CHAPTER-1

INTRODUCTION

Chapter-1 Introduction

The produced thesis comprises the aspect of polymeric azo dyes with pendent 8-hydroxy

quinoline ligands. Thus the review regarding, Chelating agents, metal complexes of azo dyes, 8-

hydroxy quinoline derivatives and polymeric ligands are given briefly as follows,

1.1 Organic Ligands (Chelating agents) and their chelates

Chelate forming reagents or chelating agents are widely used in analytical chemistry;

some of them are listed as follows:

Alkyl and arylamines are reported to form numerous metal chelates. In many chelates

ethylene diamine [1-3] is reported to form a bridge between two metal atoms (I).

CH2 NH2

CH2 NH2

CH2NH2

CH2NH2Ag

Ag

(I)

The bidentate ligand having the system (II) is found to be selective and specific for quite

a few transition metal ions. The oximes of the o-hydroxy arylaldehydes possess the above

system, hence they form the complexes (III) [4-8] with divalent metal ions like Pd2+, Cu2+, Ni2+

or Co2+.

C

OH N

C

C

R

R

M

NC

O

NC

OH

OH

H

H

R

R

2

1

(II) (III)

It is interesting to note that salicyladoxime behaves as a dibasic acid in alkaline solution,

resulting in a complex of the type (IV) and enough evidences are provided by Feigal and Bondi

[4].

(IV)

The substituent in the effective system of the benzene part of the salicylaldoxime

produces reasonable changes in the characteristics of the ligand as illustrated by investigations of

the salicylyl–hydroxamic acid [9,10] salicylaldoxime [11], 3,5-dibromo-5-nitro-6–methoxy

salicylaldoxime [12] and 3-oximino methyl salicylic acid [13,14].

O

M/n/n

N

H

R

O-Hydroxy aromatic ketoximes also possess the same reactive system having an alkyl or

aryl group on the carbon of –C=N part. Oximes of 2- hydroxy-4- methoxy, 2–hydroxy-5–

methoxy-2,4–dihydroxy, 2,5–dihydroxy and 2–hydroxyacetophenones and 2–hydroxy–1–

acetonaphthone are investigated by Ephraim [5] for his or her specificity for Cu2+. Poddar [15]

has according the employment of ortho hydroxy–acetophenone organic compound for

quantitative determination of Cu2+ and Ni2+. Neelakantam [16] and devotion [17,18] used

resacetophenone organic compound for a similar ions. 2–hydroxy-5-methyl acetophenone

organic compound, 2-hydroxy-5–methyl propiophenone organic compound and 2-hydroxy-5–

methyl benzophenone organic compound are used for measure determiantion of Cu2+, Ni2+ and

Co2+ ions [19]. Harisingh and Sharma [20] have also reported the use of 5–methyl-2–hydroxy

acetophenone oxime for gravimetric estimation of the same ions. 5-Ethyl resacetophenone oxime

[21,22] has been used for gravimetric determination of Cu2+ and Ni2+ by Naik, and Desai.

The aromatic o-hydroxy ketones and their ketoximes with Fe3+ ion form deeply coloured

complex compounds. An extensive work on the analytical properties of such oximes has been

carried out by Banks and coworkers [23]. Ephraim [24] reported that o-hydroxy acetophenone

oxime could by used as a reagent for copper. Poddar has used O-hydroxy acetophenone organic

compound as Associate in Nursing analytical chemical agent for the mensuration estimation of

copper [25], nickel [26], atomic number 23 [27], metal [28] and for the colourimetric estimation

of iron [29], atomic number 23 [30], atomic number 22 [31] and metallic element [32].

Sitaraman and Neelakantam [33] suggested the use of 2,4 dihydroxy acetophenone oxime

(resacetophenone oxime ) as an analytical reagent for iron. Raju and Neelakantam [34] proposed

its use for the quantitative separation of copper and cadmium. Kanthraj and Neelakantam [35]

used this compound for colourimetric estimation of uranium. It was utilized for the gravimetric

estimation of nickel by Bhakti and Kabadi [36] and for the colourimetric estimation of nickel by

Bhakti, Rane and Kabadi [37], who also determined the stability constants of copper and nickel

complexes of resacetophenone oxime in organic solvents [38]. Rama Rao [39] developed a spot

test technique for the detection of uranium with the aid of resacetophenone oxime.

Kadarmandalgi [40] used this reagent for a spot test technique to detect cabalt and to separate

cobalt from nickel, as well as spot test detection for manganese [41], vanadium [42] and also to

precipitate copper in presence of cadmium [43]. Kadarmandalgi, Raja Reddy and Murthy [44]

studied the ferric resacetophenone oxime complex, which was also studied photometrically by

Kadarmandalgi and Murthy [45].

2,4-Dihydroxy acetophenone organic compound was used for the hydrometric estimation

of copper and nickel by Dave and Patel [46]. They also studied the gravimetric estimation of

nickel by 2,4-dihydroxy butyrophenone oxime [47] (resbutyrophenone oxime). 2,4-Dihydroxy

propiophenone-, 2,4-dihydroxy butyrophenone, 2-hydroxy propiophenone oximes and 2-hydroxy

butyrophenone oxime have been studied as colourimetric reagents for Fe (III) by M.H.Gandhi

[48]. A few complexes of Cu2+, Ni2+ and Fe2+ with 2-acetyl alkali organic compound are

synthesized and characterised by elemental analysis. IR, UV, visible spectrographic analysis,

torque and cyclic voltammetry and their interactions with plasmid DNA are investigated [49]. A

few complexes of Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Hg2+ with 4-oxo-4H-1-

bhenzopyran-3-(carboxaldehyde-4-chlorobenzylhydrazone) (BCBH) and 4-oxo-4H-1-

benzopyran-3 (carboxaldehyde-4-methyl benzylhydrazone) (BMBH) are synthesized and

characterised. The IR spectra shows that BCBH and BMBH behave as rough ligands either

within the keto or organic compound kind [50]. A few complexes of Zn(II) and Pd(II) with N-(2-

pyridyl)-3-carboxypropanamide and N-(2-pyridyl)-2-carboxy benzamide derived from 2-

aminopyridine are ready and characterised [51]. J. R. Shah and R. P. Patel [52]. Reported the

spectrophometric studies of Cu2+ and Fe2+ complexes with 2-hydroxy-5-methyl acetophenone

semicarbazone. The composition of the complex was determined by three different methods Job,

slope ratio and mole ratio method. Harking and coworkers [53] investigated the metal chelates of

2-(2-pyridyl)-benzimidazole and 2-(2-pyridyl) imidazoline and according that their effectiveness

is owing to the system,

- N = C – C = N –

Ethylene diamine tetra aceticacid (EDTA) has been investigated and studied by many

workers since 1925. It has been found to give complexes with almost all elements under different

pH conditions. Its copper complex was first prepared by Brintzinger and Hesse [54]. Bennat and

coworkers [55] considered them to have a square planar arrangement. Garvan [56], Dwyer, and

Mellor [57] isolated the complexes of Cu2+, Ba2+, Ni2+ and from their magnetic properties and

spectral absorptions confirmed the quadrivalent nature of EDTA. Elements of zinc group

[58,59] also form complexes – Zn ( Zn –EDTA), Cd (Cd – EDTA) 4H2O, Hg (Hg- EDTA)H2O,

the last being more stable probably due to Hg-N Bond.

Ni2+complexes [60] of EDTA have been isolated as acid Na1+, Ba2+ and Ni2+ salts. Busch

and Bailer [61] isolated several acid EDTA complexes of Pd2+ and Pt2+. . The diacid complex

contain quadridentate EDTA and the tetrabasic complexes coantain bidentate EDTA.

1,2-Propylene diamine tetra acetic acid (PDTA) also possesses complex forming

potentiality like EDTA. Co2+ complex [62] have been prepared and found to be indentical with

the corresponding EDTA analogues [Co (PDTA)X]2-, where X = Cl, Br, NO2, H2O contain

quinquedentate PDTA [63] “Chel 600” (trans 1:2 cyclohexane organic compound characid

carboxylic acid acid) is utilized as a matter and it's been found that the soundness constants [64-

66] of CDTA – metal chelates ar bigger than those of their EDTA analogues.

Ethyl acetoacetate and aryl amine when treated with fused zinc chloride gave a

crystalline addition product also obtained from ethylactoacetate – anil and ZnCl2 [67]. Similar

addition products were also obtained from the above anils with cadmium and mercuric chlorides.

Various substituted anils gave similar crystalline addition products. These complexes are

photosensitive.

Similar addition products with beta - arylamino crotonates and copper chlorides have

been prepared; they are photosensitive. Such addition products were also obtained from these

crotonates with Zn2+ and cadmium chlorides [68]. The spectrophotometric study of copper2+

ethyl β–2 – methoxy anilino crotonate complex has also indicated 1:1 composition of metal –

ligand complex [69].

1-Hydroxy-5-methyl acetophenone anil and 2-hydroxy-5-benzophenone anil are used as

analytical reagents for Cu2+ particle by Joshi, Patel and Thakor [70]. The chelate forming

reagents are classified as follow [71] (i.e.Table 1.1)

Table: 1.1 List of Chelating Agents

D –S-Donating Reagents

A.1 Thioureas

� Thiourea

C

S

NHNH RR'

A.2 Thiosemicarbazones

A.3 Monothiols

� Thioglycolic acid

C

S

NHNH2

NH R

CH2COOHSH

� Thiosalicylamide

CSNH2

OH

–O-O-donating reagents

B:1 Enolisable 1, 3-Diketones

� Acetylacetone

CH3CO CH

2CO CH

3

OH

O

� Dibenzoylmethane

CO CH2COPh Ph

OH

O

Ph

Ph

B.2 Ortho-and para-diphenols

� Pyrochatachole

OH

OH

� Pyrogallol

OH

OH

OH

� Gallic acid

OH

COOH

OH

OH

� 1,5- Dihydroxynaphthalene-3,6-disulphonic acid ; Chromotropic acid

OH

SO3H

OH

HO3S

B.3 phenol carboxylic acids

� Salicylic acid (Substituted)

OH

COOH

R

B.4 Hydroxyflavones � Flavonol

O

O

OH

B.5 Hydroxyanthraquinones

� Alizarin

O

O

OH

OH

� Quinizarin

O

O OH

OH

B.6 Hydroxy xanthenes

O

O OH

R

B.7 Hydroxyl amines

CO

NH OH

C: -O-N Donating Reagents

C.1 O-substituted mono azo Dyes

N N

OH

R R'

C.2 Nitroso Compounds

OH

NO

R

C.3 Schiff’s Bases

NCH

NCH

C.4 Formazans and Derivatives

C

N N

NNH

OH

R

R'

R"

C.5 8- Quinolinol and Derivatives

N

OH

R'

R

D: -N-N- Donating Reagents

D.1 Dioximes

� Dimethylglyoxime

CH N OH

CH N OH

� 2,2-Furil dioxime

C C

N OH

N OH

D.2 Bipyridine derivatives

NOH N OH

D.3 Aryl-1, 2-diamines

� 1,2-Phenylenediamine

NH2

NH2

� 2,3-Diaminonaphthalene

NH2

NH2

1.2 Metal complexes of azo dyes

Chelating agents are becoming of increasing importance in analytical chemistry such as

in gravimetric, titrimetric and colorimetric measurements. New types of chelates and chelating

agents are constantly under investigation, for possible analytical and industrial applications. The

ever increasing number of publications on this subject may realize the growing importance of the

use of metal chelates in analytical chemistry.

It was G.T. Morgan and Drew [72] who first coined the name CHELATE from the Greek word

CHELE used for crabs claw to designate the 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 close ring. To form metal chelates of an organic compound, an organic compound

must have two or more atoms usually oxygen or nitrogen, capable of coordination with a metal

ions, i.e. it must be a base having a pair of unshared electrons available for coordination. These

coordinating atoms are so arranged that rings of five or six member including the metal ion will

be formed [73].

Colored ligands are used for qualitative or quantitative determination of the metals. For

qualitative detection, generally the spot test technique is adopted, whereas the colorimetric

procedures based on the formation of colored chelates are utilized for the quantitative

determination of metals. Colored complexes like Hemoglobin, Chlorophyll and Vitamin B-12

also important in biosciences.

The development of the spot test techniques for the detection of an organic or inorganic

substance is due to the pioneering work of Feigal [74]. Thus it is proper to give outline about

formation of chelate and complexing agents.

The formation of metal complexes has figured prominently in dyestuffs chemistry from

very early times. Indeed, mordant dyeing was based on this property. Thus the cloth to be dyed

was first impregnated with a soluble metal salt and then a soluble alkali was added to precipitate

the insoluble metal hydroxide within the fibre pores. When this mordanted cloth was immersed

in a solution of a suitable natural dye, e.g. Cochineal or Alizarin, the latter complexed with the

metal hydroxide and thus became trapped within fibre.

The natural dyes didn't contain representative of the group class: The a lot of necessary were rough anthraquinones, sometimes ortho-dihydroxy or ortho-hydroxy carboxyanthraquinone dyes. once the all-important group dyes were being pioneered metallisation was found to supply solutions to sure technical issues however the pre-eminent metals were currently the transition metals like copper, Cr and atomic number 27. Complexes of group compounds is either pre-formed or fashioned on the metallised fiber. However, it absolutely was not till 1919 that each Ciba and immunoglobulin introduced the primary premetallised dyes, 1:1 Cr(III) complicated group dyes for wool.

Metallised azo dyes are of two types: those in which the azo group is a coordinating

ligand to the metal (medially metallised type) and those in which it is not (terminally metallised

type). The former are by far commercially the most important.

Commercial uses of metal complex azo dyes

The 1:1 copper (II) complexes are widely used as both reactive and direct dyes for cotton.

Cl Reactive Red 6, a dull rubine dye, is typical. Because of their instability under dyebath

conditions the 1:2 copper (II) complexes have not found commercial use.

N

OCr

N

O

N

MeO2S

SO2Me

O

N

O

ON

N

OCu

N N

NN

H

Cl

Cl

SO3H

HO3S

HO3S

L

(1) (2)

n

-

Na+

L=H2O

Although 1:1 chromium (III) dyes are still used, they are mush less important than 1:2

chromium (III) dyes because the former are stable only at low pH values and hence have to be

applied to the fibre, usually wool, from an acidic dyebath. This adversely affects the properties of

the wool, particularly its softness. In contrast, the 1:2 Cr (III) complexes ar stable over a good

hydrogen ion concentration vary and might be applied to each wool and nylon from a neutral

dyebath: indeed, so stable are 1:2 chromium (III) complexes that they tolerate the alkaline

application conditions of reactive dyes. An example of 1:2 chromium (III) dye for wool is Cl

Acid Violet 78. The relative stability of the 1:1 metal (III) complexes permits the preparation of

unsymmetrical 1:2 metal (III) complexes by reaction with a second, totally different tridentate

chemical group molecule. In contrast, cobalt (III) does not offer such a possibility due to the

instability of the 1:1 cobalt (III) complexes. Hence only symmetrical 1:2 cobalt (III) dyes can be

made and this lack of versatility has rendered cobalt (III) dyes less important than chromium (III)

dyes.

Terminally metallized dyes

As mentioned earlier, this type of dye is of little importance commercially. A typical

example is the complex, derived from salicylic acid. In general, metal complexes derived from

dyes of this type are brighter in hue than those in which the azo group is a ligand. In contrast to

the latter, terminally metallised dyes normally undergo little shade change on metal complex

formation and little enhancement of light fastness occurs.

O

Cu

OO

O

N

NO

O

N

N

II

The ligands viz; 8-hydroxy quinoline, salicylic acid, 2,4-dihydroxy acetophenone, 2,4-

dihydroxy benzophenone and 2-hydroxy-3-naphthoic acid (i.e. Bon acid) may also offer azo

dyes. As the thought of the work is to use such ligand containing azo dyes for complexation, the

individual review about the complexation study of dyes based on these ligands has been

presented below.

1.2.1 Azo dyes and their complexes based on 8-hydroxy quinoline

Ahmed et al [75] studied the synthesis of recent disperse radical dyes from 3-(4-

aminophenyl)-1,5-diphenyl pyrazole and their one-bath colouring of wool/polyester blends.

Another report indicated that [76] coupling and nucleophilic reactions of a diazotized

pyrazolopyridine derivative with 8-hydroxy quinoline afford the dye shown below.

Me N

OHNN

NNH

Cl

N

EtO2C

The synthesis of 5,5’-(phenylenediamine diazo) and 5,5’-(o-dianisidinediazo)-8-

hydroxyquinoline has also been reported [77].

N

OH N=N

OMe( )OMe

N

OHN=N

n

Dine et al [78] synthesized some azo compounds and studied their antimicrobial

activities.

N

OH

N=NS

NN

SR

(I)

Gupta and his co-workers [79] studied, the synthesis and application of

azohetrocycles as potential biodynamic agent.

N

OH

N=NRNHSO2

From our laboratories analysis work [80] by V.S.Patel, R.G.Patel et al. ready radical disperse dyes containing 4-quinolinone ring for coloring polyester and nylon fibers.

N

N

O

Me

N=NR

(I)

Thirty two dyes I (R=aryl coupler residue) were prepared by coupling of diazotized

3-(p & m-aminophenyl)-2-methyl (3H) quinazolinone with RH and their dyeing

performances on polyester and nylon fiber were assessed. All the dyes showed honest to

smart wonderful fastness to laundry, rubbing perspiration and sublimation.

Afifi Tarek H [81] studied the synthesis and electronic spectral studies of some new

dyestuffs derived from substituted 2-aminotetra hydrobenzo[b]-thiophene.

Yang [82] investigated the application of the dye 4,4’-bis(8-hydroxyquinolyl-5-azo)-3,3’-

dimethyl biphenyl and find its application in spectrophotometric analysis.

Azo dyes with 6-azauracil cycle are also reported [83].

NH

NN

O

N=N

N

NNH

O

O

NNH

N

NH2

CO2H

O

O

NNH

N

N=N

CO2H

O

O

R 2

(I)

(II)

R 4

R3

(III)

Zerecka, Vitezslav and coworker [84] prepared soluble 1:1 chromium complex of

monoazo dyes having green color. The crystal green 1:1 chromium complex of 5,2,3-

Cl(HO)(HO3S)C6H2NH2 → 2-C10H7NH2 masked with 8-hydroxy quinoline, having low

solubility was converted to the soluble form by acidifying its alkali aqueous suspension to pH 2-

4, adding alkaline hydroxide to pH 5-9, salting out and drying. The resulting solubility is 60 g

concd. Dye/L H2O at 20 OC.

Griesbach and Lieser [85] also prepared cation exchanger using dye. To prepared cation

exchanger (exchange capacity 0.9-1.5 mmol/g) polystyrene is nitrated, reduced, diazotized and

coupled with 15 chelating compounds containing -OH and -NH2 groups e.g. chromotropic acid,

alizarinmorin, dithizone and ethylenediamine-N,N’-bis(o-hydroxyphenylacetic acid).

Vogel [86] reported 1:2 complex dye and their use in dyeing or printing substrates.

chromium complex dyes of structure where Z and Z’ are O or CO2, R and R’ are residue of

coupling compounds having 1-2 unfused benzene rings or quinoline ring and no acid substituents

and rings A and B may be substituted by other than acid groups are prepared by tetraazotizing

the corresponding diamine chromium complex and coupling with RH and R’H. Thus 2,3,5-

HO(NO2)2C6H2NH2 → 1,8,3,6-H2N(OH)C10H4(SO3H)2 was heated with chromium acetate to

give a 2:1 complex, which was tetraazotized and coupled at pH 9-13 with 8-hydroxy quinoline to

give a powered dye producing gray tones on leather.

SO3H

OR-N=N

N=N

z

A

O

HO3S SO3H

N=N-R'

HO3S

N=N

Z'

B

CrH

+

The authors [86,87] also prepared chromium complexes of azo dyes. chromium complex

azo dyes (I; R,R’= benzene or quinoline residue not substituted by acid groups; Z=Z’=O, CO2; A

and B do not contain acid groups; SO3H groups in 3 or 4 position) were prepared and were used

to dye leather fast gray shades. Thus 2-amino-4,6-dinitrophenol was diazotized, coupled with 1-

amino-8-hydroxy-3,6-napthalene-disulfonic acid. The azo intermediate heated, treated with

chromium acetate. The resulting 2:1 chromium azo complex was diazotized and coupled with 8-

hydroxy quinoline to give a compound having structure as shown below. (R,R’=8-hydroxy-5-

quinoline, rings A and B substituted in 3’ and 5’ position by NO2, Z=Z’=O, SO3H group in 3

position).

SO3H

OR-N=N

N=N

z

A

O

HO3S SO3H

N=N-R'

HO3S

N=N

Z'

B

CrH

+

3'

5'

3'

5'

4

3

34

Report [88] show that new chemical compound complexes of Co(II), Cu(II), Ni(II), Fe(II), Fe(III),

Zn(II), Cd(II) and UO2(II) with 5-(2-hydroxyphenyl-diazo)-8-hydroxy-7-quinolinecarboxaldehyde

were synthesized and characterised by thermal, magnetic, IR, electronic, 1H NMR, 13C NMR and

EPR spectra information. The IR spectral information of the metal complexes indicate that CH2 act

as bis-bidentate towards the metal ions. The electronic spectral information recommend that Co(II)

and Mn(II) complexes square measure octahedral, whereas Ni(II) complicated is sq. planner. The

complexes of Zn(II) and Cd(II) square measure tetrahedral. The chelating matter round the copper

was expected to possess distorted sq. planner structure for Cu(II). The electronic absorption and a

g/A worth square measure indicative of the start of a tetrahedral distortion. The coupling constant

of varied coordinated nuclei with Cu(II) square measure calculable from EPR spectrum of Cu(II)

complicated.

Amin and Alaa [89] have synthesized and characterized the dye and react with Mo+6 and

determined the Mo+6 in human urine. Four chemical group compounds supported diazotization

of 2-aminobenzothiazole were synthesized and characterised by elemental analysis still as by

completely different qualitative analysis techniques. The potentiality of the ready compounds as

new chromogenic reagents for the spectrophotometry determination of Mo+6 was studied. It was

extensively studied for optimum conditions affirmative the formation of the coloured complexes.

Beer’s law is obeyed within the vary zero.2-8.5 µg/mL. whereas Ringbom optimum

concentration vary was zero.8-7.5 µg/mL. The molar physical property and Sandell sensitivity of

the complexes area unit calculated. The impact of meddlesome ions on the determination of

Mo+6 was studied. The relative standared deviation for replicate determined at five.0 µg/mL of

Mo+6 area unit one.23, 1.47, 1.05 and 1.38 %. The proposed method was applied to check the

quantity of Mo+6 in human excretory product samples. The Mo levels found between zero.5-2.1

µg/100mL. Yin et al [90] also studied the photometric determination of microamounts of nickel

with 7-(4,5-dimethyl-2-thiazoly-lazo)-8-quinolinol (DMTAQ) as chromogenic application.

Zhang et al [91] studied the synthesis of a new chromogenic reagent 7-(benzothiazolyl-2-azo)-8-

hydroxyquinoline-5-sulfonic acid (BTHQSA) and its reaction with cobalt.

D.S.Raj [92] studied the coordination polymer based on hetero substance : 5-(3-acetyl-4-

hydroxy-1-phenylazo)-8-quinolinol (AHPQ). Coordination chemical compound of 5-(3-acetyl-4-

hydroxy-1-phenylazo)-8-quinolinol (AHPQ) were ready with Zn+2, Cu+2, Ni+2, Co+2 and

Mn+2. AHPQ was synthesized by coupling of diazotized 5-amino-8-quinolinol with 2-hydroxy

acetophenone. AHPQ functioned as a bis-bidentate substance. Its coordination chemical

compound was characterised by elemental analysis. IR spectral and diffuse reflection factor

spectral studies for his or her structure determination. The thermal stability and range average

relative molecular mass of those entire coordination polymers were calculable severally by TG

and nonaqueous conductometric volumetric analysis technique. The coordination polymers were

characterised by their moment of a magnet and metal to substance (M:L) magnitude relation.

AHPQ was assessed as a mordant dye on nylon fabric. It and its complexes were assessed for

monitored fungicidal activity against various plant pathogens.

Hussan Mostufa K; Awad Lbranium M.A [93] studied the new manganese (II) and iron

(II) chelates with sulfamido oxine containing azo dyes and their biological activity.

Yamamoto Daijire, Washio, Yoshifumi [94] studied the photometric determination of

metals with azo derivatives of 8-quinolinol. II. Photometric trace determination of cobalt with 5’-

(4’-sulfophenylazo)-8-quinolinol.

1.2.2 Azo dyes and their metal complexes of Salicylic acid

Dubose John and coworker [95] studied the production of azo dye with low sodium ion

content and their use.

Shakri J and Hamid N [96] studied the new azo dyes.

N

S

N=NR

S

N

Me

Ph

RN=N

(I)(II)

Yellow to violet dyes of structure I ( β-Pyridyl) and II were prepared Where R in both

series represent a dimethylaniline, naphthol as salicylic acid or m-phenylenediamine coupler

radical. The dye can be used to dye cotton, nylon and/or wool. Several of the dyes are also useful

as pH indicators for acidic media.

Vyas et al [97] studied on 6,7-benzomorphan related substance Part-II. Synthesis and

antibacterial testing of some 2’-(arylazo)-2,5-dimethyl and 2,5,9-trimethyl-6,7-benzomorphans.

R

Me

N

R'N=NMe

Zherdeva and his co-workers [98] studied the possible synthesis of direct azo dyes from

2,7-diaminobenzothieno[3,2-b]Benzothiphene.

S

S

R

R'

S

S

RN=N

N=NR

(I) (II)

Barni et al [99] prepared the disperse dyes from p-amin--methyl cinnamaldehyde.

The other scientist [100] studied in 1974, azo dispersioe dyes from 4-aminostilbene and

2-(4’-aminostyryl)thiophene.

Baul et al [101] studied the synthesis and structural characterization of some triorganotin (IV)

complexes of 5-(4-chlorophenylazo)salicylic acid crystal and molecular structure of triphenyltin

5-(4-chlorophenylazo) nonsteroidal anti-inflammatory. Specht et al [102] prepared chromium

complex azo dyes using salicylic acid. Chromium complex azo dyes were prepared by treating

azo dyes containing OH, NH2 or CO2H in the position ortho to the azo bridge in H2O at 70-100 OC and pH 2-12 with salicylic acid (I) and a Cr+2 salt mole ratio at 0.8-1.1. The dye quality was

equal to that using a 2:1 (I) to Cr+3 ratio and this process reduces the amount of I in the waste

water.

The several scientist [103] improved the dyeing on polyester fibers using a leveling

agent, a mixture of a sulfated tetronic alkali metal or ammonium salt -RC6H4 CO2 R’ (R=H or

OH and R’=Pr, iso-Pr, Cr Ph).

The other cluster [104] changed dyestuff 1:1 metal advanced with colorless ligands and

their preparation. The dyes resulted from reaction of 1:1 chromium complex of a sulfo group

containing dihydroxy azo dye with salicylic acid or 3-hydroxy-2-napthoic acid in aqueous

ethylene glycol. Thus 4,3-HO(NH2)C6H3SO3H was diazotized and coupled with 2-ClC6H3

NHCOCH2COCH3. The product was complexed 1:1 with chromium and the 1:1 complex was

treated with 2-HOC6H4CO2H in 1:10 HOCH2CH2OH-H2O at 100 OC for 2 hr. The solution of the

resulting compound was neutralized to pH 7 and converted to a water soluble brown powder,

which produced lightfast yellow shades on polyamide fibers and leather.

1.2.3 Azo dyes and their metal complexes based on 2,4-dihydroxy

acetophenone

Oberkobusch and his co-worker [105] studied the hair dyeing compositions containing

cyclopentaquinonalinium derivatives. Whereas R1, R2, R3 severally represent a atom or C1-C4

alkyl radical and R1 and R2 along might type a hoop. X1 and X2 represent an oxygen and sulfur

atom.

O

R1 R2

R3

X1

X2

Monich and Sayed Ahmed Z [106] studied the some new dyes from 4-methyl aniline-3-

sulfone-2-touidine. 4-methyl-2-(2-tolyaminosulfonyl) aniline was coupled with 26 different coupling

components to give azo dyes. Characteristics and chemical structure of each dye was

experimentally assigned. These dyes were used to color fabrics made of polyester, wool and their

blends. The colouring properties like lightweight fastness, wash fastness, solvent impact and

exhaustion studies are investigated and assessed in step with industrial grey and/or Blue

scales.Wong et al [107] studied the self-assembly of an acentric-crystals of highly

hyperpdarizable mecrocynanine dye with optimize aligment for nonlinear optics.

The scientist group [108] studied the one of the application of the dyes. Method for

forming photographic images using Silver dye bleach method. In this, where R1, R2 = OH, H ;

R3, R4 = halogen, alkyl, alkoxy, phenoxy, naphthyl, napthoxy, OCOR8 (Q R8 = alkyl, benzyl)

OHN

N

NR'

R1

R2

R3R

4

(I)

4

(II)

1.2.4 Azo dyes and their metal complexes based on 2,4-dihydroxy benzophenone

Shimizu Kanji; Hibara Toshio [109] studied, the dyeing of nitrogen containing fibers and

dyed products. The products with improved light and wetfastness are obtained by dyeing N-

containing fibers with reactive disperse dyes and containing the fiber with UV spandex.

N N

N

N=N

O

N(C2H5)

N

Me

CN

O

C8H17

2(I)

Composite fiber was immersed in an aqueous dispersion containing monoazo compound

(I) at 120 0C for 1h, soaped further immersed in an aqueous solution containing 2-OH-4-

methoxy-5-sulfobenzophenone and 2-hydroxy-4-methoxybenzophenone at 85 0C for 20 min

washed and dried to give a dyed product showing light fastness grade (JIS-L-0842, 20h) 4-5 and

water fastness grade (JIS-L-846-A) 4-5. Some of the teams [110,111] studied the hindrance of

chemistry degradation of unbleached and colored jute by ultraviolet illumination absorbers.

The Japanese staff [112] studied the advance of gas fastness of ion colored polyester fibers.

Tsatsaroni E.G and Kehayoglou A.H [113] studied the colouring of polyester with C.I. disperse

yellow forty two within the presence of varied ultraviolet illumination absorbers half II. The

impact of varied amounts (0.5-1.2 owf) of two-benztriazole (Tinuvin P and Tinuvin 320) and one

benzophenone (Ultrafast 800) sort ultraviolet illumination absorbers applied directly within the

colouring of polyester fibers with C.I. disperse yellow forty two at numerous quantity (0.5, 1.0

and 2.0 the concerns owf) or by once treatment of the colored fiber, was studied. combos of

Tinuvin 320 with numerous amounts of AN inhibitor (BHT) within the dye liquor were

additionally used and results compared. Torii Masashi and Hayakawa Kumio [114] studied the

chelates type thermal recording material with improved coloring property. A chelates type

thermal recording material containing coloring agent of benzoic acid derivative of Cu salts a p-

phenylenediamine derivative double salt with salicylic acid derivative and boric acid contains a

phenol compound. The materials may contain a leuco dye. The materials may comprise a

photosensitive layer. A layer containing the coloring agent and a phenol compound and a leuco

dye containing layer. The phenol compound may be bisphenol with alkylene and aralkylene

group or may contain ≥ 1 group of ester, sulfide, sulfonyl or carbonyl. The material showed

improved coloring property and gives low fog images.

Kaul Bansi and Pflieger Dominique [115] studied the Aluminium comlex azo dye. Dye

Al 2:1 complexes are obtained by coupling a diazotized aminophenol with a pyrazolone, a

phenolic compound and/or an acetoacetamide followed by metallization. The complexes may be

used as bulk dyes for plastics or for printing of Al. Thus 4-(3-methoxypropylaminosulfonyl)-2-

aminophenol → 2-napthol at pH 12.3 was heated with Al2(SO4)3 and the product treated with

triacetonediamini to give a product that could be used to print aluminium in bluish red shades.

1.2.5 Azo dyes and their metal complexes based on 2-hydroxy -3-naphthoic acid

Shou Huanfang and his co-workers [116] studied the synthesis and behaviours of the

color reaction of some alkylthizalyazo reagents.

Some of the scientist [117] studied the hydroxynaphthalenecarboxamide coupling

components and azo colorants there from.

OH

CONR'R"

OH

CONR'R"

R3

m R3

m

(I) (II)

Coupling component [I and II, R’=X or arylene (X)n, where n is 1-4; R2H, C1=alkyl C3-8-

cycloalkyl, aryl or X; provided that if R’ is arylene-(X)n, the R2 is not aryl; R3=C1-4 alkyl, C1-4

alkoxy, SO3H, Br, Cl, OH or NO2; m=0-3; X is a poly(oxyalkylene)substituent having from 4-

200 oxyalkylene units which are the addition products at compounds chosen from the cluster

consisting of ethene chemical compound and propene oxide] ar obtained for chemical group

colorants. The colorants are suitable for use in printing inks. Thus bon acid is condensed with

polypropylene glycol 4-aminophenyl ether to provide an amide coupling component which was

then coupled with diazotized polyethylene glycol 4-aminophenyl ether to give a colorant

(λmax~500 nm).

Sakaue Toshio and Yamada Tetsu [118] developed the new methods for the

treatment of waste water containing dye and dye intermidiate.

Coispeau, Gerard; Schafield, John David [119] studied the Azo metal pigment

composition and manufacture. In the manufacture of the title pigment YCO2M and YCO2R

YCO=polyester residue form hydroxy carboxylic acid M=H, Metal or substituted ammonium;

Z=divalent bridge group containing O or N attached to CO group; R=Primary, secondary or

tertiary amino group are incorporated into the pigment in the resination stage. Diazotized p-

toluidine sulfonic stage was added to 3-hydroxy-2-naphthoic acid. Premixed with a solution

containing water rosin and hydroxysteark acid polymer disperson and maintained at pH 10.2 to

give a pigment which was laked with CaCl2 (14.5%).

Sato and his co-workers [120] studied the monoazo lake compositions containing rosin

aluminium salts and gravure-printing inks.

Muzik Ferdinand and co-worker [121] studied the azo pigments I (M=Ca, Mg, Sr, Cd, Mn, Ni

and their combination) are manufactured by coupling of diazotized 4-aminotolu=ene-3-sulfonic

acid (II) [88-44-8] with 2-hydroxy-3-napthoic acid (III) [92-70-6] in the presence of

corresponding metal salt or by addition of the metal salt to the reaction mixture when coupling.

The coupling reaction is performed at 0-30 0C and pH 7.5-9.5 in the presence of rosin soaps or

surfactants that control the crystal form of the pigments. Thus, a red I (M=Ca) [5281-04-9]

pigments was prepared by addition of CaCl2 to the mixture after coupling of diazotized II with

III at 00.

CH3

SO3

N

N

OH

CO2

M

(I)

Wojciech, Blus Kazimierz, Sokolowska-Galda Jolanta and co-worker [122] studied the

iron complexes of monoazo compounds of 1:2 type for dyeing polyamide fibers and wool brown

shades with good resistance to water and light.

N Ar

ON

OCOR

NAr

O N

O CORFe

Where Ar = diazotized o-aminophenol or o-napthol type residues; R = OH, MeO, EtO, amino,

alkylamino or R1R2 C6H3NH; R1,R2 = H, Me, MeO, EtO or NO2.

Ruse Mircea, Oproiu Loti Cornelia and co-worker [123] studied the azo dye 1:1

chromium complexes modified with colorless ligands and their preparation. The dyes resulted

from reaction of a 1:1 chromium complex of a sulfo group containing dihydroxy azo dye with

salicylic acid or 3-hydroxy-2-napthoic acid in aqueous ethylene glycol. Thus 4,3-

HO(H2N)C6H3SO3H was diazotized and coupled with 2-ClC6H4NHCOCH2, the product was

complexed with chromium and the 1:1 complex was treated with 2-HOC6H4CO2H in 1:10

HOCH2CH2OH-H2O at 100 0 C for 2 hr. The solution of the resulting complex was neutralized to

pH 7 and converted to a water soluble brown powder, which produced lightfast yellow shades on

polyamide fibers and leather.

Patel N.C and Mehta A.G [124] studied the synthesis of quinoline based mostly biazo

dyes and their colouring performance on varied materials. Fifteen 3-[4-(arylazo)-phenylazo]-4-

hydroxy-1-methyl-2(1H)-quinolinone dyes were ready by coupling diazotized 3-(4-

aminophenylazo)-4-hydroxy-1-methyl-2(1H)-quinolinone with fifteen completely different

coupling part. The cation dyes was characterised by elemental and spectral analysis and their

colouring performance on silk, wool and nylon fibers was assessed.

Patel Vijay H, Patel Manish P and Patel Ranjan G [125-126] additionally studied the synthesis

and application of novel hetrocyclic dyes supported 11-amino-3-bromo-13 H-acenapthol [1,2-e]

pyridazino [3,2-b] quinazoline-13-one and 11-amino-13 H-acenapthol [1,2-e] pyridazino [3,2-b]

quinazoline-13-one.

Also some Indian scientists [127] studied the synthesis of 2-methyl-3-(2’-methylphenyl)-6-aryl

azo-4-azoquinazoline derivatives and their application. Some Japanese scientists [128] studied

the components useful for cosmetics, contain N-acyl lysine microparticles covered and/or mixed

with azo dye microparticles. Thus p-toluidine-m-sulfonic acid was melt in water with NaOH,

pptd. by using 35 % HCl containing N-Lauroyl lysine diazotized and coupled with β-

oxynaphthoic acid to give a dye.

German scientist Karl Heinz and co-worker [129] prepared cationic azo dyes and shown

their use.

NNHQ

R

C

O

A B N B A

R

O

C

N N Q H

R

nA-

12

1 21 2

3

n

Where A- = equivalent of anion; Q = coupling part residue, monoazo dye residue (if n=1); R =

C1-6 alkyl; R1,R2 = H, R, NO2, halogen; R3 = H, R, C1-6 radical interrupted by O, NH, NR,

1,4-piperazinediyl; A1,A2 = O, NH, (un) substituted NR; B1,B2 = C1-6 alkylene optionally

interrupted by O, NH, NR, 1,4-piperazinediyl; N=1-8.

Patel P.S, Patel S.K and Patel K.C [130] also studied the hetrocyclic monazo dyes

derived from 4-oxo-quinazoline. Patsch Manfred and Scholz Gerhard [131] studied preparation

of tris and poly azo reactive dyes, their mixtures, their production and use. Also some Japanese

scientist [132-133] prepared some azo dyes.

Iwata Yutaka and Obera Yaichi [134] studied the color pigment for cosmetics exhibiting

high bleeding and water resistance prepared by forming a dye on a chemical modified styrene

polymer. Thus, polystyrene beads were nitrated, reduced diazotized with 7% aqueous NaNO2

solution and coupled with β-napthol to give dye with desired properties.

Japanese Scientists [135] also studied the manufacture of azo lake pigments for storage

stable glossy inks.

Freeman Harold, Hsu Whie N, Esancy James F and Esancy Michelle K [136] also studied

the nucleon resonance spectra of some hydrocarbon derivatives. The chemical shifts of the ring

protons of forty two and β-monosubstituted napthalenes were appointed from 250

megacycle spectra and therefore the assignments were wont to assist within the interpretation of

the spectra of variety of hydrocarbon sulfonic acids normally used as dye intermediates. A table

of parameters was bestowed which might assist within the identification of complexe chemical

group dyes derived from these hydrocarbon derivatives. Enomoto Kazuhiro, Chiga Takao and

Tanaka Norio [137] studied the electrophotographic photorecep for containing composite azo

dye.

Necas Miroslav and Plechacek, Vaclav [138] studied the preparation of mixed laked azo

pigments. Red pigments for printing inks, varnishes and plastics with brilliant modified shades

are prepared by coupling a mixture containing 75-99.5% diazotized 2,4,5-

H2N(R1)(R2)C6H2SO3H (R1=R2=H, Cl, Me) and 0.5-25% diazotized 2,n·H2NC10H6SO3H

(n=1,5,6,7,8) with 3,2-HOC10H6CO2H (I) and laking the azo dye with Ca, Ba, Mg, Sr or Mn. A

mixture containing 96 mol% Ca salt of 2,4-HO3S MeC6H3NH2 → I (II) and 4 mol% Ca salt of

1,2,-HO3SC10H6-NH2 → I was prepared in this way and had a more bluish shade than II.

1.3 8-Hydroxy quinoline and its derivatives

8-Hydroxyquinoline (8-quinolinol, oxine) may well be thought to perform as a phenol,

however of the seven state hydroxyquinolines solely oxine exhibits vital antimicrobial activity,

and is that the just one to possess the capability to chelate metals. If the group is blocked so the

com-pound is unable to chelate, as within the alkyl group ether, the antimicrobial activity is

destroyed. the link between chelation and activity of oxine has been in¬vestigated [139, 140].

Oxine itself is inactive, and exerts activity by virtue of the metal chelates made in its reaction

with metal ions within the medium. utilized by itself or because the salt (Chinosol) or salt in

antiseptics, the result is organic process and fungistatic instead of microbiocidal. repressing

action is additional pronounced upon gram-positive than gram-negative bacteria; the growth-

preventing concentrations for staphylococci being ten ppm; for streptococci twenty ppm; for

Salmonella typhi and for E. coli a hundred ppm.[141,142]. 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 [143,144]. Iron and cupric salts were

found to prolong the antibacterial effect of oxine on teeth [145].

N

OH

N

OH

Cl

I

N

OH

Cl

Cl

N

O N

O

8-Hydroxyquinoline 5-Chloro-8-hydroxy-7-iodoquinoline

5,7-dichloro-8-hydroxyquinoline

Cu

Copper Oxinate

Certain grouping derivatives of 8-hydroxyquinoline have a record of thera¬peutic

efficaciousness within the treatment of body covering flora infections and additionally of

amebiasis. Among these area unit 5-chloro-7-iodo-8-quinolinol (iodochlor¬hydroxyquin,

Vioform), 5,7-diiodo-8-hydroxyquinoline (diiodohydroxy¬quin), and metallic element 7-iodo-

8-hydroxyquinoline-5-sulfonate (chiniofon)[146-148]. Copper 8-quinolinolate (copper

oxinate), the copper compound of 8-hydroxyquinoline, is utilized as associate degree industrial

preservative for a spread of functions, as well as the protection of wood and textiles against

fungus-caused putrefaction, and interior paints for food plants. it's twenty five times bigger

antifungal activity than oxine [149].

The reaction of 5-chloromethyl-8-quinolinol [CMQ] with various neucleophillic reagents

has been reviewed in section 1.6. It was noted that the reaction of CMQ with phenol

formaldehyde resin derivatives has not been reported. Hence, so called such derivatives have

been thought to prepare for metal chelation study. For sack of convenience review about 5-

chloromethyl-8-hydroxy quinoline are given below.

1.3.1 Reviews about 5-chloromethyl-8-hydroxy quinoline

The survey of literature 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-hydroxy quinoline. Paraformaldehyde, con.HCl and dry HCl gas [150,151]. It is

stable in form of hydrochloride other wise it hydrolyzes to methyl group [152].

The reports included the number of derivative of CMQ by the reaction of CMQ with

alcohols and secondary amines. Aristov. et. al. [153-156] have documented several reports about

number of 5-substituted derivatives from CMQ having the structures as follows.

N

OH

Br

CH2OR

N

OH

CH2OR

(I) (II)

R= Alkyl, Cycloalkyl, Benzyl

N

CH2-S-C-N-R

2

OH

S

N

CH2-NR

2

OH

The derivatives were monitored for anthelmintics, rematacides and fungicides [157].

The coumarin ring containing derivatives has also been reported [158] from CMQ

hydroxy coumarin.

N

CH2

OH

OO O

R

Me

R = Me, et, isobutyl

The dental plaque inhibitors from CMQ derivatives were prepared by Victor et.al [159]

N

OH

R

R = CHO, F, I, CH2OMe,

CH2OCH2COOCH3

H -Juerjea and Roth Hermann reported [160] that reaction between CMQ and

urea/guanidine afforded the following products.

N

OH CH2 NH C NH CH

2

O

N

OH

N,N’-bis(8-hydroxyquinolin-5-yl methyl) carbamide

N

OH CH2 NH C NH CH

2

NH

N

OH

1,3-N,N’-bis(8-hydroxyquinolin-5-yl methyl) guanidine

The fungicidal compound has been prepared having following formula [161].

N

CH2-N-CH

2-CH=CH-CH=CH-C-(CH

3)

3

OH

CH3

D. Pennelolce reported the corbostyriss derivatives containing 8-hydroxy quinoline [162].

The tetrakis 8-hydroxy quinoline methyl ethylene alkyl diamine shown below has been

prepared for their complexation [163,164].

N (CH2)

5-

10N

CH2 8HQ

CH2 8HQ

8HQ H2C

8HQ H2C

Similarly the glycine ester from CMQ has also been reported [165].

The patent has been reported about the 5-methylpiperazinyl derivatives for Fschamia

treatment [166].

N N RCH2

N

OH

R = Ph

-CF3

-CH2CH

2OH

Some reports about the metal analysis complexation and electroanalysis of these

derivatives are also found [167-169].

As CMQ having reactive group, number of ion-exchange resins has been prepared by

reaction of CMQ with active reactive group of polymers [170, 171].

The cellulose is a high molecular weight natural polymer and its reaction with CMQ

afford the 8-Hydroxy quinoline-cellulose product which is applied as good ion-exchanger [172,

173].

The well-known polymer say polystyrene and or styrene divinyl benzene copolymer were

aminated and these on treatment with CMQ afford good ion-exchangers [174-179].

CH2

N

OH

CH2

N

OH

Polymer chain

NH NH NH

CH2

N

OH

Polyethylene amine, polyethylene polyamine and polyxylene polyamines reacted with

CMQ [179]. The authors [179] suggested that these products are good metal chelating agents.

Ulkelov et.al. [180] reported the ion-exchange resin by condensation of CMQ and poly

thiocyanatoaniline.

Taken et.al. reported [181] the important aspect about florescent chelate based on

reaction product of CMQ and water soluble polymers.

W.R.David suggested [182] that polymers of olefin bearing bidentate ligands are useful

as protective coating and primers. Thus he prepared such polymer by reaction between poly (2-

hydroxy-ethylmethacrylate) and CMQ.

The chelate resin patented as reaction product between CMQ and acrylonitrile-divinyl

benzene-ethylene diamine copolymer [183].

8-hydroxy quinoline terminated polyether was prepared by the reaction between amino

terminated polyether and CMQ [184,185].

The various scientists [186-190] have reported the bis-8-hydroxy quinolines prepared

from CMQ and their co-ordination polymers

N

XO

M

N

O

M

n

CH2-O-CH2

CH2-O-CH2-CH2-O-CH2-CH2

O

O

CH2

CH2

CH2CH2 N N

X = CH2-S-CH2

Thus, the objective of the thesis work is to synthesis, characterization and the chelating

properties of azo containing amino phenol-formaldehyde resin-CMQ condense derivatives i.e.

APF-HQ oligomeric ligands.

1.4 Polymeric ligands

Polymer science has emerged as active discipline of materials science. This field

impinges on areas of trade goods, engineering and speciality polymers thereby stimulating

interest everywhere the world in exploiting newer domains. One such branch that has emerged is

chemical compound metal complexes comprising AN organic chemical compound containing

co-ordinating sites, complexed with metals. this can be of comparatively recent origin ANd an

knowledge domain approach taking into its fold areas viz; chemistry, metallurgy, environmental

and material sciences.

Though polymeric chelates are forming a subclass of coordination polymers, it is

regarded as a special kind of coordination polymers in which one or more chelate rings are

present in the repeat unit of polymer. It should be noted that the use of term metal complex as a

synonym for metal chelate is often in use. The number and variety of macromolecules

recognized as having the ability to chelate are so large that it is a difficult task to mantion

exhaustively. Hence, in the present section a brief introduction has been given about few of most

important polymers forming metal chealates with different metal ions showing special properties

for various applications.

The polymer-metal complexes could also be classified into totally different teams in line

with the position occupied by the metal, that is determined by the tactic of preparation. The ways

embody complexation between a substance operate anchored on a compound matrix and metal

particle, reaction of a multifunctional substance with metal particle and chemical action of metal

containing monomers.

A pendant metal advanced is one during which the metal particle is hooked up to the

compound matter operate, that is appended on the compound chain. supported the chelating

skills of the ligands, pendant complexes square measure classified as monodentate or polydentate

polymer-metal complexes.

When the compound backbone contains multidentate ligands the co-ordination structure

of polymer-metal advanced is portrayed in Scheme-1.

LL L

LL L

L L LLL L

+ Mn+

L L LLL L

MMM

L = Co-ordinate atom, M = metal atom

Scheme 1

When a compound matter is mixed directly with metal particle, that usually has four or

six co-ordinate bonding sites, the polymer-metal complicated shaped could also be of the intra-

polymer chelate sort or inter-polymer chelate sort as shown in Scheme-2.

L L L LL L L L

LLLL

L L L LL L L L

LLLL

+ MM M

+ MM M

A

B

A = Intra polychelate

B = Inter poly chelate

Scheme 2

A low relative molecular mass compound with multifunctional ligands on each ends of the

molecules grows into a linear network compound. The compound chain consists of co-ordinate

bonds and therefore the substance is that the bridging unit as per the subsequent illustration

(Scheme-3).

L

L

L

L

+ M

L

L

L

L

L

L

L

L

L

L

L

L

M M M

Scheme 3

Parquet polymers square measure flat, webby organic macromolecules within which a

metal is totally intermeshed. this sort of polymer-metal advanced is created by 'template reaction'

between 2 useful teams of the substance evoked by their' co-ordination to metal ions, leading to

the subsequent chelate alloy complexes (Scheme -4).

L

L

L

L

L

L

+ M

L

L

L

L

L

L

M M M

Scheme 4

Morgan and drew in 1920 [191] discovered the first chelating molecules those of with

two donor atoms. In the past, the principal commercial interest in chelate forming polymers had

in the selective removal of multivalent metal ions from industrial effluents. Later polymer

chelates of monovalent metal ions (using crown and cryptand) and monomeric complexes of

multivalent metal ions have been studied because of their speciality properties useful in ion

selective electrodes and ion exchange membranes [192-196]. Although the number of chelating

and complexing agents is very large, the donor atoms under go chelation are restricted most often

to non metallic atoms N, O and S. The ligands containing these elements is functional groups

such as: acid (-COOH), acid (-SO3H), chemical group (-OH), Nitroso (-N=O) and thiol (-SH)

[197, 198] are often classified into 3 classes like cationic , neutral and anionic ligands. Recently,

review from employees in USSR reveals that makes an attempt are created to include a colossal

variety of various chelating teams into compound network by a spread of path ways that [199,

200]. However, the anionic ligands have not been as well reviewed. Among the many ligands

into polymer networks, oxine is one of the best known for its good chelating ability. Some of

these most common ligands used in chelate forming polymers for commercial applications are

reported in Table 1.2.

Most of chelate forming ligands are investigated from at least three points of view, as the

properties of resulting polymer chelates depends upon these three functional factors.

1. Structure and nature of chelating ligand [L]

2. Coordination number of central metal atom [M]

3. Type of bonds formed between metal and ligand [M and L], and

influence of both on the behavior of metal chelates as a whole (Structure-properties

relationship).

The common polymerization reactions and methods of chemical modification of

polymers are used for the synthesis of polymer ligands [201-210]. Based on these reactions the

most prominent three classes of chelate polymers are ion-exchange resins, crosslinked polymers

with ligands attached at two or more polymers in networks, and pendent ligands forming either

unit chelating teams or building block chelating teams of the structure delineated as:

Importance of chelating polymers:

The large-scale industrial use of chelating organic compound of oxine is as

straightforward action resins in water softening and in several mining and pollution things. one

amongst these polymers is within the membrane technology. wherever the chelating result

powerfully hold the multivalent ions within the membrane and block the passage of the

commercially vital monovalent ions [211]. Another potential massive scale application of

chelating resins is within the selective removal of precious metals like U, gold from sea-water

and within the preconcentration of trace components [212-216] from dilute solutions for

selective removal and recovery of metal ions from industrial water effluents [217]. several

potential applications of chelate forming polymers as catalysts and reagents square measure

according [218] for numerous organic syntheses. changed chelate resins by introducing teams

square measure used as section transfer catalyst [219] for organic and organic chemistry

reactions.

The intensive review of literature reveals that there's considerable interest in enterprise

systematic studies on N and O donor systems primarily based compound ligands owing to their

organic chemistry significance in numerous.

Table 1.2 Common ligands used in chelate forming polymers

Sr.

No

Ligand Active structure Target

metals

Polymer

backbones

Comments

1.

Iminoacid

derivatives

N

CH2COOH

CH2COOH

Most

multivalent

metals

Mainly

polystryrene

Very important,

commercial resins,

but relatively non

selective

2.

8-hydroxy

quinoline

N

OH

Cu, Ni, Zn,

Co

Mainly condensations

Many experimental

polymer have been produced

3.

Polyamines

NH2(CH2CH2NH)-XCH2CH2NH2

Cu, Ni, Zn,

Co complex

metal anions

Polystryrene,

Poly acrylic acid,

poly ethylent

amine

Commercially and

experimental

resins with

manystructural

variation

4.

Thiourea

S C

NH2

NH

Au, Hg and

Pt metals

Polystryrene

Commercial resins have high

selectivity and capacity in acidic

Solutions

5.

Guanidine

NH C

NH2

NH

Pt metals

Polystyrene and

polycondensatio

n resin

Commercial resins

have high

selectivity and

capacity in acidic

solutions

6.

Dithiocarbam-

ate

NH C

SH

S

Hg, Cd, Zn,

Pb

Polyethyleneami

ne

Commercially

available resins.

7.

Hydroxamic

acid

C

OH

N OH

Fe, U, V

Polyacrylates

Mainly

experimental

resins, high

selectivity

8.

Amidoximes

C

N

NH

OH

Cu, Au, U

Polyacrylonitrile

Some very stable

complexes formed

9.

Crown ethers

O

O O

O

Alkali

metals

Mainly

polystyrene

Variety of

experimental

resins

10.

Mercapto

groups

SH

SH

Pb, Hg

Polystyrene,

polycondensatio

n resins

Mainly

experimental

resins,

condensation

resins.

11.

Cyclic

polyamines

NR

NR

NR

NR

Fe, Co, Mg

Polyaddition and

polycondensatio

n

Some very stable

complexes formed

12.

1,3-dicarbonyl

compound

O O

Cu, U, Fe,

Cr

Polystryrene

Many

experimental

polymers.

aspects of the human environment [220-223]. Among variety of these systems, polymer chelates

using oxine based polymeric ligands have been studied by many workers. A recent review from

workers in USSR has reported various experimental 8-hydroxyquinoline based polymers of

different structures synthesized by variety of methods [224]. This has inspired us to undertake

the work in this direction to prepare novel oxine based polymer ligands of dimethylol acetone

and dimethylol urea and their metal chelates with different metal ions with a view to access their

structure-property relationship and thermal behaviour. Hence, it is necessary to review briefly the

history of early attempts to design and tailor made routes for obtaining such polymer ligands of

oxine.

H. Horrowsks et al. synthesized the primary chelating chemical compound of oxine, by

polycondensation of oxine with aldehyde [225]. They reported the studies of typical chemical

compound chains of oxine-formaldehyde analogous to phenol-formaldehyde sort, capable of

forming chelates with metal ions. chemical compound ligands were ready by polycondensation

of oxine and aldehyde and exploitation each acidic and basic catalysts and afterward chelate with

completely different metal ions like, Zn(II), Cu(II), Ni(II), Co(II) and Mn(II) so as to attain the

mix of properties of each typical polymers and people of metal chelate crosslinks, like flexibility,

thermal stability, activity capability etc. the structures of chemical compound chelates and parent

matter additionally were elucidated on the premise of analytical, physical and spectral

knowledge. They investigated that chemical process would occur on 5- and 7- positions of oxine,

that corresponds to the p- and o- positions of phenol severally. Further, the consolidated ring of

oxine reduces the likelihood of crosslinking like that discovered in phenol-formaldehyde

atmospheric phenomenon polymers. As a result the oxine-formaldehyde polymers ar linear and

additional thermoplastic as compared to thermoset phenol-formaldehyde polymers. The more

chelation of oxine-formaldehyde with metal particle between chemical compound chains

(intramolecular crosslinking) would provide thermosetting chemical compound by forming

chelate crosslinks, which can impart increased thermal stability. The thermal stability studies of

parent ligands and their chelates have meted out by mensuration and differential mensuration

analysis. They observed that the mode of decomposition of polymer chelate is independent of the

metal ion present but different from that of free polymer ligand. The rate of decomposition of

free polymer is a function of temperature while that of chelate is not, and free polymer melts at

about 1900C but chelates do not melts, indicating that the polymer chelates are more heat

resistant compared to parent polymer ligand. Later, on many coworkers have carried out research

work concerning metal chelates of several oxine-formaldehyde polymer ligands and investigated

for their biological activities, protective coating on metal surface, ability in waste water

treatment, ion exchange properties and other speciality properties such as thermal properties,

electrical properties compared with phenol and substituted phenol based phenolic resins [226].

Perusal of literature has also revealed the other methods for the synthesis of oxine based

polymer ligands. These methods includes Friedel-craft reaction, Micheal addition reaction and

chemical modifications of polymer such as poly(oxy ethylene glycols), polyketones, polyesters

etc. these polymeric ligands are discussed in the following.

S. R. Patel and coworkers have prepared oxine-formaldehyde type polymers by Friedel-

craft alkylation of oxine respectively with methylene dichloride (CH2Cl2) and dichloroethane

(C2H4Cl2). These ligands were characterised by IR and ultraviolet illumination qualitative

analysis, body measurnments, and variety average relative molecular mass estimation. They

reported that structure elucidated of these ligands is similar to the oxine-formaldehyde polymers

obtained by polycondensation of oxine with formaldehyde. Structure property relationship of

oxine based polymer ligands have also studied by preparing analogous oxine-furfural polymers

and their metal chelates [227]. The comparative study of thermal properties of these two class of

polymers indicated that polymer ligand system of oxine-formaldehyde polymer is a lot of stable

thanks to shut approach of compound chains during this ligands whereas that of compound

backbone chains of oxine-furfural consisting of two rings – quinoline and furan joined by

methylene (-CH2-) groups as shown in given structure.

N

OH

n

N

OH

n

O

CH2 CH

oxine-formaldehyde polymer oxine-furfural polymer

T. B. Shah and coworkers [228] have reported the synthesis of polymeric chelates by

using preformed polymer ligands derived from polycondensation onlinking polyhydroxy ester

and 8-hydroxyquinoline. The polyhydroxy esters precursors were prepared by polycondensation

of diglycidyl ether of bisphenol-A respectively with succinic acid and carboxylic acid, followed

by later reaction with 5-chloromethyl-8-hydroxy quinoline coordination compound yielded

polyhydroxy organic compound containing pendent 8-hydroxyquinoline teams. These compound

ligands were chemical action with transition metal ions as shown below. each parent ligands and

their metal chelates were investigated for his or her structures and thermal behavior by IR and

reflection factor spectroscopic analysis and thermohydrometric strategies. they need conjointly

calculable torsion and metal to substance ratio. They ascertained that each one the metal chelates

additionally as parent ligands have high thermal stability and magnet property except that Zn (II)

chelate is magnetism in nature.

n

N

O

N

O

C

CH3

CH3

CH2CH CH2O OCH2 CH CH2OOC R COO

O

CH2

M/2 M/2

O

CH2

Where, R = Succinic acid Sebacic acid

Further the novel polymer ligands of polyketone type resin structure, are prepared by

Micheal addition of 8-hydroxy quinoline -5-aldehyde with acetone and methyl ethyl ketone [229]

and chemical change with metal ions like Zn(II), Co(II), Cd(II), Mg(II) and Mn(II) as shown

within the given structure.

N

O

n

CH

M/2

Where, R = H, CH3

CH

R

C

O

CH2

The resulting polymeric ligands and metal chelates both have polymer backbone structure

containing carbonyl group and 8-hydroxyquinoline as pendent group shown below. All the

samples of polymer chelates and parent polyketones are systematically investigated for their

structure determination, thermal behavior, electrical and magnetic properties.

Thus, this transient discussion concerning compound chelates of oxine concludes that

oxine-formaldehyde kind resins gave compound chelates of higher thermal stability by

introduction of open-chain chains -(-CH¬2-)- (n= 1-4) directly hooked up to oxine at 5- and/or 7-

positions. However, only one or two reports found in literature for the formation of chelating

polymers of oxine containing aliphatic chain with carbonyl groups such as polyketones (-CH2-

CO-CH2)n and with polythiourea (-NH-CS-NH-)n structure linked to 8-hydroxyquinoline in spite

of their wide industrial applications [230-232].

Hence, the driving force for the continue interest in the field of oxine polymer chelates,

as heat resistant polymers has inspired us to carry out the systematic work in the direction of

polymer metal chelates of oxine incorporated with above mentioned two structure moieties of

polyketones and polyurea type polymer ligands. For this purpose, dimethylol acetone and

dimethylol urea oligomers were used as monomers and subsequently their polymerization with

oxine to give polymer ligands of the structures:

N

OH

CH2CH2 CH2

CH2

n

N

OH

CH2NH NH CH2

n

c

o

c

o

AFO

UFO

W. B. Gurnule and D. B. Patle [233] synthesized o-Amino phenol-Melamine-

Formaldehyde co-polymer and studied their electrical conductance properties.

OH

NH2

N N

N NH2NH2

NH2

N N

N

OH

NH2

NH

NH

CH2

NH

n + n + 3n CH2O2M HCl,1250C

5 hrs

. H2On

o-amino phenol

melamine

formaldehyde

co-polymer resin

Hence from inspiration of above reported study the present work deals with a preliminary

study of application of azo containing amino phenol-formaldehyde oligomeric ligands. The work

on preparation and characterization of polymeric chelates has been carried out. Also other work

on ion exchange properties of present polymeric ligands has been presented in thesis.

Prior to the detail of the work regarding the synthesis and analysis of these polymer

ligands and their metal chelates the review about the 8-hydroxy quinoline derivative and 5-

chlormethyl-8-hydroxy quinoline and their chelate is given in the following section.

1.5 Objectives of the present work

The objectives of produced work are:

(i) To synthesis and characterize azo group containing amino phenol-formaldehyde resin-CMQ condensates i.e. oligomeric ligands.

(ii) To study the chelating properties, ion exchange properties and antibacterial activities of above prepared azo group containing amino phenol-formaldehyde resin-CMQ condensates i.e. oligomeric ligands.

1.6 Chapterization

In view of the above objectives the research work was carried out on the chelating studies

of APF-HQ resin. In this context the present thesis is compiled in the following way.

The amino phenol-formaldehyde resin (APF resin) was synthesized by condensation of 3-

amino phenol with paraformaldehyde. This APF oligomer condensed with diazonium salts of

aniline, 4-chloro aminoalkane, 4-methyl aminoalkane and 4-methoxy aminoalkane to make azo-

APF oligomer derivatives. The 5-chloromethyl-8-quinolinol were synthesized by

chloromethylation of 8-hydroxy quinoline, azo-APF oligomer derivatives was then condensed

with 5-chloromethyl-8-quinolinol to yield APF-HQ oligomeric ligands [APF-HQ-1 to APF-HQ-

4]. The details of procedure are presented in chapter-2.

Chapter-3 contains characterization of above prepared oligomeric ligands [APF-HQ-1 to

APF-HQ-4]. Their characterization includes elemental analysis, IR spectral studies, radical

determination and thermohydrometric analysis. The transition metal chelates of all the

polymeric ligands [APF-HQ-1 to APF-HQ-4] (mentioned in chapter-2) have been prepared and

their elemental and metal contents have been determined. These newly prepared metal chelates

also characterized by Infrared spectra as well as magnetic properties also analyzed. All these are

included in chapter-4 of the thesis.

All the newly prepared oligomeric ligands were analyzed for their ion exchange

properties and the results are discussed in chapter-5 of the thesis.

All the newly prepared oligomeric ligands [APF-HQ-1 to APF-HQ-4] and their metal chelates

were monitored for his or her microbicidal activity and also the results square measure

mentioned in chapter-6 of the thesis.

The thesis work is summarized in scheme-1 and 2.

NH2

R

N N Cl

R

N N Cl

R

N N

R

CH2

OH OH

NH2 NH2

CH2

OH

NH2

CH2

OH OH

NH2 NH2

CH2

OH

NH2

+

+ NaNO2 2HCl+0-50C

Benzene diazoniumchloride

+ +NaCl 2H2O

Benzene diazoniumchloride

n

Azo containing amino phenol-formaldehyde oligomer

n

3-amino phenol-formaldehyde oligomer

Where, R = H, Cl, CH3, OCH3

Scheme 1

N N

R

CH2

OH OH

NH2 NH2

CH2

OH

NH2

N N

RN

CH2

OH

N

CH2

OH

N

CH2

OH

CH2

OH OH

NH NH

CH2

OH

NH

N N

RN

CH2

O

N

CH2

O

N

CH2

O

CH2

OH OH

NH NH

CH2

OH

NH

n

Azo containing amino phenol-formaldehyde oligomer

Where, R = H, -Cl, -CH3, -OCH3

Metal Acetate

M = Cu+2, Co+2, Ni+2, Mn+2, Zn+2

n

5-chloro methyl-8-hydroxyquinoline (CMQ).

Oligomeric ligands [APF-HQ-1 to APF-HQ-4]

n

Oligomeric metal chelates of [APF-HQ-1 to APF-HQ-4]

M+2 M+2 M+2

Scheme 2