Article
J. Agric. Food Chem., Vol. 57, No. 18, 2009 8521
(4-Fluorophenyl)(3-nitrobenzylidene)amine (7) (13 ). Yield:
68%; yellow solid. Melting point: 90 °C . IR: 3078, 1626, 1526, 1440, 1094.
1H NMR: 7.10-7.13 (m, 1H, H-3-phenyl), 7.21-7.24 (m, 2H, H-4, H-6-
phenyl), 7.27-7.29 (m, 1H, H-2-phenyl), 7.63-7.67 (m, 1H, H-5-
benzylidene), 8.21-8.23 (m, 1H, H-6-benzylidene), 8.30 (m, 1H, H-4-
benzylidene), 8.34 (dd, J=0.8, 3.6 Hz, 1H, H-2- benzylidene), 8.52 (s,
1H, NdCH). HRMS calculated for C13H9FN2O2: 244.0648, found
244.2213 (Mþ).
(3-Fluorophenyl)(3-nitrobenzylidene)amine (8). Yield: 76%;
light yellow solid. Melting point: 62 °C. IR: 3073, 1632, 1585, 1474, 1077.
1H NMR: 6.90-6.93 (m, 1H, H-4-phenyl), 6.96-6.98 (m, 1H, H-5-
phenyl), 7.01-7.04 (m, 1H, H-2-phenyl), 7.35 -7.41 (m, 1H, H-6-phenyl),
7.52-7.70 (m, 1H, H-5-benzylidene), 8.34 (m, 1H, H-4-benzylidene),
8.36-8.37 (m, 1H, H-6-benzylidene), 8.53 (s, 1H, NdCH), 8.73-8.75
(m, 1H, H-2-benzylidene). HRMS calculated for C13H9FN2O2: 244.0648,
found 244.2218 (Mþ).
(2-Fluorophenyl)(3-nitrobenzylidene)amine (9). Yield: 74%;
yellow solid. Melting point: 85 °C. IR: 3085, 1629, 1583, 1456, 1087.
1H NMR: 7.15-7.23 (m, 3H, H-3, H-4, H-5-phenyl), 7.25-7.28 (m, 1H,
H-6-phenyl), 8.28-8.31 (m, 1H, H-5-benzylidene), 8.34-8.35 (m, 2H,
H-4, H-6-benzylidene), 8.46-8.50 (m, 1H, H-2-benzylidene), 8.64 (s,
1H, NdCH). HRMS calculated for C13H9FN2O2: 244.0648, found
244.6591 (Mþ).
Figure 1. Synthesis of substituted monoimines.
Furan-2-yl(3-nitrobenzylidene)amine (10). Yield: 78%; yellow
solid. Melting point: 67 °C. IR: 3086, 1615, 1531, 1499, 1221. 1H NMR:
6.30 (d, J = 3.04 Hz, 1H, H-3-phenyl), 6.36-6.38 (m, 1H, H-4-phenyl),
7.40-7.50 (m, 1H, H-5-phenyl), 7.56-7.62 (m, 1H, H-5-benzylidene), 8.11
(m, 1H, H-6-benzylidene), 8.26-8.30 (m, 1H, H-4-benzylidene), 8.40 (s,
1H, NdCH), 8.58-8.59 (m, 1H, H-2-benzylidene). HRMS calculated for
C11H8N2O3: 216.0535, found 216.1938 (Mþ).
(3-Nitrobenzylidene)(2,4,5-trichlorophenyl)amine (11). Yield:
74%; yellow solid. Melting point: 162 °C. IR: 2955, 1613, 1526, 1456, 1350,
1079, 736. 1H NMR: 6.85 (s, 1H, H-3-phenyl), 7.32 (s, 1H, H-6-phenyl),
7.69-7.79 (m, 2H, Ar-H-5, H-6-benzylidene), 8.24 (m, 1H, H-4-benzyl-
idene), 8.47-8.51 (m, 1H, H-2-benzylidene), 8.72 (s, 1H, NdCH). EI-MS
(m/z): 329.1 (Mþ þ H), 331.1 (Mþ þ 2), 333.1 (Mþ þ 4).
Figure 2. Synthesis of substituted diimines.
H-5-benzylidene), 8.22 (d, J = 8.8 Hz, 1H, H-6-benzylidene), 8.89 (s,
1H, N = CH). HRMS calculated for C13H8Cl2FN: 268.0018, found
268.1136 (Mþ).
(2,6-Dichlorobenzylidene)(4-fluorophenyl)amine (12) (14 ).
Yield: 80%; yellow solid. Melting point: 128 °C. IR: 2957, 1634, 1521,
1431, 1375, 1094, 771. 1H NMR: 7.08-7.11 (m, 1H, H-3-benzylidene),
7.13-7.15 (m, 1H, H-5-benzylidene), 7.23-7.25 (m, 2H, H-3, H-5-
phenyl), 7.27-7.30 (m, 2H, H-2, H-6-phenyl), 7.38-7.41 (m, 1H, H-4-
benzylidene), 8.65 (s, 1H, NdCH). HRMS calculated for C13H8Cl2FN:
268.0018, found 267.1173 (Mþ - H).
(2,4-Dichlorobenzylidene)(3-fluorophenyl)amine (2). Yield:
74%; white solid. Melting point: 85 °C. IR: 3026, 1615, 1462, 1099, 722. 1H
NMR: 6.62-7.02 (m, 3H, H-2, H-4, H-5-phenyl), 7.32-7.40 (m, 2H, H-6-
phenyl, H-5-benzylidene), 7.46 (d, J=2 Hz, 1H, H-3-benzylidene), 8.20 (d,
J=9 Hz, 1H, H-6-benzylidene), 8.85 (s, 1H, NdCH). HRMS calculated
for C13H8Cl2FN: 268.0018, found 268.1121 (Mþ).
(2,6-Dichlorobenzylidene)(3-fluorophenyl)amine (13). Yield:
69%; white solid. Melting point: 72 °C. IR: 2922, 1621, 1584, 1439, 773. 1H
NMR: 6.95-6.98 (m, 1H, 4-Ar-H-4- phenyl), 7.01 (m, 1H, H-5-phenyl),
7.04-7.06 (m, 1H, H-2-phenyl), 7.08-7.11 (m, 1H, H-6-phenyl),
7.22-7.26 (m, 1H, H-5-benzylidene), 7.29-7.34 (m, 1H, H-3-benzyl-
idene), 7.36-7.41 (m, 1H, H-4-benzylidene), 8.65 (s, 1H, NdCH). EI-
MS (m/z): 268.3 (Mþ), 270.2 (Mþ þ 2), 272.2 (Mþ þ 4).
(2,4-Dichlorobenzylidene)(2-fluorophenyl)amine (3). Yield:
76%; White solid. Melting point: 102 °C. IR: 3029, 1620, 1463, 1099, 741.
1H NMR: 7.07-7.13 (m, 2H, H-3, H-5-phenyl), 7.22-7.25 (m, 2H, H-4,
H-6-phenyl), 7.33-7.35 (d, J=1.4 Hz, 1H, H-3-benzylidene), 7.42-7.46
(m, 1H, H-5-benzylidene), 8.19 (d, J=8 Hz, 1H, H-6- benzylidene), 8.83 (s,
1H, NdCH). HRMS calculated for C13H8Cl2FN: 268.0018, found
268.0231 (Mþ).
(2,6-Dichlorobenzylidene)(2-fluorophenyl)amine (14). Yield:
83%; white solid. Melting point: 82 °C. IR: 3021, 1612, 1076, 756. 1H
NMR: 6.74-6.79 (m, 1H, H-4-phenyl), 6.95-6.97 (m, 1H, H-5-phenyl),
7.13-7.16 (m, 2H, H-3, H-6-phenyl), 7.18-7.25 (m, 1H, H-4-
benzylidene), 7.28-7.31 (m, 1H, H-3-benzylidene), 7.38-7.41 (m, 1H,
H-5-benzylidene), 8.75 (s, 1H, NdCH). EI-MS (m/z): 268.3 (Mþ), 270.2
(Mþ þ 2), 272.2 (Mþ þ 4).
(2,4-Dichlorobenzylidene)furan-2-ylamine (4). Yield: 83%;
yellow solid. Melting point: 50 °C . IR: 3076, 1466, 1096, 736. 1H
NMR: 6.27-6.28 (m, 1H, H-5-furyl), 6.34-6.36 (m, 1H, H-4-furyl),
7.24-7.28 (m, 2H, H-3-furyl, H-5-benzylidene), 7.39 (d, J=1.8 Hz, 1H,
H-3-benzylidene), 7.90 (d, J=8.20 Hz, 1H, H-6-benzylidene), 8.71 (s, 1H,
NdCH). HRMS calculated for C11H7Cl2NO: 238.9705, found 240.0865
(Mþ þ H).
(2,6-Dichlorobenzylidene)furan-2-ylamine (15). Yield: 77%;
yellow liquid. IR: 3078, 1650, 1580, 1431, 1326, 1011, 778. 1H NMR:
6.16-6.28 (m, 1H, H-3-phenyl), 6.34-6.38 (m, 1H, H-4-phenyl),
7.20-7.24 (m, 1H, H-5-phenyl), 7.28-7.31 (m, 1H, H-5-benzylidene),
7.36-7.39 (m, 1H, H-3-benzylidene), 7.42-7.43 (m, 1H, H-4-
benzylidene), 8.50 (s, 1H, NdCH). HRMS calculated for C11H7Cl2NO:
238.9905, found 240.0845 (Mþ þ H).
(2,4-Dichlorobenzylidene)(2,4,5-trichlorophenyl)amine (5).
Yield: 65%; yellow color solid. Melting point: 118 °C. IR: 2955, 1621,
1583, 1470, 1369, 1079, 732. 1H NMR: 7.16 (s, 1H, H-3-phenyl), 7.32-
7.38 (m, 1H, H-5-benzylidene), 7.47 (d, J=1.8 Hz, 1H, H-3-benzylidene),
7.56 (s, 1H, H-6-phenyl), 8.22 (d, J = 8.47 Hz, 1H, H-6-benzylidene),
8.76 (s, 1H, NdCH). HRMS calculated for C13H6Cl5N: 350.8943, found
350.4580 (Mþ).
N,N0-Bis(2,4-dichlorobenzylidene)propane-1,3-diamine
(16) (15 ). Yield: 77%; white solid. Melting point: 105 °C. IR: 3074,
(2,4-Dichlorobenzylidene)(2,3,4,5,6-pentafluorophenyl)amine
(6). Yield: 66%; white solid. IR: 3065, 1532, 1422, 1083, 996, 893, 753. 1H
NMR: 7.34-7.40 (m, 1H, H-5-benzylidene), 7.88 (d, J=6 Hz, 1H, H-3-
benzylidene), 8.22 (d, J = 6.4 Hz, 1H, H-6-benzylidene), 9.01 (s,
1H, NdCH). HRMS calculated for C13H4Cl2F5N: 338.9641, found
338.0766 (Mþ).
1
2943-2830, 1638, 1467. H NMR: 2.12 (m, 2H, 2-CH2), 3.73-3.78 (m,
4H, 1,3-CH2), 7.24-7.28 (m, 2H, H-5-Ar), 7.38 (d, J = 2.01 Hz, 2H, H-3-
Ar), 7.97 (d, J = 8.49 Hz, 2H, H-6-Ar), 8.60 (s, 2H, NdCH). HRMS
calculated for C17H14Cl4N2: 385.9911, found 385.1175 (Mþ).