Molecules, 2002, 7
242
residue was dissolved in dichloromethane. The mixture was cooled, stirred, and filtrated. After
removing of the remaining phthalhydrazide, the filtrate was evaporated to give the crude crystalline
solid 3a,b.
3,5-Di(aminoxymethyl)-2,6-diphenyl-4H-pyran-4-one (3a). Colourless crystals (91.5% yield), m.p.
1
127-129°C; H-NMR δ: 4.65 (s, 4H, -CH2O-), 5.3 (br, 4H, -NH2), 7.35-7.55 (m, 10H, phenyl-H); IR:
3300, 3150, 3050, 2950, 2872, 1643, 1495, 1448 cm-1; MS: m/z 338; Anal. Calcd. for C19H18N2O4: C,
67.44; H, 5.36; N, 8.28. Found: C, 67.28; H, 5.23; N, 8.30.
2,6-Di(aminoxymethyl)-3,5-diphenyl-4H-pyran-4-one (3b). Colourless crystals (67.6% yield), m.p.
1
131.5-133°C; H-NMR δ: 4.64 (s, 4H, -CH2O-), 5.37 (br, 4H, -NH2), 7.23 (m, 10H, phenyl-H); IR:
3300, 3250, 3140, 3050, 2960, 1640, 1622, 1570, 1413 cm-1; MS: m/z 338; Anal. Calcd. for
C19H18N2O4: C, 67.44; H, 5.36; N, 8.28. Found: C, 66.97; H, 5.27; N, 8.20.
General procedure for preparation of aldoxime derivatives of 4H-pyran-4-ones 4-7a,b.
To a stirred suspenion of compound 3a or 3b (0.5 g, 1.47 mmol) and 4Å molecular sieves (1.5g) in
dry dichloromethane (15 mL) at 0°C under nitrogen was slowly added benzaldehyde (0.31 g, 2.9
mmol) or 4-methylbenzaldehyde (0.36 g, 2.9 mmol). When the addition of aldehyde was complete, the
mixture was stirred at room temperature overnight. After filteration, the solvent was evaporated. The
resulting crude product was purified by column chromatography on silicagel, using 9:1 petroleum
ether - ethyl acetate as an eluent.
(E,E)-Benzal[(2,6-diphenyl-3,5-4H-pyran-4-one-diyl)bis(methylene)]dioxime (4a). Yellow oil (70.1 %
yield); 1H-NMR δ: 5.1 (s, 4H, -CH2O-), 7.2-7.85 (m, 20H, phenyl-H), 8.1 (s, 2H, -N=CH-); IR: 3050,
3017, 2983, 2875, 1644, 1607, 1500, 1446 cm-1; MS: m/z 514; Anal. Calcd. for C33H26N2O4: C, 77.03;
H, 5.09; N, 5.44. Found: C, 77.18; H, 5.10; N, 5.38.
(E,E)-Benzal[(3,5-diphenyl-2,6-4H-pyran-4-one-diyl)bis(methylene)]dioxime (4b). Yellow oil (68%
1
yield); H-NMR δ: 5.1 (s, 4H, -CH2O-), 7-7.6 (m, 20H, phenyl-H), 8.1 (s, 2H, -N=CH-); IR: 3050,
3010, 2950, 2900, 1630, 1470, 1405 cm-1; MS: m/z 514; Anal. Calcd. for C33H26N2O4: C, 77.03; H,
5.09; N, 5.44. Found: C, 76.92; H, 5.10; N, 5.30.
(E,Z)-Benzal[(2,6-diphenyl-3,5-4H-pyran-4-one-diyl)bis(methylene)]dioxime (5a). Yellow oil (10.5%
1
yield); H-NMR δ: 5.1 (s, 4H, -CH2O-), 7.1-7.8 (m, 20H, phenyl-H; 1H, -N=CH-), 8.1 (s, 1H,
-N=CH-); IR: 3050, 3010, 2980, 2872, 1640, 1600, 1480, 1440 cm-1; MS: m/z 514; Anal. Calcd. for
C33H26N2O4: C, 77.03; H, 5.09; N, 5.44. Found: C, 77.20; H, 4.92; N, 5.34.
(E,Z)-Benzal[(3,5-diphenyl-2,6-4H-pyran-4-one-diyl)bis(methylene)]dioxime (5b). Yellow oil (10%
1
yield); H-NMR δ: 5.15 (s, 4H, -CH2O-), 7-7.6 (m, 20H, phenyl-H; 1H, -N=CH-), 8.1 (s, 1H,
-N=CH-); IR: 3050, 3010, 2985, 1640, 1600, 1480, 1440 cm-1; MS: m/z 514; Anal. Calcd. for
C33H26N2O4: C, 77.03; H, 5.09; N, 5.44. Found: C, 77.29; H, 5.01; N, 5.32.