Compound 2b: 4-Hydroxyphenylcalix[4]resorcinarene (RESOH) – Pink powder; Yield:
1
9
0%; MP: > 250 � ; m/z: 891.25 [M+K]‾; H-NMR (400 MHz, DMSO-d ) δ ppm: 8.71 (s,
6
4
H, ArOH), 8.51(s, 4H, ArOH), 8.40 (d, 4H, ArOH), 6.34 – 6.64 (m, 16H, ArCH), 6.31 (d,
H, ArH), 6.29(s, 2H, ArH), 6.09 (d, 2H, ArH), 5.92 (s, 2H, ArCH), 5.43 and 5.53 (s, 2H,
2
1
3
ArCHAr);
C-NMR (100 MHz, DMSO-d ) δ ppm: 41.18, 101.56, 101.72,
6
1
1
02.01, 113.82, 120.78, 121.84, 128.47, 129.48, 129.74, 131.53, 134.39, 135.91, 152.22,
52.26, 152.54, 154.18, 154.35; IR (KBr) ῡ: 3369 (br), 3028 (w), 2908 (w), 1618 (vs), 1517
-1
(s), 1241 (s), 1075(s), 826(s),550 (s) cm
2
.4.2. Procedure used for the synthesis of Octa and Dodecacyanomethoxycalix[4]
resorcinarenes
Compound 2a/2b (0.6 mmol), chloroacetonitrile (15 mmol), potassium carbonate (8 mmol),
and 5mL of polyethylene glycol 400 were mixed in dry DMF. The mixture was stirred at
room temperature for 4 – 5h. The filtrate was added to 0.01N aqueous HCl (500 mL)
solution; precipitate obtained was washed with distilled water up to neutral pH. The
purification was done by flash column chromatography on silica gel using ethyl acetate:
methanol (9:1v/v) solvent. The product obtained was characterized by Mass spectroscopy,
1
13
FT-IR, H NMR and C NMR.
Compound 3a: Phenyl(octacyanomethoxy)calix[4]resorcinarene (RESCN) - Straw coloured
1
powder; Yield 72-75%; m/z: 1139.31 [M+K]‾; H-NMR (400 MHz, DMSO-d ) δ ppm: 6.9 -
6
7
.05 (br, 16H, ArH), 6.55 - 6.62 (m, 8H, ArH), 6.36 (m, 2H, ArH), 6.05, 5.64 - 5.66 (m, 2H,
1
3
ArH), 5.50 - 5.61(m, 4H, ArCH), 4.88 – 5.11(br, 16H, -OCH -CN); C-NMR (100 MHz,
2
DMSO-d ) δ ppm: 54.11, 54.42, 60.15, 69.74, 72.25, 116.14, 125.47, 127.90, 128.42, 152.85;
6
IR (KBr) ῡ: 3415 (m), 3027 (m), 2925 (s), 2260 (sh), 1606 (vs), 1500 (vs), 1291 (vs), 1102
-
1
(
s), 1038 (s), 896 (w), 701 (s) cm .
Compound 3b: 4-Cyanomethoxyphenyl(octacyanomethoxy)calix[4]resorcinarene
RESOHCN) Straw coloured powder; Yield 75-80%; m/z: 1359.29 [M+K]‾ ; H-NMR (400
MHz, DMSO-d ) δ ppm: 7.04 (s, 8H, ArH), 6.96 (s, 8H, ArH), 6.69 - 6.71 (m, 2H, ArH), 6.15
1
1
(
-
6
–
6.53 (m, 4H, ArH), 5.14 (s, 2H, ArH), 5.61-5.62 (m, 4H, ArCH), 4.92 – 5.16 (m, 24H,
1
3
-
OCH -CN); C-NMR (100 MHz, DMSO-d ) δ ppm: 41.52, 53.31, 54.46, 69.73, 99.9,
2
6
1
1
2
00.01, 100.05, 114.23, 116.17, 116.41, 116.52, 125.54, 126.05, 126.48, 129.01, 134.64,
35.45, 152.48, 152.73, 152.90, 154.55, 154,66; IR (KBr) ῡ: 3433(m), 3055 (sh), 2977 (m),
-1
300(sh), 1600 (s), 1508 (vs), 1286 (s), 1042 (vs), 821 (m), 677 (w) m .