Microwave-assisted synthesis of the tetradentate Schiff-bases under solvent-free and catalyst-free condition

Article abstract of DOI:10.1081/SCC-120015804

Synthesis of tetradentate Shiff bases using microwave activation under solvent-free conditions with and without support is described. This method affords high yields in very short reaction times for synthesis of tetradentate Shiff bases.

Full text of DOI:10.1081/SCC-120015804

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Microwave-Assisted Synthesis of the Tetradentate
Schiff-Bases Under Solvent-Free and Catalyst-Free
Condition
a
a
a
Maryam Mirza-Aghayan , Mitra Ghassemzadeh , Maryam Hoseini & Mohammad
a
Bolourtchian
a
Chemistry and Chemical Engineering Research Center of Iran (CCERCI) , Tehran, Iran
Published online: 16 Aug 2006.
To cite this article: Maryam Mirza-Aghayan , Mitra Ghassemzadeh , Maryam Hoseini & Mohammad Bolourtchian (2003)
Microwave-Assisted Synthesis of the Tetradentate Schiff-Bases Under Solvent-Free and Catalyst-Free Condition, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 33:4, 521-525, DOI:
10.1081/SCC-120015804
To link to this article: http://dx.doi.org/10.1081/SCC-120015804
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Õ
SYNTHETIC COMMUNICATIONS
Vol. 33, No. 4, pp. 521–525, 2003
Microwave-Assisted Synthesis of the
Tetradentate Schiff-Bases Under Solvent-Free
and Catalyst-Free Condition
Maryam Mirza-Aghayan,* Mitra Ghassemzadeh,
Maryam Hoseini, and Mohammad Bolourtchian
Chemistry and Chemical Engineering Research Center
of Iran (CCERCI), Tehran, Iran
ABSTRACT
Synthesis of tetradentate Shiff bases using microwave activation
under solvent-free conditions with and without support is described.
This method affords high yields in very short reaction times for
synthesis of tetradentate Shiff bases.
The synthesis of tetradentate Schiff base ligands is an important
reaction in organic chemistry because of their applications in chemical
*
Engineering Research Center of Iran (CCERCI), P.O. Box 14335-186, Tehran,
Correspondence: Maryam Mirza-Aghayan,
Chemistry
and
Chemical
Iran; Fax: þ98 21 8037185; E-mail: m.mirzaaghayan@ccerci.ac.ir.
5
21
DOI: 10.1081/SCC-120015804
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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22
Mirza-Aghayan et al.
[1]
transformations. The ability of the tetradentate Schiff base to form
2]
[
stable complexes with different cations is well known.
In general, the synthesis of imines has been achieved using several
[
reagents such as zinc chloride, drying agentTiCl 4, molecular sieve
3]
[4]
[5]
[6]
or alumina. Although the synthesis of tetradentate Schiff bases has been
7]
[
extensively documented and a variety of methods being available, the
use of microwave irradiation with a support solid remains unknown.
[
Microwave (MW) enhanced chemical reaction in general and on
8]
[9]
organic solid supports in particular has gained popularity over the
usual homogeneous and heterogeneous reaction. They can be conducted
rapidly and provide pure products in quantitative yield without using
solvent.
In continuation of our investigations in organic reaction in solvent-
[10]
less systems, we now report a facile preparation of tetradentate Schiff
bases under solvent-free conditions using microwave irradiation. We
started our studies with the synthesis of tetradentate Schiff bases
0
2
–5(a–b) by the reaction of salicylaldehyde (1a) or 2 -hydroxyaceto-
phenone (1b) with the corresponding diamines supported on silica gel,
which is accelerated by exposure to microwaves (Sch. 1).
However, in order to obtain better yields, an alternative procedure
using no adsorbent was developed. Without the solid inorganic support
(
silica gel), the reaction is faster and the yields are higher (Table 1). The
absence of solvent coupled with the high yield and very short reaction
times make this procedure for the preparation of tetradentate Shiff bases
more attractive.
In conclusion, we have developed a simple procedure for the
synthesis of tetradentate Schiff base that proceeds rapidly under
Scheme 1.

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Synthesis of Tetradentate Schiff-Bases
523
Table 1. Solvent-free preparation of tetradentate Shiff bases, 2–5(a–b), using
microwave irradiation.
Microwave
With silica gel
as support
Without silica gel
as support
Time
(s)
Yield
(%)
Time
(s)
Yield
(%)
ReagentProduct
Ethylenediamine
2a
2b
3a
120
240
180
360
240
300
180
300
90
90
80
55
60
40
70
30
40
10
98
98
98
65
90
55
98
50
Phenylenediamine
120
480
110
100
120
300
3b
4a
4b
5a
4
-Chlorophenylenediamine
,3-Diaminopyridine
2
5
b
solvent-free condition. Protocol for the synthesis of tetradentate Schiff
base under focused microwave irradiation in the absence of any catalyst,
solid supportor solven t, affords a clean, efficientand an environmen ta lly
friendly method.
EXPERIMENTAL
Nuclear magnetic resonance spectra were registered on a Bruker
0 MHz in CDCl utilizing tetramethylsilane as internal standard. Mass
8
3
spectra were obtained on a FTSONS GC 8000/Trio 1000 under 70 eV.
Microwave irradiation was carried out in a National oven Model 6755 at
900 W.
General Procedure for Preparation of Compounds 2–5(a–b)
Zero pointfive equimolar of ht e diamines 2–5 were added to an
equimolar amountof aldehydes 1a–b (in condition of presence of inor-
ganic solid support, the aldehyde was supported on 0.4 g of silicagel 60,
Fluka, particle size <230 mesh ASTM). The reaction mixture was
irradiated in a microwave oven for the indicated time (Table 1). The
progress of reaction was monitored by TLC. After completion of the

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24
Mirza-Aghayan et al.
reaction, the residue was taken into CHCl , filtered, washed with CHCl3
3
(
2 ꢀ 10 mL) and the filtrate was evaporated to dryness to give the corre-
sponding compound. Fine purification was achieved by column chroma-
tography using hexane–ethylacetate 9:1 as eluent.
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Received in Japan November 27, 2001

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