Jaipur National University, Jaipur

School of Basic Sciences

Department of Chemistry
2019-20

M.Sc. (Chemistry)
Dissertation: A Pre-Presentation

Presented by: Supervised by :

Abhishek Sharma Prof. (Dr.) Purnima Nag
M. Sc IV semester (Chemistry) Addl. Director - SOET
JNU – Jaipur JNU - Jaipur
 Tentative Title

Study of some Metal Hydrazone

Complexes Derived from
Cyclohexanone and 2, 4 DNPH
 CONTENTS
Aim & Objectives
Hydrazones - An Introduction
Biological Importance of Hydrazones
Metal Complexes
Metal complexes of Hydrazones –
Importance & Applications
Preparation of Ligand
Work done so far
Tentative Plan
 Aim & Objectives
❖ To prepare Metal complexes of Hydrazone derived
from Cyclohexanone and 2, 4 DNPH; avoiding use of
conc. H2SO4.

❖ To characterize each of the synthesized compound via

melting point determination, TLC, elemental analysis
and spectral methods such as IR, 1H-NMR, etc.

❖ To evaluate and compare the microbial activities

&/or antioxidant activities of synthesized
complexes among themselves as well as with that of
ligand.
 Hydrazones - An Introduction
❖ Hydrazones are a familiar class of compounds in
chemistry that refer to compounds having >C=N-N<
functional group.
❖The Nitrogen atom of the imine moiety in
hydrazones, is observed to be highly
responsible in coordinate bond formation with
Metal atom1.

❖Hydrazones act as an important intermediate

in synthesis of:

✔N-Alkyl hydrazides2 ✔2-Azetidinones5

✔Substituted 1,3,4 oxadiazolines3,4 ✔4-Thiazolidinones6

1. Lalami, L.A.; Monfared, H.H.; Noei, H.; Mayer, P.; Transition Met Chem 2011, 36, 669-677.
2. Ergenç, N.; Günay, N.S.; Eur. J. Med. Chem. 1998, 33, 143-148.
3. Durgun B.B.; Çapan G.; Ergenç, N.; Rollas, S.; Pharmazie 1993, 48, 942-943.
4. Doğan H.N.; Duran, A.; Rollas, S. ; Şener, G. ; Armutak, Y.; Keyer-Uysal, M.; Med. Sci. Res. 1998, 26, 755-758.
5. Kalsi, R.; Shrimali, M.; Bhalla, T.N. ; Barthwal, J.P.; Indian J. Pharm. Sci. 2006, 41, 353-359.
6. Küçükgüzel, Ş.G. ; Kocatepe A. ; De Clercq, E. ; Şahin F., Güllüce, M.; Eur. J. Med. Chem. 2006, 41, 353-359 .
 Biological Importance of
Hydrazones

Anticonvulsan Antidepressan Analgesic Antiinflammat

t Activity1 t Activity2 Activity3 ory Activity4

Antiplatelet Antimalarial Antimicrobial Antimycobact

Activity5 Activity6 Activity7 erial Activity8

1. Dimmock, J.R.; Vashishtha, S.C.; Stables, J.P.; Eur. J. Med. Chem. 2000, 35, 241-248.
2. Ergenç, N.; Günay, N.S.; Eur. J. Med. Chem. 1998, 33, 143-148.
3. Todeschini, A.R.; Miranda, A.L.; Silva C.M.; Parrini, S.C.; Barreiro, E.J.; Eur. J. Med. Chem. 1998, 33 , 189-199.
4. Lima, P.C., Lima, L.M.; Silva, K.C.; Leda, P.H.; Miranda, A.L.P.; Fraga, C.A.M; Barreiro, E.J.; Eur. J. Med. Chem. 2000,
35, 187-203.
5. Fraga, A.G.M.; Rodrigues, C.R.; Miranda, A.L.P.; Barreiro, E.J.; Fraga, C.A.M.; Eur. J. Pharm. Sci. 2000, 11 , 285-290.
6. Walcourt, A.; Loyevsky, M.; Lovejoy, D.B.; Gordeuk, V.R.; Richardson, D.R.; Int. J. Biochem. Cell Biol. 2004, 36 , 401-407.
7. Küçükgüzel, Ş.G.; Rollas S.; Erdeniz H.; Kiraz M.; Eur. J. Med. Chem. 1999, 34, 153-160 .
8. Bukowski L.; Janowiec, M.; Pharmazie 1996, 51, 27-30.
 Metal Complexes
Metal complexes are cationic, neutral or anionic
species, where a metal is coordinated by ligands.

A ligand is an ion or molecule that donates a lone pair

of electrons to a central metal atom to form a complex.

A no. of metals, usually transition exhibit different

oxidation states and can interact with a number of
negatively charged molecules. Some of the most
pronounced examples are Chlorophyll, Hemoglobin,
Vitamin B12, Ni(dmg)2.

Research has shown significant progress in utilization of

metal complexes as drugs to treat several human
diseases.
1. Cotton; Albert F.; Wilkinson G.; Murillo C.A.; Advanced Inorganic Chemistry 1999, Wiley-Interscience, 1355.
 Metal complexes of Hydrazones -
Importance & Applications
❖A variety of hydrazones and their metal complexes have
been reported and studied for their biological and catalytic
activities, with a no. of metals viz. V, Cu, Mn, Ti, Mo, Ni,
Co, Al, etc.1-3

❖Metal complexes of hydrazones exhibit higher biological

activity than corresponding free ligands and act as an
important catalysts for various organic
transformations such as in:

Oxidation of alkenes to Electrophilic reaction of

epoxides4 Indoles with aldehydes5

1. Lalami, L.A.; Monfared, H.H.; Noei, H.; Mayer, P.; Transition Met Chem 2011, 36, 669-677.
2. Pouralimardan, O.; Chamayou, A.C.; Janiak, C.; Monfared, H.H.; Inorg. Chim. Act. 2007, 360, 1599–1608.
3. Ebrahimipour, S.Y.; Khabazadeh, H.; Castro, J.; Sheikhshoaie, I.; Crochet, A.; Fromm, K.A.; Inorg. Chim. Act. 2015, 427, 52-61.
4. Pouralimardan, O.; Chamayou, A.C.; Janiak, C.; Monfared, H.H.; Inorg. Chim. Act. 2007, 360, 1599–1608.
5. Ebrahimipour, S.Y.; Khabazadeh, H.; Castro, J.; Sheikhshoaie, I.; Crochet, A.; Fromm, K.A.; Inorg. Chim. Act. 2015, 427, 52-61
 General Method for Preparation of
hydrazones1
Generally, hydrazones are synthesized by reaction of a
ketone/ aldehyde with a hydrazine in presence of conc.
H2SO4; making using of organic solvent such as ethanol/
methanol.

This is a simple condensation reaction in which water

molecule is expelled out and formation of imine moiety takes
place.

1. Morgan, L.R.; Jursic, B.S.; Hooper, C.L.; Neumann, D.M.; Thangaraja, K.; LeBlanca, B.; Bioorganic & Medicinal Chemistry
Letters 2002, 12, 3407–3411.
Method Used: A Greener Approach
Cyclohexanone + 2, 4 DNPH
(1 mol) (1 mol)

EtOH + Few drops of AcOH

Refluxed for 2 hrs. and cooled

Filtered under vacuum,

washed and dried

Benzophenone - 2, 4 DNPH hydrazone (98% yield)

 In this method, we have avoided MeOH & conc. H2SO4
and used EtOH as a solvent in presence of few drops of
Acetic acid.

The new method hasn’t affected the product yield and

reaction time.
 Work Done So Far
Literature survey has been done related to my topic and
is still in continuance.

Ligand has been synthesized with both methods and

primarily confirmed by TLC and melting point
determination.

Metal compounds have been procured; mainly chlorides

and acetates of Zn, Cu, Ni, Co, etc.

Metal ligand complexes synthesis is in progress using

literature method(s) taking Metal : Ligand ratio as 1 : 2.
 Tentative Plan
Synthesized compounds will be analyzed by
Elemental analysis, 1H-NMR, ESI-Mass, IR, etc.
(from MNIT, Jaipur)

Biological Screening will be carried out on different

species by standard methods (from Biotech Dept.
JNU and/or Dr. B. Lal Labs, Jaipur)

These results will be analyzed and different metal

complexes will be compared with that of free ligand.
Thank you