Facile and Mild Synthesis and Characterization of Some New Diazo Dyes on the Basis
of Schiff Bases in the Presence of Nanocrystalline Magnesium Oxide as a Base
Catalyst under Solvent-free Conditions
Hossein Naeimi,
a
* Zahra Rashid
a
and Khadijeh Rabiei
b
a
Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, 87317, I.R. Iran
b
Department of Chemistry, Faculty of Basic Science, Qom University of Technology, Qom, 37195-1519, I.R. Iran
(Received: Jul. 6, 2015; Accepted: Sept. 21, 2015; Published Online: Nov. 6, 2015; DOI: 10.1002/jccs.201500264)
In this research, some new diazo dyes including Schiff base have been synthesized by the condensation re-
action between ethylenediamine and derivatives of salicylaldehyde containing diazo functional groups in
the presence of nanocrystalline magnesium oxide as a solid base catalyst under solvent-free conditions.
Nanocrystalline magnesium oxide has been characterized by XRD, BJH and TEM techniques. The corre-
sponding products have been obtained in excellent yields and high purity. All of the obtained diazo-Schiff
bases are highly colored and can be applicable as useful diazo dyes and characterized by spectroscopy
data.
Keywords: Azo dyes; Salicylaldehyde; Nanocrystalline magnesium oxide; Solvent-free; Schiff base.
INTRODUCTION
Organic reactions under solvent-free conditions have
gained in popularity in recent year. This is because sol-
vent-free reactions usually need shorter reaction times and
simpler reactors and resulting simple and efficient work up
procedures. Furthermore, reactions, which performed un-
der solvent-free conditions especially have been important
and attracted much attention.
1
The condensation of primary amines with carbonyl
compounds yields Schiff bases.
2
Schiff base ligands have
been extensively studied in coordination chemistry mainly
due to their facile syntheses, easily tunable steric, elec-
tronic properties and good solubility in common solvents.
3
Schiff bases that have solvent dependent Uv-Vis spectra
(solvatochromicity) can be suitable NLO (non linear opti-
cal active) materials.
4
Also these compounds are a class of
important compounds in medicinal and pharmaceutical
field. They show biological activities including antimicro-
bial,
5
anticancer
6,7
and herbicidal activities and find many
important catalytic applications.
8,9
Complexes of Schiff
bases with some transition metals show significant biologi-
cal notification including antimicrobial, antibacterial, anti-
fungal and anticancer activities.
10-12
In literature survey
13-16
a number of research articles have been published on
transition metal Schiff bases.
Azo compounds are very important molecules and
have attracted much attention in both fundamental and ap-
plied research.
17
Azo dyes are compounds that contain azo
groups linked to methine or aromatic sp
2
-hybridized C-
atoms. The formation of diazotizing reagent starts with
protonation of nitrous acid under strongly acidic condi-
tions, and azo coupling carried out at low temperature in
the presence of nucleophilic coupling components. The re-
activity of a nucleophilic substrate increases with increas-
ing basicity phenolates and amines. They have been widely
used in many applications such as textile dyes,
18,19
color-
ant,
20,21
printing systems, sensor,
22-24
analytical chemistry
25
and photo chromic materials.
26,27
Metal oxide nanomaterials exhibit unique physical
and chemical properties, and have potential applications in
magnetism, catalysis, electro-optical devices, sensors, and
nanodevices.
28-30
MgO nanostructures have unique physi-
cal and chemical properties due to high surface area and
structural defects. Nanosize MgO can be used for reactive
adsorbents; they have been used to the decontamination of
chemical warfare agents, reducing chlorofluorocarbons,
31
and have strongly basic properties, which are associated
with catalysts by base in many organic reactions.
32
In continuation of our work ongoing to the prepara-
tion of Schiff bases
33,34
and anthraquinone derivatives
35
as
useful dyes, and with attention to the basic properties of
nanocrystalline MgO in our previous works
36,37
here, we
hope to report the synthesis and characterization of some
new Schiff bases containing diazo groups through conden-
J. Chin. Chem. Soc. 2015, 62, 951-958 © 2015 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 951
JOURNAL OF THE CHINESE
CHEMICAL SOCIETY Article
* Corresponding author. Tel/Fax: 98-361-5552935; Email: naeimi@kashanu.ac.ir
Supporting information for this article is available on the www under http://dx.doi.org/10.1002/jccs.201500264