Chapter 1

12

Chapter-1

Introduction

The present thesis comprises the aspect of studies a novel ligands

having general structure,

Chapter 1

13

Hence, looking to the structure, it is proper to review the post

derivatives of benzotriazole moiety, complex forming reagents (CFRs), 8-

hydroxy quinoline, Anthranilic, salicylic acid, 2-amino acetic acid and 2-amino

propanoic acid as CFRs.

1.1 Brief note on post derivatives of 1H-benzotriazole.

1H-Benzotriazoles are a significant class of compounds because of their

wide use in organic synthesis and pharmaceutical chemistry [1]. The

benzotriazoles there of are known to be important intermediates in the

preparation of organic products: β-amido ketones, aldehydes [2], β-keto

esters [3], ionic liquid and as reagents for acylation and thioacylation

reactions [4-6]. 1H-Benzotriazoles are also known to exhibit a broad spectrum

of pharmacological activities [7].

Although functionalized benzotriazole ring systems have been found

frequently in biologically active molecules, benzotriazole derivatives as MCR

partners are rather under-represented. This review offers a short and non-

exhaustive summary of various post derivatives of 1H-benzotriazole reported

by various researchers.

Recently, Jimit.S.Patel et al [8] have successfully synthesized ethyl-1H-

benzotriazole-1-ylacetate 1 which was engaged with hydrazine to form 2-(1H-

benzotriazole-1-yl) acetohydrazide 2 and also exploited the antifungal and

antibacterial activity.

Chapter 1

14

O

ON

N

N

CH3

O

NH-NH2N

N

N

O

NH-NHN

N

N

R

12

3

M bretner et al [9] have synthesized benzotriazole ribofuranosides by

the vorbruggen condensation method. In this method the sililation with HMDS

and TCS followed by treatment with ABR 5 in acetonitrile in the presence of

TMS-triflate gave benzotriazole ribofuranosides 6 in a very good yields.

Chapter 1

15

Nouria A. Al-Awadi et al [10] reported new derivatives of benzotriazole

7 used in the synthesis of complex.

Bennamane et al [11] reported the reactivity of enaminoes towards

electrophile reagents of benzotriazole.

Chapter 1

16

Byeong Hyo Kim et al [12] synthesize unique electrochemical reductive

cyclization of 10 towards 11 or 12 directly in high yields using constant

current electrolysis reaction conditions which would be more useful for the

mass production compared to any other chemical methods.

NO2

N

OH

N

R R'

N

N

N

HO

R

R'

O

N

N

N

HO

R

R'

1011

12

Chung Yi Wu et al [13] reported stable benzotriazole esters, esters 13-

16 showed that there was a time dependent decrease in enzyme activity as a

function of the inhibition concentration.

Chapter 1

17

They also synthesized compound 19 by using TBAF assisted N-

alkylation of 1H-benzotriazole.

N

NH

N

R

Br

O

TBAF R

ON

N

N17

18

19

R= NO2, Et2N

Augusto rivera and his co-workers [14] reported mannich-type

reactions in which benzotriazole reacts with formaldehyde and 2-naphthol

used instead of phenols [15]. They also reported an X-ray structural analysis

of 20 and its crystallographic characterizations.

Chapter 1

18

M.T. Patel also reported hydrazone of acetyl benzotriazole 21 which is

afforded by reaction of hydrazide and acetyl benzotriazole [16].

Claudio M.P., Helio A.S., Karla P.G. and Aline T.G. [17] reported new

derivatives of benzotriazole i.e. N-[(1-hydrazino)acetyl]-benzotriazole 23,

which is afforded by reaction of benzotriazole 22 with chloro acetyl chloride

followed by refluxed with hydrazine hydrate. They also synthesize derivatives

of benzotriazole.

Chapter 1

19

1.2 Brief notes on complex forming reagents CFRs:

1.2.1 Introduction

A review of this field is considered useful since conflicting or

insufficient information about the behavior and reactivity of particular CFRs is

frequently reported. Much of the present research with CFRs 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 reagents for particular

applications.

Earlier studies of 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

Chapter 1

20

analyte. More recently modern structural 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 CFRs 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 new CFRs, or in optimizing

the reactivity of a known reagent, is to increase sensitivity, selectivity or

method reliability for an analyte.

1.2.2 Analysis of CFRs

The reactivity of an CFRs ligand depends on the nature and steric

arrangement of the donor atoms, usually O, N, S, in the ligand [18-22], the

number of donor atoms bond to the analyte, the type of outer electronic shell

of the analyte ion [23-26] and the overall structure of the reagent [27]. In

particular, the nature of chelate ring stabilization [28,29] and the base

strength of the ligand are important. Much valuable information can be

obtained from mixed or non-aqueous solution studies over a broad range of

experimental conditions [30-32]. The detailed reaction scheme, the

stoichiometry, stability and properties of the complex formed are usually

determined by spectrophotometer, potentiometer [33-38] or solvent

extraction [39-44] in some cases with computer treatment [45-47], of

tabulated or graphical data. Optimum conditions for the use of CFRs in a

particular method may be deduced from investigation of distribution diagrams

or response surfaces with respect to the various components. Analytically

useful interactions are usually based on the formation of chelates, ion

association complexes, ternary or quaternary complex with various organic or

inorganic ligands [48-65].

Chapter 1

21

In addition to the traditional methods of investigation of CFRs the

significance of NMR and kinetic studies of fast reactions with chromogenic

reagents has recently grown in importance. The use of 13C-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 tautometric equilibria of reagents and

their dependence on solvent. 13C-NMR spectra show, for example, the

quinone/hadrazone structures of some N-heterocyclic azo dyes in solution but

that the regular structure occurs in the corresponding metal chelates. 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. Relatively little solid state information is available 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 [66].

1.2.3 The regulation of coordination selectivity of CFRs.

Important factors for coordination selectivity of a CFR towards metallic

or non-metallic ions are 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 electronic

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 [67-70]. 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 Cu1+ is not blocked and it is thus

selective [71].

Chapter 1

22

A special form of selectivity, known as internal masking, results 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)-aminomethyl] naphthalene-3,6-disulphonic acid [72,73]

the 1 and 8-dihydroxy groups are responsible for the chromogenic reaction of

Ti4+ but several other ions such as Fe3+ , Ai4+ , Zr4+ & Th4+ are simultaneously

bound with the iminodiacetic acid group of the excess reagent forming almost

colorless chelates and are thus masked 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.

The cause and nature of analytical reactivity and selectivity has been

well established for various CFR groups such as 2,2’-bipyridine, 1,10-

phenanthroline and related reagents [74-79], dioximes of aliphatic 1,2-

diketones [80-84], reagents containing phenolic hydroxyl [85-87] derivatives

of 8-hydroxyquinoline [88,89], 2,2’-disubstituted bis-azo dyes and analogues

[90] 2-hydroxy substituted N-heterocyclic azo dyes [91-95], functionalized

crown ethers [96] and others [97-100].

1.2.4 Significance of complexing reagent CFRs.

Because of the large and growing number of available CFR it is

important for the practicing analyst to have compilations of the most

important reagents for specific applications. Some monographs [101,102]

and special publications [103-105] 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 reagents [106-109].The list of important CFRs

is shown below.

Chapter 1

23

Important CFRs are as follows

Name Structure

8-Quinolinol and its

Derivatives

N

OH

R

R'

Salicylic acid and its

Derivatives

OH

COOH

R

Pyrocatechol

OH

OH

Pyrogallol

OH

OH

OH

Gallic acid

OH

OH

OH

COOH

Alizarin

O

OH

OH

O

Chapter 1

24

Name Structure

Hydroxyxanthenes

O

OHO

R

0-substituted monoazo

Dyes

N=N

OH

R R

Nitroso Compounds

OH

NO

R

Schiff’s Bases

N

N

CH

CH

Formazans and

Derivatives

NH N

N=N

C

OH

R''

R

R'

Dimethylglyoxime

C=N-OHCH3

C=N-OHCH3

Chapter 1

25

Name Structure

Thiosemicarbazones

NH-C-NH NH-R

S

Thioglycolic acid

HS-CH2-COOH

Thiosalicylamide

CSNH2

OH

Ethylene diamine tetra

acetic acid

(EDTA)

CH2

CH2

NN

HOOC

COOH

COOH

HOOC

Anthranilic acid and

its Derivatives

∝ -Amino acid

Chapter 1

26

1.3 8-Hydroxyquinoline and its derivatives as complex

forming reagents (CFRs)

8-Hydroxyquinoline (8-quinolinol, oxine) might be thought to function

as a phenol, but of the 7 isomeric hydroxyquinolines only oxine exhibits

significant antimicrobial activity, and is the only one to have the capacity to

chelate metals. If the hydroxyl group is blocked so that the compound is

unable to chelate, as in the methyl ether, the antimicrobial activity is

destroyed. The relationship between chelation and activity of oxine has been

investigated [110-112]. Oxine itself is inactive, and exerts activity by virtue of

the metal chelates produced in its reaction with metal ions in the medium.

Used by itself or as the sulfate (Chinosol) or benzoate in antiseptics, the

effect is bacteriostatic and fungistatic rather than microbiocidal. Inhibitory

action is more pronounced upon gram-positive than gram-negative bacteria;

the growth-preventing concentrations for staphylococci being 10 ppm; for

streptococci 20 ppm; for Salmonella typhosa and for E. coli 100 ppm [113,

114]. 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 [115,

116]. Iron and cupric salts were found to prolong the antibacterial effect of

oxine on teeth [117].

Certain halogen derivatives of 8-hydroxyquinoline have a record of thera-

peutic efficacy in the treatment of cutaneous fungus infections and also of

amebic dysentery. Among these are 5-chloro-7-iodo-8-quinolinol (iodochlor-

hydroxyquin, Vioform), 5,7-diiodo-8-hydroxyquinoline (diiodohydroxyquin),

and sodium 7-iodo-8-hydroxyquinoline-5-sulfonate (chiniofon) [118-120].

Chapter 1

27

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

Copper 8-quinolinolate (copper oxinate), the copper compound of

8-hydroxyquinoline, is employed as an industrial preservative for a variety

of purposes, including the protection of wood and textiles against fungus-

caused rotting, and interior paints for food plants. It has 25 times greater

antifungal activity than oxine [121].

1.4 Salicylic acid and its derivatives as complex forming

reagents (CFRs)

Salicylic acid and its bi-substituted derivatives are well known complex

forming reagent (CFRs). Salicylic acid forms water soluble complexes [122-

125]. In aqueous solution the salicylate ion generally functions as a divalent

bidentate ligand [126] and forms uncharged chelates with divalent cations. In

fact this reagent finds many applications in analytical chemistry of inorganic

species [127].

Chapter 1

28

Complexes of several transition metals with salicylic acid and mono-

substituted salicylic acid have been investigated. The Uo2+2 complexes of

salicylic acid and various bi-substituted salicylic acid have been reported

[128].

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 [129-140]. The

Uo2+2 complex of 4-iodosalicylic acid have been reported. 4-chloro and 4-

bromosalicylic acid are also reported. However, transition metal complexes of

only 4-bromosalicylic acid have been investigated [141].

Aromatic carboxylic acid and phenolic compounds can mimic the

Al(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 Al(III) in microorganisms(catecholate-based

siderophores) or in plants (e.g. tea). Because of the high basicity of the donor

groups, salicylates (∑pK ~17) and especially catecholates (∑pK ~22) chelate

Al(III) through the two negatively charged O donors with high stabilities. The

binding strength however is reduced considerably by proton competition in

neutral aqueous solution [142]. A cooperative 27Al and 13C-NMR study of the

Al(III)-phyhalicacid (PA), -salicylic acid (SA) and –tiron (TR) systems revealed

that the binding constants at pH ~3 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 [143].

Salicylic acid and its derivatives from mono and bis-chelates, the latter

looses two protons above pH~6, resulting in the mixed hydroxo complexes

[AlL2(OH)]2- and [AlL2 (OH)2]

3- [144-148]. In spite of some indications [149,

150], it does not readily from an octahedral tris complex since the binding

strength of a third salicylate chelate is not competitive enough to suppress

Chapter 1

29

metal ion and complex hydrolysis or even the precipitation of Al(OH)3 at pH

> 7. An27Al-NMR study of the hydrolysis of Al(III) in the presence of salicylate

demonstrated that formation of the [Al13 (OH)32]7+ hydroxo tridecamer is

hindered at a ligand to metal ratio higher than 0.5, but colloids are produced

above pH ~ 4.5 . The 1:1 complex is detected at ~3ppm (downfield from the

signal due to [Al(H2O)6]3+) [151,152]. The signal corresponding to the

complex [AlL2]– is assumed to be too broad to be detected. The rate of

exchange of water molecules on the Al(III) ion is increased by over three

orders of magnitude when salicylate or sulphosalicylate ligands are present in

the inner coordination sphere (17O-NMR study ). There is apparently a

correlation between the exchange rate and the ligand basicity. The

potentiometric speciation study by Di Marco et al. [153] with two structurally

similar ligands, 2-hydroxyphenylethanone and 2- hydroxybenzeneacetic acid,

revealed very similar Al(III)-binding ability with that of salicylate.

In contrast with salicylates, catechol derivatives have much higher

affinity for Al(III) in the basic pH range, where the precipitation of Al(OH)3 is

prevented by formation of the octahedral tris complex AlL3 [154-157]. The

stability of this complex is so high that it can efficiently hinder formation of

the very stable tetrahedral hydroxo complex [Al (OH)4]- , even at pH~12.

Oligomeric hydroxo-bridged species are also assumed to be present in low

concentration in the pH range 5-7. A multinuclear (27Al, 13C and 1H) NMR

study of catechol complexation confirmed the pH-metric speciation model

[158]. The different resonances observed in the 27Al-NMR spectra were

assigned to the following species: the tris chelate at 31.3 ppm (with respect

to [Al(H2O)6]+, the hydroxo complex [AlL2 (OH)]

2- at between 31.5 and 32

ppm, the bis chelate complex [AlL2] 2- at 26 ppm and[AlL ]

+ at 11 ppm (a very

broad signal). The bandwidth of the tris chelate signal is relatively low (v1/2

~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

Chapter 1

30

>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 [AlL3]

3- (tiron is a unsymmetrical bidentate ligand) were identified in the 1H- and

13C-NMR spectra [159,160]. 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 Al(III) binder in

humans. As a hard metal ion, Al(III) prefers chelation at the negatively

charged catecholate locus rather than at the side-chain amino group of

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. At physiological pH, the

main species is an (O- ,O-)-coordinated tris complex, with ammonium groups

remaining protonated.

1.5 Anthranilic acid and its derivatives as complex

forming reagents (CFRs)

Anthranilic acid form coordination complexes with many metals. The

structure of complexes with gallium and aluminium [161], lithium, sodium and

potassium [162], magnesium [163], thalium [164], rubidium and cesium

[165] have all been determined by x-ray crystallography. The stability of

chelates with copper and cadmium has also been investigated [166].

The new mixed ligand complex of Fe(III) with N,N-dimethyl-1,4-

phenylenediamine and anthranilic acid on aqueous media have been reported

[167]. The complexes of cinnamaldehyde anthranilic acid have been

investigated. The dissociation constant and the stability constants of its

complexes with Mn+2, Co+2, Ni+2, Cu+2, La+3, Ce+3, Uo2+2 and Th+4 in

Chapter 1

31

monomeric and polymeric forms also carried out by potentiometric studies

[168].

Arylidene-anthranilic acid Schiff base complexes with Th+4, Uo2+2, La+3,

Ce+3 and Zr+4 have been reported [169], also investigated the molecular

structure effect of these compounds on their tendency towards complex

formation.

The complexes of rhodium with N-phenyl anthranilic acid and

anthranilic acid have investigated [170]. The lanthanide complexes with N-

phenyl anthranilic acid also have been reported [171], also reported thermal

decomposition process and mechanisum of those complexes. The mixed

ligand metal complexes of o-benzoyl benzoic acid and anthranilic acid have

been reported [172].

1.6 Amino acids as complex forming reagents (CFRs)

Glycine, ethylenediaminetetraacetic (EDTA) acid ethelenediamine (En)

are some of the leading complexing agents used in the Cu CMP (Chemical

Mechanical Planarization) industry [173,181]. Aksu et. al. reported

electrochemical studies of glycine, EDTA and En on Cu. They concluded that

glycine shows highest efficiency as complexing agents as compared to other

two studies [173,181]. That glycine in presence of hydrogen peroxide

facilitates the active dissolution of Cu.

The mixed ligand complexes of copper(II) ion with drug dapsone and

primary ligand and the amino acids viz glycine, leucine, glutamine, valine,

methionine and phenyl alanine as secondary ligand have been reported [182].

The coordination complexes of Mn(II), Co(II), Ni(II), Cu(II) and Cd(II)

with two amino acids glycine and phenylalanine have been investigated [183].

The binary and ternary complexes of Cu(II) metal ion with nicotinamide and

Chapter 1

32

carboxylic acids (glycine, alanine, valine, cysteine and penicillamine) have

been reported [184].

1.7 Research lacks about 5-benzoyl benzotriazole-8-hydroxy quinoline, 5-benzoyl benzotriazole-salicylic acid and 5-benzoyl benzotriazole-anthranilic acid condensate:

Looking to systematic literature survey of post derivatives especially

work done on 1-N atom of benzotriazole, it was found that number of

derivatives of were benzotriazole synthesis by different researchers except

derivatives of benzotriazole specially at 1-N atom. But not major reports were

found for post derivative of benzotriazole (specially at work done at 1-N

atom) employed for metal complexation, except very few references [16,

17,185-187]. Hence, metal complexation study of 5-benzoyl benzotriazole -8-

hydroxy quinoline, 5-benzoyl benzotriazole-salicylic acid and 5-benzoyl

benzotriazole-anthranilic acid clubbed compound i.e. ligand has not been

reported. Hence, 5-benzoyl benzotriazole-8-hydroxy quinoline, 5-benzoyl

benzotriazole-salicylic acid and 5-benzoyl benzotriazole-anthranilic acid

clubbed compound has been thought to prepare for novel ligands.

1.8 Objectives:

The objective of the thesis work is to explore synthesis,

characterization and the chelating properties of 5-benzoyl benzotriazole -8-

hydroxy quinoline, 5-benzoyl benzotriazole-salicylic acid, 5-benzoyl

benzotriazole-anthranilic acid, 5-benzoyl benzotriazole-2-amino acetic acid

and 5-benzoyl benzotriazole-2-amino propanoic acid merged condensate.

1.9 The present work:

According to the objectives the Ph.D research work was carried out.

The work is bifurcated into following chapters of the proposed thesis.

Brief introduction about different techniques used for characterization

of compounds will be presented in chapter-2.

Chapter 1

33

synthesis and characterization of novel ligands (L-1 to L-7) will be

included in this chapter.

Different complex forming agents are taken. Here we are studied using

5-amino-8-hydroxyquinolinol, 4-amino-salicylic acid, 5-amino-salicylic acid,

Anthranilic acid, 5-bromo anthranilic acid, 2-amino acetic acid and 2-amino

propanoic acid moiety. Amino group presence in above moiety condensed

with N-(1-chloroacetyl)-5-benzoyl benzotriazole by removal of HCl to yield

novel ligands (L-1 to L-7).

These derivatives i.e. L-1 to L-7 were characterized by elemental and

spectral features. All these are included in chapter-3.

The various transition metal chelates of all the novel ligands

(mentioned in chapter-3) were prepared and characterized primarily. The

methods for metal chelates preparation and metal: ligand (M:L) stoichiometry

are presented in chapter- 4.

The various transition metal chelates of all the novel ligands are

characterized by Infrared and reflectance spectral studies, electrical

conductivity and magnetic moment measurements as well as by reflectance

spectral study. All these are presented in chapter-5.

The chapter-6 comprises the evaluation of antimicrobial activity of all

the ligands and their metal chelates. The plant pathogens have been selected

for this study.

The whole work is summarized in schemes–1 to 7.

Chapter 1

34

Scheme 1

Chapter 1

35

Benzoyl Benzotriazole(1)

ClCOCH2Cl

N

N

NC

COCH2NH

(2)

Ligand : L-2

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

COOHH2N

OH

COOH

OH

N

N

NC

COCH2NH COO

OH

N

N

N C

OOC

HO

NHCH2CO

M

4-amino salicylic acid

Metal Acetate

NH

N

NC

PhO

N

N

NC

COCH2Cl

PhO

Ph

O

PhO

PhO

Scheme 2

Chapter 1

36

Benzoyl Benzotriazole(1)

ClCOCH2Cl

N

N

NC

COCH2NH

(2)

Ligand : L-3

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

COOH

OH

COOH

OH

N

N

NC

COCH2NH

COO

OH

N

N

N C

OOC

HO

NHCH2CO

M

5-amino salicylic acid

H2N

Metal Acetate

N

N

NC

COCH2Cl

PhO

NH

N

NC

PhO

PhO

Ph

Ph

O

O

Scheme 3

Chapter 1

37

Scheme 4

Chapter 1

38

Scheme 5

Chapter 1

39

Benzoyl Benzotriazole(1)

ClCOCH2Cl

N

N

NC

COCH2NH

(2)

Ligand : L-6

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

Metal Acetate

H2CHOOC NH2

2-amino acetic acid

H2C COOH

N

N

NC

COCH2NHH2C COO

N

N

N C

H2COOC COCH2NH

M

N

N

NC

COCH2Cl

Ph

O

NH

N

NC

PhO

Ph

Ph

Ph

O

O

O

Scheme 6

Chapter 1

40

Benzoyl Benzotriazole(1)

ClCOCH2Cl

N

N

NC

COCH2NH

(2)

Ligand : L-7

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

Metal Acetate

HCHOOC CH3 2-amino propanoic acid

HC COOH

N

N

NC

COCH2NH CH

COO

N

N

N C

HCOOC COCH2NH

M

NH2

CH3

H3C

CH3

N

N

NC

COCH2Cl

Ph

O

NH

N

NC

PhO

Ph

Ph

Ph

O

O

O

Scheme 7

Chapter 1

41

References: 01. Eicher, T.; Hauptmann, S. The Chemistry of Heterocycles, Wiley- VCH

GmbH & Co. KGaA, Weinheim, (2003).

02. Katritzky, A. R.; Fang, Y.; Silina, A. J. Org. Chem., 64, 7622, (1999).

03. Katritzky, A. R.; Wang, Z.; Wang, M.; Wilkerson, C. R.; Hall, C. D.;

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