The synthesis and characterization of novel dibenzosulfide diamine and the application in the determination of heavy metals

Article abstract of DOI:10.1080/10426500600619484

New 2,2′-thio-bis [4-methyl (2-amino phenoxy) phenyl ether] (IV) was synthesized. The structure of this compound was confirmed on IR, ¹H, and ¹³C NMR data. A simple, efficient, and sensitive procedure is described for the spectrophot

Full text of DOI:10.1080/10426500600619484

Phosphorus, Sulfur, and Silicon, 181:2321–2326, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500600619484
The Synthesis and Characterization of Novel
Dibenzosulfide Diamine and the Application
in the Determination of Heavy Metals
Abbas Shockravi
Marzieh Chaloosi
Masoomeh Zakeri
Shahla Mozaffari
Esmaile Rostami
Ebrahim Abouzari-Lotf
Faculty of Chemistry, Teacher Training University, Tehran, Iran
New 2,2ꢀ-thio-bis [4-methyl (2-amino phenoxy) phenyl ether] (IV) was synthesized.
1
13
The structure of this compound was confirmed on IR, H, and C NMR data.
A simple, efficient, and sensitive procedure is described for the spectrophotometric
determination of a trace amount of Cd(II) or Co(II) in the presence of Zn(II) with
this diamine.
Keywords Cadmium; cobalt; diamine; dibenzosulfide; sulfide
INTRODUCTION
The determination of a trace amount of cadmium has received con-
siderable attention in the battle against environmental pollution. In
the determination of cadmium, various methods, including ICP-MS,1
ion choromatography,2 anodic stripping,3 and electrothermal atomic
absorption spectrometry,4 have been used. Many of these methods ei-
ther are time-consuming or require complicated and expensive instru-
ments. Therefore, methods that could determine a low concentration
of heavy metal ions rapidly and conveniently were researched.5−7 The
determination of a cadmium ion has been performed using different
ligands such as dithizone (diphenylthiocarbazone),8−10 2-aminobenzoic
acid (anthranic acid),11 2,2ꢀ-bipyridine,12 8-hydroxy quinoline,13 sodium
diethyldithiocarbamate,14 2-acetyl-2-thiazoline hydrazone,15 and N-
(5,6-dihydro-4H-1,3-thiazin-2-yl)-2-aminobenzimidazole.16
Received September 26, 2005; accepted January 30, 2006.
Address correspondence to Abbas Shockravi, Faculty of Chemistry, Teacher Training
University, No. 49, Mofatteh Ave., Tehran, 15614, Iran. E-mail: shockravi@saba.tmu.ac.ir
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A. Shockravi et al.
SCHEME 1
In continuation of our previous research for the synthesis of
new dibenzosulfoxide and dibenzosulfide monomers and macrocyclic
compounds,17−20 we now wish to report a new interesting dibenzosul-
fide diamine (IV) and its application for the efficient and simple deter-
mination of cadmium.
The dibenzosulfide (II) was synthesized based on the reported
procedure21 in a 65% yield. The treatment of II with the 1-fluoro-2-
nitro benzene in the presence of K2CO3 at refluxed DMF gave III in
90% yields (Scheme 1). A basic reduction of III with ammonium chlo-
ride in the presence of Zn at refluxed dry methanol afforded IV in a
90% yield (Scheme 2).
SCHEME 2
RESULTS AND DISCUSSION
In this article, we describe the syntheses of new 2,2ꢀ-thio-bis [4-methyl
(2-amino phenoxy) phenyl ether] (IV) by the reaction of 1-fluro-2-
nitro benzene with II, followed by a reduction. Our motive behind
the synthesis of this type of ligands was to examine their possible
applications in the cation recognition processes. Although this work

Novel Dibenzosulfide Diamine
2323
FIGURE 1 Electronic spectra of the diamine (IV) ligand in chloroform at
different concentrations.
is focused on the determination of cadmium, the evidence obtained in
this research indicate that this ligand could also be used for the deter-
mination of cobalt with the same procedure.
The electronic absorption spectra of a ligand with various concen-
trations are represented in Figure 1. An examination of Figure 1 in-
dicates that the electronic spectra of this ligand are largely depending
on the concentration. Increasing the compound concentration results
in increasing the absorbance of both bands at 254 and 286 nm, where
beyond a certain concentration of the compound (9.96 × 104−4 M) a very
broad bond is observed. This behavior can be ascribed to the association
of molecules through intermolecular hydrogen bonding.
The electronic absorption spectra of ligand and complexes of Cd+2
,
Zn+2, and Co+2 in the same concentration are shown in Figure 2. As can
be noticed, the absorption spectra of ligand-Cd and ligand-Co reflects
the presence of maximum absorptions at 208 and 244 nm, respectively,
which the ligand does not absorb appreciably. The electronic spectrm of
ligand-Zn does not show absorption. Therefore, there is no interference
from Zn+2 in the determination of Cd+2 and Co+2 with this ligand.
EXPERIMENTAL
Reagent and Material
All experiments were performed with analytical-reagent grade chemi-
cals and pure solvents. Doubly distilled water was used for preparation
aqueous solutions.

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A. Shockravi et al.
FIGURE 2 Electronic spectra of complexes of diamine (IV) ligand with Cd+2
Co+2, and Zn+2
,
.
The ligand was synthesized and purified as described herein.
Ligand stock solution (1.07 × 10−3 mol/L) was prepared in chloroform.
Stock solutions of 100 ppm of Cd(II), Zn(II), and Co(II) were made by
dissolving an appropriate amount of high purity cadmium nitrate, zinc
oxide, and cobalt nitrate (Merck, Germany) in distilled water, respec-
tively. Working solutions were prepared by an appropriate dilution of
stock solution.
Apparatus
The melting points (uncorrected) were measured by an Electrothermal
engineering LTD9100 apparatus. Elemental analysis was performed by
a CHN-O-Rapid Heraeus elemental analyzer (Wellesley, MA). IR spectra
1
were measured on a Perkin-Elmer model 543, H NMR and 13C NMR
spectra were obtained using a Bruker Avance DRX 500 apparatus.
A Milton Roy Model 1201 photomultiplier tube spectrophotometer
was interfaced with an IBM PCS-486 microcomputer by the spectro
program that was developed to convert the absorption data acquired
with the spectrometer used.
Ligand Synthesis and Procedures
2,2ꢀ-Thio-bis [4-methyl (2-nitro phenoxy) phenyl ether] (III)
A mixture of II, (1 mmol, 0.246 gr) and potassium carbonate (2
mmol, 0.331 gr) was added into a solution of DMF (100 mL) in a 500-mL

Novel Dibenzosulfide Diamine
2325
round-bottom flask. Then o-fluoro nitro benzene (2 mmol) was added,
and the suspension mixture was heated to a reflux temperature and
held for 24 h; then the mixture was allowed to cool to r.t. and subse-
quently poured into 700 mL of water to precipitate into a yellow solid.
The crude product was recrystallized from acetonitrile to afford a crys-
talline dinitro compound (75% yield) (see Scheme 1); m.p. 103–105◦C;
IR (KBr) 3109, 3079, 2920, 1610, 1583, 1511, 1487, 1475, 1338, 1249,
1240, 1107, 1053, 864, 850, 843, 754 cm−1; 1H NMR (500 MHz, CDCl3);
δ 2.32 (s, 6H, J = 8.4 Hz), 6.75–6.77 (d, 2H J = 8.4Hz), 6.89–6.90 (d, 2H,
J = 8.2 Hz), 7.08–7.12 (m, 4H), 7.18 (s, 2H), 7.34–7.37 (t, 2H, J = 7.5
Hz), 7.90–7.92 (d, 2H, J = 8 Hz) ppm; 13C NMR (500 MHz, CDCl3); δ
151.96, 151.31, 140.73, 136.25, 134.49, 134.23, 130.40, 126.61, 125.81,
122.61, 121.09, 118.97, 21.01 ppm; Elemental analysis: (found values)
C (63.91), H (4.12), N (5.76); (calculated values) C (63.93), H (4.13),
N (5.73).
2,2ꢀ-Thio-bis [4-methyl (2-amino phenoxy) phenyl ether] (IV)
A suspension of the intermediate III (1 mmol, 0.488 g) in 100 mL
of methanol containing Zn (20 mmol, 1.3 g) and ammonium chloride
(excess) was heated to a reflux temperature for 18–20 h. The reaction
mixture was cooled to r.t. and filtered through celite to remove the cat-
alyst, and the filtrate was concentrated under reduced pressure. The
product was recrystallized from ethanol and water to afford a white
crystalline diamine compound (85% yield) (see Scheme 2); m.p. 116–
118◦C; IR (KBr) 3462, 3370, 3034, 2924, 1620, 1597, 1584, 1510, 1500,
1476, 1459, 1302, 1266, 1226, 1137, 1058, 897, 819, 745 cm−1; 1H NMR
(500 MHz, CDCl3); δ2.27 (s, 6H), 3.14 (b, 4H), 6.63–6.69 (m, 2H), 6.75–
6.80 (m, 6H), 6.91–7.0 (m, 4H), 7.15–7.16 (d, 2H, J = 3Hz) ppm; 13C
NMR (500 MHz, CDCl3); δ 153.5, 143.4, 137.9, 133.2, 133.0, 129.3, 124.7,
124.4, 119.6, 118.8, 117.0, 116.6, 20.6 ppm; Elemental analysis: (found
values) C (72.84), H (5.63), N (6.57); (calculated values) C (72.87), H
(5.64), N (6.54).
The Spectrophotometric Determination of Cations
Absorption spectra of IV in different concentrations were recorded
between 200 and 500 nm (Figure 1). The absorption spectra of com-
plexes are shown in Figure 2. The concentration of the ligand was 1.59 ×
10−5 M, and the concentrations of metals were the same (10 ppm).
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