Microwave-assisted synthesis of biphenyl-4,4'-dicarboxylic acid arylhydrazones in water medium

Full text of DOI:10.1134/S1070363214020327

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 2, pp. 335–337. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © V.V. Yurachka, L.I. Yuzhik, V.A. Tarasevich, V.E. Agabekov, V.K. Ol’khovik, 2014, published in Zhurnal Obshchei Khimii, 2014,
Vol. 84, No. 2, pp. 341–343.
LETTERS
TO THE EDITOR
Microwave-Assisted Synthesis of Biphenyl-4,4'-dicarboxylic Acid
Arylhydrazones in Water Medium
V. V. Yurachka, L. I. Yuzhik, V. A. Tarasevich, V. E. Agabekov, and V. K. Ol’khovik
Institute of Chemistry of New Materials, National Academy of Sciences of Belarus,
ul. Skoriny 36, Minsk, 220141 Belarus
e-mail: uozh@ichnm.basnet.by
Received August 19, 2013
DOI: 10.1134/S1070363214020327
Arylhydrazones like semicarbazones, thiosemi-
carbazones, and guanylhydrazones are used in the
preparation of pharmaceuticals [1], metal complexes
[2] and bioactive heterocyclic compounds [3].
irradiation in an aqueous medium when using
polystyrenesulfonic acid as a catalyst [9]. At the same
time, the data on the synthesis of substituted arylhyd-
razones of aromatic dicarboxylic acids are absent in
the literature.
Most of the known methods for arylhydrazones
synthesis include refluxing the reaction mixture in
methanol or ethanol for 16–24 h. In the case of
carbonyl compounds containing electron-withdrawing
groups the synthesis was performed under acid
catalysis conditions [4].
In this work, we obtained the substituted arylhyd-
razones of biphenyl-4,4'-dicarboxylic acid, the poten-
tial biologically active compounds, in an aqueous
medium under microwave irradiation.
The reaction proceeded via protonation of the
carbonyl group followed by condensation with hyd-
razide to form hydrazinocarbinol. The addition of acid
affects the reaction rate and causes an increase in the
yield of the desired products [7]. Further protonation
of the carbonyl group improves the solubility of some
carbonyl compounds in water.
At the same time many condensation and addition
reactions (for example, the Barbier and the Mannich
types reactions, Diels–Alder cycloaddition and
Knoevenagel condensation) occur also in aqueous
media [5]. However, efficient performance of organic
reactions in an aqueous media often requires complete
dissolution of the reagents. For this purpose organic
solvents are often added to the reaction mixture or the
reactions are carried out at heating [6]. It is known [7]
that the presence of water in the condensation of
amines with carbonyl-containing organic compounds
decreases the imines yield. Meanwhile, it has been
shown [8] that the reaction of aromatic aldehydes and
aliphatic amines in aqueous medium at 100°C afford
the corresponding imine with a yield of 65–90%.
Spectral data of the compounds obtained under
microwave-assisted synthesis completely corresponded
to those of arylhydrazones synthesized according to
standard procedure [10].
The reaction products (yield 69–77%) are high-
melting (Tdecomp > 320°C) crystalline substances,
poorly soluble in organic solvents. All the obtained
arylhydrazones are soluble in dimethyl sulfoxide and
dimethylformamide.
In many cases the use of microwave irradiation in
organic synthesis allows considerable reduction of the
reaction time, increase in the yields of the desired
products and minimization of the byproducts formation.
In conclusion, the developed by us envirom-
mentally friendly microwave-assisted synthesis of the
substituted arylhydrazones of biphenyl-4,4'-dicar-
boxylic acid in an aqueous medium in the presence of
an acid significantly reduces the reaction time (to
120 min) and provides good yields of the obtained
compounds. Furthermore, carrying out the reaction in
Aryl and heterocyclic hydrazones can be
synthesized starting from arylhydrazine, aldehydes or
ketones with yields up to 90% under microwave
335

336
YURACHKA et al.
Scheme 1.
Y
X
O
O
O
H
2
+
Z
H2N−HN
NH−NH2
I
II−VI
O
O
Y
X
X
Y
H+,
o
H2O, 20 C, 2 h
N−HN
NH−N
HC
Z
CH
Z
VII−XI
X = Y = H, Z = OH (II, VII); X = H, Y = OH, Z = OCH3 (III, VIII); X = Z = OCH3, Y = H (IV, IX); X = Y = H, Z = Cl
(V, X); X = Z = H, Z = NO2 (VI, XI).
an aqueous medium facilitates isolation of the reaction
products (see Scheme 1).
N,N'-Bis[3-hydroxy-4-methoxybenzylidene]bi-
phenyl-4,4'- dicarbohydrazide (VIII). Yield 77%. IR
spectrum (KBr), ν, cm–1: 3425–3099, 1645, 1612,
1583, 1525, 1444, 1297, 1278, 1252, 1221, 1174,
1135, 1063, 1014, 901, 877, 837, 753. 1H NMR
spectrum, δ, ppm: 11.73 s (2H, >NH), 9.86 s (2H,
OH), 8.29 s (2H, =CH), 8.00 d (4H, Нmeta, JHH 8.2 Hz),
7.89 d (4H, Нortho, JHH 8.1 Hz), 7.25 s (2H, 2,2'-Bn),
7.03 d (2H, 6,6'-Bn, JHH 7.9 Hz), 6.95 d (2H, 5,5'-Bn,
JHH 7.9 Hz), 3.77 s (6H, OCH3). Found, %: С 66.09; Н
4.68; N 9.93. C30H26N4O6. Calculated, %: С 66.91; Н
4.83; N 10.41.
General procedure of the synthesis. The
appropriate benzaldehyde derivative (2.2 mmol),
1 drop of conc. sulfuric acid, and 20 mL of water were
added to the finely ground dihydrazide of biphenyl-
4,4'-dicarboxylic acid (1.0 mmol, 0.27 g) obtained by
hydrazinolysis of its dimethyl ester [10]. The reaction
mixture was stirred at 120°C for 120 min. Microwave
power was varied from 850 W at the start of the
reaction to 4.3 W when temperature rises to 120°C (7–
10 s). After the reaction completion, the product was
filtered off, dried and recrystallized from ethanol–
benzene mixture (1 : 2).
N,N'-Bis[2,4-dimethoxybenzylidene]biphenyl-4,4'-
dicarbohydrazide (IX). Yield 77%. IR spectrum
(KBr), ν, cm–1: 1344, 1212, 1839, 1649, 1610, 1540,
1503, 1459, 1418, 1356, 1286, 1208, 1160, 1121,
1038, 905, 835, 752. 1H NMR spectrum, δ, ppm: 11.76
s (2H, >NH), 8.71 s (2H, =CH), 8.01 d (4H, Нmeta, JHH
8.3 Hz), 7.88 d (4H, Нortho, JHH 8.3 Hz), 7.79 d (2H,
6,6'-Bn, JHH 9.2 Hz), 6.63–6.61 m (4H, 3,3',5,5'-Bn),
3.83 s (6H, 4,4'-OCH3), 3.79 s (6H, 2,2'-OCH3).
Found, %: С 66.97; Н 5.11; N 9.52. C32H30N4O6.
Calculated, %: С 67.84; Н 5.3; N 9.89.
Biphenyl-4,4'-dicarboxylic acid dihydrazide (I).
IR spectrum (KBr), ν, cm–1: 3403, 3360, 3307, 3080,
3057, 3030, 3017, 1650, 1620, 1530, 1483, 1453,
1440, 1370, 1340, 1317, 1287, 1223, 1167, 1100,
1
1003, 980, 927, 907, 900, 843, 817, 750, 737, 710. H
NMR spectrum, δ, ppm: 9.83 s (2H, NH), 7.89 d (4H,
Нmeta, JHH 8.3 Hz), 7.78 d (4H, Нpara, JHH 8.3 Hz), 4.52
s (4H, NH2). Found, %: С 61.71; Н 4.98; N 20.47.
C14H14N4O2. Calculated, %: С 62.22; Н 5.19; N 20.74.
N,N'-Bis[4-hydroxybenzylidene]biphenyl-4,4'-di-
carbohydrazide (VII). Yield 75%. IR spectrum
(KBr), ν, cm–1: 3357, 3240, 3059, 1649, 1607, 1587,
1543, 1511, 1492, 1367, 1289, 1238, 1169, 1147,
N,N'-Bis[4-chlorobenzylidene]biphenyl-4,4'-di-
carbohydrazide (X). Yield 71%. IR spectrum (KBr),
ν, cm–1: 3441, 3223, 3058, 1649, 1609, 1544, 1489,
1365, 1293, 1146, 1090, 1060, 1114, 914, 838, 824,
1
1064, 1004, 965, 936, 840, 751. H NMR spectrum, δ,
1
ppm: 11.63 s (2H, >NH), 9.94 s (2H, OH), 8.36 s (2H,
=CH), 8.02 d (4H, Нmeta, JHH 7.5 Hz), 7.91 d (4H,
Нortho, JHH 6.5 Hz), 7.53 d (4H, Нortho, JHH 6.5 Hz), 6.81
d (4H, Нmeta, JHH 7.5 Hz). Found, %: С 69.86; Н 4.42;
N 11.53. C28H22N4O4. Calculated, %: С 70.29; Н 4.60;
N 11.72.
751. H NMR spectrum, δ, ppm: 11.99 s (2H, >NH),
8.44 s (2H, =CH), 8.03 d (4H, Нmeta, JHH 8.0 Hz), 7.91
d (4H, Нortho, JHH 8.3 Hz), 7.74 d (4H, 2,2',6,6'-Bn, JHH
8.3 Hz), 7.51 d (4H, 3,3,5,5'-Bn, JHH 8.2 Hz). Found,
%: С 65.53; Н 3.58; N 10.61. C28H20N4O2Cl2.
Calculated, %: С 65.24; Н 3.88; N 10.87.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 2 2014

MICROWAVE-ASSISTED SYNTHESIS OF BIPHENYL-4,4'-DICARBOXYLIC ACID
337
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N,N'-Bis[3-nitrobenzylidene]biphenyl-4,4'-di-
carbohydrazide (XI). Yield 69%. IR spectrum (KBr),
ν, cm–1: 3441, 3212, 3052, 1653, 1607, 1527, 1345,
1289, 1148, 1071, 1004, 948, 895, 842, 750, 737, 694.
1H NMR spectrum, δ, ppm: 12.19 s (2H, >NH), 8.56 d
(2H, 2,2'-Bn, JHH 13.7 Hz), 8.24 d (4H, 4,4',6,6'-Bn,
JHH 7.2 Hz), 8.15 s (2H, =CH), 8.04 d (4H, Нmeta, JHH
7.3 Hz), 7.92 d (4H, Нortho, JHH 7.8 Hz), 7.75–7.72 m
(2H, 5,5'-Bn). Found, %: С 60.31; Н 3.43; N 15.29.
C28H20N6O6. Calculated, %: С 60.43; Н 3.70; N 15.67.
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Reactions were carried out in a Monowave 300
reactor for microwave synthesis (Anton Paar GmbH)
with a maximum radiation power 850 W and a
frequency 2455 MHz.
1H NMR spectra (DMSO-d6) were recorded on a
Bruker Avance 500 spectrometer. IR spectra were
registered on a Bruker TENSOR 27 spectrophotometer
from a thin layer. Elemental analysis was performed
on an Elementar Vario Micro Cube.
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