SYNTHESIS AND BIOLOGICAL STUDIES OF 4-aminoantipyrine DERIVED SCHIFF BASE COMPLEXES

(Dissertation submitted to Sri S.R.N.M. College, Sattur affiliated to Madurai Kamaraj University in partial
fulfillment for the award of the degree of

(MASTER OF SCIENCE IN CHEMISTRY)

By

V.BHARATHI Reg. No: PCH175101

M.KAYALVIZHI Reg. No: PCH175112

Under the guidance of

Mrs.V.SOUNDARANAYAKI M.Sc., B.Ed.,

Assistant professor of chemistry,

Sri S. Ramasamy Naidu Memorial College,

Sattur – 626203

DEPARTMENT OF CHEMISTRY

SRI S. RAMASAMY NAIDU MEMORIAL COLLEGE

(AN AUTONOMOUS INSTITUTIONS)

SATTUR - 626203.

APRIL – 2019

Mrs. .V.SOUNDARANAYAKI M.Sc., B.Ed.,

Assistant professor of chemistry,

Sri. S. Ramasamy Naidu Memorial College,

Sattur – 626203.

CERTIFICATE
 This is to certify that this dissertation entitled "SYNTHESIS AND BIOLOGICAL STUDIES
OF 4-aminoantipyrine DERIVED SCHIFF BASE COMPLEXES” submitted by V.BHARATHI (Reg. No:
PCH175101), M.KAYALVIZHI (Reg. No: PCH175112), for the award of the degree of MASTER OF
CHEMISTRY is the bonafide record of work carried out by them under my guidance and that it has not
previously formed the basis for the award of any degree, diploma, associateship, fellowship or any other
similar title.

Place: sattur Signature of the Supervisors

Date:

Counter signed by

The Head of the Department Signature of the Examiner

DECLARATION

We, V.BHARATHI (Reg. No: PCH175101), M.KAYALVIZHI (Reg. No: PCH175112), do hereby declare
that this project work is bonafide record of work carried out by us under the guidance and the
supervision of Mrs. V.SOUNDARANAYAKI, Assistant Professor of chemistry,
Sri S. Ramasamy Naidu Memorial College, Sattur being submitted to Sri S. Ramasamy Naidu Memorial
College, Sattur affiliated to Madurai Kamaraj University, Madurai in partial fulfillment for the award of
the degree of MASTER OF SCIENCE IN CHEMISTRY and that it has not previously formed the basis for the
award of any degree, diploma, associateship, fellowship or any other similar title.

Place: Sattur

Date: Signature of the Candidates

 ACKNOWLEDGMENT

First of all, I would like to heartily thank the lord almighty without whose grace no work could have
been started. I pay my earnest thanks to our college management for providing this opportunity.

My primary thanks go to my guide Mrs. V.SOUNDARANAYAKI, Assistant professor and Department

of Chemistry, Sri S. Ramasamy Naidu Memorial College, Sattur. I derived great inspiration and
encouragement from her to pursue this project work. I owe much of this to her able guidance and
helpful criticism.

I am very much thankful toMrs.M.SELVAMARIAMMAL, Assistant professor and Head of the

Department of Chemistry, Sri S. Ramasamy Naidu Memorial College, Sattur for her active and invaluable
assistance rendered in the successful completion of my project work.

I record my sincere thanks to our Principal Dr. S. Ganeshram Sri S. Ramasamy Naidu Memorial
College, Sattur for providing me the necessary facilities for the preparation of this project.

My sincere thanks to entire faculty members and lab assistants of the Department of Chemistry.
Once again I thank everyone who helps in this project work.

Place: Sattur V.BHARATHI

Date: M.KAYALVIZHI

CONTENTS

S.NO TITLE PAGE NO

1 INTRODUCTION
2 SCOPE OF THE WORK

3 MATERIALS AND METHODS

4 RESULTS AND DISCUSSION

5 CONCLUSION

6 REFERENCE

INTRODUCTION

Synthesis and biological studies of 4-aminoantipyrine Schiff base complexes

Introduction:

In chemistry, a coordination complex consists of a central atom or ion, which is usually metallic and is
called the coordination center, and a surrounding array of bound molecules or ion, that are in turn
known as a ligand or complexing agents. Many metal-containing compounds, especially those of
transition metals are coordination complexes. A coordination complex whose center is a metal atom is
called a metal complex. Coordination complexes are so pervasive that their structure and reaction are
described in many ways, sometimes confusingly. The atom within a ligand that is bonded to the central
metal atom or ion is called the donor atom. In a typical complex, a metal ion is bonded to several donor
atoms, which can be the same or different. A polydentate (multiple bonded) ligands is a molecule or ion
that bonds to the central atom through several of the ligand atoms; ligand with 2,3,4 or even 6 bonds to
the central atom are common. These complexes are called chelate complexes; the formation of such
complexes is called chelation, complexation, and coordination. The central atom or ion together with all
ligands comprise the coordination sphere. The central atoms or ion and the donor atoms comprise the
first coordination sphere. Coordination refers to the “coordinate covalent bonds’’ (dipolar bonds)
between the ligands and the central atom. Originally, a complex implied a reversible association of
molecules, atoms, or ions through such weak chemical bonds. As applied to coordination chemistry, this
meaning has evolved. Some complexes are formed virtually irreversible and many are bound together
by bonds that are quite strong. The number of donor atoms attached to the
central atom or ion is called the coordination number. The most common coordination numbers are 2,
4, and especially 6. A hydrated ion is one kind of a complex ion, a species formed between a central
metal ion and one or more surrounding ligands, molecules or ions that contain at least one lone pair of
electrons.

If all the ligands are monodentate, the n the number of donor atoms equals the number of ligands.
For example, the cobalt (II) hexahydrate ion or the hexaaquacobalt (II) ION [Co (H2O) 6]2+ is a hydrated-
complex ion that consists of six water molecules attached to a metal ion Co. The oxidation state and the
coordination number reflect the number of bonds formed between the metal ion and the ligand in the
complexion. However, the coordination number of [Pt (en) 2 2+] is 4 (rather than) since it has two
bidentate ligands, which contain four donor atoms in total.

Any donor atom will give a pair of electrons. There are some donor atoms or groups which can
offer more than one pair of electrons. Such are called bidentate or polydentate. In some cases, an atom
or a group offers a pair of electrons to two similar or different central metal atom or acceptors- by a
division of the electron pair into a three-center two-electron bond. These are called bridging ligands. In
coordination chemistry, a structure is first described by its coordination number, the number of ligands
attached to the metal. Usually one can count the ligand attached, but sometimes even the counting can
become ambiguous. Coordination numbers are normally between two and nine, but large numbers of
ligands are not uncommon for the lanthanides and actinides. The number of bonds depends on the size,
charge, and electron configuration of the metal ion and the ligands. Metal ions may have more than one
coordination number. Typically the chemistry of transition metal complexes is dominated by
interactions between s and p molecular orbitals of the donor atoms in the ligands and the d-orbital’s of
the metal ions. The s, p and d orbitals of the metal can accommodate 18 electrons. The maximum
coordination number for a certain metal is thus related to the electronic configuration of the metal ion
and to the ratio of the size of the ligands and the metal ion. Large metals and small ligands lead to high
coordination number Eg: [Mo (CN) 8]4-. Small metals with large ligand lead to low coordination
numbers, Eg: Pt [P (CMe3)] 2. In bioinorganic chemistry and bioorganometallic chemistry,
coordination complexes serve either structural or catalytic functions. An estimated 30% of proteins
contain metal ions. Examples include the intensely colored vitamin B12, the heme group in hemoglobin,
the cytochromes, the chlorine group in chlorophyll, and carboxypeptidase, a hydrolytic enzyme
important in digestion. Another complex ion enzyme is catalase, which decomposes the cell’s waste
hydrogen peroxide. Homogeneous catalysis is a major application of coordination compounds for the
production of organic substances. Processes include hydrogenation, hydroformylation, and oxidation.

Schiff base:

Schiff base is one of the condensation reactions of aldehydes (or) ketones with primary amines.
Schiff bases form stable complexes with various transition and inner transition metals.In recent years
most of the bioinorganic chemist shows there an interest in Schiff base metal complexes for developing
the anticancer activity of complexes with high efficiency [1-4].

Generally, Schiff bases have various biological activities like antibacterial, antifungal and anticancer
activity. Schiff base metal complexes which are based on amino acid have efficient pharmacological
activity against various pathogens [5].

Importance 4-aminoantipyrine:

4-aminoantipyrine is a pyrazolone a member of the class of pyrazoles that is antipyrine substituted

at C-4 by an amino group.It is a metabolite of aminopyrine and of metamizole.

It has a role as a non-steroidal anti-inflammatory drug, a non-narcotic analgesic, an antirheumatic

drug a peripheral nervous system drug, an antipyretic, a drug metabolite and a marine xenobiotic
metabolite [6].

It is a primary amine compound and a pyrazolone. It derives from antipyrine. 4-amino antipyrine
has an N-phenyl group and a CH2 group on either side of the polar carbonyl group thus resembles N-
substituted amides. The carbonyl group in 4-amino antipyrine is a potential donor due to a large dipole
moment and strong basic characters [7].

Schiff bases and metal complexes of 4-amino antipyrine and also known for their great variety of
application in the area of catalysis and biological activity ranging from antitumor, fungicide, bactericide
and antiviral activities [8-11].

1.1Serine:
 Serine is an amino acid which has alpha-amino group gives protonated NH3+ ions. Under biological
condition and alpha-carboxyl group (deprotonated coo- form in physiological condition) and a side chain
having a hydroxyl methyl group. It is a polar amino acid. It has great importance in metabolisms like
biosynthesis of purines and pyrimidines. It is the precursor for several amino acids include glycine and
cysteine. The so-called nerve gases and many substances used in insecticides have been shown to act by
combining with a residue of serine in the active site of acetyl chloride esterase, inhibiting enzyme
completely. The deficiency of this serine derivative causes defects in a human being like congenital
microcephaly, severe psychomotor retardation.

Structure of serine

Serine is important to overall good health, both physical and mental. Serine is especially important to
the proper functioning of the brain and central nervous system.

Serine helps from the phospholipids needed to make every cell in our body. It is also involved in
the function of RNA and DNA, fat and fatty acid metabolism, muscle formation, and the maintenance of
a healthy immune system. The proteins used to form the brain, as well as the protective myelin sheaths
cover the nerves, contain serine. Without serine, the myelin sheaths could fray and becomes less
efficient at delivering messages between the brain and nerve endings in the body, essential short-
circuiting mental function.

Serine is also needed to produce tryptophan, an amino acid that is used to make serotonin a mood
determination brain chemical. Both serotonin and tryptophan shortages have been linked to depression,
insomnia, confusion, and anxiety. Research suggests that low levels of serine may contribute to chronic
fatigue syndrome (CFS) and fibromyalgia (FM)

Serine helps produce immunoglobulin and antibodies for a strong immune system, and also acids in
the absorption of creatine, a substance made from an amino acid that helps build and maintain all the
muscles in the body, including the heart.

Serine supplementation is available in capsule, tablet and powder form. It can be purchased as a
stand-alone supplement or more commonly in the combination of amino acid supplements and sports
drinks.

Serine is a constituent of phospholipids which help seal in moisture, so it also often included as a
natural moisturizing agent in many cosmetics.
1.2Biological importance of Schiff base and its complexes:

1.2.1Antibacterial properties:

The most important properties of the Schiff base are antimicrobial screening. Among these, the
Schiff base and its complex act against both gram-positive and gram-negative bacteria [12]. It is noted
that the Schiff base is much more active against bacteria than the Schiff base alone. This explained by
Tweedy’s chelation theory which says that chelation due to partial sharing of positive charge with donor
groups and possible π- electron delocalization within the whole chelating ring system reduces the
polarity of metal ion to the considerable extent, thereby increases the lipophilicity of the complexes and
enhances the interaction between the metal ion and lipoid biolayer, thus easy to make the diffusion of
metal ion through cell membrane. This makes the Schiff base metal complex are much more reactive
against microbes. The antibacterial activity of the complex and ligand is determined by using
staphylococcus aureus as standard [13-16].

1.2.2Antifungal properties:

Schiff base and its complexes have promising antifungal property.The activity of Schiff base and
its complexes against fungi strains such as odium caricae was determined using well diffusion
method[17].

1.2.3Antihypertensive activity:

The amine-based Schiff base complexes have found to be as good antihypertensive agents. It
makes the Schiff base complexes are very important one in the pharmacy field. This property was
examined by the rat that proves the Schiff bases have the potential to act as an antihypertensive drug
[18-22].

1.2.4Anti diabetic property:

The oxovanadium complexes with mixed ligands and with ONO donor Schiff base ligand was
evaluated for PTP inhibition. PTP 1B was identified as a key enzyme for insulin resistance. By inhibiting
the PTP, thereby increase in insulin level. The kinetic analysis results that oxo vanadium complexes have
competitive inhibiting property on PTP1B. Thereby the uses of this Schiff base complex identified its
usage as an antidiabetic drug [22].

1.2.5Antioxidant activity:

The harmful effect of free radicals and other oxidants in the human body can be prevented by
enzymatic and non-enzymatic antioxidant protections.
 Important function antioxidant is to prevent the formation of free radicals in the human body. The
Schiff base and its complexes have more biological applications among that antioxidant property is a
significant one. Nowadays, bioinorganic chemists are interested in preparing the anticancer drug on the
basis of the Schiff base complexes [25]. Copper Schiff base complexes are much most effective inhibitor
even in minimum quantity requirement.

1.2.6Anti depressant activity:

The Schiff bases were found to have antidepressant activity. The synthesized Schiff base complex
have amine, halogens which are exhibited significant antidepressant and no tropic activities [30].

1.2.7Anti cancer/Antitumor property:

A novel series of Schiff bases which are involving heterocycles have invitro antitumor activity
against a murine leukemia cell line, a human leukocyte cell line using MTT assay. The Cu (II) complex of
Schiff base ligands generally has more therapeutic uses among that the good potential for anti cancer
property is a marked one.

1.3Biological activities of metal complexes:

1.3.1Copper:

Copper complexes have much more importance in biochemical action and a constituent of various
exogenously administered compounds in humans and also play as an essential trace metal. It latter
action it is bound to ligands of various types of complexes that interact with biomolecules, mainly
proteins and nucleic acid and former action it is bound to ceruloplasmin, albumin, and other proteins.
The multifaceted role of copper in a biological system is demonstrated by several studies. In particular,
the involvement of copper in human diseases has been described from a medical, chemical and
biological view focusing on the molecular physiology of copper transport. Much of the current research
effort is cited on copper homeostasis and its relation to iron metabolism as well as the role of copper in
biological processes related to human physiology and pathology while a lot of the functions that have
been proposed to account for homeostasis of inorganic non-complexed copper in humans have been
described, only a limited number of review studies have focused on the multiple biochemical events
which could be directly implicated in the uses of copper complexes in medicine. The copper complexes
have the antimicrobial, antitumor, antirheumatic activity. The copper complexes have non-steroidal
anti-inflammatory property.

1.3.2Vanadium:
 Organometallic chemistry of vanadium is well developed although it has mainly only academic
significance. Health benefits of vanadium and its potential as an anticancer agent have been reviewed.
Vanadium is more important in marine environments than terrestrial. Vanadium is present in the
coordination complex amavadin in fungal fruit-bodies.

In mammals, deficiency of vanadium results in reduced growth in rats. Vanadyl sulfates as a dietary
supplement have been researched as a means of increasing insulin sensitivity or otherwise improving
glycemic control in people who are diabetic. There is no rigorous evidence that oral vanadium
supplementation improves glycemic control in type2 diabetes. The routine use of vanadium for this
purpose cannot be recommended. In astrobiology, it has been suggested that discrete vanadium
accumulation on Mars could be a potential microbial biosignature when used in conjunction with Raman
spectroscopy and morphology.

1.3.3 Zinc:

Zinc participates in more than 200 enzymatic reactions in the body. It plays a key role in the synthesis
and stabilization of genetic material. It is necessary for cell division and the synthesis and degradation of
hydrocarbons, lipids, and proteins. It is therefore considered as essential for tissue growth.

As a part of the enzyme copper-zinc superoxide dismutase (Cu/Zn SOD), it helps in protection of cells
and some compounds from the harmful effects of free radicals.

Zinc is necessary for the structure and normal function of cell membranes. It participates in the
creation of connective tissue, teeth, bones, nails, hair, and skin. Zinc plays an important role in the
absorption of calcium in the bones and affects the action of growth hormone.

Zinc is considered as one of the most important nutrients for the immune system because it is
essential for the formation of antibodies, white blood cells, thyroid gland, and hormone function.
Therefore, it is important to preserve the resistance to infection and for wound healing.
 One of the important roles of zinc is secretion, synthesis, and use of insulin. It also protects pancreatic
β-cells (the cells that produce insulin) from falling apart. Zinc is involved in the metabolic processes of
the thyroid and adrenal glands, ovaries. It is important for the normal development of male sex
hormones and the prostate. Normal functioning of the skin requires the presence of zinc. It is involved in
the functioning of the sweat glands, activating local hormones, creating a protein that binds vitamin A,
in control of inflammation and tissue regeneration.

Zinc is essential for normal growth and development of the fetus and for milk production during
lactation. Zinc levels in pregnancy are associated with normal development of the palate, lip, brain, eyes,
heart, bones, lungs and the urogenital system in infants. Adequate intake of zinc is essential for normal
fetal growth and normal maintenance of pregnancy.

It is involved in the creation of hydrochloric acid in the stomach and in the conversion of fatty acid to
prostaglandins, which regulate body processes such as heart rate and blood pressure. Zinc is necessary
for muscle contraction and maintenance of acid-base balance in the body.

1.4 Application of Schiff base and its complexes:

1.4.1Catalysis:

Aromatic Schiff base or their metal complexes catalyze reaction on oxygenation, hydrolysis,
electro-reduction, and decomposition. Copper complexes derived with amino acid, enhance 10-50 times
hydrolysis rate more than the simple copper (II) ion [32]. Some metal complexes of polymer bound
Schiff base show catalytic activity on a decomposition of hydrogen peroxide and oxidation of ascorbic
acid.

1.4.2Pharmaceutical industry:

Schiff base and its complexes have much more biological activities like Antifungal, Antiviral,
Anticancer, Antiulcer, Antihypertensive properties, etc. These properties of the Schiff bases and its
complexes found its application pharmacy field in a large amount. The medicines which are made by
using Schiff bases are much more effective than other drugs [32-35].

Eg: Silver (I) Schiff base complex gave effective results up to 74.7% towards c. mosaic virus.

1.4.3Agriculture field:

1.4.3.1 Synergistic action on insecticides:

 Schiff bases derived from sulfane thiadiazole and salicylaldehyde and their complexes show
toxicities against insects. Alpha-amino acid act as intermediate in the synthesis of photostable
pyrethroid insecticides [37]. Fluorination aldehyde part of Schiff bases enhances insectoaracicidal
activity.

Eg: Schiff base and it's metal complexes of Mo (IV) show insecticidal activities against bollworm and
promote cell survival late of mung bean sprouts.

1.4.3.2Plant - growth regulator:

Schiff bases show remarkable activities on plant hormone such as the auxins on root growth.
Schiff bases of ester and carboxylic acid show remarkable activity as a plant growth hormone [38].

Eg: Schiff bases of thiadiazole have good plant growth regulator activity towards auxin and cytokine.

1.4.4Polymers:

Some Schiff base metal complexes act as an initiator of emulsion polymerization and
copolymerization of dienyl and vinyl monomers. Photochemical degradation of natural rubber yield
amine-terminated liquid natural rubber (ATNR) when carried out in solution, in the presence of ethylene
diamine. ATNR on reaction with glyoxal yield Schiff base which improves aging resistance [38].

1.4.5Dyes:

Schiff base unsymmetrical complexes give fast colors to leathers, food packages, wools, etc. Azo
groups containing metal complexes are used for dyeing cellulose polyester textiles. Some Schiff base
metal complexes used to mass dye poly fibers [39]. Novel tetradentate Schiff base act as a chromogenic
reagent for determination of Ni in some natural food samples.

1.4.6Miscellaneous application:

Tetradentate Schiff base and its metal complexes with Cu (II) and Zn (II) Show the miscellaneous
effect on a membrane in amylase productions [40]. Zn (II) complexes stimulated amylase transportation
through a membrane while Cu (II) complexes inhibit it some Schiff bases possess simple harmonic.
SCOPE OF THE WORK

SCOPE OF THE WORK

The aim of this project is as follows:

To synthesis Schiff base ligand from serine, 4-aminoantipyrine, and acetophenone.

To synthesis various metal complex using copper, vanadium, zinc chloride salts with serine Schiff base
ligand.

Using UV, IR, H1NMR, ESR and CV spectroscopic techniques to characterize both ligand and various
metal complexes.

To study the antibacterial activity and antifungal activity of complex on (Staphylococcus aureus and
odium Garcia).
MATERIALS AND METHODS

MATERIALS AND METHODS

1. Serine:

Serine was used of analar grade and of 99.9% purity.

2. 4-Aminoantipyrine:
 4-Aminoantipyrine was of MERCK, AR grade and of 99% purity.

3. Acetophenone:

Acetophenone was used of MERCK, AR grade and of 99% purity.

4. Copper chloride:

Cucl2 are of AR grade and 90-100% purity and is of S.D.FINE CHEM Limited make. It is used as such
without further purification.

5. Zinc chloride:

Zncl2 is of MERCK make. It is 95% purity and is used as such without further purification.

6. Vanadium sulfate:

VOSo4 is of MERCK make. It is 95% purity and is used as such without further purification.

7. Ethanol:

It is used after distillation.

UV-Visible:

The UV-Visible spectra of the Samples were recorded at ambient temperature for solutions prepared
in Acetonitrile using a Jasco model r-530 spectrophotometer at a range of 200-1200nm.

Fourier Transform Infrared Spectra:

FTIR spectra of the samples were measured in the KBr pellet in the range of 4000-400cm-1 using
SHIMADZU recorded at ANJAC, SIVAKASI.

1H NMR:

The 1H-NMR spectrum of ligand was recorded in BRUKER 300MHz spectrometer at Madurai Kamaraj
University, Madurai DMSO was used as a solvent.

ESR:
 ESR spectrum of the copper complex was recorded JOEL, JES-FA 200 ESR spectrometer at LNT. DMSO
was used as a solvent.

Antibacterial studies:

Antibacterial activity of the ligand and their complexes were studied using the bacteria
(Staphylococcus aureus) as standard.

Antifungal studies:

Antifungal activity of the ligand and its complexes were studied using fungi strain (odium carciae)
through well diffusion method.

Synthesis of Schiff base complex:

Scheme 1:

An equimolar quantity of 4-Aminoantipyrine and acetophenone were taken. 4-Aminoantipyrine was

dissolved in ethanol and it was mixed to the acetophenone and the mixture was stirred well for 5
minutes. The solid red-orange product was obtained.

Scheme 2:

An equimolar amount of AP4AAP and the amino acid was taken in a round bottom flask and it was
dissolved in 30ml ethanol. The anhydrous potassium carbonate was added and the mixture was refluxed
for about 12 hours. The solid product obtained was filtered and then dried.

Scheme 3:

The 1:2 ratio of CuCl2 / ZnCl2 /VOSo4 and Schiff base was taken in a 100 ml conical flask and the
mixture was stirring about 3hrs. The product collected during this process was filtered, dried and
recrystallised.
RESULT AND DISCUSSION
Result and discussion:

UV –visible spectra:

The electronic spectra of the Schiff base ligand and its metal complexes were recorded in
acetonitrile solution at room temperature and the values are shown in. The values help us to determine
the structure of the complex formed. The electronic spectra of copper complex display d-d transition
bands in the region 701 nm which was due to 2Eg to 2T2g transition; this d-d transition band shows the
copper complex has octahedral geometry. The vanadium complex the strong absorption at 307 nm
which is respect to the transition 3A1g to3T1g, by this we conclude that the vanadium complex have
Square planar geometry [18-20]

Fig (a)

Fig (b)

IR spectra:

IR spectral data of ligand and its complexes have shown in the table. In the spectrum of copper (II)
complexes the band of –NH observed in the range 1649 cm-1. It indicates the presence of -NH2 group
in the ligand which gets shifted to 1649 cm, this indicates the complexation. The value at 1649 cm-1
indicates the C=O in a ligand which shifted to1749 cm-1 in the complex. The band at 527 cm-1 and 451
cm-1 corresponds to the M-O and M-N bond respectively [12].
 IR spectral data of ligand and its Cu (II) complex and vanadium complex is shown in the table. The
ligand NH peak at 1627cm-1 is shifted to 1650 cm-1 in vanadium complex shows the complexation. The
aromatic C-H band of ligand at 1492 cm-1 is shifted to 1494 cm-1 in the complex.

The C=O at 1696 cm-1 in ligand shifted to 1678 cm-1 in the complex. In Zinc complex, NH band
is at 1649 cm-1, CH band at 1494 cm-1, C=O band at 1723 cm-1, M-O band at 501cm-1 and M-N band at
447 cm-1 are absorbed. This shows the formation of the zinc complex [17].

Table1: IR data of the copper, vanadium and zinc complexes.

Table: 1

Compound N-H C-H C=O M-O M-N

Ligand 1627 1492 1696 - -

Cu(II) complex 1649

1497 1749 527 451

VO(II) complex 1650 1495 1678 526 497

Zn(II) complex 1649 1494 1723 501 447

The spectrum of the Ligand, Cu (II) complex, VO (II) complex and Zn (II) complex is given below as (c),
(d), (e) and (f).

Fig (c)

Fig (d)

Fig (e)

Fig (f)

H1NMR spectra:
 The H1 NMR spectra of the Schiff base and its zinc complex were recorded at room temperature in
DMSO [15-16]. The ligand shows signals of phenyl multiplet at 7.2 to 7.5ᵟ. The zinc complex shows
signals of phenyl multiplet at 8.3ᵟ. This result favors the formation of the complex. There is no
appreciable change in other peaks such as C-CH3 and N-H3 at 2.8ᵟ and 3.4ᵟ respectively.

Fig (g)

Fig (h)

ESR spectra:

ESR report of the paramagnetic Cu (II) complexes provides the evidence on the distribution of the
unpaired electrons; apparently, elucidate the nature of bonding between the metal ions with its ligand
[19]. ESR spectra of Cu (II) complex, dissolved in DMSO were recorded at liquid nitrogen temperature
(LNT). The ESR spectrum of the complex is depicted in Fig(i).

The Spin-Hamiltonian parameters of Cu (II) complex have been calculated and are given in the
table: From the spectral data, the copper complex shows an axially symmetric g-tensor factors of get(
) > g┴ ( ) > ge ( ) which indicates that Cu (II) metal having unpaired electron
predominantly localizes in the ground state dx2 -y2 orbital and also provides the AII ( )> A┴( )
proposing that the complex is present in octahedral geometry . The geometrical parameters of G explain
the achievements of exchange interaction in between the metal-metal centers in crystalline compound
which can be determined by using the following equation [20].

G= (gII – 2)/ (g┴-2)

The value is obtained between the range of 110 and 170, it indicates the complex is in an
octahedral geometry.

Fig (i)

Cyclic voltammetry:
 Cyclic voltammetry helps to evaluate the effect of ligands on the redox potential of the central
metal ion in complexes. The electrochemical reversible nature of the Cu (II)/Cu (III) or VO (II)/VO (III)
redox systems in complexes depend on the nature of the ligand. Cyclic voltammetry has been shown to
be a particularly useful technique in the study of this type, aiding one to measure the existence of short-
lived species, as well as to study the ligand’s structural parameters such as size and degree of
conjugation [32].

Cyclic voltammogram of the Cu (II) and VO (II) complexes was recorded in DMSO solution. The scan rates
were varied from ( ). Several peaks were observed in the cathodic and anodic sections of the
cyclic voltammogram. The plot of peak currents of all the peaks was correlated with the square root of
the sweep rate, resulting in a straight line in all the complexes. This demonstrates the diffusion
controlled mass transport.

The cyclic voltammogram of the copper complex in DMSO solution (Fig. ) shows a reversible peak for the
couple: Cu(II) to Cu(III) at Epa = ( )V with the direct cathodic peak for Cu(III) to Cu(II) at Epc = 0.53 V.
Further, it exhibits two irreversible peaks characteristic for Cu (II) to Cu (I) (Epc = ( v) and Cu (I) to Cu
(0) Epc = ( ) V reduction. In the anodic side, the direct oxidation of Cu (0) to Cu (II) is observed with a
strong stripping peak at Epa = ( ) V. The two- electron transfer nature of the process is established by
the comparison of Ipc and Ipa values ().

The cyclic voltammogram of the Vanadyl complex in DMSO solution (Fig. ) shows a well-defined redox
process corresponding to the formation of the VO(II)/VO(III) couple at Epa =
Antimicrobial studies:

SAMPLE ZONE OF INHIBITION IN DIAMETER

(IN mm)

Control Standard Sample

VS’cu NZ 12 37

VS’-ligand NZ 12 10

The synthesized complexes were subjected to antimicrobial studies. The antifungal property
of the complex is determined using odium carciae through well diffusion method [15]. The antibacterial
studies of the complex are made out using Staphylococcus aureus as standard. Antibacterial and
Antifungal data were shown in table (2) and (3) below respectively.

Table: 2
Table: 3

SAMPLE ZONE OF INHIBITION IN DIAMETER (IN mm)

Control Standard Test

VS’-ligand NZ 28 11

VS’cu NZ 28 12
CONCLUSION

Conclusion:

This work depicted the synthesis and characterization of 4-Aminoantipyrine derived Schiff base
and their metal (II) complexes. The Schiff base ligand was behaving as a hexadentate ligand. The bonding
of ligand and the metal ion is determined by UV, IR, CV, 1HNMR spectra. The structure of the complexes
also determined by the spectra’s Antimicrobial study of synthesized metal complexes shows that the
metal complexes have high antifungal and antibacterial activities.

REFERENCE
References:

[1] H.K. Liu, P.J. Sadler, Metal complexes as DNA intercalators, Acc. Chem. Res. 44 (2011) 349–
359.

[2] U. Jungwirth, C.R. Kowol, B.K. Keppler, C.G. Hartinger, W. Berger, P. Heffeter, Anticancer
activity of metal complexes: Involvement of redox processes, Antioxid. Redox Signal. 15 (2011) 1085–
1127.

[3] S.L.H. Higgins, T.A. White, B.S.J. Winkle, K.J. Brewer, Redox, Spectroscopic, and photophysical
properties of Ru−Pt mixed-metal complexes incorporating 4,7-diphenyl1,10-phenanthroline as efficient
DNA binding and photocleaving agents, Inorg. Chem. 50 (2011) 463–470.

[4] S. Kathiresan, S. Mugesh, J. Annaraj, M. Murugan, Mixed-ligand copper(II) Schiff base

complexes: the vital role of co-ligands in DNA/protein interactions and cytotoxicity, New J. Chem. 41
(2017) 1267-1283.

[5] Alagarraj Arunadevi, Rajakkani Paulpandiyan, Natarajan Raman:DNA interaction, molecular

docking and biological profile of tetra dentate histidine based metallointercalators.
DOI:10.1016/j.molliq.2017.06.091

[6] Priti Deshmukh, Pradeep Kumar Soni*, Amit Kankoriya, Anand K. Halve, Renu Dixit : 4-
Aminoantipyrine: A SIGNIFICANT Tool fpr the synthesis of biologically Active Schiff Base and Metal
complexes(2015)

[7] Dhanaraj CJ, Nair MS, Synthesis, Characterization, and Antimicrobial Studies of Some Schiff
Base Metal(II) Complexes, J Coord Chem, 62(24), 2009, 4018-4028

[8] . Farghaly AM, Hazza AA, Abouzeit-Har MS, Sharabi FM, Nonsteroidal Anti-inflammatory
Agents,4-[1-(3,5-disubstituted-2-thiothio-1,3,5-perhydrotriazinyl)]-2,3-dimethyl-1-phenyl-5-
pyrazolones, Pharmazie, 35(10), 1980, 596-598.

[9]. Hithoshi T, Tamao N, Hideyuki A, Fujiwara M, Matsushita T, Preparation and Characterization

of Novel Cyclic Tetranuclear Manganese(III) Complexes: MnIII 4(X-salmphen)6 (X-salmphenH2 = N,N′-di-
substituted-salicylidene-1,3-diaminobenzene (X = H, 5-Br). Polyhedron, 16(21), 1997, 3787-3794.
 [10]. Hossain ME, Alam MN, Begum J, Akbar Ali AM, Nazimuddin M, Smith FE, Hynes RC, The
Preparation, Characterization, Crystal Structure and Biological Activities of Some Copper(II) Complexes
of the 2-benzoylpyridine Schiff Bases of S-methyl- and Sbenzyldithiocarbazate, Inorg Chim Acta, 249(2),
1996, 207-213.

[11]. Joseph J, Nagashri K, Ayisha G, Rani B, Synthesis, Characterization and Antimicrobial Activities
of Copper Complexes Derived from 4- aminoantipyrine Derivatives, J Saudi Chem Soc, 17, 2013, 285–
294.

[12]. P. Priya, S.V. Arunachalam, N. Sathya, V. Chinnusamy, C. Jayabalakrishnan, Catalytic and

antimicrobial studies of binuclear ruthenium(III) complexes containing bis-β- diketones, Transit. Met.
Chem. 34 (2009) 437-442.

[13]. U. Sing, I. Jialal, Oxidative stress and atherosclerosis, Pathophysiology. 13 (2006) 129-142.

[14]. K. Sas, H. Robotka, J. Toldi, L. Vecsei, Mitochondria, metabolic disturbances, oxidative stress and
the kynurenine system, with focus on neurodegenerative disorders, J. Neurol. Sci. 257 (2007) 221-239.

[15]. Seemon Packianathan, Ganesan Kumaravel,Natrajan Raman : DNA interaction, antimicrobial and
molecular docking studies of biologically intresting schiff base complexes incorporating 4-formyl-N,N-
dimethylaniline and propylenediamine.DOI:10.1002/aoc.3577. (2016)

[16]. M.Choudhary, R.N. Patel, S.P.Rawat, J.Mol.struct. (2014),1070,94.

[17]. Synthesis, spectral characterization of Schiff base transition metal complexes: DNA cleavage and
antimicrobial activity studies. N RAMAN,* J DHAVEETHU RAJA and A SAKTHIVEL. (2014)

[18]. 4-Aminoantipyrine: A Significant Tool for the Synthesis of Biologically Active Schiff Bases and Metal
ComplexesPriti Deshmukh, Pradeep Kumar Soni*, Amit Kankoriya, Anand K. Halve, Renu Dixit:(2015).

[19]. Abdel-Rehim SS, Magdy AM Ibrahim, Khaled KF, 4-Aminoantipyrine as an Inhibitor of mild Steel
Corrosion in HCl Solution, J Applied Electrochemistry, 29(5), 1999, 593-599.

[20].DNA binding propensity and nuclease effiay of biosensitive Schiff base complexes containing
pyrazolone moiety. Rajakkani paulpandiyan and NatarajanRaman*

[21].Probing of effective pyrazolone based metallonucleases: Molecular docking and in vitro biological
critiques. Alagarraj Arunadevi, Rajakkani paulpandiyan and NatarajanRaman.

[22].Synthesis and characterization of 4-aminoantipyrine based Schiff baseomplexes:antimicrobial

cytotoxicity and DNA cleavage studies. R.Jayalakshmi, V.Jayakkumar, D,Dhivya priya, Dr.R.Rajavel.

[23].S.Sathyanarayana, J.C.Davorusak, J.B.Charies, tris(phenonthroline) ruthenium(II) enantiomer

interaction with DNA:mode and specificity of binding, Biochemistry 32(1993) 2573-2583.

[24]. Geary, W.G. The Use of Conductivity Measurements in Organic Solvents for the Characterisation of
Coordination Compounds. Coord. Chem. Rev. 1971, 7, 81-122.
[25]. Hamming, M.; Foster, N. Interpretation of Mass Spectra of Organic Compounds; Academic Press:
New York, USA, 1972.

[26]. Silverstein, R.M.; Webster, F.X. Spectrometric Identification of Organic Compounds; Wiley: New
Delhi, India, 2007.

[27]. Singh, G.S.; Pheko, T. Spectroscopic Characterization of the 1-Substituted 3,3’-Diphenyl-4-(2’-

hydroxyphenyl)azetidine-2-ones: Application of 13C NMR, 1H-13C COSY NMR and Mass Spectroscopy.
Spectrochim. Acta, Part A. 2008, 70, 595-600.

[28]. Wehrli, F.W.; Marchand, A.P.; Wehrli, S. Interpretation of Carbon-13 NMR Spectra; Wiley: New
York, USA, 1988.

[29]. Swamy, S.J.; Pola, S. Spectroscopic Studies on Co(II), Ni(II) Cu(II) and Zn(II) Complexes with a N4-
Macrocyclic Ligands. Spectrochim. Acta, Part A 2008, 70, 929-933.

[30]. Tudor R., Siminia P., Veronica L., Carmen Ch and Raluca C., Copper (II) Complexes with ligands
derived from 4-Amino-2,3 dimethyl -1-phenyl-3-pyrazoline-5-one :synthesis and bioliogical activity,
Molecules, 11, 904 (2006) .

[31].Raman N, Raja SJ, Joseph J, Raja JD, Synthesis, Spectral Characterization and DNA Cleavage Study of
Heterocyclic Schiff base Metal Complexes, J Chilean Chem Soci, 52, 2007, 1138-1148.

[32]. Agarwal RK, George P, Agarwal H, Chandra J, Synthesis, Magneto- Spectral and Thermal Studies of
Cobalt(II) and Nickel(II) Complexes of 4-[N-(4-Dimethylamino benzylidene) amino] Antipyrine, Synthetic
React Inorganic Metal-Organic Chemistry, 27, 1997, 251- 268.

[33]. Agarwal RK, Singh, Sharma DK, Synthesis, Spectral, and Biological Properties of Copper(II)
Complexes of Thiosemicarbazones of Schiff bases Derived from 4-Aminoantipyrine and Aromatic
Aldehydes, Bioinorg Chem Appl, 59509, 2006, 1-10.

[34]. Rosu T, Pasculescu S, Lazar V, Chifiriuc C, Cernat R, Copper(II) Complexes with Ligands Derived from
4-Amino-2,3-dimethyl-1- phenyl-3-pyrazolin-5-one, Synthesis and Biological Activity, Molecules, 11,
2006, 904-914.

[35]. Dong-Dong Y, Yan Lan J, Lu S, Synthesis Charecterisation of Diorganotin(IV) Schiff Base Complexes
and their in-vitro Antitumour Activity, Chinese J Chem, 19, 2001, 1136.

[36]. Piotr P, Bogumil B, Spectroscopic Studies and PM3 Semiempirical Calculations of Schiff bases of
Gossypol with L-Amino Acid Methyl Esters, Biopolymers, 67, 2002, 61-69.

[37]. Miao Ru, Shuoliong Li, Rudong Y, Lan Y, Wenbing Y, Synthesis and Crystal Structure of Schiff Base
Pyrazolone, Indian J Chem, 42A, 2003, 318-321.

[38]. Choi YK, Chjo KH, Park SM, Doddapaneni N, Oxygen Reduction at Co ( II ) 2 ‐ Disalophen Modified
Carbon Electrodes, J Electrochem Soc, 142, 1995, 4107-4112.
[39]. Katia B, Simon L, Anne R, Gerard C, Francoise D, Bernard M, Synthesis and Characterization of New
Chiral Schiff Base Complexes with Diiminobinaphthyl or Diiminocyclohexyl Moieties as Potential
Enantioselective Epoxidation Catalysts Inorg Chem, 35, 1996, 387-396.

[40]. Elhady HA, Aly HM, Saleh NM, Syntheses and Antimicrobial Activity of new Benzofuran, Pyrrole,
Imidazole and Thioxoimidazolidin Incorporating Antipyrine Moiety, Int J Adv Res, 2(3), 2014, 806- 816.

[41]. Mostafa M, El-Gazzar MG, Alsaid MS, Synthesis, Characterization and Anti-Breast Cancer Activity of
New 4-Aminoantipyrine-Based Heterocycles, Int J Mol Sci, 15, 2014, 7539-7553.

[42]. Hayvali Z,1, Ünver H, Svoboda I, Synthesis, Spectroscopic, Spectrophotometric and Crystallographic
investigations of 4-{[(1E)- (3,4-dimethoxyphenyl)methylene] amino}-1,5-dimethyl-2-phenyl- 1,2-
dihydro-3H-pyrazol-3-one and 4-{[(1E)-(2-hydroxy-5- methoxyphenyl)methylene]amino}-1,5-dimethyl-2-
phenyl-1,2- dihydro-3H-pyrazol-3-one, Acta Chim Slov, 57, 2010, 643-650.

[43]. Vaghasiya YK, Nair R, Soni M, Baluja S, Chanda S, Synthesis, Structural Determination and
Antibacterial Activity of Compounds Derived from Vanillin and 4-aminoantipyrine, J Serb Chem Soc,
69(12), 2004, 991-998.

[44]. Liang H, Yu Q, Rui-Xiang Hu, Zhou ZY, Zhou XG, Synthesis, Crystal Structure and Spectroscopic
Properties of a Copper(II) Complex of the Schiff-Base Derived from Picolinaldehyde N-oxide and 4-
Aminoantipyridine, Transition Metal Chemistry, 27, 2002, 454-457.

[45]. Gabriela T, Catalina DS, Ana-maria Z, Alexandra J, Cristina T, Preliminary Screening of Biological
Activities of Some new Schiff Bases of Isatins, Farmacia, 62(1), 2014, 14-22.