3)3],
1.29 [s,18H, C[(CH3)3], 3.31 (d, 4H, ArCH2Ar), 3.53–4.38
(m, 16H, ArCH2Ar, OCH2CH2O, OCH2CH2), 6.82 (d, 4H,
ArH), 7.12(d, 4H, ArH), 7.93 (d, 4H, ArHNO2), 8.17(d,4H,
ArHNO2). Anal calcd. for C38H42O8: C, 69.48; H, 7.71; N,
2.38. Found: C, 69.07; H, &.69; N, 2.21. FAB-MS (m/z):
628.5 (M?), found: 629.0.
General procedure for the preparation of alkali metal
solutions
Compound 2f
The calix[4]arene, 1d (0.60 g, 0.95 mmol) was dissolved in
THF/toluene (10:1, 25 mL) and NaH (0.05 g, 1.91 mmol)
was added. The mixture was refluxed for half an hour and a
The metal carbonates (Na2CO3, K2CO3) were accurately
weighed and 100 ppm solutions (25 mL) of both the car-
bonates were prepared in distilled water. The prepared
123