SYNTHESIS OF (E,E)-N1,N5-DISUBSTITUTED
1597
7.35 ppm and a triplet at 7.48 ppm, respectively. The
protons of benzylidene compounds IIIb–IIIg are
registered as two doublet signals at 7.91 (C2',6',2'',6'') and
C26H22N2O2. Calculated, %: С 79.16; Н 5.62; N 7.10;
O 8.11.
(E,E)-N1,N5-Di-(4',4''-dimethylbenzylidene-
amino)naphthalene-1,5-diamine (IIIc). Yield 67%,
bright yellow crystalline solid, decomp. 280°C. IR
spectrum, ν, cm–1: 3441, 2917, 2854, 1594, 1528,
1
7.43 ppm (C3',5',3'',5''). In the H NMR spectra of com-
pounds IIIh–IIIk containing two substituents in the
aromatic ring the benzylidene protons signals are
present as two doublets of doublets and a singlet at
7.12 (C6',6''), 6.95 (C5',5'') and 7.67 ppm (C2',2''),
respectively. The 1H NMR spectrum of compound IIIa
contains the benzylidene protons signals in the range
1
1371, 1774, 793. Н NMR spectrum, δН, ppm: 3.30 s
(12Н, СH3), 7.15 d (4H, С3',3''Н, С5',5''Н, J 7.5 Hz), 7.30
t (2Н, С3,7Н, J 5.2 Hz), 7.36 d (4Н, С2',2''Н, С6',6''Н, J
7.8 Hz), 7.43 d (2Н, С2,6Н, J 7.4 Hz), 7.65 d (2Н,
С4,8Н, J 7.7 Hz), 8.37 s (2Н, HC=N). Found, %: С
79.94; Н 6.75; N 13.31. C28H28N4. Calculated, %: С
79.97; Н 6.71; N 13.32.
of 8.04–8.07 (C2',2",C6',6''
)
and 7.50–7.55 ppm
(C3',3'',C4',4'',C5',5''), respectively.
1
According to the H NMR spectroscopy, the E,E-
isomer is predominant. The Z,Z-isomer of azomethine
is present in the reaction mixture only in trace
amounts. The corresponding signals of the N=HC,
C2',6',2'',6'' and C3',5',3'',5'' protons are shifted upfield by
0.1 ppm owing to the shielding by the naphthalene
moiety.
(E,E)-N1,N5-Di-(4',4''-fluorobenzilidene)naph-
thalene-1,5-diamine (IIId). Yield 90%, dark yellow
crystalline solid, mp 202–203°C. IR spectrum, ν, cm–1:
3063, 3039, 2923, 2877, 2856, 1623, 1591, 1506,
1
1225, 1150, 1092. Н NMR spectrum, δН, ppm: 7.22 d
(2Н, С2,6Н, J 7.8 Hz), 7.34–7.37 m (4H, С3',3''Н, С5',5''Н,
J 7.5 Hz), 7.50 t (2Н, С3,7Н, J 4.5 Hz), 8.07–8.13 m
(4Н, С2',2''Н, С6',6''Н, 2Н, С4,8Н), 8.66 s (2Н, 2HC=N).
Found, %: С 77.86; Н 4.32; F 10.26; N 7.55.
C24H16F2N2. Calculated, %: С 77.82; Н 4.35; F 10.26;
N 7.56.
(E,E)-N1,N5-Disubstituted benzilidenenaphthalene-
1,5-diamines (IIIa–IIIk) (general procedure). A
mixture of 0.01 mol of 1,5-diaminonaphthalene I and
0.02 mol of arylcarbaldehyde IIa–IIk was dissolved in
50–100 ml of 96% ethanol and boiled for 45–60 min.
The resulting solution was allowed to stand for 20–
30 h at a temperature of 20–23°C. The precipitate
formed was filtered off on a glass frit filter, washed
with a small amount of 96% ethanol, then with diethyl
ether, and dried in a vacuum. The resulting compounds
IIIa–IIIk are sufficiently pure, and the recrys-
tallization is not required.
(E,E)-N1,N5-Di-(4',4''-chlorobenzylidene)naph-
thalene-1,5-diamine (IIIe). Yield 97%, bright yellow
crystalline solid, mp 199–200°C. IR spectrum, ν, cm–1:
3035, 2921, 2871, 1622, 1591, 1567, 1084, 1012, 824,
787. 1Н NMR spectrum, δН, ppm: 7.27 d (2Н, С2,6Н, J
8.7 Hz), 7.53 t (2Н, С3,7Н, J 5.6 Hz), 7.62 d (4H,
С3',3''Н, С5',5''Н, J 8.7 Hz), 8.07 d (4Н, С2',2''Н, С6',6''Н, J
8.7 Hz), 8.16 d (2Н, С4,8Н, J 10.0 Hz), 8.72 s (2Н,
HC=N). Found, %: С 71.46; Н 3.98; Cl 17.60; N 6.96.
C24H16Cl2N2. Calculated, %: С 71.47; Н 4.00; Cl
17.58; N 6.95.
(E,E)-N1,N5-Dibenzylidenenaphthalene-1,5-di-
amine (IIIa). Yield 85%, dark yellow crystalline solid,
mp 190°C. IR spectrum, ν, cm–1: 3081, 3049, 2923,
1
2823, 1622, 1619, 1579. Н NMR spectrum, δН, ppm:
7.24 d (2H, С2,6Н, J 7.3 Hz), 7.50–7.55 m (6Н, С3',3''Н,
С4',4''Н, С5',5''Н, 2Н, С3,7Н), 8.04–8.07 m (2Н, С2',2''Н,
2Н, С6',6''Н), 8.15 d (2H, С4,8Н, J 7.4 Hz), 8.69 s (2Н,
2HC=N). Found, % С 86.17; Н 5.41; N 8.43.
C24H18N2. Calculated, %, С 86.20; Н 5.43; N 8.38.
(E,E)-N1,N5-Di-(4',4''-bromobenzylidene)naph-
thalene-1,5-diamine (IIIf). Yield 75%, bright yellow
crystalline solid, mp 222–223°C. IR spectrum, ν, cm–1:
3076, 3041, 3020, 2921, 2878, 1621, 1578, 1564,
1
1065, 1006, 786. Н NMR spectrum, δН, ppm: 7.11 d
(E,E)-N1,N5-Di-(4',4''-methoxybenzylidene)naph-
thalene-1,5-diamine (IIIb). Yield 69%, brown crys-
talline solid, mp 201–202°C. IR spectrum, ν, cm–1:
(2Н, С2,6Н, J 8.3 Hz), 7.50 t (2Н, С3,7Н, J 5.0 Hz),
7.66 d (4H, С3',3''Н, С5',5''Н, J 8.6 Hz), 7.90 d (4Н,
С2',2''Н, С6',6''Н, J 8.7 Hz), 8.23 d (2Н, С4,8Н, J 8.3 Hz),
8.52 s (2Н, HC=N). Found, %: С 58.58; Н 3.24; Br
32.48; N 5.70. C24H16Br2N2. Calculated, %: С 58.56; Н
3.28; Br 32.47; N 5.69.
1
2959, 2833, 1617, 1604, 1576, 1251, 1167, 1023. Н
NMR spectrum, δН, ppm: 3.90 s (6Н, 2ОСH3), 7.02 m
(4H, С3',3''Н, С5',5''Н), 7.08 d (2Н, С2,6Н, J 11.5 Hz),
7.47 t (2Н, С3,7Н, J 4.2 Hz), 7.98 d (4Н, С2',2''Н, С6',6''Н,
J 9.6 Hz), 8.22 d (2Н, С4,8Н, J 9.6 Hz), 8.49 s (2Н,
HC=N). Found, %: С 79.17; Н 5.60; N 7.12 O 8.10.
(E,E)-N1,N5-Di-(4',4''-nitrobenzilidene)naph-
thalene-1,5-diamine (IIIg). Yield 76%, red-orange
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 9 2012