Chapter-5 Synthesis and Characterization of...
Transcript of Chapter-5 Synthesis and Characterization of...
Chapter-5
Department of Chemistry, S.P.University 191
Chapter-5 Synthesis and Characterization of Ligands
5.1 Introduction
Complex forming (Chelating) agents are becoming of increasing
importance in analytical chemistry such as in gravimetric, titrimetric
and colorimetric measurements. New types of complexes and complex
forming agents are constantly under investigation, for possible
analytical and industrial applications. The growing importance of the
use of metal chelates in analytical chemistry may be realized by the
ever-increasing number of publications on this subject. In the past
few years, inorganic chemistry has been greatly enriched by the
continuing development of coordination chemistry. There are many
new directions in coordination chemistry such as molecular
magnetism, supramolecular chemistry, bioinorganic chemistry,
medicinal chemistry and biosensors.
It was G.T. Morgan and Drew [1] who first coined the name
CHELATE from the Greek word CHELE used for crabs claw to
designate to cyclic structures which arise from the union of metallic
ions with organic or inorganic molecules, with two or more points of
attachments to produce a closed ring.
Coordination compounds were known when Alfred Werner
proposed, that Co(III) bears six ligands in an octahedral geometry. The
theory allows to understand the difference between coordinated and
ionic chloride in the coordination compound. Ligand may be attached
to the metal through a single atom (monodentate) or bound to the
metal through two or more atoms (bidentate or polydentate etc.).
When a bi- or polydentate ligand uses two or more donor atoms
bonded to a single metal ion, it is said to form a chelate complex.
Such complexes tend to be more stable than similar complexes
containing unidentate ligands.
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Prior to the 1980`s, research in the field of complex forming
reagents (CFRs) was one of the most active research area in inorganic
and analytical chemistry. The development of CFRs was stimulated by
research and progress in coordination chemistry and by studies of
complex equilibrium in solution. CFR are essential in the application
of highly efficient separation procedures such as high performance
liquid chromatography. From the reagent/reaction chemistry
viewpoint it is more logical to classify CFRs based on the
characteristic functional group of donor atoms in the various
reagents. The list of some important CFR is presented below.
Acetyl acetone
Dibenzolymethane
Phenol Class compounds
Pyrocatechol
OH
OH
Pyrogallol
OH
OH
OH
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Gallic acid
Salicylic acid
OH
COOH
R
flavones
Hydroxyanthraquinones
Alizarin
Quinizarin
O
OH
OH
O
O-N-Donating Reagents
0-substituted monoazo Dyes
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Nitroso Compounds
Schiff’s Bases
8-Quinolinol and Derivatives
N-N-Donating Reagents
Dimethylglyoxime
Benzil dioxime
Aryl-1, 2-diamines
1,2-Phenylenediamine
2,3-Diaminonaphthalene
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5.1.1 Formation of Complexes
The formation of complex and its stability depends upon the
following three aspects.
(A) The central metal atom
(B) The complex forming groups of molecules
(C) The nature of the metal-ligand bond
(A) The Central Metal Atom
The nature and the oxidation state of the central metal atom
influences to a considerable extent the properties of a metal complex.
The influence of the central metal atom can be studied by comparing
the compounds formed by a series of different metal atoms in a given
oxidation state with a particular chelating agent [2].
(B) The Complex Forming Group(s) of Molecules
The organic molecules possessing the ability to form complex
rings are very large. When a molecule functions as a complex forming
agent it must fulfill two of the most important conditions given below.
(I) The organic molecule must have at least one ore more
appropriate functional groups, the donor atoms of which are capable
of combining with the metal atom by donating a pair of electrons. The
functional group may be
(II) An acidic group which may combine with the metal atom by
replacement of hydrogen or a coordinating group.
(III) Permit the ring formation with a metal atom as the closing
member. However, these two conditions are necessary but are not
sufficient always for the formation of a complex ring. Steric factors
occasionally The functional group must be appropriately situated in
the molecule to influence complexation as in the case of the complexes
of Cu2+ and Fe2+ with 2,9-dimethyl-1,10 phenanthroline [3].
The perusal of the literature reveals that an organic reagent,
which forms a chelate or an inner complex with a metal ion, is
superior to the rest in analytical work. When an organic molecule
containing both an acidic and basic functional groups operate, an
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inner complex or a chelate result. The formation [4, 5] of this ring
may involve either a primary (ionic) or a secondary (coordinating)
valence and may be formed by two primary or two secondary or one
primary and one secondary valence. Vallarino and Quagliano [6]
believed that the inner complex is a completely chelated nonionic
structure formed usually by the union of a metal ion with a bidentate
ligand of a uninegative charge.
An organic compound having a suitable number of reactive
groups can act as a chelate forming ligand depending upon the
coordination number of the metal ion. The ligand may be bidentate,
tridentate or quadridentate and may develop a complex ring of varied
sizes.
A variety of chelates of metal ions with organic reagents having
bidentate groups have been studied [7-11]. When group like-COOH,
-CONH2, - SO3H or –OH is suitably placed with a group like –S-, -NH2,
-OH or = N-OH, the latter groups are found to be coordinating with a
metal ion which is linked through primary valence (ionic) to the fomer.
Copper and boron were found to form complexes [12,13] with
organic reagents having a –COOH and –OH both acidic groups.
The oxygen of the carboxyl group in vicinity to a phenolic –OH
group is found to be coordinating. Aromatic o-hydroxy compounds like
salicylaldehyde or o-hydroxy acetophenone are reported to form inner
complexes [14,15] with Co2+, Ni2+, Cu2+ and Fe2+ such compounds
develop a six membered heterocyclic ring.
Morgan and coworkers [16,17] have investigated complex of β-
diketones with Be2+, Cu2+, Zn2+, Cd2+ and also with Zr4+, Hf4+, Al3+,
Fe3+, Cr3+, Co3+ etc. and found them to be stable and soluble in
organic solvents.
Wolf and coworkers [18] have reported the exchange of reaction
of diketone ligands with acetyl acetonato complexes of Fe3+, Rh3+ and
Ru3+. Hazell and coworkers [19] have reported a unidentate beta
diketo ligand through its respective methylene group.
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Alpha and beta amino carboxylic acids and ortho and meta
aminophenols are capable of forming complexes [20-22] with many
metal ions. The ability to coordinate metal ions in the body renders o-
aminophenol carcinogenic [23]. Charles and Freiser [24] reported
greater stability of metal complexes of o-aminophenol than that of the
diketones and substituted salicylaldehyde derivatives.
(C) The Nature of the Metal Ligand Bond
It is necessary to understand the nature of the bond between
metal and ligand, for the proper interpretation of the structure of
metal complexes. The complex ions such as [PtCl6]2-, [Co(NH3)6]3+ etc.
were subject of intensive investigations to find out the factors
responsible for their stability the explain the existence of these
compounds. Various theoretical approaches to this problem were
developed but it was Jorgensen [25] who proved that the earlier
theories proposed by the various authors [26-30] were fallacious.
Werner proposed his coordination theory for the recognition of
the existence of the species such as [PtCl6]2-, [Co(NH3)6]3+ etc. He
explained the formation and existence of these species by suggesting
that the valency of the atom and the number of bonds it can form may
not be identical. He postulated that the combining power of an atom
is divided into two spheres of attraction the inner co-ordinate sphere
and the outer ionization sphere. Neutral molecules or negative ions
are coordinated around the central metal ion in the inner sphere.
Number of such groups is the coordination number of the metal ion.
Negative ions are loosely attached to outer-sphere and can be
ionizable. So inner-sphere satisfies the secondary valency (non
ionizable valency) and outer-sphere satisfies the primary valency
(ionizable valency).
Lewis [31] and Langmuir [32] were the first to interpret the
nature of the covalent bond as “Sharing of electrons between two
bonding atoms in which each atom contributes one electron”. Later
on Sidgwick [33] developed an electronic interpretation to explain the
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bonding in metal complexes and he had introduced the idea of
coordinate bond by accepting the Lewis concept of covalent bond.
5.2 8-Hydroxyquinoline and Its Derivatives
8-Hydroxyquinoline (8-quinolinol, oxine) might be thought to
function as a phenol, but out of the 7 isomeric hydroxyquinolines only
oxine exhibits significant antimicrobial activity, and is the only one to
have the capacity to chelate metals. If the hydroxyl group is blocked
so that the compound is unable to chelate, as in the methyl ether, the
antimicrobial activity is destroyed. The relationship between chelation
and activity of oxine has been investigated [34-36]. Oxine itself is
inactive, and exerts activity by virtue of the metal chelates produced
in its reaction with metal ions in the medium. Used by itself or as the
sulfate (Chinosol) or benzoate in antiseptics, the effect is bacteriostatic
and fungistatic rather than microbiocidal. Inhibitory action is more
pronounced upon gram-positive than gram-negative bacteria; the
growth-preventing concentrations for staphylococci being 10 ppm; for
streptococci 20 ppm; for Salmonella typhosa and for E. coli 100 ppm.
[37-38]. However, a 1% solution requires at least 10 hours to kill
staphylococci and 30 hours for E. coli bacilli. The oxine benzoate was
the most active antifungal agent in a series of 24 derivatives of
quinoline tested. A 2.5% solution of this compound was successful in
treating dermatophytosis [39-40]. Iron and cupric salts were found to
prolong the antibacterial effect of oxine on teeth [41]. Certain halogen
derivatives of 8-Hydroxyquinoline have a record of therapeutic efficacy
in the treatment of cutaneous fungus infections and also of amebic
dysentery. Among these are 5-Chloro-7-iodo-8-quinolinol
(iodochlorhydroxyquin, Vioform), 5,7-Diiodo-8-hydroxyquinoline
(diiodohydroxyquinoline), and sodium 7-Iodo-8-hydroxyquinoline-5-
sulfonate (chiniofon)[42-44]. Copper 8-Quinolinolate (copper oxinate),
the copper compound of 8-Hydroxyquinoline, is employed as an
industrial preservative for a variety of purposes, including the
protection of wood and textiles against fungus-caused rotting, and
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interior paints for food plants. It has 25 times greater antifungal
activity than oxine [45].
One of the derivative of 8-hydroxyquinoline is 5-Chloromethyl-8-
hydroxyquinoline. The literature survey reveals that 5-Chloromethyl-
8-hydroxy quinoline (CMQ) is a versatile derivative of 8-
hydroxyquinoline. It can be easily prepared by the room temperature
reaction of 8-hydroxyquinoline, formaldehyde, conc.HCl and dry HCl
gas [46,47]. It is stable in form of hydrochloride other wise it
hydrolyzes to methyl group [48]. The reports [46,47] included the
number of derivative of CMQ by the reaction of CMQ with alcohols and
secondary amines. Aristov. et. al. [49-52] have documented several
reports about number of 5-substituted derivatives from CMQ having
the structures as follows.
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The tetrakis 8-hydroxyquinoline methyl ethylene alkyl diamine
shown below has been prepared for their complexation [53,54].
Some reports about the metal analysis complexation and
electroanalysis of these derivatives are also found [55-57].
The cellulose is a high molecular weight natural polymer and its
reaction with CMQ afford the 8-Hydroxyquinoline-cellulose product
which is applied as good ion-exchanger [58,59].
The well-known polymer say polystyrene and or styrene divinyl
benzene copolymer were aminated and these on treatment with CMQ
afford good ion-exchangers [60-61].
8-hydroxyquinoline terminated polyether was prepared by the
reaction between amino terminated polyether and CMQ [62-63].
The various scientists have reported the Bis-8-hydroxy
quinolines prepared from CMQ and their co-ordination polymers [64-
69].
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Se bastien Madonna et al., reported Structure–activity
relationships and mechanism of action of antitumor bis 8-
Hydroxyquinoline substituted benzylamines. They reported that, a
series of twenty six 8-hydroxyquinoline substituted amines,
structurally related to compounds were synthesized to evaluate the
effects of structural changes on antitumor activity and understand
their mechanism of action. The studies were performed on a wide
variety of cancer cell lines within glioma and carcinoma models. The
results obtained from chemical models and biological techniques such
as microarrays suggest the following hypothesis that a quinone
methide intermediate which does not react with DNA but which gives
covalent protein thiol adducts. Micro-array analysis showed that the
drugs induce the expression of a variety of stress related genes
responsible for the cytotoxic and cytostatic effects in carcinoma and
glioblastoma cells respectively. The described analogues could
represent new promising anti-cancer candidates with specific action
mechanisms, targeting accessible thiols from specific proteins and
inducing potent anti-cancer effects [70].
Balaram Ghosh et al., recently synthesized 8-quinolinol and N-
substituted piperazine in one combined molecule and studied in vivo
activity indicates potential application in symptomatic and
neuroprotective therapy for parkinson’s disease [71].
Ruogu Peng et al., synthesized Fluorescent Sensors for Fe3+
containing 8-Hydroxyquinoline. They reported that a series of 5-
dialkyl(aryl)aminomethyl-8-hydroxyquinoline dansylates were
synthesized and their fluoroionophoric properties toward
representative alkali ions, alkaline earth ions and transition metal
ions were investigated. Among the selected ions, Fe3+ caused
considerable quenching of the fluorescence, while Cr3+ caused
quenching to some extent. The absence of any significant fluorescence
quenching effects of the other ions examined, especially Fe2+, renders
these compounds highly useful Fe3+ selective fluorescent sensors [72].
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Feng Wang et al., reported they reported that a series of
dendritic 8-Hydroxyquinoline (8-HQ) and 5-Dialkyl(aryl)aminomethyl-
8-HQ derivatives were synthesized and their fluoroionophoric
properties toward representative alkali, alkaline earth, group IIIA and
transition metal ions were investigated. Among the selected ions, Zn(II)
enhanced the fluorescence of N-Di-(methoxycarbonylethyl)aminoethyl-
3-[4-(8-hydroxyquinolin-5-ylmethyl)piperazin-1-yl]-propanoic amide]
by 31-fold, while Al(III) caused enhancement to some extent. The
absence of any significant fluorescence enhancement by the other ions
examined renders a highly useful Zn(II)-selective fluorescent sensor
[73].
L. Feng reported snthesis and photophysics of novel 8-
hydroxyqquinoline aluminum metal complex with fluorine units [74].
Discovery of a new family of Bis-8-hydroxyquinoline substituted
benzylamines with pro-apoptotic activity in cancer cells and their
synthesis, structure-activity relationship and action mechanism
studies reported by V. moret et al., [75].
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S. C. Panchani et al., recently reported Coordination Polymeric
chain assemblies of some metal ions containing 8-Hydroxyquinoline
moieties. They also studied thermal behavior of this polychelates [76].
G. J. Kharadi et al., also reported some coordination polymeric
chains of metal ions containing 8-Hydroxyquinoline moiety [77].
They also reported In-vitro antimicrobial, thermal and spectral
studies of mixed ligand Cu(II) heterochelates of clioquinol and
coumarin derivatives [78].
5.3 Synthesis and Characterization of Ligands
5.3.1 Synthesis of 5-Chloromethyl-8-quinolinol (CMQ)
5-Chloromethyl-8-quinolinol (CMQ) was prepared by
chloromethylation of 8-Hydroxyquinoline (Oxine) according to the
method reported in literature [72,79]. The detail of the procedure is
given below.
A stream of hydrogen chloride gas was blown through a solution
of 8-hydroxyquinoline (0.1 mol) and formaldehyde (20 mL, 37%) in
37% hydrochloric acid (50 mL) for 8 hours at 50°C. After filtration, the
product was washed with 37% hydrochloric acid and dried to afford
CMQ in 85% yield.
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5.3.2 Synthesis of Ligand 5-((5-(Pyridine-4-yl)-1,3,4-oxadiazole-2-
ylthio)methyl)quinolin-8-ol (L-1) (10)
To the mixture of 5-(Pyridine-4-yl)-1,3,4-oxadiazole-2-thiol (26.0
mmol) and triethylamine (80.8 mmol) in dry pyridine (40 ml), CMQ
(26.9 mmol) was added with continuous stirring. The contents were
refluxed for 150 min. The completion of the reaction was confirmed by
TLC. The excess of pyridine was distilled off and the residue was
poured into the ice-cold water to yield a light green product which was
filtered and washed with hot water and ethyl acetate and then dried
over a vacuum desiccator. Yield, 75%; m.p., 253–255˚C. Found (%): C,
60.70, H, 3.59, N, 16.69. C17H12N4O2S (336.00) Calculated (%): C,
60.71, H, 3.57, N, 16.66. IR: 3294 (O–H), 1640 (C=N), 1500 (Ar C=C),
730 (C–S ); 1H NMR: 9.87 (1H, s, protons -OH), 8.91( 2H, d, pyridine
ring), 7.82 (2H, d, pyridine ring), 7.01-8.01 (5H, m, oxine), 4.49 (2H, s,
protons S–CH2); 13C NMR: 164.9, 151.4, 149.10, 148.89, 143.7, 137.2,
131.9, 128.3, 127.1, 126.3, 121.9, 121.1, 112.8, 36.0.
5.3.3 Synthesis of Ligand 5-((3-(Methylthio)-5-(pyridine-4-yl)-4H-
1,2,4-triazole-4-ylamino)methyl)quinoline-8-ol (L-2) (11)
To the mixture of 3-(Methylthio)-5-(pyridine-4-yl)-4H-1,2,4-
triazole-4-amine (26.0 mmol) and triethylamine (80.8 mmol) in dry
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pyridine (40 ml), CMQ (26.9 mmol) was added with continuous
stirring. The contents were refluxed for 150 min. The completion of
the reaction was confirmed by TLC. The excess of pyridine was
distilled off and the residue was poured into the ice-cold water to yield
a green product which was filtered and washed with hot water and
ethyl acetate and then dried over a vacuum desiccator. Yield, 70%;
m.p., >300˚C. Found (%): C, 59.30, H, 4.47, N, 23.09. C18H16N6OS
(364.42) Calculated (%): C, 59.32, H, 4.43, N, 23.06. IR: 3312 (O–H),
3410 (-NH),1601 (C=N), 1510 (Ar C=C), 735 (C–S ); 1H NMR: 9.88 (1H,
s, protons -OH), 8.79-7.85( 4H, 2d, pyridine ring), 7.00-8.49 (5H, m,
oxine), 4.30 (2H, s, –CH2), 2.64 (3H, s, S-CH3), 8.80 (1H, s, -NH); 13C
NMR: 160.01, 152.10, 151.40, 148.75, 147.20, 137.15, 134.10,
132.00,131.90, 128.28, 126.30, 126.90, 121.30, 112.20, 56.80,
14.90.
5.3.4 Synthesis of Ligand 1-((4-Ethylpiperazine-1-yl)methyl)-4-((8-
hydroxyquinolin-5-yl)methylamino)-3-(pyridine-4-yl)-1H-
1,2,4-triazole-5(4H)-thione (L-3) (12)
To the mixture of equimolar 3-((4-Ethylpiperazin-1-yl)methyl)-5-
(pyridin-4-yl)-1,3,4-oxadiazole-2(3H)-thione and hydrazine hydrate in
n-butanol refluxed for 3 hrs and then acidified it with dil HCl yielded
4-Amino-1-((4-ethylpiperazine-1-yl)methyl)-3-(pyridine-4-yl)-1H-1,2,4-
triazole-5(4H)-thione.
To the mixture of 4-Amino-1-((4-ethylpiperazine-1-yl)methyl)-3-
(pyridine-4-yl)-1H-1,2,4-triazole-5(4H)-thione (26.0 mmol) and
triethylamine (80.8 mmol) in dry pyridine (40 ml), CMQ (26.9 mmol)
was added with continuous stirring. The contents were refluxed for
150 min. The completion of the reaction was confirmed by TLC. The
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excess of pyridine was distilled off and the residue was poured into the
ice-cold water to yield a light green product which was filtered and
washed with hot water and ethyl acetate and then dried over a
vacuum desiccator. Yield, 65%; m.p., >300˚C. Found (%): C, 60.51, H,
5.97, N, 23.49. C24H28N8OS (476.60) Calculated (%): C, 60.48, H, 5.92,
N, 23.51. IR: 3200 (O–H), 3360 (-NH), 1640 (C=N), 1517 (Ar C=C), 743
(C–S ); 1H NMR: 9.81 (1H, s, protons -OH), 8.73-8.01( 4H, 2d,
pyridine ring), 6.99-8.00 (5H, m, oxine), 3.90 (2H, s, –CH2), 2.30 (8H,
two t, pip.), 4.51 (2H, s, -CH2, exocyclic), 1.1 (3H, t, -CH3), 2.12 (2H, q,
-CH2), 8.85 (1H, s, -NH); 13C NMR: 151.30, 148.12, 122.70, 140.00,
179.10, 161.00, 131.11, 121.70, 149.20, 128.50, 137.20, 126.30,
126.97, 112.81, 52.90, 58.17, 70.11, 50.10, 14.12, 51.10.
The techniques used for the characterization of ligands 10,11,12
are discussed in Chapter-2.
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Fig
. 5
.1 I
R S
pectr
um
of
Com
pound 1
0
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Fig
. 5.2
IR
Spectr
um
of
Com
poun
d 1
1
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Fig
. 5.3
IR
Spectr
um
of
Com
pound 1
2
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Fig. 5.4 1H NMR Spectrum of Compound 10
Fig. 5.5 1H NMR Spectrum of Compound 11
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Fig. 5.6 1H NMR Spectrum of Compound 12
Fig. 5.7 13C NMR Spectrum of Compound 10
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Fig. 5.8 13C NMR Spectrum of Compound 11
Fig. 5.9 13C NMR Spectrum of Compound 12
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5.4 Results and Discussion
All the ligands (10, 11, 12) are soluble in polar organic solvents.
The C, H and N contents of all the ligands consistent with their
predicted structure. The Infrared spectral data, 1H NMR spectral data
and 13C NMR spectral data are given individually and IR, PMR and
CMR spectrum for ligands are scanned in fig. 5.1-5.9. IR and PMR
spectrum of ligands shows –OH band and peak respectively.
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1456. [2] L. E. Godycki and R. E. Rundle, Acta. Cryst. 6, 487, (1953). [3] D.B. Fox, J.R. Hall and R.A. Plowman. Aust. J. Chem. 15, 235,
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[33] N. V. Sidgwick,; J. Chem Soc, 13 ,725, (1923). [34] A. Albert, S. D. Rubbo, Br. J. Exp. Pathol., 34, 119 (1953). [35] S. D. Rubbo, A. Albert, M. I. Gibson, Br. J. Exp. Pathol., 31, 425
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