C.A.B. Rodrigues et al. / Dyes and Pigments 99 (2013) 642e652
645
746.45, 684.73, 553.57, 410.84 cmꢀ1. 1H NMR (400 MHz, CDCl3)
2xCHAr), 8.00 (d, J ¼ 8.2 Hz, 2H, 2xCHAr), 7.06 (s, 1H, CH]C), 6.73
(d, J ¼ 7.3 Hz, 4H, 4xCHAr), 3.09 (s, 12H, 2xN(CH3)2). 13C NMR
d
8.19 (d, J ¼ 7.1 Hz, 2H, 2xArH), 8.04 (d, J ¼ 9.1 Hz, 2H, 2xArH),
7.44 (dt, J ¼ 16.7, 7.1 Hz, 3H, 3xArH), 7.08 (s, 1H, CH]C), 6.76 (d,
(101 MHz, CDCl3) d 169.21, 161.51, 152.99, 151.61, 134.12 (CHAr),
J ¼ 9.1 Hz, 2H, 2xArH), 3.11 (s, 6H, eN(CH3)2). 13C NMR (101 MHz,
129.69 (CHAr), 129.59, 112.84, 111.83(CHAr), 111.41(CHAr), 40.11
(2xN(CH3)2). MS (ESIþ) m/z calc for [C20H21N3O2þ1]: 336.17,
found: 336.2 [M þ H]þ, Elemental analysis: (Found: %N, 12.46; %
C, 71.44; %H, 6.58. Calc. for C20H21N3O2 % N,12.53, % C, 71.62, % H,
6.31).
CDCl3)
d 168.49, 163.98, 153.50, 134.21, 134.16, 131.94, 130.30,
130.25, 128.77, 127.69, 111.56, 40.18(-N(CH3)2). MS (ESIþ) m/z
calc for [C18H16N2O2 þ 1]: 293.12, found: 293.2 [M þ H]þ.
Elemental analysis: (Found: %N, 9.39; %C, 73.76; %H, 5.77. Calc.
for C18H16N2O2 % N, 9.58, % C, 73.95, % H, 5.52).
Compound IX: (Z)-4-(4-((E)-2-(1H-benzo[d]imidazol-2-yl)vinyl)
benzylidene)-2-phenyloxazol-5(4H)-one, Light orange solid, yield:
Compound V: (Z)-4-[4-(dimethylamino)benzylidene]-2-phenyl-
oxazol-5(4H)-one, Bright orange needles. Yield: 45% (recrystal-
lized from ethyl acetate).M.p.: 218e219 ꢁC. IR (KBr): 3080.32,
3035.96, 3022.45, 3005.1, 1784.15, 1762.94, 1647.21, 1606.7,
1595.13, 1581.63, 1568.13, 1529.55, 1490.97, 1448.54, 1375.25,
ꢁ
52% (washed with methanol). M.p.: 233 C (decomposition). IR
(KBr): 3066.82, 3034.03, 2995.45, 1788.01, 1762.94, 1637.56,
1597.06,1560.41,1419.61,1325.1,1313.52,1298.09,1163.08, 983.7,
700.16 cmꢀ1 1H NMR (DMSO-d6, 400 MHz)
. d (ppm) 8.38 (d,
1323.17, 1296.16, 1195.87, 1161.15, 1126.43, 856.39, 813.96 cmꢀ1
.
J ¼ 8.3 Hz, 2H), 8.16 (d, J ¼ 7.3 Hz, 2H), 7.84 (d, J ¼ 8.3 Hz, 2H),
7.79e7.61 (m, 4H), 7.57 (dd, J ¼ 5.9, 3.2 Hz, 2H), 7.39 (t, J ¼ 8.2 Hz,
2H), 7.21 (dd, J ¼ 6.0, 3.1 Hz, 2H). 13C NMR (DMSO-d6, 101 MHz)
1H NMR (CDCl3, 400 MHz)
d
(ppm) 8.14 (d, J ¼ 6.9 Hz, 4H,
4xCHAr), 7.65e7.42 (m, 3H, 3xCHAr), 7.20 (s, 1H, eCH¼Ce]),
6.75 (d, J ¼ 8.8 Hz, 2H, 2xCHAr), 3.09 (s, 6H,- N(CH3)2).13C NMR
d
(ppm) 207.05, 167.35, 163.52, 151.04, 138.84, 134.22, 134.18,
(CDCl3, 101 MHz)
d
(ppm) 168.55, 160.58, 152.16, 134.86, 133.35,
133.87, 133.65, 133.33, 130.40, 129.85, 128.49, 128.02, 125.58,
122.83, 120.10. MS (ESIþ) m/z calc for [C25H17N3O2þ1]: 392.42,
found: 424.3 [M þ MeOH]þ, 392.2 [M þ H]þ, Elemental analysis:
(Found: %N, 9.74; %C, 69.79; %H, 5.40. Calc. for C25H17N3O2.2H2O:
% N, 9.83, % C, 70.25, % H, 4.95).
Compound X: (Z)-4-(4-((E)-2-(1H-benzo[d]imidazol-2-yl)vinyl)
benzylidene)-2-(4-nitrophenyl)oxazol-5(4H)-one, Orange solid,
yield: 69%, (washed with methanol), M.p.: 247 ꢁC (decomposi-
tion) IR (KBr): 3421.72, 3367.71, 3327.21, 3170.97, 3107.32,
3049.46, 2924.09, 2854.65, 2752.42, 1795.73, 1653, 1593.2,
1521.84, 1355.96, 1311.59, 1228.66, 1161.15, 1099.43, 985.62,
864.11, 815.89, 742.59, 705.95 cmꢀ1, 1H NMR (400 MHz, DMSO-
132.30, 128.79, 128.33, 127.77, 126.34, 121.82, 111.82, 40.11
(N(CH3)2). HRMS calc for C18H16N2O2: 292.120629, found:
292.120841. MS (ESIþ) m/z calc for [C18H16N2O2 þ 1]: 293.12,
found: 315.1 [M þ Na]þ, 293.1 [M þ H]þ. Elemental analysis:
(Found: %N, 9.32; %C, 73.93; %H, 5.30. Calc. for C18H16N2O2: % N,
9.88, % C, 73.95, % H, 5.52).
Compound VI: (Z)-4-(4-(dimethylamino)benzylidene)-2-(4-nitro-
phenyl)oxazol-5(4H)-one, Dark green solid, yield: 20%, (washed
with methanol), M.p.: 275e277 ꢁC(decomposition), IR (KBr):
3072.6, 2912.51, 2368.59, 1786.08, 1762.94, 1639.49, 1604.77,
1585.49, 1544.98, 1508.33, 1502.55, 1483.26, 1436.97, 1381.03,
1325.1, 1313.52, 1292.31, 1261.45, 1236.37, 1192.01, 1159.22,
1126.43, 1095.57, 1068.56, 979.84, 943.19, 891.11, 854.47, 800.46,
d6)
d
8.44 (d, J ¼ 8.9 Hz, 2H, 2xArH), 8.38 (t, J ¼ 9.2 Hz, 4H, 4xArH),
7.85 (d, J ¼ 8.4 Hz, 2H, 2xArH), 7.79 (d, J ¼ 16.5 Hz, 1H, eCH]C),
7.61 (dd, J ¼ 6.0, 3.1 Hz, 2H, 2xArH), 7.50 (s, 1H, eCH]C), 7.40 (d,
702.09 cmꢀ1 1H NMR (300 MHz, CDCl3)
d
8.32 (td, J ¼ 9.1, 6.9 Hz,
4H, 4 xCHAr), 8.14 (d, J ¼ 8.7 Hz, 2H, 2 xCHAr), 7.31 (s, 1H), 6.76 (d,
J ¼ 16.5 Hz, 1H, eCH]C), 7.27 (dd, J ¼ 6.0, 3.1 Hz, 2H, 2xArH).13
C
J ¼ 9.2 Hz, 2H, 2 xCHAr), 3.14 (s, 6H, (eN(CH3)2))., 13C NMR
NMR (101 MHz, DMSO-d6)
d 166.89, 162.01, 150.49 (2xCHAr),
(101 MHz, CDCl3)
d
167.72, 152.72, 135.90, 135.49, 132.00, 128.38,
150.43, 138.89, 134.30, 133.63 (2xCHAr), 132.31, 131.24, 129.76
(2xCHAr), 128.28 (2xCHAr), 124.88 (2xCHAr), 124.14, 123.59
(2xCHAr),115.25. MS (ESIþ) m/z calc for [C25H16N4O4 þ 1]: 437.12
found: 437.2 [M þ H]þ. Elemental analysis: (Found: %N,11.30; %C,
61.24; %H, 4.71. Calc. for C25H16N4O4.3H2O: % N,11.42, % C, 61.22, %
H, 4.52).
127.48, 124.05, 111.99, 77.33, 77.02, 76.70, 40.17. MS (ESIþ) m/z
calc for [C18H15N3O4þ1]: 338.11 found: 392.1 [M þ MeOH þ Na]þ,
360.1 [M þ Na]þ, 338.1 [M þ H]þ. Elemental analysis: (Found: %N,
12.59; %C, 64.08; %H, 4.60. Calc. for C18H15N3O4 % N, 12.46, % C,
64.09, % H, 4.48).
Compound VII: (Z)-4-(4-(4-(dimethylamino)benzylidene)-5-oxo-
4,5-dihydrooxazol-2-yl)benzonitrile, Dark red solid, yield: 37%
(recristalization from ethyl acetate), M.p.: 238e240 ꢁC. IR (KBr):
3440.19, 2922.28, 2234.63, 1788.84, 1767.84, 1641.49, 1611.59,
1602.91, 1567.23, 1559.51, 1530.58, 1380.13, 1328.05, 1198.81,
1187.24, 1165.05, 1128.41, 1098.51, 981.81, 893.08, 848.72, 811.1,
Compound XI: 4-((Z)-4-(4-((E)-2-(1H-benzo[d]imidazol-2-yl)vi-
nyl)benzylidene)-5-oxo-4,5-dihydrooxazol-2-yl)benzonitrile,
Orange solid, yield: 39% (recristalization from ethyl acetate),
M.p.: 221e223 ꢁC. IR (KBr): 3438.26, 2360.01, 2332.04, 2327.22,
2229.81, 1793.88, 1771.69, 1708.04, 1648.24, 1643.42, 1633.78,
1598.09,1372.41,1325.15,1312.62,1304.9,1291.4,1182.41,1161.2,
688.62, 559.38, 412.78 cmꢀ1. 1H NMR (400 MHz, CDCl3)
d
8.22 (d,
1099.47, 983.74, 852.57, 814.96, 737.8, 687.65, 565.17 cmꢀ1
.
1H
8.43 (d, J ¼ 8.4 Hz,
J ¼ 8.1 Hz, 2H, 2 xCHAr), 8.13 (d, J ¼ 8.1 Hz, 2H, 2 xCHAr), 7.78 (d,
J ¼ 8.1 Hz, 2H, 2 xCHAr), 7.29 (s, 1H, eC]CH-), 6.77 (d, J ¼ 8.6 Hz,
2H, 2 xCHAr), 3.13 (s, 6H, (eN(CH3)2). 13C NMR (101 MHz, CDCl3)
NMR (400 MHz, DMSO-d6, 2 drops of TFA)
d
2H, 2xArH), 8.28 (d, J ¼ 8.5 Hz, 2H, 2xArH), 8.09 (d, J ¼ 8.5 Hz,
2H, 2xArH), 8.02 (d, J ¼ 16.6 Hz, 1H, eCH]CHe), 7.88 (d,
J ¼ 8.4 Hz, 2H, 2xArH), 7.81 (dd, J ¼ 6.2, 3.1 Hz, 2H, 2xArH), 7.56
(dd, J ¼ 6.1, 3.1 Hz, 2H, 2xArH), 7.47 (s, 1H, eCH]Ce), 7.44 (d,
J ¼ 16.6 Hz, 1H, eCH]CHe).13C NMR (101 MHz, DMSO-d6, drops
d
143.57, 135.46, 135.35, 132.51, 130.33, 127.98, 127.36, 112.22,
111.80, 40.32 (eNCH3), 40.21 (eNCH3). MS (ESIþ) m/z calc for
Na]þ, 318.3
[C19H15N3O2þ1]: 318.12, found: 340.1 [M
þ
[M þ H]þ, Elemental analysis: (Found: %N, 13.03; %C, 71.85; %H,
4.68. Calc. for C19H15N3O2 % N, 13.24, % C, 71.91, % H, 4.76).
Compound VIII: (Z)-4-(4-(dimethylamino)benzylidene)-2-(4-
(dimethylamino)phenyl)oxazol-5(4H)-one, Orange solid, yield:
31%, (washed with methanol), M.p.: 268e270 ꢁC, IR (KBr):
2899.01, 2856.58, 2812.21, 1774.51, 1757.15, 1701.22, 1647.21,
1597.06, 570.06, 1517.98, 1502.55, 1483.26, 1433.11, 1413.82,
1363.67, 1319.31, 1301.95, 1253.73, 1230.58, 1186.22, 1157.29,
1122.57, 1101.35, 1066.64, 1020.34, 1004.91, 983.7, 945.12,
885.33, 864.11, 815.89, 790.81, 758.02, 736.81, 692.44, 530.42,
of TFA) d: 172.47, 166.75, 162.70, 148.16, 141.75, 136.80, 134.34,
133.60, 133.05, 131.86, 131.34, 129.55, 129.09, 126.66, 118.47,
115.92, 114.28, 112.05. MS (ESIþ) m/z calc for [C26H16N4O2þ1]:
417.13, found: 417.26 [M þ H]þ, Elemental Analysis: (Found: %N,
12.45; %C, 69.91; %H, 5.24. Calc. for C26H16N4O2.CH3OH.H2O: % N,
12.01, % C, 69.52, % H, 4.75).
Compound XII: (Z)-4-(4-((E)-2-(1H-benzo[d]imidazol-2-yl)vinyl)
benzylidene)-2-(4-(dimethylamino)phenyl)oxazol-5(4H)-one, Or-
ange solid, yield: 34%, (washed with methanol), M.p.: 201e
203 ꢁC (decomposition), IR (KBr): 3689.83, 3441.01, 3421.72,
2958.8, 2929.87, 1780.3, 1762.94, 1701.22, 1637.56, 1618.28,
414.7 cmꢀ1. 1H NMR (400 MHz, CDCl3)
d
8.12 (d, J ¼ 8.4 Hz, 2H,