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