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.

Chapter-5


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

Chapter-5


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

Chapter-5


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].

Chapter-5


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].

Chapter-5


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].

Chapter-5


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.

Chapter-5


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

Chapter-5


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

Chapter-5


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.

Chapter-5


Fig

. 5

.1 I

R S

pectr

um

of

Com

pound 1

0

Chapter-5


Fig

. 5.2

IR

Spectr

um

of

Com

poun

d 1

1

Chapter-5


Fig

. 5.3

IR

Spectr

um

of

Com

pound 1

2

Chapter-5


Fig. 5.4 1H NMR Spectrum of Compound 10


Chapter-5



Fig. 5.7 13C NMR Spectrum of Compound 10

Chapter-5




Chapter-5


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.

Chapter-5


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