N-[(E)-3-alkoxy-4-hydroxy(alkoxy, alkanoyloxy, aroyloxy)-benzylidene]-4- phenoxyanilines

Article abstract of DOI:10.1134/S1070428009100121

Condensation of 4-phenoxyaniline with benzaldehydes of the vanillin series in methanol gave the corresponding Schiff bases, N-[(E)-3-alkoxy-4- hydroxy(alkoxy, alkanoyloxy, aroyloxy)benzylidene]-4-phenoxyanilines.

Full text of DOI:10.1134/S1070428009100121

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 10, pp. 1496–1502. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © E.A. Dikusar, V.I. Potkin, N.G. Kozlov, M.M. Ogorodnikova, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45,
No. 10, pp. 1512–1518.
N-[(E)-3-Alkoxy-4-hydroxy(alkoxy, alkanoyloxy, aroyloxy)-
benzylidene]-4-phenoxyanilines
E. A. Dikusar, V. I. Potkin, N. G. Kozlov, and M. M. Ogorodnikova
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, ul. Surganova 13, Minsk,
220072 Belaruse-mail: evgen_58@mail.ru
Received October 16, 2008
Abstract—Condensation of 4-phenoxyaniline with benzaldehydes of the vanillin series in methanol gave the
corresponding Schiff bases, N-[(E)-3-alkoxy-4-hydroxy(alkoxy, alkanoyloxy, aroyloxy)benzylidene]-4-phen-
oxyanilines.
DOI: 10.1134/S1070428009100121
We previously reported on the synthesis of Schiff
bases of the vanillin series and their film-forming
properties and sensitivity to heat and light [1–3]. The
synthesized compounds turned out to be promising as
materials for the preparation of nanofilms and nano-
materials based thereon [4–6].
vanillal (3-ethoxy-4-hydroxybenzaldehyde), and ethers
and esters derived therefrom with 4-phenoxyaniline
(II) in boiling anhydrous methanol we obtained the
corresponding aromatic Schiff bases IIIa–IIIu and
IVa–IVl in 84–90% yield. The reactions were com-
plete in 10–15 min under mild conditions in the ab-
sence of a catalyst, which favored conservation of
labile ester groups. According to the 1H NMR data, the
purity of the isolated compounds was 96±1%.
The goal of the present work was to develop a pre-
parative procedure for the synthesis of new aromatic
Schiff bases containing hydroxy, ether, and ester
groups, as well as carborane fragments. By condensa-
tion of vanillin (4-hydroxy-3-methoxybenzaldehyde),
Compounds IIIa–IIIu and IVa–IVl are colorless or
slightly colored crystalline or glassy substances. They
Scheme 1.
CHO
O
O
N
+
R
R
H2N
R'O
OR'
I
II
IIIa–IIIt, IVa–IVk
R
O
N
O
O
N
O
R
IIIu, IVl
III, R = H, R′ = Me (a); R = MeO, R′ = H (b), Me (c), MeC(O) (d), EtC(O) (e), PrC(O) (f), Me2CHC(O) (g), Me(CH2)6C(O) (h),
Me(CH2)8C(O) (i), Me(CH2)16C(O) (j), H2C=C(Me)C(O) (k), PhCH2C(O) (l), PhCH(Me)CH2C(O) (m), PhC(O) (n),
2,4-Cl2C6H3C(O) (o), 4-BrC6H4C(O) (p), 3-O2NC6H4C(O) (q), MeOC(O) (r), EtOC(O) (s), 1,2-C2B10H11-1-C(O) (t); R = MeO (u);
IV, R = EtO, R′ = H (a), Me (b), MeC(O) (c), EtC(O) (d), PrC(O) (e), Me2CHC(O) (f), Me2CHCH2C(O) (g), 4-MeC6H4C(O) (h),
MeOC(O) (i), EtOC(O) (j), 1,2-C2B10H11-1-C(O) (k); R = EtO (l).
1496

N-[(E)-3-ALKOXY-4-HYDROXY(ALKOXY, ALKANOYLOXY, AROYLOXY)BENZYLIDENE]-...
1497
contained no impurities of the initial reactants, and no
additional purification was necessary. The structure of
IIIa–IIIu and IVa–IVl was proved by their elemental
analyses, IR and H NMR spectra, and determination
of the molecular weight by cryoscopy. Protons in the
N-[(E)-3-Alkoxy-4-hydroxy(alkoxy, alkanoyloxy,
aroyloxy)benzylidene]-4-phenoxyanilines IIIa–IIIt
and IVa–IVk (general procedure). A solution of
5 mmol of aldehyde I and 5 mmol of 4-phenoxyaniline
(II) in 30 ml of anhydrous methanol was heated for
15 min under reflux. The hot solution was filtered
through a folded filter paper, and the filtrate was
cooled and kept for 10–15 h at 5°C. The precipitate
was filtered off through a glass filter or separated by
decanting, washed with a small amount of methanol,
and dried in air.
1
HC=N group of IIIa–IIIu and IVa–IVl gave a singlet
1
at δ 8.41–8.51 ppm in the H NMR spectra, which is
typical of Schiff bases with E configuration of the
double C=N bond [7].
The E configuration of these compounds was also
confirmed by quantum-chemical calculations of heats
of formation (Hf) of E and Z isomers of Schiff bases
IIIa, IIIc, IIId, IVa, IVc, and IVd. The calculations
were performed in terms of MNDO PM3 semiempiri-
cal approximation [8, 9] using GAMESS software [10]
with complete optimization of geometric parameters
(bond lengths, bond angles, and dihedral angles). The
following values of Hf (kcal/mol) were obtained for the
E isomers (the corresponding values for the Z isomers
are given in parentheses): IIIa, 27.2 (28.0); IIIc, –7.1
(–6.3); IIId, –49.3 (–47.8); IVa, –18.9 (–18.2);
IVc), –55.9 (–55.5); IVd, –60.1 (–59.6). Thus the
E isomers are more energetically favorable (by 0.4–
1.5 kcal/mol) than their Z isomers, which is consistent
with the data reported previously for structurally relat-
ed compounds [3, 4]. The calculated energy barrier to
the E–Z transformation was 6–8 kcal/mol; this value is
lower by 3–5 kcal/mol than the energy barrier to the
E–Z transformation of Schiff bases derived from bi-
phenyl-4-amine [2]. Computer simulation of the ther-
mal E–Z isomerization of Schiff bases IIIa, IIIc, IIId,
IVa, IVc, and IVd showed that stretching and bending
vibrations of the phenoxyphenyl group provide the main
contribution to the reduction of the energy barrier [11].
Bis{2-alkoxy-4-[(E)-4-phenoxyphenylimino-
methyl]phenyl} succinates IIIu and IVl (general
procedure). A solution of 5 mmol of bis(4-formyl-2-
methoxyphenyl) succinate or bis(2-ethoxy-4-formyl-
phenyl) succinate and 10 mmol of 4-phenoxyaniline
(II) in 30 ml of anhydrous methanol was heated for
15 min under reflux. The hot solution was filtered
through a folded filter paper, and the filtrate was
cooled and kept for 10–15 h at 5°C. The precipitate
was filtered off through a glass filter, washed with
a small amount of methanol, and dried in air.
N-[(E)-4-Methoxybenzylidene]-4-phenoxyaniline
(IIIa). Yield 88%, mp 105–106°C. IR spectrum, ν,
cm–1: 3080, 3061, 3035, 3020, 3008 (C–Harom); 2962,
2945, 2922, 2879, 2845, 2844 (C–Haliph); 1622 (C=N);
1606, 1588, 1575, 1509, 1500, 1491, 1417 (C=Carom);
1280, 1264, 1251, 1190, 1181, 1168, 1105, 1076, 1030
(C–O); 872, 852, 826, 816, 785, 765, 745, 693
1
(δC–Harom). H NMR spectrum, δ, ppm: 3.88 s (3H,
Me), 6.90–7.95 m (13H, Harom), 8.42 s (1H, CH=N).
Found, %: C 79.48; H 5.72; N 4.28. M 291.5.
C20H17NO2. Calculated, %: C 79.19; H 5.65; N 4.62.
M 303.4.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenol (IIIb). Yield 90%, mp 77–78°C. IR spectrum,
ν, cm–1: 3500 (OH); 3080, 3063, 3035, 3020, 3003
(C–Harom); 2980, 2065, 2939, 2920, 2913, 2860, 2840
(C–Haliph); 1624 (C=N); 1593, 1518, 1511, 1500, 1488,
1467, 1453, 1428 (C=Carom); 1289, 1236, 1209, 1180,
1152, 1121, 1099, 1071, 1027, 1012 (C–O); 867, 852,
841, 823, 787, 753, 727, 711, 693, 613 (δC–Harom).
1H NMR spectrum, δ, ppm: 3.95 s (3H, Me), 6.05 br.s
(1H, OH), 6.80–7.75 m (12H, Harom), 8.38 s (1H,
CH=N). Found, %: C 75.53; H 5.48; N 3.97. M 311.2.
C20H17NO3. Calculated, %: C 75.22; H 5.37; N 4.39.
M 319.4.
EXPERIMENTAL
The IR spectra were measured on a Nicolet
Protégé-460 spetrophotometer with Fourier transform
from samples prepared as KBr pellets. The H NMR
spectra were recorded on a Tesla BS-587A instrument
at 100 MHz from 5% solutions in CDCl3 using tetra-
methylsilane as internal reference. The elemental com-
positions were determined with an accuracy of ±0.1%
on an Elementar Vario EL-III CHNOS analyzer. The
molecular weights were determined by cryoscopy in
benzene.
1
Initial vanillin and vanillal esters I were synthe-
sized according to the procedures described in [12–
15]; 4-phenoxyaniline (II) was commercial product of
analytical grade (purity 99%), mp 83–84°C.
N-[(E)-3,4-Dimethoxybenzylidene]-4-phenoxy-
aniline (IIIc). Yield 90%, mp 107–108°C. IR spec-
trum, ν, cm–1: 3095, 3080, 3062, 3040, 3022, 3014
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 10 2009

DIKUSAR et al.
1498
(C–Harom); 2975, 2936, 2920, 2910, 2890, 2870, 2846,
2835 (C–Haliph); 1624 (C=N); 1596, 1588, 1582, 1516,
1498, 1488, 1463, 1448, 1417 (C=Carom); 1274, 1238,
1210, 1140, 1099, 1070, 1019 (C–O); 865, 850, 825,
810, 806, 796, 778, 755, 735, 694, 616 (δC–Harom).
1H NMR spectrum, δ, ppm: 3.96 s (3H, 3-OMe), 4.00 s
(3H, 4-OMe), 6.80–7.75 m (12H, Harom), 8.40 s (1H,
CH=N). Found, %: C 75.87; H 5.79; N 3.95. M 326.0.
C21H19NO3. Calculated, %: C 75.66; H 5.74; N 4.20.
M 333.4.
substance. IR spectrum, ν, cm–1: 3080, 3064, 3039,
3008 (C–Harom); 2975, 2937, 2875, 2849, 2827
(C–Haliph); 1761 (C=O); 1628 (C=N); 1589, 1505,
1488, 1468, 1417, 1370 (C=Carom); 1276, 1239, 1214,
1199, 1150, 1123, 1094, 1035 (C–O); 865, 838, 790,
1
755, 693, 620 (δC–Harom). H NMR spectrum, δ, ppm:
1.37 d (6H, Me2CH), 2.88 m (1H, CH), 3.94 s (3H,
MeO), 6.80–7.70 m (12H, Harom), 8.43 s (1H, CH=N).
Found, %: C 74.38; H 6.11; N 3.28. M 379.3.
C24H23NO4. Calculated, %: C 74.02; H 5.95; N 3.60.
M 389.5.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl acetate (IIId). Yield 85%, glassy substance. IR
spectrum, ν, cm–1: 3080, 3065, 3038, 3010 (C–Harom);
2968, 2939, 2922, 2873, 2844, 2833 (C–Haliph); 1766
(C=O); 1626 (C=N); 1589, 1506, 1499, 1488, 1465,
1418, 1369 (C=Carom); 1277, 1239, 1213, 1195, 1151,
1120, 1033, 1010 (C–O); 904, 858, 837, 790, 756, 693,
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl octanoate (IIIh). Yield 90%, glassy substance.
IR spectrum, ν, cm–1: 3080, 3065, 3039, 3008
(C–Harom); 2954, 2928, 2870, 2856 (C–Haliph); 1764
(C=O); 1628 (C=N); 1589, 1505, 1488, 1465, 1417,
1371 (C=Carom); 1276, 1240, 1214, 1197, 1139, 1121,
1102, 1034 (C–O); 875, 857, 840, 790, 755, 740, 725,
1
660, 620 (δC–Harom). H NMR spectrum, δ, ppm:
1
2.34 s (3H, Me), 3.95 s (3H, MeO), 6.80–7.70 m (12H,
692 (δC–Harom). H NMR spectrum, δ, ppm: 0.94 t
H
arom), 8.42 s (1H, CH=N). Found, %: C 73.42;
(3H, Me), 1.34 m (8H, CH2), 1.80 m (2H, MeCH2),
2.58 t [2H, CH2C(O)], 3.94 s (3H, MeO), 6.80–7.70 m
(12H, Harom), 8.43 s (1H, CH=N). Found, %: C 75.85;
H 7.10; N 2.84. M 437.0. C28H31NO4. Calculated, %:
C 75.48; H 7.01; N 3.14. M 445.6.
H 5.43; N 3.54. M 347.9. C22H19NO4. Calculated, %:
C 73.12; H 5.30; N 3.88. M 361.4.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl propanoate (IIIe). Yield 88%, glassy sub-
stance. IR spectrum, ν, cm–1: 3080, 3066, 3038, 3009
(C–Harom); 2981, 2941, 2919, 2879, 2848, 2830
(C–Haliph); 1764 (C=O); 1627 (C=N); 1589, 1504,
1499, 1488, 1464, 1418, 1369 (C=Carom); 1276, 1239,
1213, 1195, 1135, 1074, 1033 (C–O); 880, 858, 837,
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl decanoate (IIIi). Yield 90%, glassy substance.
IR spectrum, ν, cm–1: 3080, 3065, 3039, 3005
(C–Harom); 2953, 2926, 2870, 2854 (C–Haliph); 1764
(C=O); 1628 (C=N); 1589, 1505, 1488, 1465, 1417,
1370 (C=Carom); 1276, 1240, 1214, 1198, 1138, 1121,
1111, 1034 (C–O); 875, 857, 838, 790, 756, 740, 725,
1
790, 760, 740, 693, 620 (δC–Harom). H NMR spec-
trum, δ, ppm: 1.28 t (3H, Me), 2.54 q (2H, CH2), 3.94 s
(3H, MeO), 6.80–7.70 m (12H, Harom), 8.42 s (1H,
CH=N). Found, %: C 73.82; H 5.77; N 3.32. M 361.5.
C23H21NO4. Calculated, %: C 73.58; H 5.64; N 3.73.
M 375.4.
1
693 (δC–Harom). H NMR spectrum, δ, ppm: 0.91 t
(3H, Me), 1.20–1.54 m (12H, CH2), 1.84 m (2H,
MeCH2), 2.64 t [2H, CH2C(O)], 3.94 s (3H, MeO),
6.80–7.70 m (12H, Harom), 8.43 s (1H, CH=N). Found,
%: C 76.34; H 7.66; N 2.61. M 461.4. C30H35NO4. Cal-
culated, %: C 76.08; H 7.45; N 2.96. M 473.6.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl butanoate (IIIf). Yield 87%, glassy substance.
IR spectrum, ν, cm–1: 3080, 3066, 3038, 3008
(C–Harom); 2966, 2936, 2875, 2850, 2828 (C–Haliph);
1763 (C=O); 1627 (C=N); 1589, 1506, 1488, 1465,
1417, 1370 (C=Carom); 1277, 1240, 1214, 1197, 1147,
1122, 1100, 1070, 1033 (C–O); 857, 837, 790, 755,
693, 620 (δC–Harom). H NMR spectrum, δ, ppm:
1.05 t (3H, Me), 1.64 m (2H, MeCH2), 2.54 t [2H,
CH2C(O)], 3.94 s (3H, MeO), 6.80–7.70 m (12H,
H
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl octadecanoate (IIIj). Yield 90%, mp 42–
43°C. IR spectrum, ν, cm–1: 3080, 3066, 3039, 3004
(C–Harom); 2956, 2915, 2873, 2849 (C–Haliph); 1759
(C=O); 1627 (C=N); 1589, 1509, 1499, 1489, 1471,
1417, 1370 (C=Carom); 1277, 1242, 1214, 1198, 1138,
1121, 1106, 1031 (C–O); 875, 854, 837, 790, 757, 740,
1
1
722, 692 (δ C–Harom). H NMR spectrum, δ, ppm:
arom), 8.42 s (1H, CH=N). Found, %: C 74.29;
0.90 t (3H, Me), 1.10–2.12 m (30H, CH2), 2.68 t [2H,
CH2C(O)], 3.94 s (3H, MeO), 6.80–7.70 m (12H,
H 6.05; N 3.23. M 376.1. C24H23NO4. Calculated, %:
C 74.02; H 5.95; N 3.60. M 389.5.
H
arom), 8.43 s (1H, CH=N). Found, %: C 78.23;
H 8.86; N 2.02. M 569.5. C38H51NO4. Calculated, %:
C 77.91; H 8.77; N 2.39. M 585.8.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 2-methylpropanoate (IIIg). Yield 89%, glassy
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 10 2009

N-[(E)-3-ALKOXY-4-HYDROXY(ALKOXY, ALKANOYLOXY, AROYLOXY)BENZYLIDENE]-...
1499
C 76.91; H 5.15; N 3.03. M 409.7. C27H21NO4. Calcu-
lated, %: C 76.58; H 5.00; N 3.31. M 423.5.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 2-methylprop-2-enoate (IIIk). Yield 84%,
mp 126–127°C. IR spectrum, ν, cm–1: 3100, 3085,
3055, 3045, 3017 (=CH2, C–Harom); 2982, 2970, 2930,
2885, 2850, 2835 (C–Haliph); 1730 (C=O); 1683 (C=C);
1627 (C=N); 1598, 1584, 1503, 1492, 1477, 1461,
1419, 1376 (C=Carom); 1274, 1231, 1212, 1199, 1151,
1124, 1099, 1031 (C–O); 873, 860, 838, 820, 803, 775,
762, 743, 715, 698, 645, 618, 603 (δC–Harom). 1H NMR
spectrum, δ, ppm: 2.10 s (3H, Me), 3.94 s (3H, MeO),
5.80 s and 6.41 s (1H each, =CH2), 6.80–7.75 m (12H,
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 2,4-dichlorobenzoate (IIIo). Yield 88%,
mp 92–93°C. IR spectrum, ν, cm–1: 3095, 3075, 3060,
3045, 3020 (C–Harom); 2974, 2940, 2925, 2876, 2850,
2830 (C–Haliph); 1721 (C=O); 1629 (C=N); 1589,
1506, 1488, 1460, 1455, 1417, 1377 (C=Carom); 1279,
1240, 1214, 1195, 1151, 1140, 1123, 1104, 1075, 1032
(C–O); 880, 862, 855, 832, 796, 780, 761, 755, 740,
1
720, 695, 675, 622 (δC–Harom). H NMR spectrum, δ,
H
arom), 8.45 s (1H, CH=N). Found, %: C 73.97;
ppm: 3.95 s (3H, MeO), 6.70–8.50 m (15H, Harom),
8.50 s (1H, CH=N). Found, %: C 65.98; H 4.47;
Cl 13.88; N 2.50. M 480.3. C27H19Cl2NO4. Calculated,
%: C 65.60; H 4.28; Cl 14.34; N 2.83. M 494.4.
H 5.83; N 3.25. M 360.4. C23H21NO4. Calculated, %:
C 73.58; H 5.64; N 3.73. M 375.4.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl phenylacetate (IIIl). Yield 85%, glassy sub-
stance. IR spectrum, ν, cm–1: 3092, 3063, 3033, 3010
(C–Harom); 2966, 2936, 2921, 2874, 2848, 2830
(C–Haliph); 1763 (C=O); 1626 (C=N); 1589, 1510,
1499, 1488, 1464, 1455, 1417, 1371 (C=Carom); 1277,
1239, 1214, 1199, 1152, 1119, 1074, 1032 (C–O); 860,
840, 791, 755, 729, 694, 660, 650, 620 (δC–Harom).
1H NMR spectrum, δ, ppm: 3.82 s (2H, CH2), 3.94 s
(3H, MeO), 6.80–7.75 m (17H, Harom), 8.45 s (1H,
CH=N). Found, %: C 77.19; H 5.48; N 2.92. M 422.8.
C28H23NO4. Calculated, %: C 76.87; H 5.30; N 3.20.
M 437.5.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 4-bromobenzoate (IIIp). Yield 87%, mp 118–
119°C. IR spectrum, ν, cm–1: 3095, 3082, 3060, 3040,
3030, 3011 (C–Harom); 2970, 2940, 2922, 2870, 2860,
2845, 2835 (C–Haliph); 1739 (C=O); 1629 (C=N);
1588, 1510, 1496, 1481, 1460, 1420, 1395 (C=Carom);
1294, 1262, 1239, 1214, 1202, 1161, 1113, 1072, 1031,
1010 (C–O); 866, 845, 820, 810, 751, 695, 676, 620
1
(δC–Harom). H NMR spectrum, δ, ppm: 3.95 s (3H,
MeO), 6.70–8.20 m (16H, Harom), 8.51 s (1H, CH=N).
Found, %: C 64.93; H 4.19; Br 15.45; N 2.34.
M 492.6. C27H20BrNO4. Calculated, %: C 64.55;
H 4.01; Br 15.91; N 2.79. M 502.4.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 3-phenylbutanoate (IIIm). Yield 87%, glassy
material. IR spectrum, ν, cm–1: 3086, 3075, 3028, 3004
(C–Harom); 2965, 2934, 2878, 2855, 2830 (C–Haliph);
1761 (C=O); 1627 (C=N); 1589, 1505, 1500, 1488,
1464, 1454, 1417, 1369 (C=Carom); 1277, 1239, 1214,
1198, 1149, 1131, 1981, 1033 (C–O); 880, 857, 838,
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 3-nitrobenzoate (IIIq). Yield 86%, mp 119–
120°C. IR spectrum, ν, cm–1: 3110, 3100, 3090, 3070,
3050, 3040, 3010 (C–Harom); 2978, 2940, 2925, 2880,
2845, 2830 (C–Haliph); 1742 (C=O); 1630 (C=N); 1620,
1590, 1586, 1506, 1500, 1488, 1466, 1440, 1418, 1370
(C=Carom); 1539, 1352 (NO2); 1283, 1252, 1232, 1211,
1197, 1150, 1121, 1110, 1100, 1080, 1035 (C–O); 865,
857, 840, 825, 815, 775, 755, 714, 705, 690, 655, 620
1
790, 758, 745, 700, 622 (δC–Harom). H NMR spec-
trum, δ, ppm: 1.45 d (3H, Me), 2.92 d (2H, CH2),
3.40 q (1H, CH), 3.94 s (3H, MeO), 6.80–7.74 m
(17H, Harom), 8.45 s (1H, CH=N). Found, %: C 77.82;
H 5.96; N 2.75. M 451.6. C30H27NO4. Calculated, %:
C 77.40; H 5.85; N 3.01. M 465.5.
1
(δC–Harom). H NMR spectrum, δ, ppm: 3.94 (3H,
MeO), 6.70–9.15 m (16H, Harom), 8.49 s (1H, CH=N).
Found, %: C 69.68; H 4.47; N 5.60. M 455.3.
C27H20N2O6. Calculated, %: C 69.23; H 4.30; N 5.98.
M 468.5.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl benzoate (IIIn). Yield 84%, mp 112–113°C.
IR spectrum, ν, cm–1: 3070, 3030, 3010 (C–Harom);
2970, 2945, 2925, 2884, 2850, 2830 (C–Haliph); 1743
(C=O); 1629 (C=N); 1593, 1506, 1487, 1465, 1450,
1416, 1370 (C=Carom); 1278, 1255, 1233, 1212, 1195,
1151, 1121, 1080, 1061, 1035, 1024 (C–O); 871, 844,
810, 790, 760, 740, 710, 692, 680, 619 (δC–Harom).
1H NMR spectrum, δ, ppm: 3.94 s (3H, MeO), 6.70–
8.20 m (17H, Harom), 8.49 s (1H, CH=N). Found, %:
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl methyl carbonate (IIIr). Yield 84%, mp 83–
84°C. IR spectrum, ν, cm–1: 3090, 3080, 3070, 3060,
3016, 3002 (C–Harom); 2978, 2953, 2940, 2920, 2880,
2840, 2830 (C–Haliph); 1764 (C=O); 1628 (C=N); 1597,
1587, 1508, 1490, 1485, 1465, 1440, 1417, 1373
(C=Carom); 1275, 1265, 1256, 1235, 1213, 1194, 1151,
1119, 1103, 1056, 1034 (C–O); 871, 858, 830, 800,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 10 2009

DIKUSAR et al.
1500
776, 758, 730, 720, 694, 650, 620 (δC–Harom). 1H NMR
spectrum, δ, ppm: 3.94 (3H, 3-MeO), 3.97 s [3H,
4-MeOC(O)], 6.85–7.75 m (12H, Harom), 8.44 s (1H,
CH=N). Found, %: C 70.35; H 5.21; N 3.28. M 367.7.
C22H19NO5. Calculated, %: C 70.02; H 5.07; N 3.71.
M 377.4.
(C–Haliph); 1621 (C=N); 1593, 1519, 1512, 1505, 1488,
1440, 1399, 1385 (C=Carom); 1287, 1249, 1201, 1163,
1123, 1111, 1071, 1043 (C–O); 866, 858, 837, 830,
815, 787, 780, 746, 711, 691, 614 (δC–Harom). 1H NMR
spectrum, δ, ppm: 1.48 t (3H, Me), 4.22 q (2H, CH2O),
6.05 br.s (1H, OH), 6.85–7.70 m (12H, Harom), 8.36 s
(1H, CH=N). Found, %: C 75.94; H 5.85; N 3.94.
M 320.6. C21H19NO3. Calculated, %: C 75.66; H 5.74;
N 4.20. M 333.4.
Ethyl 2-methoxy-4-[(E)-4-phenoxyphenylimino-
methyl]phenyl carbonate (IIIs). Yield 85%, mp 73–
74°C. IR spectrum, ν, cm–1: 3070, 3060, 3040, 3008
(C–Harom); 2985, 2960, 2928, 2900, 2880, 2850, 2830
(C–Haliph); 1756 (C=O); 1626 (C=N); 1589, 1510,
1499, 1489, 1441, 1430, 1385 (C=Carom); 1279, 1244,
1215, 1200, 1162, 1123, 1063, 1045 (C–O); 880, 860,
840, 822, 790, 786, 747, 691, 621 (δC–Harom). 1H NMR
spectrum, δ, ppm: 1.45 t (3H, Me), 3.93 s (3H, MeO),
4.18 q (2H, CH2), 6.85–7.72 m (12H, Harom), 8.43 s
(1H, CH=N). Found, %: C 70.89; H 5.62; N 3.19.
M 376.2. C23H21NO5. Calculated, %: C 70.58; H 5.41;
N 3.58. M 391.4.
N-[(E)-3-Ethoxy-4-methoxybenzylidene]-4-phe-
noxyaniline (IVb). Yield 89%, mp 93–94°C. IR spec-
trum, ν, cm–1: 3090, 3070, 3060, 3040, 3017, 3001
(C–Harom); 2985, 2970, 2924, 2871, 2840 (C–Haliph);
1622 (C=N); 1592, 1587, 1577, 1512, 1501, 1487,
1433, 1385 (C=Carom); 1269, 1234, 1207, 1190, 1164,
1138, 1111, 1026 (C–O); 868, 834, 820, 805, 788, 773,
1
740, 730, 691, 616 (δC–Harom). H NMR spectrum, δ,
ppm: 1.52 t (3H, Me), 3.95 s (3H, MeO), 4.26 q (2H,
CH2O), 6.70–7.65 m (12H, Harom), 8.39 s (1H, CH=N).
Found, %: C 76.45; H 6.23; N 3.74. M 334.7.
C22H21NO3. Calculated, %: C 76.06; H 6.09; N 4.03.
M 347.4.
2-Methoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 1,3-dicarbadodecaborane-1-carboxylate
(IIIt). Yield 84%, mp 120–121°C. IR spectrum, ν,
cm–1: 3080, 3062, 3045, 3015 (C–Harom, C–Hcarb); 2967,
2929, 2880, 2845 (C–Haliph); 2606 (B–H); 1745 (C=O);
1630 (C=N); 1589, 1505, 1488, 1464, 1417, 1384
(C=Carom); 1325, 1279, 1242, 1218, 1193, 1167, 1147,
1125, 1029 (C–O); 876, 855, 840, 820, 790, 750, 740,
2-Ethoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl acetate (IVc). Yield 90%, glassy substance. IR
spectrum, ν, cm–1: 3080, 3065, 3039, 3012 (C–Harom);
2981, 2934, 2900, 2881, 2845 (C–Haliph); 1766 (C=O);
1626 (C=N); 1589, 1509, 1499, 1488, 1440, 1394,
1369 (C=Carom); 1278, 1240, 1210, 1163, 1120, 1041,
1010 (C–O); 873, 857, 836, 790, 753, 693, 670, 620
1
690, 630, 610 (δC–Harom, δC–Hcarb.). H NMR spec-
trum, δ, ppm: 3.12 br.s (1H, CH, carborane), 3.94 s
(3H, MeO), 6.70–7.80 (12H, Harom), 8.42 s (1H,
CH=N). Found, %: C 56.83; H 5.74; B 21.68; N 2.42.
M 473.6. C23H27B10NO4. Calculated, %: C 56.43;
H 5.56; B 22.08; N 2.86. M 489.6.
1
(δC–Harom). H NMR spectrum, δ, ppm: 1.43 t (3H,
CH3CH2), 2.34 s (3H, Me), 4.14 q (2H, CH2O), 6.70–
7.70 m (12H, Harom), 8.43 s (1H, CH=N). Found, %:
C 73.90; H 5.76; N 3.37. M 362.8. C23H21NO4. Calcu-
lated, %: C 73.58; H 5.64; N 3.73. M 375.4.
Bis{2-methoxy-4-[(E)-4-phenoxyphenylimino-
methyl]phenyl} succinate (IIIu). Yield 87%, mp 161–
162°C. IR spectrum, ν, cm–1: 3090, 3080, 3060, 3040,
3015 (C–Harom); 2970, 2944, 2934, 2900, 2870, 2845,
2830 (C–Haliph); 1748 (C=O); 1626 (C=N); 1598, 1588,
1504, 1489, 1468, 1417, 1372 (C=Carom); 1273, 1243,
1211, 1194, 1166, 1150, 1117, 1034 (C–O); 873, 863,
838, 818, 790, 780, 751, 740, 685, 675, 620 (C–Harom).
1H NMR spectrum, δ, ppm: 3.07 s (4H, CH2), 3.94 s
(6H, MeO), 6.80–7.70 m (24H, Harom), 8.43 s (2H,
CH=N). Found, %: C 73.58; H 5.24; N 3.50. M 706.5.
C44H36N2O8. Calculated, %: C 73.32; H 5.03; N 3.89.
M 720.8.
2-Ethoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl propanoate (IVd). Yield 87%, glassy sub-
stance. IR spectrum, ν, cm–1: 3080, 3065, 3039, 3009
(C–Harom); 2981, 2940, 2900, 2881, 2830 (C–Haliph);
1764 (C=O); 1627 (C=N); 1588, 1500, 1488, 1431,
1394 (C=Carom); 1275, 1240, 1213, 1161, 1136, 1121,
1074, 1042 (C–O); 885, 874, 857, 838, 790, 755, 693,
1
620 (δC–Harom). H NMR spectrum, δ, ppm: 1.38 t
[3H, CH3CH2C(O)], 1.43 t (3H, CH3CH2O), 2.68 q
[2H, CH2C(O)], 4.14 q (2H, CH2O), 6.70–7.70 m
(12H, Harom), 8.43 s (1H, CH=N). Found, %: C 74.43;
H 6.11; N 3.35. M 370.9. C24H23NO4. Calculated, %:
C 74.02; H 5.95; N 3.60. M 389.5.
2-Ethoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenol (IVa). Yield 89%, mp 63–64°C. IR spectrum,
ν, cm–1: 3350 (O–H); 3080, 3065, 3035, 3004
(C–Harom); 2980, 2065, 2934, 2910, 2878, 2847
2-Ethoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl butanoate (IVe). Yield 84%, glassy substance.
IR spectrum, ν, cm–1: 3080, 3065, 3039, 3008
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 10 2009

N-[(E)-3-ALKOXY-4-HYDROXY(ALKOXY, ALKANOYLOXY, AROYLOXY)BENZYLIDENE]-...
1501
(C–Harom); 2975, 2934, 2900, 2875, 2830 (C–Haliph);
1763 (C=O); 1627 (C=N); 1589, 1505, 1500, 1487,
1431, 1390, 1368 (C=Carom); 1276, 1240, 1213, 1161,
1143, 1120, 1075, 1042 (C–O); 878, 856, 837, 790,
2-Ethoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl methyl carbonate (IVi). Yield 84%, mp 72–
73°C. IR spectrum, ν, cm–1: 3090, 3080, 3064, 3035,
3004 (C–Harom); 2990, 2977, 2965, 2939, 2920, 2880,
2844, 2830 (C–Haliph); 1758 (C=O); 1627 (C=N); 1597,
1587, 1508, 1490, 1484, 1465, 1416, 1385, 1371
(C=Carom); 1277, 1252, 1236, 1214, 1200, 1197, 1151,
1120, 1097, 1056, 1034 (C–O); 869, 855, 835, 817,
794, 777, 760, 750, 740, 715, 695, 645, 635, 619
1
755, 693, 620 (δC–Harom). H NMR spectrum, δ, ppm:
1.03 t [3H, Me(CH2)2], 1.44 t (3H, MeCH2O), 1.64 m
(2H, MeCH2CH2), 2.54 t [2H, CH2C(O)], 4.14 q (2H,
CH2O), 6.70–7.70 m (12H, Harom), 8.43 s (1H, CH=N).
Found, %: C 74.72; H 6.25; N 3.12. M 391.0.
C25H25NO4. Calculated, %: C 74.42; H 6.25; N 3.47.
M 403.5.
1
(δC–Harom). H NMR spectrum, δ, ppm: 1.42 t (3H,
CH3CH2), 3.97 s (3H, MeO), 4.14 q (2H, CH2O),
6.80–7.75 m (12H, Harom), 8.44 s (1H, CH=N). Found,
%: C 70.86; H 5.53; N 3.32. M 380.2. C23H21NO5. Cal-
culated, %: C 70.58; H 5.41; N 3.58. M 391.4.
2-Ethoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 2-methylpropanoate (IVf). Yield 86%,
mp 87–88°C. IR spectrum, ν, cm–1: 3090, 3070, 3061,
3052, 3017 (C–Harom); 2982, 2970, 2934, 2895, 2884,
2873, 2840, 2827 (C–Haliph); 1755 (C=O); 1629 (C=N);
1600, 1589, 1581, 1510, 1500, 1493, 1480, 1465, 1432,
1415, 1390, 1380, 1368 (C=Carom); 1285, 1270, 1239,
1213, 1167, 1118, 1099, 1040 (C–O); 880, 863, 837,
794, 778, 745, 735, 702, 655, 645, 619 (δC–Harom).
1H NMR spectrum, δ, ppm: 1.37 d (6H, Me2C), 1.42 t
(3H, Me), 2.88 m (1H, CH), 4.18 q (2H, CH2O), 6.80–
7.72 m (12H, Harom), 8.43 s (1H, CH=N). Found, %:
C 74.83; H 6.34; N 3.06. M 393.4. C25H25NO4. Calcu-
lated, %: C 74.42; H 6.25; N 3.47. M 403.5.
2-Ethoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl ethyl carbonate (IVj). Yield 83%, glassy sub-
stance. IR spectrum, ν, cm–1: 3090, 3078, 3040, 3015
(C–Harom); 2982, 2937, 2901, 2876, 2822 (C–Haliph);
1765 (C=O); 1628 (C=N); 1589, 1507, 1499, 1488,
1432, 1394, 1369 (C=Carom); 1279, 1244, 1215, 1200,
1163, 1122, 1097, 1055, 1043 (C–O); 874, 857, 837,
1
815, 790, 776, 755, 693, 619 (δC–Harom). H NMR
spectrum, δ, ppm: 1.20–1.70 m (6H, Me), 4.00–4.50 m
(4H, CH2O), 6.80–7.75 m (12H, Harom), 8.43 s (1H,
CH=N). Found, %: C 71.45; H 5.89; N 3.30. M 382.8.
C24H23NO5. Calculated, %: C 71.10; H 5.72; N 3.45.
M 405.4.
2-Ethoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 3-methylbutanoate (IVg). Yield 84%, mp 47–
48°C. IR spectrum, ν, cm–1: 3090, 3065, 3039, 3010
(C–Harom); 2980, 2962, 2934, 2900, 2873, 2815
(C–Haliph); 1762 (C=O); 1627 (C=N); 1589, 1505, 1500,
1488, 1431, 1393, 1369 (C=Carom); 1290, 1275, 1240,
1213, 1197, 1160, 1153, 1120, 1099, 1042 (C–O); 876,
2-Ethoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 1,3-dicarbadodecaborane-1-carboxylate
(IVk). Yield 88%, mp 132–133°C. IR spectrum, ν,
cm–1: 3090, 3061, 3045, 3005 (C–Harom, C–Hcarb); 2979,
2961, 2931, 2897, 2884, 2860, 2830 (C–Haliph); 2608
(B–H); 1758 (C=O); 1625 (C=N); 1589, 1508, 1488,
1456, 1424, 1388 (C=Carom); 1290, 1237, 1212, 1190,
1160, 1115, 1105, 1036 (C–O); 869, 828, 796, 770,
728, 718, 691, 630, 619 (δC–Harom, δC–Hcarb). 1H NMR
spectrum, δ, ppm: 1.45 t (3H, Me), 3.12 br.s (1H, CH,
carborane), 4.18 q (2H, CH2O), 6.65–7.75 m (12H,
1
857, 838, 790, 755, 695, 621 (δC–Harom). H NMR
spectrum, δ, ppm: 1.13 d (6H, Me2C), 1.42 t (3H, Me),
1.43–2.90 m (3H, CH, CH2), 4.14 q (2H, CH2O), 6.70–
7.70 m (12H, Harom), 8.43 s (1H, CH=N). Found, %:
C 75.08; H 6.74; N 3.04. M 409.5. C26H27NO4. Calcu-
lated, %: C 74.80; H 6.52; N 3.35. M 417.5.
2-Ethoxy-4-[(E)-4-phenoxyphenyliminomethyl]-
phenyl 4-methylbenzoate (IVh). Yield 85%, mp 80–
81°C. IR spectrum, ν, cm–1: 3090, 3070, 3040, 3009
(C–Harom); 2980, 2970, 2924, 2900, 2878, 2848, 2820
(C–Haliph); 1733 (C=O); 1626 (C=N); 1611, 1587, 1498,
1488, 1430, 1390, 1370 (C=Carom); 1269, 1260, 1243,
1212, 1196, 1172, 1161, 1118, 1070, 1042, 1018
(C–O); 873, 855, 837, 790, 780, 750, 744, 691, 625
H
arom), 8.42 s (1H, CH=N). Found, %: C 57.73;
H 5.89; B 21.07; N 2.54. M 488.5. C24H29B10NO4.
Calculated, %: C 57.24; H 5.80; B 21.47; N 2.78.
M 503.6.
Bis{2-ethoxy-4-[(E)-4-phenoxyphenylimino-
methyl]phenyl} succinate (IVl). Yield 85%, mp 155–
156°C. IR spectrum, ν, cm–1: 3070, 3060, 3040, 3004
(C–Harom); 2975, 2929, 2895, 2880, 2850, 2830
(C–Haliph); 1758 (C=O); 1630 (C=N); 1600, 1589, 1510,
1499, 1487, 1426, 1395 (C=Carom); 1287, 1266, 1235,
1214, 1198, 1161, 1124, 1116, 1040 (C–O); 860, 840,
815, 793, 780, 740, 693, 665, 620 (δC–Harom). 1H NMR
1
(δC–Harom). H NMR spectrum, δ, ppm: 1.34 t (3H,
CH3CH2), 2.48 s (3H, CH3C6H4), 4.18 q (2H, CH2O),
6.70–8.25 m (16H, Harom), 8.49 s (1H, CH=N). Found,
%: C 77.46; H 5.70; N 2.74. M 438.8. C29H25NO4. Cal-
culated, %: C 77.14; H 5.58; N 3.10. M 451.5.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 10 2009

DIKUSAR et al.
1502
6. Azarko, V.A., Dikusar, E.A., Potkin, V.I., Kozlov, N.G.,
and Yuvchenko, A.P., Optika neodnorodnykh struktur –
2007: materialy mezhdunarodnoi nauchno-praktiche-
skoi konferentsii (Optics of Heterogeneous Structures
2007. Proc. Int. Scientific and Practical Conf.),
Mogilev: Mogilev. Gos. Univ. imeni A.A. Kuleshova,
2007, p. 27.
7. Dyer, J.R., Applications of Absorption Spectroscopy of
Organic Compounds, Englewood Cliffs: Prentice–Hall,
1965. Translated under the title Prilozheniya absorbtsi-
spectrum, δ, ppm: 1.44 t (6H, CH3CH2), 3.07 s [4H,
(CH2)2], 4.14 q (4H, CH2O), 6.80–7.70 m (24H, Harom),
8.43 s (2H, 2CH=N). Found, %: C 74.01; H 5.39;
N 3.51. M 735.7. C46H40N2O8. Calculated, %: C 73.78;
H 5.38; N 3.74. M 748.8.
This study was performed under financial support
by the Byelorussian Republican Foundation for Basic
Research (project no. Kh08-227).
onnoi
spektroskopii
organicheskikh
soedinenii,
REFERENCES
Moscow: Khimiya, 1970, p. 92.
8. Stewart, J.J.P., J. Comput. Chem., 1989, vol. 10, p. 209.
9. Stewart, J.J.P., J. Comput. Chem., 1989, vol. 10, p. 221.
10. Shmidt, M.W., Baldridge, K.K., Boatz, J.A., El-
bert, S.T., Gordon, M.S., Jensen, J.H., Koseki, S.,
Matsunaga, N., Nguyen, K.A., Su, S.J., Windus, T.L.,
Dupuis, M., and Montgomery, J.A., J. Comput. Chem.,
1993, vol. 14, p. 1347.
11. Nakanishi, K., Infrared Absorption Spectroscopy.
Practical, San Francisco: Holden-Day, 1962. Translated
under the title Infrakrasnye spektry i stroenie organi-
cheskikh soedinenii, Moscow: Mir, 1965, p. 22.
12. Dikusar, E.A., Vyglazov, O.G., Moiseichuk, K.L., Zhu-
kovskaya, N.A., and Kozlov, N.G., Zh. Prikl. Khim.,
2005, vol. 78, p. 122.
1. Dikusar, E.A., Kozlov, N.G., Potkin, V.I., Azarko, V.A.,
and Yuvchenko, A.P., Russ. J. Gen. Chem., 2007, vol. 77,
p. 278.
2. Dikusar, E.A., Kozlov, N.G., Potkin, V.I., Azarko, V.A.,
and Yuvchenko, A.P., Russ. J. Gen. Chem., 2007, vol. 77,
p. 1766.
3. Dikusar, E.A., Kozlov, N.G., Potkin, V.I., Azarko, V.A.,
and Yuvchenko, A.P., Russ. J. Gen. Chem., 2008, vol. 78,
p. 281.
4. Dikusar, E.A., Kozlov, N.G., Tlegenov, R.T., and Uteni-
yazov, K.U., Azometiny na osnove vanilina i vanilalya
(Schiff Bases Derived from Vanillin and Vanillal),
Karakalpakstan: Nukus, 2007, p. 207.
5. Azarko, V.A., Dikusar, E.A., Yuvchenko, A.P., Pot-
kin, V.I., and Kozlov, N.G., Abstracts of Papers, Mezhdu-
narodnaya nauchno-tekhnicheskaya konferentsiya “Poli-
mernye kompozity i tribologiya” (Polikomtrib-2007) (Int.
Scientific and Technical Conf. “Polymeric Composite
Materials and Tribology”), Gomel’, 2007, p. 102.
13. Dikusar, E.A. and Kozlov, N.G., Khim. Prirodn. Soedin.,
2005, p. 74.
14. Dikusar, E.A. and Kozlov, N.G., Russ. J. Org. Chem.,
2005, vol. 41, p. 992.
15. Dikusar, E.A., Zh. Prikl. Khim., 2006, vol. 79, p. 1043.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 10 2009