Preparative synthesis of 4-hydroxy(alkyloyloxy, aryloyloxy)-3- methoxy(ethoxy)phenylmethylene(4-carboxyphenyl)amines

Article abstract of DOI:10.1134/S1070428002120084

By reactions of vanillin, vanillal, and their esters with 4-aminobenzoic acid in methanol formerly unknown E-isomers of azomethines (Schiff's bases) were prepared. Pleiades Publishing, Inc. 2006.

Full text of DOI:10.1134/S1070428002120084

ISSN 1070-4280 Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 2, pp. 206-213. Ó Pleiades Publishing, Inc. 2006.
Original Russian Text Ó E.A. Dikusar, N.G. Kozlov, N.A. Zhukovskaya, V.I. Potkin, M.M. Ogorodnikova, V.M. Zelenkovskii, 2006, published in
Zhurnal Organicheskoi Khimii, 2006, Vol. 42, no. 2, pp. 223-230.
Preparative Synthesis of 4-Hydroxy(Alkyloyloxy, Aryloyloxy)-3-
methoxy(ethoxy)phenylmethylene(4-carboxyphenyl)amines
E.A. Dikusar, N.G. Kozlov, N.A. Zhukovskaya, V.I. Potkin,
M.M. Ogorodnikova, and V.M. Zelenkovskii
Institute of Physical Organic Chemistry, Belarussian Academy of Sciences, Minsk, 220072 Belarus
e-mail: loc@ifoch.bas-net.by
Received December 17, 2004
Abstract—By reactions of vanillin, vanillal, and their esters with 4-aminobenzoic acid in methanol formerly unknown
E-isomers of azomethines (Schiff’s bases) were prepared.
DOI: 10.1134/S1070428002120084
&22+
Azomethines (Schiff’s bases) are widely used as
biologically active compounds, liquid crystals, dyes,
luminophors, and polymer stabilizers [1–4]. Based on
azomethines efficient drugs were developed exhibiting
antidepressant, anticonvulsant, antimicrobial, soponific,
psychotropic, nematocidal, antiphlogistic, antitumor, etc.
action [5, 6]. Owing to the presence of a polarized C=N
heterobond the azomethines are valuable initial products
for the synthesis of heterocyclic compounds [7] and
b-arylaminoketones, efficient agents of topical anesthesia
[8, 9].
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In this study we developed a preparative synthesis
of previously unknown derivatives of available natural
aldehydophenols (vanillin and vanillal) and of their esters
I. The condensation of vanillin and esters I with 4-amino-
benzoic acid (II) in anhydrous methanol while heating at
reflux gave rise to 4-hydroxy(alkyloyloxy, aryloyloxy)-3-
methoxy-(ethoxy)phenylmethylene(4-carboxyphenyl)-
amines IIIa–IIIy and IVa–IVk. The reaction was
complete within 1.5–2 h, occurred under mild conditions
with no catalyst that ensured the retention of the labile
ester group. As a result of the process initial compounds
I and II were converted in preparative yields 90–95%
into the corresponding azomethines with a reactive
carboxy group IIIa–IIIy and IVa–IVk. It is presumable
that the synthesized compounds IIIa–IIIy and IVa–IVk
would prove to be promising for investigating their
biological, phototropic, and photochromic activity, spectral
characteristics, for preparation therefrom valuable
products and optical materials [6], and for further
application as accessible synthons in a condensation with
CH-acids in order to obtain b-arylaminoketones [8, 9].
III, R = Me, R' = H (a), C(O)Me (b), C(O)Et (c), C(O)Pr-n(d),
C(O)Pr-i (e), C(O)(CH2)6Me (f), C(O)(CH2)8Me (g),
C(O)(CH2)11Me (h), C(O)(CH2)16Me (i), C(O)CH=CH2 (j),
C(O)CMe=CH2 (k), C(O)(CH2)7CH=CH(CH2)7Me-cis (l),
C(O)CH2C6H5 (m), C(O)CH2CHMeC6H5 (n),
C(O)(CH2)2OC6H4Me-4(o), C(O)C6H5 (p), C(O)C6H4Me-4
(q), C(O)C6H4Cl-2(r), C(O)C6H4Cl-4 (s), C(O)C6H3Cl2-2,4
(t), C(O)CH2OC6H3Cl2-2,4 (u), C(O)CH2Br (v),
C(O)C6H4Br-4 (w), C(O)C6H4NO2-3 (x), 1/2
[(O)C(CH2)2C(O)] (y); IV, R = Et, R1 = H (a), C(O)Me (b),
C(O)Et (c), C(O)Pr-n (d), C(O)Pr-i(e), C(O)CH2CHMe2 (g),
C(O)C6H5 (g), C(O)C6H4Me-4 (h), C(O)C6H4Cl-2 (i),
C(O)C6H4Cl-4 (j), 1/2 [(O)C(CH2)2C(O)] (k).
The structure of prepared azomethines IIIa–IIIy and
IVa–IVk was confirmed by elemental analysis, IR, UV,
1H NMR spectra, and by titrimetric evaluation of the
molecular weight. According to the 1H NMR spectra the
azomethines obtained were individual E-isomers of 98±1%
1
purity. In the H NMR spectra of these compounds the
206

PREPARATIVE SYNTHESIS OF 4-HYDROXY(ALKYLOYLOXY,ARYLOYLOXY)-3-...
207
characteristic signals of the proton HC=N appeared as
The used methanol was repeatedly applied after
a singlet at 8.5 ppm. The chemical shift of the proton in distillation through a Vigreux column.
the Z-isomer is located ususlly by 0.5 ppm downfield due
to its occurrence in the deshielding field of the benzene
ring from the amino acid part of the molecule [10].
4-Hydroxy-3-methoxyphenylmethylene(4-
carboxyphenyl)amine (IIIa). Yield 94%, mp 208–209°C
–1
(from methanol). IR spectrum, n, cm : 1850–3650 (OH),
In order to confirm the spatial arrangement of
compounds obtained IIIa–IIIy and IVa–IVk we carried
out quantum-chemical calculations of the heat of formation
(Hf) for E- and Z-isomers of compounds IIIb, IIIp, IVb,
and IVg in the framework of the semiempirical approxim-
ation MNDO-PM3 [11] applying GAMESS [12] soft-
ware. We performed a total optimization of all bond
lengths, bond and dihedral angles in the compounds under
investigation. The calculations gave the following values
of Hf, kcal mol-1, for E-isomers: –136.6 (IIIb), –100.8
(IIIp), –141.5 (IVb), –105.6 (IVg); for Z-isomers: –136.1
(IIIb), –100.3 (IIIp), –141.1 (IVb), –104.8 (IVg). The
quantum-chemical calculations revealed that the E-con-
figuration is more energetically favorable by 0.4–
0.7 kcal mol-1 than the Z-configuration. The data of the
quantum-chemical calculations are well consistent with
the X-ray diffraction analysis studies of related compounds
[13–15].
3071, 3009 (CHAr and =CH), 2960, 2924, 2852 (CHAlk),
1681, 1660 (C=O), 1630 (C=N), 1584, 1513, 1454, 1430,
1367 (Ar), 1315, 1284, 1218, 1167, 1121, 1026, 973 (CO),
855, 816, 777, 740, 697, 659, 635, 613 (CHAr). UV
spectrum, lmax (e): 206 (16000), 234 (10000), 295 (11000),
1
335 (14000). H NMR spectrum, d, ppm: 3.96 s (3H,
CH3O), 6.50 br.s (1H, OH), 6.55–7.95 m (7H, C6H3 and
C6H4), 8.50 s (1H, HC=N), 9.82 s (1H, CO2H). Found,
%: C 66.57; H 5.02; N 4.89. M 265.6. C15H13NO4.
Calculated, %: C 66.41; H 4.83; N 5.16. M 271.3.
4-Acetoxy-3-methoxyphenylmethylene(4-
carboxyphenyl)amine (IIIb). Yield 90%, mp 212–
–1
213°C (from methanol). IR spectrum, n, cm : 2000–3620
(OH), 3080, 3010 (CHAr and =CH), 2975, 2940, 2920,
2890, 2880, 2840, 2800 (CHAlk), 1759, 1681 (C=O), 1629
(C=N), 1600, 1581, 1510, 1464, 1449, 1420, 1369 (Ar),
1315, 1287, 1270, 1219, 1194, 1160, 1114, 1031, 1014, 976,
949 (CO), 873, 860, 834, 774, 756, 699, 673, 640, 609
(CHAr). UV spectrum, lmax (e): 205 (23000), 220 (18000),
EXPERIMENTAL
1
280 (22000), 295 (22000), 315 (13000). H NMR
IR spectra were recorded on a Fourier spectrometer
Nicolet Protege-460 from samples pelletized with KBr.
UV spectra were measured on a spectrophotometer
Specord UV Vis from 1´10–4 M solutions in methanol.
1H NMR spectra were registered on a spectrometer Tesla
BS-587A (100 MHz) from 5% solutions in (CD3)2SO,
chemical shilts were measured from an internal reference
OMTS. The molecular weights were determined by
alkalimetric titration of carboxy groups with 0.1 N solution
of NaOH in the presence of phenolphthalein as indicator.
Vanillin esters I were prepared by procedure [16].
spectrum, d, ppm: 2.28 s (3H, CH3COO), 3.88 s (3H,
CH3O), 6.40–8.10 m (7H, C6H3 and C6H4), 8.53 s (1H,
HC=N) , 9.94 s (1H, CO2H). Found, %: C 65.46; H 5.04;
N 4.20. M 298.1. C17H15NO5. Calculated, %: C 65.17;
H 4.83; N 4.47. M 313.3.
4-Propionyloxy-3-methoxyphenylmethylene(4-
carboxyphenyl)amine (IIIc). Yield 92%, mp 184–185°C
–1
(from methanol). IR spectrum, n, cm : 2000–3650 (OH),
3075, 3055, 3010 (CHAr and =CH), 2965, 2939, 2924, 2875,
2851, 2800 (CHAlk), 1757, 1683 (C=O), 1630 (C=N), 1599,
1585, 1504, 1464, 1417, 1367 (Ar), 1315, 1287, 1275, 1216,
1204, 1167, 1138, 1125, 1076, 1033, 1010, 971 (C–O),
891, 865, 823, 804, 774, 748, 698, 661, 612 (CHAr). UV
spectrum, lmax (e): 206 (24000), 220 (19000), 280 (22000),
295 (22000), 315 (14000). 1H NMR spectrum, d, ppm:
1.27 t (3H, CH3CH2), 2.54 q (2H, CH2), 3.88 s (3H,
CH3O), 6.40–8.12 m (7H, C6H3 and C6H4), 8.52 s (1H,
HC=N), 9.93 s (1H, CO2H). Found, %: C 66.32; H 5.41;
N 4.07. M 309.6. C18H17NO5. Calculated, %: C 66.05;
H 5.23; N 4.28. M 327.3.
4-Hydroxy(alkyloyloxy, aryloyloxy)-3-methoxy-
(ethoxy)phenylmethylene(4-carboxyphenyl)-amines
IIIa–IIIy and IVa–IVk (Schiff’s bases). General
procedure. In 50–100 ml of anhydrous methanol was
dissolved 0.01 mol of vanillin, vanillal, or their ester I,
and 0.01 m,ol of 4-aminobenzoic acid (II) (for compounds
IIIy and IVk 0.02 mol) was added, the solution obtained
was heated at reflux for 1.5–2 h and left standing for
20–30 h at 20–23°C. The separated precipitate of
azomethines IIIa–IIIy and IVa–IVk was filtered on
a glass frit, washed with a little of methanol, and dried in
a vacuum. The obtained compounds IIIa–IIIy and IVa–
IVk were sufficiently pure and did not require
recrystallization.
4-Butyryloxy-3-methoxyphenylmethylene(4-
carboxyphenyl)amine (IIId). Yield 92%, mp 139–140°C
–1
(from methanol). IR spectrum, n, cm : 2100–3650 (OH),
3080, 3069, 3008 (CHAr and =CH), 2965, 2935, 2877, 2850,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 2 2006

DIKUSAR et al.
208
2825, 2800 (CHAlk), 1757, 1676 (C=O), 1633 (C=N), 1589,
1576, 1508, 1466, 1429, 1417, 1380, 1369 (Ar), 1319, 1276,
1218, 1198, 1173, 1149, 1138, 1123, 1104, 1080, 1031, 1012,
975, 966, 945 (CO), 872, 853, 826, 775, 747, 699, 662,
640, 616 (CHAr). UV spectrum, lmax (e): 205 (23000),
220 (19000), 280 (22000), 295 (21000), 315 (13000).
1H NMR spectrum, d, ppm: 1.05 t (3H, CH3), 1.65 m
(2H, CH2), 2.55 t (2H, CH2), 3.87 s (3H, CH3O), 6.42–
8.15 m (7H, C6H3 and C6H4), 8.53 s (1H, HC=N),
9.92 s (1H, CO2H). Found, %: C 67.11; H 5.80; N 3.83.
M 325.9. C19H19NO5. Calculated, %: C 66.85; H 5.61;
N 4.10. M 341.4.
1218, 1196, 1170, 1141, 1120, 1076, 1033, 1012, 987, 973,
946 (CO), 871, 855, 839, 808, 790, 777, 746, 722, 700,
660, 636, 616 (CHAr). UV spectrum, lmax (e): 205
(22000), 220 (18000), 280 (23000), 295 (21000), 315
(12000). 1H NMR spectrum, d, ppm: 0.90 t (3H, CH3),
1.20–1.55 m [12H, (CH2)6], 1.85 t (2H, CH2), 2.65 t (2H,
CH2), 3.85 s (3H, CH3O), 6.44–8.15 m (7H, C6H3 and
C6H4), 8.52 s (1H, HC=N), 9.93 s (1H, CO2H). Found,
%: C 70.88; H 7.49; N 2.95. M 418.5. C25H31NO5.
Calculated, %: C 70.57; H 7.34; N 3.29. M 425.5.
4-Tridecanoyloxy-3-methoxyphenylmethylene-
(4-carboxyphenyl)amine (IIIh). Yield 91%, mp 122–
–1
4-Isobutyryloxy-3-methoxyphenylmethylene-(4-
123OC (from methanol). IR spectrum, n, cm : 2100–3650
carboxyphenyl)amine (IIIe). Yield 90%, mp 168–
169°C (from methanol). IR spectrum, n, cm : 2050–3630
(OH), 3076, 3050, 3015 (CHAr and =CH), 2949, 2920,
2851, 2790 (CHAlk), 1754, 1680 (C=O), 1627 (C=N), 1602,
1586, 1504, 1471, 1456, 1417, 1372, (Ar), 1318, 1275,
1260, 1231, 1217, 1196, 1173, 1155, 1139, 1117, 1090, 1059,
1034, 1014, 984, 947, 920 (CO), 876, 866, 839, 810, 791,
777, 747, 719, 700, 662, 615 (CHAr). UV spectrum, lmax
(e): 205 (23000), 220 (19000), 280 (22000), 295 (21000),
–1
(OH), 3080, 3050, 3010 (CHAr and =CH), 2969, 2933,
2875, 2851, 2830 (CHAlk), 1754, 1677 (C=O), 1631 (C=N),
1589, 1568, 1507, 1466, 1429, 1417, 1385, 1369, 1345 (Ar),
1317, 1276, 1217, 1172, 1152, 1124, 1093, 1028, 980, 965,
945 (CO), 869, 853, 815, 775, 740, 720, 695, 660, 615
(CHAr). UV spectrum, lmax (e): 205 (23000), 220 (18000),
1
315 (13000). H NMR spectrum, d, ppm: 0.90 t (3H,
1
280 (22000), 295 (22000), 315 (12000). H NMR
CH3), 1.32 m [18H, (CH2)9], 1.77 m (2H, CH2), 2.64 t
(2H, CH2), 3.84 s (3H, CH3O), 6.45–8.15 m (7H, C6H3
and C6H4), 8.54 s (1H, HC=N), 9.93 s (1H, CO2H).
Found, %: C 72.21; H 8.16; N 2.84. M 459.2. C28H37NO5.
Calculated, %: C 71.92; H 7.98; N 3.00. M 467.6.
spectrum, d, ppm: 1.36 d [6H, (CH3)2C], 2.90 quintet
(1H, CH), 3.88 s (3H, CH3O), 6.43–8.14 m (7H, C6H3
and C6H4), 8.52 s (1H, HC=N), 9.93 s (1H, CO2H).
Found, %: C 67.06; H 5.77; N 3.87. M328.3. C19H19NO5.
Calculated, %: C 66.85; H 5.61; N 4.10. M 341.4.
4-Stearoyloxy-3-methoxyphenylmethylene(4-
4-Capryiloyloxy-3-methoxyphenylmethylene-(4-
carboxyphenyl)amine (IIIi). Yield 90%, mp 33–34°C
(from methanol). IR spectrum, n, cm : 2200–3700 (OH),
–1
carboxyphenyl)amine (IIIf). Yield 92%, mp 141–142°C
–1
(from methanol). IR spectrum, n, cm : 2030–3600 (OH),
3080, 3050, 3010 (CHAr and =CH), 2955, 2918, 2849, 2800
(CHAlk), 1752, 1676 (C=O), 1634 (C=N), 1605, 1590,
1570, 1510, 1470, 1430, 1420, 1375, 1365 (Ar), 1325, 1276,
1225,1195,1175,1150,1136,1125,1115,1100,1060,1032,
1020, 990, 980, 970, 940, 920 (CO), 871, 855, 840, 805,
795, 780, 745, 720, 700, 655, 630, 617 (CHAr). UV
spectrum, lmax (e): 204 (21000), 220 (18000), 280 (21000),
295 (20000), 315 (11000). 1H NMR spectrum, d, ppm:
0.90 t (3H, CH3), 1.10–2.10 m [30H, (CH2)15], 2.70 t
(2H, CH2), 3.87 s (3H, CH3O), 6.45–8.15 m (7H, C6H3
and C6H4), 8.54 s (1H, HC=N), 9.92 s (1H, CO2H).
Found, %: C 74.07; H 9.02; N 2.19. M 529.8. C33H47NO5.
Calculated, %: C 73.71; H 8.81; N 2.60. M 537.7.
3080, 3010 (CHAr and =CH), 2960, 2920, 2975, 2850, 2820,
2800 (CHAlk), 1757, 1681 (C=O), 1632 (C=N), 1593, 1571,
1505, 1463, 1419, 1380, 1360 (Ar), 1315, 1286, 1222, 1197,
1196, 1169, 1152, 1135, 1112, 1075, 1034, 1010, 980, 945
(CO), 868, 850, 830, 780, 755, 747, 720, 705, 660, 635,
615 (CHAr). UV spectrum, lmax (e): 205 (23000), 220
(18000), 280 (22000), 295 (21000), 315 (13000). 1H NMR
spectrum, d, ppm: 0.93 t (3H, CH3), 1.34 m [8H, (CH2)4],
1.80 m (2H, CH2), 2.60 m (2H, CH2), 3.87 s (3H, CH3O),
6.45–8.15 m (7H, C6H3 and C6H4), 8.53 s (1H, HC=N),
9.92 s (1H, CO2H). Found, %: C 69.84; H 7.03; N 3.23.
M 384.0. C23H27NO5. Calculated, %: C 69.50; H 6.85;
N 3.52. M 397.5.
4-Acryloyloxy-3-methoxyphenylmethylene(4-
4-Decanoyloxy-3-methoxyphenylmethylene-(4-
carboxyphenyl)amine (IIIj). Yield 90%, mp 160–161°C
(from methanol). IR spectrum, n, cm : 2050–3600 (OH),
3090, 3068, 3013 (CHAr and =CH), 2980, 2945, 2922, 2879,
2850, 2820, 2795 (CHAlk), 1760, 1677 (C=O), 1633 (C=N),
1590, 1570, 1507, 1467, 1429, 1417, 1404, 1369 (Ar), 1318,
1277, 1218, 1198, 1173, 1144, 1117, 1031, 1012, 967, 943
–1
carboxyphenyl)amine (IIIg). Yield 90%, mp 152–
–1
153°C (from methanol). IR spectrum, n, cm : 2100–3540
(OH), 3075, 3050, 3010 (CHAr and =CH), 2956, 2924,
2853, 2800 (CHAlk), 1749, 1683 (C=O), 1630 (C=N), 1588,
1570, 1507, 1471, 1452, 1417, 1374, 1360 (Ar), 1314, 1276,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 2 2006

PREPARATIVE SYNTHESIS OF 4-HYDROXY(ALKYLOYLOXY,ARYLOYLOXY)-3-...
209
(CO), 899, 872, 853, 793, 775, 746, 698, 672, 615 (CHAr).
UV spectrum, lmax (e): 206 (25000), 220 (22000), 278
(23000), 295 (21000), 315 (13000). 1H NMR spectrum,
d, ppm: 3.88 s (3H, CH3O), 5.84–6.88 m (CH=CH2),
6.50–8.15 m (7H, C6H3 and C6H4), 8.55 s (1H, HC=N),
9.94 s (1H, CO2H). Found, %: C 66.82; H 4.74; N 4.16.
M 320.7. C18H15NO5. Calculated, %: C 66.46; H 4.65;
N 4.31. M 325.3.
295 (21000), 315 (12000). 1H NMR spectrum, d, ppm:
3.82 s (2H, CH2), 3.89 C (3H, CH3O), 6.40–8.10 m (12H,
C6H3, C6H4 and C6H5), 8.54 s (1H, HC=N), 9.94 s (1H,
CO2H). Found, %: C 71.18; H 5.12; N 3.32. M 381.9.
C23H19NO5. Calculated, %: C 70.94; H 4.92; N 3.60.
M 389.4.
4-(2-Phenylbutyryloxy)-3-methoxyphenyl-
methylene(4-carboxyphenyl)amine (IIIn). Yield 90%,
–1
4-Methacryloyloxy-3-methoxyphenylmethylene-
mp 141–142°C (from methanol). IR spectrum, n, cm :
(4-carboxyphenyl)amine (IIIk). Yield 92%, mp 204–
205°C (from methanol). IR spectrum, n, cm : 2130–3630
2050–3650 (OH), 3090, 3070, 3030, 3005 (CHAr and
=CH), 2965, 2930, 2870, 2845, 2830, 2800 (CHAlk), 1759,
1686 (C=O), 1631 (C=N), 1601, 1583, 1508, 1465, 1452,
1419, 1380, 1362 (Ar), 1313, 1277, 1263, 1221, 1197, 1154,
1145, 1120, 1104, 1081, 1057, 1023, 994, 940 (CO), 875,
860, 845, 805, 780, 760, 745, 700, 650, 610 (CHAr). UV
spectrum, lmax (e): 208 (29000), 220 (21000), 280 (21000),
295 (21000), 315 (11000). 1H NMR spectrum, d, ppm:
1.44 d (3H, CH3), 2.90 d (2H, CH2), 3.40 q (1H, CH),
3.88 s (3H, CH3O), 6.42–8.12 m (12H, C6H3, C6H4 and
C6H5), 8.55 s (1H, HC=N), 9.93 s (1H, CO2H). Found,
%: C 72.26; H 5.78; N 3.14. M 394.0. C25H23NO5.
Calculated, %: C 71.93; H 5.55; N 3.36. M 417.5.
–1
(OH), 3080, 3045, 3008 (CHAr and =CH), 2980, 2930,
2880, 2845, 2830, 2800 (CHAlk), 1731, 1690 (C=O), 1631
(C=N), 1589, 1570, 1509, 1459, 1417, 1376 (Ar), 1320,
1290, 1278, 1219, 1202, 1173, 1153, 1121, 1034, 1012, 980,
945 (CO), 869, 852, 815, 804, 774, 745, 700, 665, 640,
625 (CHAr). UV spectrum, lmax (e): 206 (26000), 221
(23000), 277 (23000), 295 (22000), 315 (12000). 1H NMR
spectrum, d, ppm: 2.10 t (3H, CH3), 3.87 s (3H, CH3O),
5.80 t (1H, =CH), 6.40 t (1H, =CH), 6.50–8.15 m (7H,
C6H3 and C6H4), 8.54 s (1H, HC=N), 9.93 s (1H, CO2H).
Found, %: C 67.61; H 5.08; N 3.87. M 331.4. C19H17NO5.
Calculated, %: C 67.25; H 5.05; N 4.13. M 339.3.
4-[2-(4-Toluyloxy)propionyloxy]-3-methoxy-
4-Oleoyloxy-3-methoxyphenylmethylene(4-
phenylmethylene(4-carboxyphenyl)amine (IIIo).
carboxyphenyl)amine (IIIl). Yield 90%, mp 111–112°C Yield 94%, mp 213–214°C (from methanol). IR spectrum,
–1
–1
(from methanol). IR spectrum, n, cm : 2150–3650 (OH),
n, cm : 2200–3700 (OH), 3100, 3074, 3060, 3040, 3006
3076, 3047, 3007 (CHAr and =CH), 2960, 2924, 2852, 2800
(CHAlk), 1756, 1676 (C=O), 1633 (C=N), 1592, 1508,
1466, 1430, 1416, 1380 (Ar), 1319, 1278, 1220, 1199, 1173,
1150, 1116, 1031, 970, 940 (CO), 880, 860, 840, 780, 745,
735, 720, 700, 660, 640, 615 (CHAr). UV spectrum,
(CHAr and =CH), 2981, 2941, 2921, 2889, 2854, 2800
(CHAlk), 1751, 1689 (C=O), 1629 (C=N), 1603, 1589,
1570, 1509, 1481, 1461, 1417, 1397, 1365 (Ar), 1321, 1278,
1260, 1242, 1222, 1199, 1175, 1161, 1118, 1045, 1032, 971
(CO), 875, 854, 840, 811, 775, 747, 701, 650, 617 (CHAr).
UV spectrum, lmax (e): 206 (31000), 221 (24000), 280
lmax (e): 205 (25000), 220 (23000), 277 (22000), 295
(22000), 315 (12000). 1H NMR spectrum, d, ppm: 0.90 t
(3H, CH3), 1.08–2.20 m [22H, (CH2)5 and (CH2)6], 2.60
t (2H, CH2), 3.86 s (3H, CH3O), 5.40 t [2H, 2(=CH)],
6.45–8.20 m (7H, C6H3 and C6H4), 8.55 s (1H, HC=N),
9.94 s (1H, CO2H). Found, %: C 74.23; H 8.62; N 2.38.
M 527.5. C33H45NO5. Calculated, %: C 73.99; H 8.47;
N 2.61. M 535.7.
(23000), 295 (21000), 315 (11000). H NMR spectrum,
1
d, ppm: 2.32 s (3H, CH3), 3.10 t (2H, CH2O), 3.89 s (3H,
CH3O), 4.40 t (2H, CH2C=O), 6.40–8.10 m (11H, C6H3
and 2C6H4), 8.54 s (1H, HC=N), 9.94 s (1H, CO2H).
Found, %: C 69.58; H 5.61; N 2.97. M413.9. C25H23NO6.
Calculated, %: C 71.93; H 5.55; N 3.36. M 417.5.
4-Benzoyloxy-3-methoxyphenylmethylene(4-
4-Phenylacetoxy-3-methoxyphenylmethylene-(4-
carboxyphenyl)amine (IIIp). Yield 92%, mp 226–
227°C (from methanol). IR spectrum, n, cm : 2040–3600
–1
carboxyphenyl)amine (IIIm). Yield 90%, mp 157–
–1
158°C (from methanol). IR spectrum, n, cm : 2100–3650
(OH), 3090, 3067, 3030, 3006 (CHAr and =CH), 2969,
2936, 2880, 2850, 2832, 2800 (CHAlk), 1725, 1694 (C=O),
1630 (C=N), 1601, 1587, 1570, 1506, 1467, 1454, 1421,
1378 (Ar), 1318, 1275, 1259, 1220, 1201, 1173, 1153, 1128,
1080, 1965, 1040, 1030, 1012, 1005, 987 (CO), 867, 852,
810, 804, 774, 747, 715, 699, 685, 655, 635, 620 (CHAr).
UV spectrum, lmax (e): 208 (21000), 241 (21000), 280
(17000), 320 (12000). 1H NMR spectrum, d, ppm: 3.87 s
(OH), 3100, 3064, 3037, 3006 (CHAr and =CH), 2960,
2923, 2877, 2853, 2835, 2795 (CHAlk), 1758, 1677 (C=O),
1631 (C=N), 1602, 1590, 1570, 1506, 1499, 1466, 1455,
1429, 1417, 1371, 1348 (Ar), 1317, 1277, 1217, 1197, 1173,
1151, 1134, 1121, 1113, 1032, 1012, 970, 942 (CO), 872,
853, 795, 775, 745, 729, 698, 667, 636, 616 (CHAr). UV
spectrum, lmax (e): 207 (30000), 220 (22000), 280 (22000),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 2 2006

DIKUSAR et al.
210
(3H, CH3O), 6.50–8.15 m (12H, C6H3, C6H4 and C6H5),
8.60 s (1H, HC=N), 10.00 s (1H, CO2H). Found, %:
C 70.45; H 4.73; N 3.76. M 372.6. C22H17NO5.
Calculated, %: C 70.39; H 4.56; N 3.73. M 375.4.
M 395.5. C22H16ClNO5. Calculated, %: C 64.48; H 3.93;
Cl 8.65; N 3.42. M 409.8.
4-(2,4-Dichlorobenzoyloxy)-3-methoxyphenyl-
methylene(4-carboxyphenyl)amine (IIIt). Yield 90%,
–1
4-(4-Methylbenzoyloxy)-3-methoxyphenyl-
mp 219–220°C (from methanol). IR spectrum, n, cm :
methylene(4-carboxyphenyl)amine (IIIq). Yield 93%,
2050–3650 (OH), 3095, 3080, 3040, 3010, 3000 (CHAr
and =CH), 2964, 2927, 2872, 2853, 2800 (CHAlk), 1745,
1711, 1689 (C=O), 1630 (C=N), 1602, 1589, 1508, 1460,
1450, 1429, 1417, 1378 (Ar), 1316, 1280, 1234, 1198, 1170,
1154, 1120, 1089, 1034 (CO), 871, 860, 830, 800, 780,
761, 740, 700, 675, 650, 635, 619 (CHAr), 550 (CCl). UV
spectrum, lmax (e): 210 (47000), 221 (30000), 257 (24000),
–1
mp 250–251°C (from methanol). IR spectrum, n, cm :
2040–3550 (OH), 3070, 3954, 3041, 3008 (CHAr and
=CH), 2872, 2850, 2830, 2795 (CHAlk), 1731, 1681 (C=O),
1625 (C=N), 1597, 1573, 1511, 1466, 1445, 1417, 1350
(Ar), 1314, 1280, 1218, 1203, 1160, 1120, 1109, 1070, 1032,
1020, 1010, 970 (CO), 869, 853, 837, 810, 775, 749, 720,
700, 687, 660, 640, 625 (CHAr). UV spectrum, lmax (e):
209 (23000), 220 (25000), 253 (28000), 280 (18000), 320
(12000). 1H NMR spectrum, d, ppm: 2.46 s (3H, CH3),
3.88 s (3H, CH3O), 6.50–8.20 m (11H, C6H3 and 2C6H4),
8.60 s (1H, HC=N), 10.00 s (1H, CO2H). Found, %:
C 71.25; H 5.14; N 3.41. M 384.1. C23H19NO5.
Calculated, %: C 70.94; H 4.92; N 3.60. M 389.4.
1
280 (21000), 295 (22000), 310 (12000). H NMR
spectrum, d, ppm: 3.90 s (3H, CH3O), 6.50–8.50 m (10H,
2C6H3 and C6H4), 8.62 s (1H, HC=N), 10.01 s (1H,
CO2H). Found, %: C 59.89; H 3.58; Cl 15.65; N 2.87.
M440.2. C22H15Cl2NO5. Calculated, %: C 59.48; H 3.40;
Cl 15.96; N 3.15. M 444.3.
4-(2,4-Dichlorophenoxyacetoxy)-3-methoxy-
phenylmethylene(4-carboxyphenyl)amine (IIIu).
Yield 95%, mp 195–196°C (from methanol). IR spectrum,
4-(2-Chlorobenzoyloxy)-3-methoxyphenyl-
methylene(4-carboxyphenyl)amine (IIIr). Yield 93%,
–1
–1
mp 209–210°C (from methanol). IR spectrum, n, cm :
n, cm : 2030–3630 (OH), 3100, 3080, 3045, 3020, 3000
2000–3640 (OH), 3095, 3067, 3020 (CHAr and =CH),
2990, 2960, 2923, 2873, 2852, 2800 (CHAlk), 1754, 1677
(C=O), 1629 (C=N), 1602, 1586, 1506, 1465, 1427, 1418,
1372 (Ar), 1319, 1277, 1241, 1218, 1192, 1165, 1152, 1125,
1091, 1082, 1034, 1024, 965 (CO), 875, 856, 809, 776,
748, 706, 696, 665, 650, 617 (CHAr), 552 (CCl). UV
spectrum, lmax (e): 207 (42000), 220 (26000), 257 (20000),
(CHAr and =CH), 2990, 2972, 2955, 2921, 2875, 2851,
2830, 2800 (CHAlk), 1774, 1686 (C=O), 1630 (C=N), 1589,
1538, 1508, 1480, 1419, 1392, 1370 (Ar), 1316, 1290, 1278,
1245, 1220, 1195, 1169, 1148, 1118, 1104, 1087, 1074, 1045,
1031, 1015, 960, 940 (CO), 871, 860, 850, 835, 802, 773,
755, 715, 697, 655, 640, 617 (CHAr), 545, 555 (CCl). UV
spectrum, lmax (e): 205 (42000), 220 (25000), 280 (23000),
295 (21000), 315 (12000). 1H NMR spectrum, d, ppm:
3.89 s (3H, CH3O), 5.00 s (2H, CH2), 6.45–8.10 m (10H,
2C6H3 and C6H4), 8.60 s (1H, HC=N), 9.98 s (1H,
CO2H). Found, %: C 58.64; H 3.77; Cl 14.72; N 2.60.
M465.8. C23H17Cl2NO6. Calculated, %: C 58.24; H 3.61;
Cl 14.95; N 2.95. M 474.3.
1
280 (22000), 295 (22000), 315 (13000). H NMR
spectrum, d, ppm: 3.91 s (3H, CH3O), 6.50–8.27 m (11H,
C6H3 and 2C6H4), 8.62 s (1H, HC=N), 10.02 s (1H,
CO2H). Found, %: C 64.82; H 4.16; Cl 8.39; N 3.20.
M 393.7. C22H16ClNO5. Calculated, %: C 64.48; H 3.93;
Cl 8.65; N 3.42. M 409.8.
4-(4-Chlorobenzoyloxy)-3-methoxyphenyl-
4-Bromoacetoxy-3-methoxyphenylmethylene-
methylene(4-carboxyphenyl)amine (IIIs). Yield 93%,
mp 256–257°C (from methanol). IR spectrum, n, cm :
(4-carboxyphenyl)amine (IIIv). Yield 90%, mp 205–
206°C (from methanol). IR spectrum, n, cm : 2030–3650
–1
–1
(OH), 3100, 3085, 3058, 3040, 3005 (CHAr and =CH),
2989, 2955, 2922, 2895, 2876, 2853, 2800 (CHAlk), 1768,
1692 (C=O), 1627 (C=N), 1602, 1586, 1575, 1500, 1470,
1451, 1429, 1416, 1406, 1378 (Ar), 1315, 1280, 1257, 1219,
1197, 1185, 1171, 1151, 1113, 1029, 1008, 975 (C–O), 871,
846, 818, 794, 774, 761, 746, 733, 697, 684, 655, 616
(CHAr), 543 (CBr). UV spectrum, lmax (e): 207 (25000),
221 (19000), 280 (24000), 295 (24000), 315 (15000).
1H NMR spectrum, d, ppm: 3.89 s (3H, CH3O), 4.40 s
(2H, CH2), 6.40–8.12 m (7H, C6H3 and C6H4), 8.54 s
(1H, HC=N), 9.94 s (1H, CO2H). Found, %: C 52.29;
2050–3650 (OH), 3086, 3059, 3010, 3000 (CHAr and
=CH), 2971, 2931, 2880, 2853, 2800 (CHAlk), 1730, 1696
(C=O), 1633 (C=N), 1590, 1509, 1489, 1463, 1452, 1427,
1416, 1372 (Ar), 1313, 1278, 1258, 1217, 1199, 1170, 1151,
1120, 1096, 1076, 1036, 1016, 982 (CO), 868, 848, 773,
749, 712, 699, 680, 660, 637, 620 (CHAr), 547 (CCl). UV
spectrum, lmax (e): 205 (40000), 220 (26000), 255 (18000),
1
280 (23000), 295 (20000), 315 (12000). H NMR
spectrum, d, ppm: 3.92 s (3H, CH3O), 6.45–8.25 m (11H,
C6H3 and 2C6H4), 8.63 s (1H, HC=N), 10.04 s (1H,
CO2H). Found, %: C 64.87; H 4.10; Cl 8.31; N 3.29
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PREPARATIVE SYNTHESIS OF 4-HYDROXY(ALKYLOYLOXY,ARYLOYLOXY)-3-...
211
H 3.76; Br 19.96; N 3.31. M 387.0. C17H14BrNO5.
Calculated, %: C 52.06; H 3.60; Br 20.37; N 3.57.
M 392.2.
M 618.7. C34H28N2O10. Calculated, %: C 65.38; H 4.52;
N 4.49. M 624.6.
4-Hydroxy-3-ethoxyphenylmethylene(4-
4-(4-Bromobenzoyloxy)-3-methoxyphenyl-
carboxyphenyl)amine (IVa). Yield 90%, mp 199–200°C
–1
methylene(4-carboxyphenyl)amine (IIIw). Yield 94%,
(from methanol). IR spectrum, n, cm : 1830–3550 (OH),
–1
mp 267–268°C (from methanol). IR spectrum, n, cm :
3070, 3051, 3000 (CHAr and =CH), 2984, 2930, 2897, 2855,
2820, 2800 (CHAlk), 1692 (C=O), 1628 (C=N), 1581,
1523, 1478, 1431, 1419, 1397, 1373 (Ar), 1315, 1294, 1245,
1218, 1168, 1121, 1045, 1018, 992, 976 (CO), 863, 851,
830, 811, 770, 753, 701, 657, 612 (CHAr). UV spectrum,
2000–3640 (OH), 3090, 3065, 3044, 3010 (CHAr and
=CH), 2960, 2934, 2920, 2900, 2870, 2852, 2824, 2795
(CHAlk), 1731, 1670 (C=O), 1632 (C=N), 1604, 1586,
1524, 1504, 1486, 1465, 1424, 1410, 1401 (Ar), 1315, 1293,
1278, 1261, 1220, 1200, 1175, 1155, 1119, 1071, 1050, 1036,
1012, 970 (CO), 897, 876, 847, 804, 777, 752, 730, 704,
681, 658, 637 (CHAr), 551 (CBr). UV spectrum, lmax (e):
206 (40000), 220 (28000), 257 (28000), 280 (24000), 295
(22000), 315 (12000). 1H NMR spectrum, d, ppm: 3.89 s
(3H, CH3O), 6.50–8.20 m (11H, C6H3 and 2C6H4),
8.61 s (1H, HC=N), 10.00 s (1H, CO2H). Found, %:
C 58.37; H 3.82; Br 17.14; N 2.81. M 442.9.
C22H16BrNO5. Calculated, %: C 58.17; H 3.55; Br 17.59;
N 3.08. M 454.3.
lmax (e): 206 (15000), 235 (10000), 295 (11000), 337
(13000). 1H NMR spectrum, d, ppm: 1.30 t (3H, CH3),
4.18 q (2H, CH2), 6.52 br.s (1H, OH), 6.50–7.95 m (7H,
C6H3 and C6H4), 8.50 s (1H, HC=N), 9.80 s (1H, CO2H).
Found, %: C 67.59; H 5.43; N 4.70. M 280.7. C16H15NO4.
Calculated, %: C 67.36; H 5.30; N 4.91. M 285.3.
4-Acetoxy-3-ethoxyphenylmethylene(4-
carboxyphenyl)amine (IVb). Yield 90%, mp 144–145°C
–1
(from methanol). IR spectrum, n, cm : 2030–3600 (OH),
3073, 3050, 3005 (CHAr and =CH), 2987, 2935, 2888, 2850,
2810 (CHAlk), 1766, 1683 (C=O), 1629 (C=N), 1599, 1578,
1509, 1470, 1425, 1393, 1366 (Ar), 1316, 1288, 1267, 1218,
1194, 1164, 1115, 1040, 1011, 980 (CO), 862, 837, 774,
763, 720, 700, 675, 640, 615 (CHAr). UV spectrum, lmax
(e): 205 (22000), 220 (19000), 280 (22000), 295 (21000),
4-(3-Nitrobenzoyloxy)-3-methoxyphenyl-
methylene(4-carboxyphenyl)amine (IIIx). Yield 92%,
–1
mp 256–257°C (from methanol). IR spectrum, n, cm :
2030–3600 (OH), 3105, 3075, 3050, 3035, 3000 (CHAr
and =CH), 2985, 2975, 2930, 2885, 2850, 2830, 2800
(CHAlk), 1749, 1679 (C=O), 1635 (C=N), 1610, 1594,
1570, 1508, 1481, 1458, 1415, 1380, 1320 (Ar), 1533, 1348
(NO2), 1314, 1283, 1248, 1219, 1195, 1151, 1118, 1100,
1074, 1054, 1033, 1002, 973 (CO), 872, 862, 815, 801,
770, 730, 713, 701, 655, 620 (CHAr). UV spectrum,
1
315 (12000). H NMR spectrum, d, ppm: 1.43 t (3H,
CH3), 2.30 s (3H, CH3COO), 4.13 q (2H, CH2), 6.40–
8.12 m (7H, C6H3 and C6H4), 8.52 s (1H, HC=N), 9.93 s
(1H, CO2H). Found, %: C 66.32; H 5.43; N 4.07.
M 316.5. C18H17NO5. Calculated, %: C 66.05; H 5.23;
N 4.28. M 327.3.
lmax (e): 205 (28000), 220 (44000), 260 (27000), 280
(24000), 295 (22000), 315 (12000). 1H NMR spectrum,
d, ppm: 3.90 s (3H, CH3O), 6.50–9.15 m (11H, C6H3 and
2C6H4), 8.63 s (1H, HC=N), 10.04 c (1H, CO2H). Found,
%: C 63.08; H 4.01; N 6.30. M 417.6. C22H16N2O7.
Calculated, %: C 62.86; H 3.84; N 6.66. M 420.4.
4-Propionyloxy-3-ethoxyphenylmethylene(4-
carboxyphenyl)amine (IVc). Yield 93%, mp 175–176°C
–1
(from methanol). IR spectrum, n, cm : 2030–3650 (OH),
3074, 3053, 3035, 3010 (CHAr and =CH), 2982, 2942,
2922, 2900, 2883, 2853, 2800 (CHAlk), 1759, 2684 (C=O),
1629 (C=N), 1600, 1529, 1513, 1476, 1462, 1426, 1398,
1354 (Ar), 1314, 1290, 1270, 1223, 1165, 1144, 1113, 1078,
1041, 1011, 982 (CO), 872, 849, 825, 804, 774, 762, 700,
666, 611 (CHAr). UV spectrum, lmax (e): 205 (23000),
220 (20000), 280 (21000), 295 (20000), 315 (11000).
1H NMR spectrum, d, ppm: 1.37 t (3H, CH3), 1.42 t (3H,
CH3), 2.68 q (2H, CH2), 4.15 q (2H, CH2), 6.40–8.14 m
(7H, C6H3 and C6H4), 8.53 s (1H, HC=N), 9.94 s (1H,
CO2H). Found, %: C 67.09; H 5.87; N 3.84. M 330.6.
C19H19NO5. Calculated, %: C 66.85; H 5.61; N 4.10.
M 341.4.
4-Succinyloxy-3-methoxyphenylmethylene(4-
carboxyphenyl)amine (IIIy). Yield 94%, mp 255–256°C
–1
(from methanol). IR spectrum, n, cm : 2030–3650 (OH),
3071, 3000 (CHAr and =CH), 2970, 2924, 2837, 2851, 2795
(CHAlk), 1760, 1681 (C=O), 1632 (C=N), 1599, 1586,
1507, 1468, 1450, 1419, 1370 (Ar), 1314, 1277, 1220, 1200,
1169, 1152, 1124, 1032, 1013, 968 (CO), 874, 862, 835,
807, 775, 753, 745, 700, 671, 636, 610 (CHAr). UV
spectrum, lmax (e): 206 (45000), 220 (35000), 280 (43000),
295 (43000), 315 (24000). 1H NMR spectrum, d, ppm:
3.06 s [4H, (CH2)2], 3.88 s (6H, 2CH3O), 6.40–8.12 m
(14H, 2C6H3 and 2C6H4), 8.53 s (2H, 2HC=N), 9.94 s
(2H, CO2H). Found, %: C 65.57; H 4.84; N 4.25.
4-Butyryloxy-3-ethoxyphenylmethylene(4-
carboxyphenyl)amine (IVd). Yield 93%, mp 168–169°C
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 2 2006

DIKUSAR et al.
212
–1
(from methanol). IR spectrum, n, cm : 2030–3600 (OH),
3070, 3050, 3020 (CHAr and =CH), 2980, 2970, 2933, 2900,
2875, 2850, 2830, 2800 (CHAlk), 1758, 1685 (C=O), 1626
(C=N), 1601, 1581, 1514, 1428, 1395 (Ar), 1314, 1288,
1248, 1220, 1190, 1166, 1119, 1085, 1041, 1012, 975 (CO),
869, 846, 808, 775, 763, 753, 696, 664, 613 (CHAr). UV
spectrum, lmax (e): 205 (22000), 220 (20000), 280 (22000),
295 (22000), 315 (12000). 1H NMR spectrum, d, ppm:
1.04 t (3H, CH3), 1.43 t (3H, CH3), 1.64 m (2H, CH2),
2.54 t (2H, CH2), 4.14 q (2H, CH2), 6.45–8.15 m (7H,
C6H3 and C6H4), 8.52 s (1H, HC=N), 9.94 s (1H, CO2H).
Found, %: C 67.92; H 6.13; N 3.80. M 350.4. C20H21NO5.
Calculated, %: C 67.59; H 5.96; N 3.94. M 355.4.
2845, 2830, 2800 (CHAlk), 1727, 1693 (C=O), 1632 (C=N),
1603, 1592, 1571, 1509, 1431, 1390, 1380 (Ar), 1317, 1295,
1278, 1261, 1222, 1195, 1161, 1125, 1081, 1064, 1051, 1026,
1015, 990 (CO), 866, 850, 805, 790, 775, 755, 698, 684,
655, 640, 620 (CHAr). UV spectrum, lmax (e): 208
(22000), 240 (22000), 280 (17000), 320 (11000). 1H NMR
spectrum, d, ppm: 1.26 t (3H, CH3), 4.18 q (2H, CH2),
6.48–8.15 m (12H, C6H3, C6H4 and C6H5), 8.62 s (1H,
HC=N), 10.02 s (1H, CO2H). Found, %: C 71.23; H 5.16;
N 3.60. M 380.8. C23H19NO5. Calculated, %: C 70.94;
H 4.92; N 3.60. M 389.4.
4-(4-Methylbenzoyloxy)-3-ethoxyphenyl-
methylene(4-carboxyphenyl)amine (IVh). Yield 94%,
–1
4-Isobutyryloxy-3-ethoxyphenylmethylene(4-
mp 213–214°C (from methanol). IR spectrum, n, cm :
carboxyphenyl)amine (IVe). Yield 90%, mp 191–192°C
(from methanol). IR spectrum, n, cm : 2020–3620 (OH),
2020–3700 (OH), 3100, 3071, 3040, 3000 (CHAr and
=CH), 2983, 2920, 2879, 2851, 2800 (CHAlk), 1727, 1688
(C=O), 1631 (C=N), 1593, 1511, 1429, 1385 (Ar), 1318,
1276, 1270, 1227, 1202, 1182, 1163, 1128, 1079, 1043, 1020,
990 (CO), 875, 850, 830, 805, 780, 755, 743, 700, 680,
665, 630, 625, 615 (CHAr). UV spectrum, lmax (e): 208
(22000), 220 (25000), 253 (27000), 280 (19000), 320
(12000). 1H NMR spectrum, d, ppm: 1.26 t (3H, CH3),
2.48 s (3H, CH3), 4.19 q (2H, CH2), 6.45–8.12 m
(11H, C6H3 and 2C6H4), 8.63 s (1H, HC=N), 10.02 s
(1H, CO2H). Found, %: C 71.68; H 5.29; N 3.24. M 389.9.
C24H21NO5. Calculated, %: C 71.45; H 5.25; N 3.47.
M 403.4.
–1
3075, 3060, 3020, 3000 (CHAr and =CH), 2980, 2930,
2880, 2850, 2830, 2800 (CHAlk), 1755, 1685 (C=O), 1625
(C=N), 1600, 1586, 1572, 1508, 1469, 1425, 1394, 1367,
1352 (Ar), 1316, 1290, 1275, 1216, 1160, 1124, 1099, 1042,
1011, 975 (CO), 867, 835, 820, 774, 755, 700, 660, 615
(CHAr). UV spectrum, lmax (e): 206 (23000), 220 (21000),
1
280 (22000), 295 (23000), 315 (13000). H NMR
spectrum, d, ppm: 1.35 d [6H, (CH3)2C], 1.44 t (3H, CH3),
2.92 quintet (1H, CH), 4.14 q (2H, CH2), 6.45–8.15 m
(7H, C6H3 and C6H4), 8.54 s (1H, HC=N), 9.94 s (1H,
CO2H). Found, %: C 67.90; H 6.10; N 3.88. M 352.8.
C20H21NO5. Calculated, %: C 67.59; H 5.96; N 3.94.
M 355.4.
4-(2-Chlorobenzoyloxy)-3-ethoxyphenyl-
methylenen(4-carboxyphenyl)amine (IVi). Yield 94%,
–1
4-Isovaleroyloxy-3-ethoxyphenylmethylene(4-
mp 198–199°C (from methanol). IR spectrum, n, cm :
carboxyphenyl)amine (IVf). Yield 90%, mp 156–157°C
(from methanol). IR spectrum, n, cm : 2030–3640 (OH),
2020–3620 (OH), 3100, 3080, 3070, 3040, 3010 (CHAr
and =CH), 2990, 2989, 2920, 2870, 2800 (CHAlk), 1753,
1675 (C=O), 1630 (C=N), 1597, 1588, 1575, 1503, 1470,
1423, 1400, 1340 (Ar), 1316, 1281, 1260, 1234, 1216, 1189,
1162, 1150, 1134, 1108, 1082, 1024, 963 (CO), 875, 864,
825, 815, 790, 776, 749, 740, 704, 695, 681, 660, 640, 630,
615 (CHAr), 545 (CCl). UV spectrum, lmax (e): 208
(43000), 220 (25000), 258 (21000), 280 (22000), 295
(22000), 315 (12000). 1H NMR spectrum, d, ppm: 1.27 t
(3H, CH3), 4.19 q (2H, CH2), 6.50–8.28 m (11H, C6H3
and 2C6H4), 8.64 s (1H, HC=N), 10.02 s (1H, CO2H).
Found, %: C 65.35; H 4.41; Cl 8.07; N 3.10. M 416.2.
C23H18ClNO5. Calculated, %: C 65.18; H 4.28; Cl 8.36;
N 3.30. M 423.9.
–1
3085, 3070, 3030, 3005 (CHAr and =CH), 2965, 2935,
2875, 2855, 2830, 2800 (CHAlk), 1763, 1682 (C=O), 1627
(C=N), 1600, 1587, 1572, 1505, 1427, 1392, 1370 (Ar),
1315, 1288, 1275, 1245, 1215, 1170, 1154, 1119, 1089, 1039,
975 (CO), 870, 854, 830, 800, 775, 745, 730, 700, 655,
630, 620 (CHAr). UV spectrum, lmax (e): 205 (21000),
220 (22000), 280 (22000), 295 (23000), 315 (12000).
1H NMR spectrum, d, ppm: 1.12 d [6H, (CH3)2C], 1.42 t
(3H, CH3), 1.42–2.90 m (3H, CH and CH2), 4.12 q (2H,
CH2), 6.45–8.20 m (7H, C6H3 and C6H4), 8.52 s (1H,
HC=N), 9.93 s (1H, CO2H). Found, %: C 68.63; H 6.44;
N 3.50. M 355.7. C21H23NO5. Calculated, %: C 68.28;
H 6.28; N 3.79. M 369.4.
4-(4-Chlorobenzoyloxy)-3-ethoxyphenyl-
4-Benzoyloxy-3-ethoxyphenylmethylene(4-
methylene(4-carboxyphenyl)amine (IVj). Yield 93%,
mp 227–228°C (from methanol). IR spectrum, n, cm :
2000–3630 (OH), 3100, 3090, 3073, 3055, 3020, 3003
(CHAr and =CH), 2983, 2934, 2900, 2870, 2854, 2800
–1
carboxyphenyl)amine (IVg). Yield 93%, mp 227–228°C
–1
(from methanol). IR spectrum, n, cm : 2040–3670 (OH),
3069, 3040, 3007 (CHAr and =CH), 2984, 2960, 2924, 2876,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 2 2006

PREPARATIVE SYNTHESIS OF 4-HYDROXY(ALKYLOYLOXY,ARYLOYLOXY)-3-...
213
(CHAlk), 1736, 1693 (C=O), 1630 (C=N), 1591, 1509,
tov, R.N., Opt. Spektrosk., 1964, vol. 17, p. 558.
1488, 1432, 1400, 1376 (Ar), 1320, 1283, 1259, 1225, 1205,
1175, 1162, 1123, 1090, 1071, 1042, 1013, 982 (CO), 866,
847, 821, 795, 775, 748, 698, 678, 662, 616 (CHAr), 549
(CCl). UV spectrum, lmax (e): 205 (39000), 220 (27000),
255 (19000), 280 (22000), 295 (20000), 315 (13000).
1H NMR spectrum, d, ppm: 1.28 t (3H, CH3), 4.20 q
(2H, CH2), 6.42–8.28 m (11H, C6H3 and 2C6H4), 8.64 s
(1H, HC=N), 10.04 s (1H, CO2H). Found, %: C 65.38;
H 4.37; Cl 8.12; N 3.06. M 418.0. C23H18ClNO5.
Calculated, %: C 65.18; H 4.28; Cl 8.36; N 3.30. M 423.9.
4. Roddar, S. and Sara, N., Indian J. Appl. Chem., 1970,
vol. 33, p. 242.
5. Minbaev, B.U., Shiffovy osnovaniya (Shiff’s Bases),Alma-
Ata: Nauka,1989, p. 140.
6. Minbaev, B.U. and Yashnova, N.I., Fiziko-khimicheskie
svoistva shiffovykh osnovanii (Physico Chemical
Properties of Shiff’s Bases),Alma-Ata: Nauka, 1990, p. 232.
7. Kozlov, N.S., 5,6-Benzokhinoliny (5,6-Benzoquinolines),
Minsk: Nauka i Tekhnika, 1970, p. 134.
8. Kozlov, N.G. and Basalaeva, L.I., Zh. Obshch. Khim., 2004,
vol. 74, p. 1003.
9. Profft, E. and Runge, F., and Jumar, A., Zh. Prakt. Khem.,
1954, vol. 1, p. 57.
4-Succinyloxy-3-ethoxyphenylmethylene(4-
carboxyphenyl)amine (IVk). Yield 90%, mp 247–248°C
–1
(from methanol). IR spectrum, n, cm : 2020–3640 (OH),
3071, 3005 (CHAr and =CH), 2979, 2926, 2872, 2855, 2800
(CHAlk), 1765, 1683 (C=O), 1628 (C=N), 1600, 1588,
1504, 1475, 1431, 1394, 1374 (Ar), 1314, 1274, 1216, 1194,
1166, 1158, 1112, 1039, 1011, 970 (CO), 864, 852, 840,
791, 773, 755, 728, 696, 672, 630, 613 (CHAr). UV
spectrum, lmax (e): 207 (44000), 220 (35000), 280 (42000),
295 (42000), 315 (23000). 1H NMR spectrum, d, ppm:
1.25 t (6H, 2CH3), 3.06 s [4H, (CH2)2], 4.19 q (4H,
2CH2), 6.42–8.12 m (14H, 2C6H3 and 2C6H4), 8.52 s
(2H, 2HC=N), 9.94 s (2H, CO2H). Found, %: C 66.43;
H 5.08; N 4.20. M 640.3. C36H32N2O10. Calculated, %:
C 66.25; H 4.94; N 4.29. M 652.7.
10. Daier, D.R. and Dyer, J.R., Applications of Absorption
Spectroscopy of Organic Compounds, Englewood Cliffs:
Prentice Hall, 1965. Translated under the title Prilozheniya
absorbtsionnoi spektroskopii organicheskikh
soedinenii, Moscow: Khimiya, 1970.
11. Stewart, J.J.P., J. Comput. Chem., 1989, vol. 10, p. 221.
12. Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T.,
Gordon, M.S., Jensen, J.H., Koseki, S., Matsunaga, N.,
Nguyen, K.A., Su, S.J., Midus, T.L., Dupnis, M., and
Montgomery, J.A., J. Comput. Chem., 1993, vol. 14, p. 1347.
13. Kozlov, N.G., Dikusar, E.A., Zelenkovskii, V.M., Potkin, V.I.,
Shirokii, V.L., Murashko, V.L., Khrustalev, V.N., andAnti-
pin, M.Yu., Zh. Obshch. Khim., 2004, vol. 74, p. 965.
14. Dikusar, E.A., Kozlov, N.G., Zelenkovskii, V.M.,
Zhukovskaya, N.A., Murashko, V.L., Zalesskaya, E.G.,
Moiseichuk, K.L., and Yuvchenko,A.P., Zh. Obshch. Khim.,
2003, vol. 73, p. 1352.
The study was carried out under the financial support
of the Foundation for Basic Research of Belarus Republic
(grant X03-079).
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