39
·Chapter 1 Introtfuction
·Chapter
1
Introtfuction
Chapter-1
1.1 INTRODUCTION:
The titles of the produced thesis suggest that the study is in connection
with the complexation study of salicylic acid - benzotriazole derivative. Hence
it is proper to review about the complex forming agents, salicylic acid and
benzotriazole derivatives.
Complex forming (Chelating) agents are becoming of
commercial importance because they maintain the quality of industrial
products analytically [1]. New types complex forming agents are continuously
under investigation, for possible analytical and industrial applications.
Morgan and Drew [2] 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 closed ring.
· To form metal complexes of an organic compound, an organic
compound must have two or more atoms usually oxygen or nitrogen, capable
of coordination with a metal ion, that is, 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 membered including the metal ion will be
formed.
Coloured complexes are used for qualitative or quantitative
determination of the elements. For qualitative detection, generally the spot
test technique is followed, whereas the colorimetric procedures based on the
formation of colored complexes utilized for the quantitative determination of
elements. Coloured complexes like Hemoglobin, Chlorophyll and Vitamin B-12
are also important in biosciences.
1
Chapter-1
The development of the spot test techniques for the detection of an
organic or inorganic substance is due to the pioneering work of Feigal [3].
Thus it is proper to give outline about formation of complex and complexing
agents.
1.2 FORMATION OF COMPLEXES:
The formation of complex and its stability depends upon the following
three factors:
A. The central metal atom
B. The complex forming groups of molecules
C. The nature of the metal-ligand bond
A The Central Metal Atom:
The nature and the oxidation state of the central metal atom
influences to a considerable extent the properties of a metal complex. The
influence of the central metal atom can be studied by comparing the
compounds formed by a series of different metal atoms in a given oxidation
state with a particular chelating agent.
B. The Complex Forming Molecule:
The organic molecules possessing the ability to form complex rings are
very large. When a molecule functions as a complex forming agent it must
fulfill two of the most important conditions given below:
(I) The organic molecule must have at least two appropriate functional
groups, the donor atoms of which are capable of combining with the metal
atom by donating a pair of electrons. The functional group may be an acidic
2
Chapter-1
group which may combine with the metal atom by replacement of hydrogen
or a coordinating group.
(II) The functional group must be appropriately situated in the molecule to
permit the ring formation with a metal atom as the closing member.
However, these two conditions are necessary but are not sufficient
always for the formation of a complex ring. Steric factors occasionally
influence complexation.
The perusal of the literature shows that an organic reagent, which
forms a chelate or an inner complex with a metal ion, is superior to the rest
in analytical work. When an organic molecule containing both an acidic and
basic functional group operate, an inner complex or a chelate result. The
formation of this ring may involve either a primary (ionic) or a secondary
(coordinating) valence and may be formed by two primary or two secondary
or one primary and one secondary valence.
An organic compound having a suitable number of reactive groups can
act as a chelate forming ligand depending upon the coordination number of
the metal ion. The ligand may be bidentate, tridentate or quadridentate and
may develop a complex ring of varied sizes.
A variety of chelates of metal ions with organic reagents having
bidentate groups have been studied. When group like -COOH, -CONH2, S03H
or -OH is suitably placed with a group like -5-, -NH2, -OH or =N-OH, the
latter groups are found to be coordinating with a metal ion which is linked
through primary valence (ionic) to the former.
3
Chapter-1
Copper and boron were found to form complexes with organic reagents
having a -cOOH and -QH both acidic groups. Thus the details about the
complexing agents are discussed in the next section.
C The Nature of The Metal Ligand Bond:
It is necessary to understand the nature of the bond between metal
and ligand, for the proper interpretation of the structure of metal complexes
[1-7]. The complex ions such as [ptCI6f, [Co (NH3)5]3+ etc. were subject of
intensive investigation to find out the factors responsible for their stability and
explain the existence of these compounds. Various theoretical approaches to
this problem were developed but it was Jorgensen [8] who proved that the
earlier theories proposed by the various authors[9,10] were fallacious.
Werner [11] proposed his coordination theory for the recognition of
the existence of the species such as [PtCI6f-, [Co (NH3)5]3+ etc. He explained
the formation and existence of these species by suggesting that the valency
of the atom and the number of bonds it can form may not be identical. He
postulated that the combining power of an atom is divided into two spheres
of attraction the inner co-ordinate sphere and the outer - ionization sphere.
Neutral molecules or negative ions are coordinated around and central metal
ions in the inner sphere. Number of such groups is the coordination number
of the metal ion. Negative ions are loosely attached to outer-sphere and can
be ionizable. So inner-sphere satisfies the secondary valency (non-ionizable
valency) and outer-sphere satisfies the primary valency (ionizable valency).
Lewis [12] and Langmuir [13] were the first to interpret the nature of
the covalent bond as "Sharing of electrons between two bonding atoms in
which each atom contributes one electron". Later on Sedgwick [14]
developed an electronic interpretation to explain the bonding in metal
4
Chapter-1
complexes and he had introduced the idea of coordinate bond by accepting
the Lewis concept of covalent bond.
1.3 COMPLEX FORMING REAGENTS [CFRsl {i.e. LIGANDS)
1.3.1 INTRODUCTION :
Prior to 1980's, research in the field of complex forming reagents (CFRs)
was one of the most active research areas in inorganic analytical chemistry
[15-22]. The development of CFRs was stimulated by research and progress
in coordination chemistry and by studies of complex equilibria in solution [21-
28]. At present the significance of CFR is considered by many as having
decreased in favor of instrumental methods, especially for routing, trace and
automated analysis, However, CFR remain essential for many current,
frequently used methods such as molecular spectrophotometry in the UV
visible region, luminescence analysis and the liquid-liquid extraction of
neutral, anionic and cationic species. In addition, CFR are essential in the
application of highly efficient separation procedures such as high performance
liquid chromatography, pre-concentration of trace elements, a variety of
continuous and automated analytical procedures, methods such as AAS, ESR,
NMR, NAA and some electro analytical methods.
A review of this field is considered useful since conflicting or insufficient
information about the behavior and reactivity of particular CFR is frequently
reported. Much of the present research with CFR deals with known or
modified analogue reagents which are useful or promising for analytical
practice. There remains a need to select and optimize conditions for the most
sensitive, selective and reliable regents for particular applications.
5
Chapter-1
Earlier studies or CFRs were aimed at long term preparative work and
modifications of reagent structures, experimental evaluation of their
reactivity, selectivity and properties of the complex species formed with the
analyte. More recently modern structure methods together with theoretical
and empirical numerical approaches have become important, especially for
radiation absorbing reagents and their reaction products. The expected
properties can then be interpreted using models of atomic and electronic
structure. Such work contributes to a better knowledge and understanding of
CFRs so that the selectivity and reactivity of each new CFR may be predicted.
The formation of binary, ternary or quaternary complex species may also lead
to the establishment of complex equilibria which must be elucidated. In
general, the main aim in preparing a new CFR or in optimizing the reactivity
of a known reagent, is to increase sensitivity ,selectivity or methods reliability
for an analyte.
1.3.2 EXPERIMENTAL CHRACRERISATION OF CFR:
The reactivity of a CFR ligand depends on the nature and steric
arrangement of the donor atoms, usually 0, N, S in the ligand [29-31], the
number of donor atoms bond to the analyte, the type of outer electronic shell
of the analyte ion [30-32] and the overall structure of the reagent. In
particular, the nature of chelate ring stabilization [33,34] and the basis
strength of the ligand [35-37] are important. Much valuable information can
be obtained from mixed or non-aqueous solution studies over abroad rang of
experimental conditions [38-40]. The detailed reaction scheme, the
stochiometry stability and properties of the complex formed are usually
determined by spectrophotometry [16-19], potentiometry [39-42] or solvent
extraction [ 43] in some cases with computer treatment [ 43-48] of tabulated
or graphical data. Optimum conditions for the use of a CFR in a particular
method may be deducted from investigation of distribution diagrams or
6
Chapter-1
response surfaces with respected to the various components [38-49].
Analytically useful interactions are usually based on the formation of chelates,
ion association complexes, ternary or quaternary complex with various
organic or inorganic ligands [50-57].
Ternary species of interest may be 'inner sphere complexes' such as Mln
XpHx (OH)y or Mm L1H x (OH)y involving different kinds of bonding
between the components or 'outer sphere' ion association complexes such as
[ MLnXxf or [MLnHxf. Inner sphere complexes are if particular significance
for zirconium, hafnium, nobelium, tantalum, molybdenum, tungsten, platinum
metals, lanthanides and actinides [52]. Complexes with anionic dyes or basic
cationic dyes with charged colorless metal or non metal species are often
characterized by each of extraction as well as considerable spetrophotometric
or fluorimetric sensitivity [50-54]. The additional ligand in ternary species
may also provide masking of interferents or may hinder metal ion or complex
hydrolysis, however the sensitivity of a particular reaction may decrease in
comparison with the parent binary species [53].
In addition to the traditional methods of investigation of CFR the
significance of NMR and kinetic studies of fast reactions with chromogenic
reagents has recently grown in importance. The use of 13 C-NMR and 1H
NMR enables distinctions to be made between alternative structures of
reagent species and reaction products. It is also possible to obtain
information about the rate of exchange and position of tutometric equilibrium
of reagents and their dependence on solvent. 13 C-NMR spectra show, for
example, the quinine/hidrazone structure occurs in the corresponding metal
chelates [38-40]. Rapid scanning of absorption spectra of reagents and their
reaction products provides information about the forms of the reagent during
stepwise complexation or successive coordination of various reagent donor
atoms during reaction [56]. Relatively little solid state information is available
7
Chapter-1
concerning analyte-CFR bonding. The structure, properties and nature of the
bonding in the reaction product may be evaluated by diffuse reflectance IR,
UV, NMR, or ESR spectroscopy or by X-ray diffraction [58].
1.3.3 THE NATURE OF COORDINATION SELECTIVITY:
Careful consideration of the coordination selectivity of a CFR towards
metallic or non-metallic ions is the usual precursor to studies aimed at
improving analytical selectivity [59-65]. Important factors are in the particular
donor atoms in the reagents' coordination centre, the nature of the donor
receptor interaction between the analyte and the CFR and the various
geometrical and steric factors influencing the centre of analytical reactivity. In
addition, the size and electron configuration of the analyte ion control the
ability of the ion for covalent metal ion-reagent bonding involving back
coordination or electron transfer between reagent and analyte orbital [66,67].
Thus the well-known chromogenic reaction of Fe2+ with 1,10- phenanthroline
and its derivatives does not take place if substituents are introduce into
positions adjacent to the functional group of the reagent or these positions
are blocked by further benzene nuclei. However the reaction with Cu2+ is not
blocked and it thus selective [58-67].
The introduction of substituents may introduce changes in the basicity
and the hydrophobicity of ligands which may affect reactivity and course of
reaction. Thus, in contrast to 8-hydroxyquinoline, the lack of reaction of
aluminum with 2-methyl-8-hydroxyquinoline in aqueous solution unlike the
reactions with Cr3+, Fe3+ or Ga3+ [57-68] is not, as was thought earlier, due to
the small size of Al3+ being unable to accommodate three ligand molecules
but rather to the lowering of the formation constant, the pH must be raised
to such a level that the competing reaction, the precipitation of aluminum
hydroxide predominates [68].
8
Chapter-1
A special form of selectivity, known as internal masking, result from
the competition between two different reagents donor atom groupings in a
single reagent molecule which can bind separately the selected analyte and
the interfering species. For example in 1,8,dihydroxy-2-[N,N
bis(carboxymethyl)-amino methyl] naphthalene-3,6-disulphonic acid [69,70]
the 1 and 8-dihydroxy groups are responsible for the chromogenic reaction of
Ti4+ but several other ions such as Fe4+, Al4+ ,Zr4+ and Th4+ are
simultaneously bound with the iminodiacetic acid group of thr excess reagent
forming almost colorless chelates and are thus masked [69] the formation of
ternary or quaternary complex species may result in larger differences in
stabilities between complexes of different analyte and hence selectivity in
comparison to binary species [60].
Complete structural characterization of reagents is important as lack of
such knowledge has, in the past, caused confusion over the mode of action of
what were, it now appears, likely to be the same compound. For example the
product of the self coupling of diazotized 1-amino-8-hydroxynaphthalene-
3,6disulphonic acid [71], which forms a selective reagent for the calcium ion,
has been named calcian and calcichrome with bis azo and cyclic tris azo
structures given, respectively [71]. Polarographic studies support the bis-azo
structure [72]. Detailed NMR and synthetic studies now confirm the product
as mono azo, 2, 8, 8'-trihydroxy-1,1'-azonaphthalene-3,5,6,6'-tetrasulphonic
acid [73].
The cause and nature of analytical reactivity and selectivity has been
well established for various CFR groups such as 2,2'
bipyridine,1,10phenanthroline and related reagents [67,74,75], dioximes of
aliphatic 1,2-diketones [76,77], reagents containing phenolic hydroxyl [78]
derivatives of a-hydroxyquinoline [63], 2,2'-disubstituted bis-azo dyes and
9
Chapter-1
analogues [79] 2-hydroxy substituted N-heterocyclic azo dyes [80,81],
functionalized crown ethers and others [82,83].
1.3.4 ANALYTICAL IMPORTANT CFRs:
Because of the large and growing number of available CFRs it is
important for the practicing analyst to have compilations of the most
important reagents for specific applications. Some monographs [16-20,84,85]
and special publications [89,90] provide comprehensive collections, most
classifying the reagents according to the analyte. From the reagent/reaction
chemistry viewpoint it is more logical to classify based on the characteristic
functional group of donor atoms in the various reagents since this primarily
determines the reactivity of the reagent [17-19]. The list of important CFRs is
presented in Tablel.l.
The important complex forming reagents are classified as follows [91]
(i.e. Table 1.1)
10 ----------------------------------------------------
Table: 1.1 Chelating agents.
-Q-0-donating reagents
A:1 Enolisable 1, 3-Diketones
~ Acetylacetone
~ Dibenzoylmethane
Ph-CO-CH-CO-Ph 2
Chapter-1
~0
II ----------------------------------------------------
Chapter-1
A.2 0-and peri-diphenols
~ Pyrochata
chole OH &OH .//
~ Pyrogallol OH
~OH OH
~ Gallic acid COOH
I ~
.// HO OH
OH
~ 1,5- Dihydroxynaphthalene-3,6-disulphonic acid ; Chromotropic acid
OH
OH
------------------------------------------------ 12
A.3 phenol carboxylic acids
~ Salicylic acid
A.4 Hydroxyflavones
~ Flavonol
A.S Hyroxyanthraquinones
);> Alizarin
)::oH ~ R
0
0 H
0
Chapter-1
OH
------------------------------------------------- 13
Chapter-1
>- Quinizarin 0 OH
0 OH
A.6 Hydroxyxanthenes
0 OH
R
A.7 Hydroxylamines
NH-OH
bo-o
8: -0-N Donating Reagents
8.1 a-substituted monoazo Dyes
HO
D-N=N-h R ~
14 ------------------------------------------------
8.2 Nitroso Compounds
8.3 Schiff's Bases
8.4 Formazans and Derivatives
NO
OH
R
CH=N--o
CH=N--o
~R
HOY
F\ NH-N=y __;==\ ~~ N=N ~
Chapter-1
R'
15 ------------------------------------------------
B.S 8-Quinolinol and Derivatives
c:-N-N- Donating Reagents
C.l Dioximes
~ Dimethylglyoxime
~ Benzildioxime
R
OH
IH=N-OH
CH=N-OH
N-OH
o-Il -o c-R ~ /;
~ 2,2 furil dioxime
N-OH
N-CH
/!} ~-c ~ "'-o ll~o/
HO-N·
Chapter-1
16 ------------------------------------------------
C.2 Bipyridine derivatives
C.3 Aryl-1, 2-diamines
);> 1,2-Phenylenediamine
);> 2,3-Diaminonaphthalene
D -S-Donating Reagents
D.l Thioureas
);> Thiourea
HO
s II
R'-NH-C-NH-R
Chapter-1
OH
17 -------------------------------------------------
0.2 Thiosemicarbazones
s II
NH-C-NH-NH-R 2
0.3 Monothiols
);;> Thioglycolic acid
);;> Thiosalicylamide
Chapter-1
~CSNH2
~OH
18 -------------------------------------------------
Chapter-1
1.4 SALICYLIC ACID AS COMPLEXING AGENT :
Salicylic acid and its bi-substituted derivatives are well known
complexing agent. Salicylic acid forms water soluble complexes [92-95]. In
aqueous solution the salicylate ion generally functions as a divalent bidentate
ligand [96] and forms uncharged chelates with divalent cations. In fact this
reagent finds many applications in analytical chemistry of inorganic species
[97].
Complexes of several transition metals with salicylic acid and mono
substituted salicylic acid have been investigated [93, 94]. The Uo2 +2
complexes of salicylic acid and various bi-substituted salicylic acid have been
reported [98].
Complexes of various 4-substituted salicylic acid have been
investigated. Water insoluble metal complexes of 4-aminosalicylic acid (PAS)
have been reported and investigated for tuberculolstatic effect [99-110]. The
Uo2 +2 complex of 4-iodosalicylic acid have been reported[ ]. Both 4-chloro
and 4-bromosalicylic acid are reported. However, transition metal complexes
of only 4-bromosalicylic acid have been investigated [111].
Aromatic carboxylic acid and phenolic compounds can mimic the
AI(III)-binding ability of the rather complicated high molecular mass, fulvic
acid and humic acid present in soil. These functional groups may be of
importance in the binding of AI(III) in microorganisms( catecholate-based
siderophores) or in plants (e.g. tea).
Because of the high basicity of the donor groups, salicylates (L:pK
"'17) and especially catecholates (L:pK rv22) chelate AI(III) through the two
negatively charged 0 donors with high stabilities. The binding strength
19 ----------------------------------------------------
Chapter-1
however is reduced considerably by proton competition in neutral aqueous
solution [112]. A cooperative 27 AI and 13C-NMR study of the AI(III)
phyhalicacid (PA), -salicylic acid (SA) and -tiron (TR) systems revealed that
the binding constants at pH rv3 obeyed the sequence TR>SA>PA, indicating
that the stabilities of the complexes depend on the chelate ring size in the
order of 5>6>7-membered ring [113].
Salicylic acid and its derivatives from mono and bis-chelates, the latter
looses two protons above pHrv6, resulting in the mixed hydroxo complexes
[Alb (OH)] 2- and [AIL2 (OH)2]
3- [114-118]. In spite of some indications
[119,120], it does not readily from an octahedral tris complex since the
binding strength of a third salicylate chelate is not competitive enough to
suppress metal ion and complex hydrolysis or even the precipitation of
AI(OH) 3 at pH > 7. An 27 AI-NMR study of the hydrolysis of AI(III) in the
presence of salicylate demonstrated that formation of the [AI13 (OH) 32] 7+
hydroxo tridecamer is hindered at a ligand to metal ratio higher than 0.5, but
colloids are produced above pH rv 4.5 . The 1:1 complex is detected at
rv3ppm (downfield from the signal due to [AI(H20)6]3+) [121,122]. The signal
corresponding to the complex [AIL2] - is assumed to be too broad to be
detected. The rate of exchange of water molecules on the AI(III) ion is
increased by over three orders of magnitude when salicylate or
sulphosalicylate ligands are present in the inner coordination sphere ct7oNMR study [122] ). There is apparently a correlation between the exchange
rate and the ligand basicity. The potentiometric speciation study by Di Marco
et al. [123] with two structurally similar ligands, 2-hydroxyphenylethanone
and 2- hydroxybenzeneacetic acid, revealed very similar AI(III)-binding ability
with that of salicylate.
20 ----------------------------------------------------
Chapter-1
In contrast with salicylates, catechol derivatives have much higher
affinity for AI(III) in the basic pH range, where the precipitation of AI(OH)3 is
prevented by formation of the octahedral tris complex AIL3 [118,123-127].
The stability of this complex is so high that it can efficiently hinder formation
of the very stable tetrahedral hydroxo complex [AI (OH)4]- , even at pH"'12.
Oligomeric hydroxo-bridged species are also assumed [118,124] to be
present in low concentration in the pH range 5-7. A multinuclear ( 27 AI, 13C
and 1H)NMR study of catechol complexation confirmed the pH-metric
speciation model [128]. The different resonances observed in the 27 AI-NMR
spectra were assigned to the following species: the tris chelate at 31.3 ppm
(with respect to [AI(H20)6t, the hydroxo complex [Alb (OH)] 2- at between
31.5 and 32 ppm, the bis chelate complex [AIL2] 2- at 26 ppm and[AIL] + at
11 ppm (a very broad signal). The bandwidth of the tris chelate signal is
relatively low (v112 "'340 Hz), revealing the threefold symmetry of this species
(species with symmetry lower than octahedral or tetrahedral ususlly give rise
to broad signals; the D3 symmetry of the catechol tris chelate is not cubic
symmetry, but relatively narrow signals are generally observed for this
species). At pH >9.5, new peaks are detected in the range 50-60 ppm; they
are assigned to tetrahedral mixed hydroxo complexes. With tiron ( 4,5-
dihydroxy-1,3-benzenedisulfonic acid), the meridional and facial isomers of
the chelate [AIL3] 3
- (tiron is a unsymmetrical bidentate ligand) were identified
in the 1H- and 13C-NMR spectra [129,130]. In the facial isomer, the ligands
are magnetically equivalent; in the meridional isomer, the three ligands are
distinct. The meridional to facial ratio was found to be 3:1, as expected from
statistical consideration.
Catecholamines that attain significant concentrations in various body
fluids, e.g. in the cerebrospinal fluid, can be important AI(III) binder in
humans. As a hard metal ion, AI(III) prefers chelation at the negatively
charged catecholate locus rather than at the side-chain amino group of
____________________________________________________ 21
Chapter-1
catecholamines, and catechol-like binding therefore predominates in a wide
pH range. Even for L-DOPA (3,4-dihydroxyphenylalanine), with its chelating
glycinate locus, only catecholate coordination occurs [127]. At physiological
pH, the main species is an (0- ,a-)-coordinated tris complex, with ammonium
groups remaining protonated.
1.5 1(H)-1, 2, 3, BENZOTRIAZOLE AND ITS MANNICH REACTION
Benzotriazole is an important heterocyclic compound
Benzotriazole (BT)
It's prime application is as corrosion inhibitors for copper or copper alloys
[33,34]. Ciba Geigy has introduced benzotriazole derivative under the trade
name Trinavin -P[35]. It is applied as an UV light absorber for stabilizing
plastics and other organic materials against discolouration determination [35].
It is also employed as photographic emulsion stabilizer [36]. In the peptide
synthesis it act in from of an active ester [37]. Number of derivatives of
benzotriazole have been prepared for metal complexation study [38] .One
such area in which the (benzotriazole organic ligand) combined molecule has
not been developed so far.The ligand like salicylic acid is well known for
analytical as well as pharmacological agent. If benzotriazole and salicylic acid
molecules combined for one molecule,it may improve the properties up to
some extent. Hence it was thought to undetake the study benzotriazole-4-
aminosalicylic acid combined molecules.
---------------------------------------------------- 22
Chapter-1
The mannich reactiction of BT is reported by several scientist
and tested as either pharmaceutical or microbicidal properties of the
derivatives [ 128-145]. Their structures are as follows.
n--~ ~ .... /N
N
I CH2-R
R=NH- phenyl, morphoninyl, Piperadinyl
Allan et al [143] and Bekier et al [144] reported the bishydroxyethylamino
methol derivative of Benzotriazole as hydraulic fluied.
For patents [145-147] and are full reports [148] indicated that aminoalkyl (i.e
Mannich base) products at BT are good additives for lubricanting oils. The
mannich base reaction products are also known as good metal corrosion
inhibiters [149,150] and as sweetner [151].
---------------------------- 23
Chapter-1
1.6 OBJECTIVES:
The objectives of the proposed work are
(i) To synthesis and characterize the salicylic acid- Benzotriazole
merged molecules.
(ii) To study the complexation behavior of such novel ligands (i.e
salicylic acid- Benzotriazole merged molecules).
1.7 THE PRESENT WORK:
In view of above objectives the Ph.D. research work was carried out
and distributed into 6 chapters of the thesis.
The Various Benzotriazole-salicylic acid merged moieties (termed as
ligand) was prepared by mannich reaction of N-alkyl substituted 4-
aminosalicylic acid with lH-benzotriazole was carried out. The synthetic
details about such reaction products are furnished in chapter-2.
Chapter-3 comprises the elemental analysis, IR and NMR spectra
studies, estimation of number of COOH group and thermo gravimetric study
of all novel ligands. The transition metal complex of all the novel ligands has
been prepared. Their detail synthesis and elemental analysis are presented in
chapter-4.
24 ----------------------------------------------------
Chapter-1
The chapter-S deals with the spectral studies, magnetic properties
and thermo gravimetric analysis of al the chelates. The microbicidal activity
of all the ligands and their complexes was monitored against the plant
pathogens. The study is summarized in chapter-6.
The reaction rout is scanned in scheme-1.
25 ----------------------------------------------------
O:N II N
N H
Benzotriazole
HCHO
Formaldehyde
~R
~OH COOH
4-Am ino salicylic acid derivative
~
N II
_....N
CH OH
~H2
n COOH
1----I(J-R
Ligands (HL-1 to HL-9)
Metal salt
~~ R ~N/N HzO - I
~.~, HO"'- ~/ooc---c>-j IIJ~ /l'/cH2 N coo OH I
I - H20 N::JC:N ~ R II I
N ~ Metal complex
Scheme 1
Where, R = -H , -CH3 , -CH2CH3 , -CH2CH2CH3 , -7HCH3
CH3
CH3 I
-C-CH3 I CH3
Chapter-1
26
Chapter-1
REFERENCES:
1. G. T. Morgan and H. D. Kdrew, J. Chern. Soc., 117 (1920) 1456.
2. H. F. Walton, "Principles and methods of Chemical Analysis". Prentice
Hall 85 (1952).
3. F. Feigal, "Chemistry of Specific, Selective and Sensitive Reactions"
Academic Press, (1949).
4. B. B. Fox, J. R. Halland and R. A. Plowman, Australian J. Chern. 5 (1962).
5. Yoe and Sarver, Organic reagents in Inorganic analysis; Blackiston,
Philadelphia (1940).
6. Chemistry of coordination compounds, Reinhod Publication N.Y. (1956).
7. Stosic, J. Amer. Chern. Soc.; 67 (1945) 362.
8. Jorgensen, J. Prakt Chern., 33 (1886) 489.
9. Berzelius, "Essai Sur Ia theoria des proportions chemique as Sur I"
Influence Chemique de 'I; electricite Paris, (1819).
10. Graham, "Elements of Chemistry" London (1837).
11. A. Werner, "Nature Anschaugenl" 4th ed., vieweg Braunscheveg. (1920).
12. G. N. Lewis, J. Amer. Chern. Soc.; 38 (1916) 762.
13. I. Langmuir; J. Amer. Chern. Soc.; 41 (1919) 869.
14. Sidgwick, N. V., J. Chern Soc., 13 (1923) 725.
15. Pilepenko, A.T., Zh. Vsesoyuzn. Khim. Obshch. 25, (6), 651 (1980).
27 ---------------------------------------------------
Chapter-1
16. Holzbecher, Z., Divis, L., Kral, M., Sucha, L., and Vlacil, F., Handbook of
Organic Reageents in Inorganic Analysis, E. Horwood, Chichester, 1976.
17. Sandell, E,B.,m and Onishi, H., Photometric Determination of Traces of
Metals, General Aspects, 4th Ed. Pt, I, Individual metals, Pt IIA,(A1-Li),
Pt II B,(Mg -Zr), Wiley, New York, 1978,1986,1989.
18. Korenman, OI.M., Organicheskie Reagentv V. Neorg. Analize,
Spravochnik, Himia, Moscow 1980.
19. Chent, K.,L, Ueno, K., and Imamura, T., Handbook Or Organic Analytical
Reagents, CRC Press, Boca Raton 1982.
20. Flaschka, H.A., and Barneard, A.J. (Ed.), Chelates in AnalyticaiChemistry,
Vol.1- 5, M.Dekker,New York 1967-1976.
21. Dwyer, F.P., and Mellor, D.P.(Ed.), Chelatin Agents and Metal Chelates,
Academic Press, New York, 1964.
22. Ringbom, A., Complexation in Analytical Chemistry, Interscience Publi.,
NewYork, 1963.
23. Rossotti, H., The Study of Ionic Equilibria, Longman, London.1978.
24. Perrin, D.D., Masking and Demasking of Chemical Reactions, Wiley
interscinece, New York, 1970.
25. Burgess, J., Metal Ions in Solution, Wiley, New York 1978.
26 . Inczedy, J.Analytical Application of Complex Equilibria, Akademial Kiado,
Budapest, and Horwood, Chichester, 1976.
28 ------------------------------------------------------
Chapter-1
27. Hartley, F.R., Burgess,m C., and alcock, R., Solution Equilibria, Horwood,
Chichester, 1980.
28. Kortly, S., and sucha, L., Handbook of Chemical Equilibria in Analytical
Chemistry, Horwood, Chichester, 1980.
29. Feigl, F., and Anger, V., Spot Tests in Inorganic Analysis, 6th Ed., Elsevier,
Amsterdam,1972.
30. Schwarzenbach, G., Wiss. Z. Kari-Marx-Univ. Leipzig.
Math.Naturwiss.Reihe,24,349(1975).
31. Jungreis, E., Spot Test Analysis, Wiley, New York, 1985.
32. Ahrland, S., Chatt, J., and Davis, N.R.Quart. Revs.12,265(1958).
33. Sawin, S.N., and Kuzin, E.L. Zh. Anal. Khim .. 22, 1058(1967).
34. Calvin, M., and Bailes, R.H., J. Amer. Chern Soc.,68,949(1946.)
35. Martell, A.E., and Calvin, M., Chemistry of the Metal Chelate compounds,
Prentice Hall, New York 1952.
36. Chaberek, St., and martell, A. E. Organic Sequestering Agents, Wiley, New
York,1959.
37. Bell, C.F. Principles and Application of Metal Chelation, Clarendon press
Oxford, 1977.
38. Sommer, L., Kuban, V., and langova, M., Fresenius' Z. Anal. Chern., 310
51(1982)
39. Schlafer, H.L., Komulexbildung in Losung, Springer, Berlin, 1961.
---------------------------------------------------- 29
Chapter-1
40. Rosotti, F.J.C, and Rostti, H., The Determination of Stability Constants,
McGraw Hill, New York 1961.
41. Bartusek, m., Folia Fac. Sci. Nat Univ. Purkynianae Brun. 5, Nr l.{Chemia)
37 (1964).
42. Beck, M.T., Chemistry of Complex Equilibria, Akademiai Kiado, Budapest,
and van Nostrand, Reinhold, London 1970.
43. Varchlabsky, M., and Sommer, L. J. Inorg, Nuci Chern., 31 3527 (1969).
44. Burns, D.T., Analvt.proc., 19,355, (1982).
45. Gamp, H., Maeder, M., Meyer, C.R., and Zuberbluher, A.D., Tlanta, 33,
943(1986)
46. Havel, J., and Meloun, M., Talanta, 33, 525 (1986).
47. Laouena, A., and Suet, E., Talanta, 32, 245 (1985).
48. Stay, J.(Ed.), The Solvent Extraction of Metal Chelates, Pergamon Press,
Oxford, 1964.
50. Pilipenko, A.T., and Tananaiko, M.M., Talanta 28, 745.
51. Pilipenko, A.T., and Tananaiko, M.M Talanta 21, 501.
52. Pilipenko, A.T., and Tananaiko, M.M, Raznoligandrive I Raznometal'nye,
Kompleksy I ikh Primeneine v Analiticheskoi Khimii, Izd. Khimia,
Moscow,1983.
53. Hinze, L.W., In; Solution Chemistry of Surfactants(Ed. Mittal, K.L.) Voi. 1,
Plenum Press, New York, 1979.
54. Koch, S., and Ackermann, G., Z. Chern., 20, 228 (1980).
30 ----------------------------------------------------
Chapter-1
56. Callahan., J.H., and Cook, K.D., Anal. Chem.56, 1632(1984).
57. Fedorov, LA, Zhukov, M.S. and Ermakov, A.N., Zh.Anal. Khim., 39, 1568
(1984).
58. Burger, K., Coordination Chemistry; Experimetal Methods, Akademiai
Kiada, Budapest, 1973.
59. Gen', L.I., Ivanov, V.M., Vilkova, O.M, and Golubistskii, G.B., Zh. Anal.
Khim, 37, 987 (1982).
60. Pilipenko, A.T., Svransky, L.I., Z ubenko, A.l., Sheptun, V.L., and
Miroshnikov,P.N., Zh. Anal. Khim., 39, 997 (1984).
61. Gribov, L.A., Savin. S.B., Oriv, N.N, J. Moi, Struct. 88, 172(1982).
62. Sawin, S.B., Petrova, T.V., and Dzherayan. T.G., Zh. Anal. Khim., 35,
1485(1980).
63. Gribov, L.A., Sawin, S.B., and Raikhshtat, M.M., Zh.Anal. Khim., 35,
1469(1980).
64. Savvin, S.B. and Chernova, R.K.(eds), Reports of VI USSR Conference on
Organic Reagents in Analytical Chemistry, Vo1s 1 and 2, Moscow(1989).
65. Petrukhin, O.M., and Borshch, N.A., Koord.Khim., 8,22(1982).
66. Kuznestov, V.i., Bolshakova, LV., and Fan Min-E, Zh. Anai.Khim.,18,
160(1963).
67. Schilt, A.A., Analytical Application of 1.10-Phenanthroline and Related
Compounds, Pergamon Press, Oxford, 1969.
---------------------------------------------------- 31
Chapter-1
68. Irving, H.M.N.H., Pure and Applied Chern., 50,1129 (1978).
69. Basargin, N.N., Akhmedli. M.K., and Shirinov, M.M., Zh. Anal. Khim., 23
1813 (1968).
70. Basargin, N.N., Zh. Ana;. Khim., 22, 1445 (1967).
71. Lukih, A.M., Smirnova, K.a., and Zavarikhina, G.B., Zh. Anal. Khim., 18,
444 (1963)
72. Mendes-Bezerra, A.E., and Stephe, W.I., Analyst, 94, 1117 (1969).
73. Stead, C.V., J. Chern. Soc. (C) 694 (1970).
74. Diehl, H., and Smith, G.F., The Iron Reagents Bathophenantholine.
2.4.6-Tripvridvl-s-triazine. Phenyl-2-pyridy1 ketoxime, G.F. Smith
Chemical Corp., Columbus, Ohio 1960.
75. Diehl, H., and Smith, F.G., The Copper Reagents: Cuproine. Neocuproine.
Bathocuproine, _ G.F. Smith ChemicaiCorp., Columbus, Ohio 1958.
76. Burger, K., Selectivity and Analytical Application of Dimethylglyoxime and
Related Dioximes, In: Flaschkar, H. A., and Barnard, A.J. Jr. (Ed.),
Chelates in Analytical Chemistry, Vol. II, p. 179, Dekker, New York 1969.
77. Sommer, L., Proc. Sympos. Coord. Comp., Agra (India) Pt. 3, 210 (1960).
78. Sommer, L., Fresenius, Z. Anal. Chern., 187, 263 (1962). 192. Bartusek,
M., Chern. Listy, 73, 1036 (1979).
79. Langova, M. And Sommer, L., Folia Fac. Sci. Nat. Univ. Purkynianae
Brun. 9(Chemia) Nr. 6pt. 2 (1968).
------------------------------------------------- 32
Chapter-1
80. Ivanov, V. M., Geterotsiklicheskie Azotsoderzhashine Azosoedinenia, Izd.
Nauka,Moskow (1982).
81. Takagi, M., and Nakamura, H.,J. Coord. Chern. 15, 53 (1986).
82. Melson, G.A. (Ed.), Coordination Chemistry of Macrocyclic Compounds,
Plenum Press, New York (1979).
83. Marczenko, Z. Separation and Spectrophotometric Determination of
Elements.Horwood, Chichester, (1986).
84. Malat, M., Extrakcni Spectrophotometric kovo a nekovu, SNTL, Praha
(1988).
85. M. Kantharaj and K. Neelakantam, J. Sc. Ind. Res., 1113 (1952) 79-80.
86. K.S. Bhakti and M.B. Kabadi, J. Sci. Ind. Res; 1713, (1952) 346.
87. K.S. Bhakti, A.T. Rane, M.B. Kabadi, Bull. Chern. Soc. 36 (1963) 1689-93;
C.A. 60 (1964) 8876.
88. Orgsnicheskie Reaktiw dla Oueideleoya Neorganicheskich Iovov.
Razional'nyi assortiment, Moskow (1970).
89. IUPAC Tables of Spectropohtometric Absorption Data of Compounds Used
for The Colorimetric Determination of Elements, Butterworth, London
(1963).
90. Flockhart, B.D. and Thorburn, D., Pure and Appl. Chern., 59, 915 (19
92. Park, M. V.,
j. Chern. Soc. (A), Inorg. Phy. Thermo, 816-820 (7), (1966).
33 ---------------------------------------------------
Chapter-1
93. Vartak, D. G., and Menon N. G.,
J. Inorg. Nucl. Chern., 33, 1003_-1011 (1971).
94. Idem., Ibid., 26, 1027 (1964).
95. Josef, H., Lumir, S., Chern. Absr., 72, 83489 h (1970).
96. Perrin. D. D., Nature, London, 182, 741 (1958).
97. Frank, J. Weltcher., Organic Analytical Reagents Page 118 (part II).
98. Jahagirdav, D. V. And Khanolkar, D. D., J. Inorg. Nucl. Chern., 35, 921
(1973).
99. Rao, M. J. and Seshaish, U. V., Bull. Chern. Soc. Japan, 39, (12), 2668-
2671_ (1965).
100. Khakimove, Kh. And Azizove, M. A., Chern. Abstr., 60, 14112 h (1964).
101. Dick., I. J., Lepea, A., and Neascu, M., Chern. Abstr., 68, 56045 q
(1968).
102. Ohta, H., Chern. Abstr., 53, 213141 g (1959).
103. Jin Tsin-Jao, Sommer, L. And Okae, A. Chern. Abstr., 59, 9450 e
(1959).
104. Mukherjee, Anal. Chern. Acta., 13, 273 (1955).
105. Suranova and Olenovich, Chern. Abstr., 46, 11877 (1950).
106. Papa, Gr., Ciurea, I. C., and Lazar, C., Chern. Abstr., 61, 3685 f (1964).
107. Galateanu, loan, Chern. Abstr., 64, 10737 b (1966).
108. Parije, H., and Ong. Sian Gwan, Chern. Abstr., 68, 87021 h (1968).
109. Prasad, Sarju, and Pandey L. P., Chern. Abstr., 71, 119145 g (1969).
34 -------------------------------------------------
Chapter-1
110. Negoiu, D., and Vasilescu, C., Chern. Abstr., 57, 382 c (1962).
111. Jahagirdar D. V., and Kanolkar D. D., Ind. J. Chern., 13 (20, 168-71
(1975).
112. T. Kiss. E. Farkas, Perspectives on Bioinorganic Chemistry, vol. 3, JAI
Press, London (1996).
113. T. Yokoyama, H. Abe, T. Kurisaki, H. Wakita, Anal. Sci. 13, 425 (1997).
114. L. 0. Ohman, S. Sjoberg, Acta. Chern. Scand. Sect. A 37, 875 (1983).
115. F. Zonnevillje, K. Brunisholz, Inorg. Chim. Acta. 102, 205 91985).
116. L. H. J. Lajunen, P. Kokkonen, R. Anntila, Finn. Chern. Lett. 15, 101
(1988).
117. P. Charlet, J. P. Deloume, G. Due, G. Thomas-David, Bull. Soc. Chim.
France 683 (1985).
118. T. Kiss, K. Atkari, M. Jezowska-Bojczuk. P. Decok, J. Coord. Chern. 29,
81 (1993).
119. L. H. J. Lajunen, J. Ind. Chern. Soc. 59, 1238 (1982).
120. L. Hawelkova, M. Bartusek, Collection Czech. Chern. Comm. 34, 3722
(1969).
121. D. J. Sullivan, J. P. Nordin, B. L. Phillips, W. H. Casey, Geochim.
Cosmochim.Acta 63, 1471 (1999).
122. T. Yokoyama, H. Abe, T. Kurisaki, H. Wakita, Anal. Sci. 13, 425 (1997).
123 V. B. Di Marco, A. Tapparo, G. G. Bombi, Ann. Chim(Rome) 89, 397
(1999).
35 -------------------------------------------------
Chapter-1
124. L. 0. Ohman, S. Sjoberg, Polyhedron .2, 1329 (1983).
125. J. A. Kennedy, H. K. J. Powell, J. Aust. Chern. 38, 659 (1985).
126. A. E. Martell, R. J. Motekaitis, R. M. Smith, Polyhedron .2 171 (1990).
127. T. Kiss,I. Sovago R. B. Martin, J. Am. Chern. Soc. 111, 3611 (1989).
128. R.S Varma, Indian, J.Chem, Sect B. 1976, 14 B(a) 718-19 (Eng)
129. Somei, Masahori, Matsubara, Mari, Kunda, Japan. Chern Phasm. Bull
1978, 26(8). 2522-34.
130. I.Collino, F, Volpe S. Boll. Chim Farm 1982, 121( 4) (I tal).
131. F.Collino,S.Volpe.Boii.Chim,Farm.1982,121(8),408-20 (Itall)
132. S. A Hussain; Najma; I.H Qureshi, Pak. J. Sci Ind. Res 1987,
30(3) 97-9.
133. A.R.Katrit2K, Hughes, Christy, Rachwal J. Heterocyed chem. 1989.
26(6), 1579-88.
134. A.R.Katrit2KD, kunihiko. Org. prep. Proceed Int 1989.21(3) 340-1.
135. A.Rkatrit2KD, Lalit, Laszlo. J. chem.Soc. Parkin Trans 1 1990(3) 667-72
136. Wang, Tin xy, Heng tens, china youji Huacylene 1992, 12(21) 198-201.
137. wang, Jin, 2404,Xuhjun. Fan. Du, china, xyuxye, xyebao, 1992. 50(5)
36 -------------------------------------------------
Chapter-1
504-7 (Cht)
138. A. R. Katrit2Kg, 2.1 Joung. N. Janshel Tetrahedren 1992. 48(23) 4921-
8.
139. Wanj, Jin, Du, Shaobin Bao, weiling, Jhou, Huaseue shiji 1993, 15(1)
19-20, 30 (Chine)
140. Shung chen, Junxiao, yougreh, wu, chehlie, yin, Beijing, shifan daxue
xuebao ziran kexueban 1993, 29(4) 512-3 (Ch).
141. A R. Katrit2kg, Gulu2ku, Bur barua, Rachxyall Black. J. Herrogd. chem,
1994 31(4), 917-23.
142. S. A. Hussain, Sartaraz, tahira B. Murtaza, Najma, Faizi, shasheen
(Karachi,Pak, 75280) Pak.J. Sci Ind.Res 1998 41(2). 63-67 (Eng).
143. A. R. Katrit2kg, shobanu, Navajuth. U.S.A organometallic. 1992. 11(3).
1381-4 (Eng)
144. Bekierz, crerard, Gibas, Jozet, Muchli, Bodzek, Kamila, Honorate, Pol.
PI 154, 395, 31 DEC 1991 Appl. 274. 198.4 PD.
145. Sung, Roclneg L: Zaleski, Benjumin 4, (Texaco.lng) U.S. 4, 278, 553,
14 Jul 1981. Appl. 109702, 04 Jan 1980 3PP.
------------------------------------------------- 37
Chapter-1
146. Nippon Oil Co. Ltd JPN. 26 Oct 1984 Appl. 83164. 136. 13 Apr 1983
SPP.
147. Chibnik, Sheldon. J.S, O.S 4, 717. 492. OS Jan 1988. Appl. 813, 813. 27
Dec 1985 JPP.
148. Sun. Xiang Dong Sun. Xy Dong, Zhung Jin Shiyou, Huugchi Gaodeng,
xyexiao, xubao, 2003, 16(3), 51-54(China).
149. Matsui, Naoyuki, Yameduchi, Toshiyuki, JPN, 02 Oct 1985. Appl. 84/49.
322. 16 mar 1984 3PP.
150. R. Buechner, Brendel Helga, Raunpt, Hartmann, Kluus, oe hler Felf.
Ger. (East) DD 273,631, 22 Nov 1989. Appl. 317,411, 01 Jul 1988. 4PP.
151. A.R.Katrit2kg shobanan, P.A.Harris, Org.Prep. Proceed. Ind. 1992. 24(2)
121-6 (Eng).
38 ------------------------------------------------
