Synthesis, chemical properties, and antimicrobial activity
535
6H, 2CH3), 2.41 (dd, JAB = 16.4 Hz, JAX = 3.9 Hz, 2H,
2(HA, CH2)), 3.02 (dd, JAB = 16.5 Hz, JBX = 5.9 Hz, 2H,
2(HB, CH2)), 3.88–3.98 (m, 2H, 2CH), 6.99–8.07 (m, 12H,
HAr), 10.39 (s, 2H, 2NH) ppm; 13C NMR (75 MHz,
DMSO-d6): d = 18.42 (CH3), 37.68 (COCH2), 51.22
(NCH2), 114.49, 115.27, 122.23, 126.02, 129.37, 130.91,
134.32, 141.65, 145.45, 151.27 (CAr), 156.55, 169.91,
then cooled. Crystals formed were filtered and washed with
H2O to afford 0.11 g (90%) 8. M.p.: 215–216 °C; Ref. [23]
m.p.: 215–216 °C.
Method B. A mixture of 2 g 5b (4.9 mmol), 10 cm3
AcOH, and 30 cm3 concentrated HBr was heated under
reflux for 1.5 h and then cooled. Crystals formed were
filtered and washed with H2O to afford 0.87 g (85%) 8.
Melting point and NMR spectral data of 8 synthesized by
method B are the same as the ones obtained by method A.
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179.90 (CO) ppm; IR (KBr): m = 3,188 (NH), 1,717,
1,683, 1,671 (C=O) cm-1; MS (APCI?, 25 eV): m/z
(%) = 595 [M?H]? (100).
General procedure for preparation of diphenoxy-
substituted naphthoquinone derivatives 9a–9c
and 10a–10c
1,1’-[(1,4-Dihydro-1,4-dioxo-2,3-naphthalenediyl)bis-
(oxy-4,1-phenylene)]bis(5,6-dihydropyrimidine-
2,4(1H,3H)-dione) (10a, C30H22N4O8)
1
Yield 4.8 g (85%); m.p.: 262–263 °C (from dioxane); H
A mixture of 2.27 g 1 (10.0 mmol), the appropriate 2a–2c
or 3a–3c (20.0 mmol), 3 g Na2CO3, and 25 cm3 DMSO
was stirred at room temperature for 48 h, and afterwards
diluted with 75 cm3 H2O. The precipitate formed was fil-
tered, washed with H2O, and purified by recrystallization or
column chromatography.
NMR (300 MHz, DMSO-d6): d = 2.68 (t, J = 6.6 Hz, 4H,
2COCH2), 3.72 (t, J = 6.6 Hz, 4H, 2NCH2), 7.16, 7.22
(2d, J = 9.2 Hz, 8H, HAr), 7.89–8.05 (m, 4H, HAr), 10.34
(s, 2H, 2NH) ppm; 13C NMR (75 MHz, DMSO-d6):
d = 30.98 (COCH2), 44.67 (NCH2), 116.09, 126.01,
126.63, 130.92, 134.30, 137.02, 145.99, 152.15 (CAr),
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154.42, 170.57, 179.96 (CO) ppm; IR (KBr): m = 3,069
1,1’-[(1,4-Dihydro-1,4-dioxo-2,3-naphthalenediyl)bis-
(oxy-3,1-phenylene)]bis(5,6-dihydropyrimidine-
2,4(1H,3H)-dione) (9a, C30H22N4O8)
(NH), 1,727, 1,693, 1,684 (C=O) cm-1; MS (APCI?,
25 eV): m/z (%) = 567 [M?H]? (100).
1
Yield 5.0 g (87%); m.p.: 268–269 °C (from dioxane); H
1,1’-[(1,4-Dihydro-1,4-dioxo-2,3-naphthalenediyl)bis-
(oxy-4,1-phenylene)]bis(5,6-dihydro-5-methylpyrimidine-
2,4(1H,3H)-dione) (10b, C32H26N4O8)
NMR (300 MHz, DMSO-d6): d = 2.66 (t, J = 6.6 Hz, 4H,
2COCH2), 3.68 (t, J = 6.7 Hz, 4H, 2 NCH2), 6.98–8.07
(m, 12H, HAr), 10.37 (s, 2H, 2NH) ppm; 13C NMR
(75 MHz, DMSO-d6): d = 30.88 (COCH2), 44.43 (NCH2),
113.11, 113.52, 120.06, 126.04, 129.15, 130.89, 134.32,
143.01, 145.55, 151.90 (CAr), 156.43, 170.46, 179.92 (CO)
Yield 4.98 g (84%); m.p.: 288–289 °C (purified by column
chromatography, acetone:CHCl3 1:5, Rf = 0.64); 1H NMR
(300 MHz, DMSO-d6): d = 1.11 (d, J = 6.9 Hz, 6H,
2CH3), 2.80–2.88 (m, 2H, 2CH), 3.54–3.71 (m, 4H,
2CH2), 7.16, 7.22 (2d, J = 9.2 Hz, 8H, HAr), 7.89–8.05
(m, 4H, HAr), 10.32 (s, 2H, 2NH) ppm; 13C NMR
(75 MHz, DMSO-d6): d = 12.14 (CH3), 34.83 (COCH2),
50.89 (NCH2), 116.08, 125.99, 126.54, 130.92, 134.28,
136.93, 145.99, 152.13 (CAr), 154.40, 173.20, 179.94 (CO)
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ppm; IR (KBr): m = 3,216 (NH), 1,736, 1,690, 1,674
(C=O) cm-1; MS (APCI?, 25 eV): m/z (%) = 567
[M?H]? (100).
1,1’-[(1,4-Dihydro-1,4-dioxo-2,3-naphthalenediyl)bis-
(oxy-3,1-phenylene)]bis(5,6-dihydro-5-methylpyrimidine-
2,4(1H,3H)-dione) (9b, C32H26N4O8)
ꢀ
ppm; IR (KBr): m = 3,069 (NH), 1,735, 1,685, 1,668
(C=O) cm-1; MS (APCI?, 25 eV): m/z (%) = 595
[M?H]? (100).
1
Yield 5.3 g (89%); m.p.: 248–249 °C (from dioxane); H
NMR (300 MHz, DMSO-d6): d = 1.10 (d, J = 6.9 Hz,
6H, 2CH3), 2.75–2.88 (m, 2H, 2CH), 3.52–3.66 (m, 4H,
2CH2), 6.98–8.07 (m, 12H, HAr), 10.36 (s, 2H, 2NH) ppm;
13C NMR (75 MHz, DMSO-d6): d = 12.10 (CH3), 34.78
(COCH2), 50.63 (NCH2), 113.15, 113.42, 119.93, 126.04,
129.15, 130.89, 134.32, 142.95, 145.53, 151.92 (CAr),
1,1’-[(1,4-Dihydro-1,4-dioxo-2,3-naphthalenediyl)bis-
(oxy-4,1-phenylene)]bis(5,6-dihydro-6-methylpyrimidine-
2,4(1H,3H)-dione) (10c, C32H26N4O8)
Yield 4.9 g (82%); m.p.: 264–265 °C (from EtOH); 1H
NMR (300 MHz, DMSO-d6): d = 1.09 (d, J = 6.5 Hz,
6H, 2CH3), 2.42 (dd, JAB = 16.4 Hz, JAX = 3.6 Hz, 2H,
2(HA, CH2)), 3.06 (dd, JAB = 16.4 Hz, JBX = 6.0 Hz, 2H,
2(HB, CH2)), 3.89–3.98 (m, 2H, 2CH), 7.16, 7.21 (2d,
J = 9.1 Hz, 8H, HAr), 7.89–8.06 (m, 4H, HAr), 10.35 (s,
2H, 2NH) ppm; 13C NMR (75 MHz, DMSO-d6):
d = 18.38 (CH3), 37.70 (COCH2), 51.42 (NCH2), 116.31,
126.02, 128.73, 130.93, 134.30, 135.57, 145.79, 151.47
(CAr), 154.95, 170.02, 179.95 (CO) ppm; IR (KBr):
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156.42, 173.11, 179.91 (CO) ppm; IR (KBr): m = 3,182
(NH), 1,720, 1,692, 1,678 (C=O) cm-1; MS (APCI?,
25 eV): m/z (%) = 595 [M?H]? (100).
1,1’-[(1,4-Dihydro-1,4-dioxo-2,3-naphthalenediyl)bis-
(oxy-3,1-phenylene)]bis(5,6-dihydro-6-methylpyrimidine-
2,4(1H,3H)-dione) (9c, C32H26N4O8)
1
Yield 5.4 g (91%); m.p.: 197–198 °C (from dioxane); H
NMR (300 MHz, DMSO-d6): d = 1.07 (d, J = 6.5 Hz,
123