SYNTHESIS, CHARACTERIZATION AND APPLICATION OF TWO

SCHIFF BASE LIGAND

Summer Internship Program 2017
A Summer Internship Report
Submitted to the Controller of Examination, Tezpur University,

Napaam, Tezpur Assam 784001

Submitted By

SUSHMITA NATH
Integrated MSc. Chemistry, 4th semester

The Assam Kaziranga University

Under the guidance of

Dr. SANJAY PRATIHAR

Associate Professor

DEPARTMENT OF CHEMICAL SCIENCES

TEZPUR UNIVERSITY, NAPAAM

ASSAM 784001
Dedicated to my beloved parents, Janu and Joy.
 DECLARATION BY THE CANDIDATE

I hereby declare that the work presented in this report Synthesis, characterization and
application of two Schiff Base ligand was carried out by me during Summer Internship
Program 2017, at Tezpur University, under the supervision of Dr. Sanjay Pratihar,
Department of Chemical Sciences, Tezpur University. So far my knowledge concerns, this
report is entirely fresh and has not been reported anywhere for my degree either by me or
by anyone else.

Date : Sushmita Nath

Place : Integrated MSc. Chemistry, 4th semester

The Assam Kaziranga University

 ACKNOWLEDGEMENT

I hereby express my heartfelt gratitude to all those persons who helped me in completion of
my summer internship. This gives me immense pleasure to acknowledge the valuable
contribution offered to me by my supervisor Dr. Sanjay Pratihar, DST inspire faculty, Dept. of
Chemical Sciences, Tezpur University for his esteemed supervision, incessant support and
inspiration throughout the period of the project. This project work would not have been
successful without his help.
CONTENTS

1. Introduction
2. Importance of Schiff Base
3. Known Schiff Base and their Utility
3.1. Salen
3.1.1. Salen complex
(a) Copper Salen ligand complex
(b)Nickel Salen ligand complex

3.2 AG-1

4. Unknown Complexes

4.1. L1
(a) Copper L1 Complex
(b) Nickel L1 complex
(c) Iron L1 complex
4.2. L2
(a) Copper L2 Complex
(b) Nickel L2 complex
(c) Iron L2 complex
1. Introduction

Schiff bases are aldehyde- or ketone-like compounds in which the carbonyl group is replaced by an
imine or azomethine group. They are widely used for industrial purposes and also exhibit a broad range
of biological activities. Schiff bases, named after Hugo Schiff , are formed when any primary amine
reacts with an aldehyde or a ketone under specific conditions. Structurally, a Schiff base (also known as
imine or azomethine) is a nitrogen analogue of an aldehyde or ketone in which the carbonyl group (C
O) has been replaced by an imine or azomethine group.

Schiff bases are some of the most widely used organic compounds. They are used as pigments and dyes,
catalysts, intermediates in organic synthesis, and as polymer stabilisers. Schiff bases have also been
shown to exhibit a broad range of biological activities, including antifungal, antibacterial, antimalarial,
antiproliferative, anti-inflammatory, antiviral, and antipyretic properties [2,3]. Imine or azomethine groups
are present in various natural, natural-derived, and non-natural compounds. The imine group present in
such compounds has been shown to be critical to their biological activities.

2. Importance of Schiff bases

Schiff bases have a large number of synthetic uses in organic chemistry. Acylation of Schiff bases8,9 by
acid anhydrides, acid chlorides and acyl cyanides is initiated by attack at the nitrogen atom and leads to
net addition of the acylating agent to the carbon-nitrogen double bond. Reactions of this type have been
put to good use in natural product synthesis.
Schiff bases appear to be an important intermediate in a number of enzymatic reactions involving
interaction of an enzyme with an amino or a carbonyl group of the substrate. One of the most important
types of catalytic mechanism is the biochemical process which involves the condensation of a primary
amine in an enzyme usually that of a lysine residue, with a carbonyl group of the substrate to form an
imine, or Schiff base. Stereochemical investigation carried out with the aid of molecular model showed that
Schiff base formed between methylglyoxal and the amino group of the lysine side chains of proteins can
bent back in such a way towards the N atom of peptide groups that a charge transfer can occur between
these groups and oxygen atoms of the Schiff bases.
3. Known Schiff Base Ligands and their Utility

3.1. Salen

Salen is the abbreviation for a popular chelating ligand used in coordination chemistry andhomogeneous
catalysis. The name salen is a contraction for salicylaldehyde and ethylenediamine. The ligand is a bright
yellow micaceous solid that is soluble in polar organic solvents.

SalenH2 is commercially available. It was first prepared by Pfeiffer. It is often generated in situ followed by
the addition of the metal salt, but the ligand is also easily prepared as a pure organic compound by the
condensation of ethylenediamine and salicylaldehyde.

Chiral Salen-based ligands are widely used in the field of asymmetric catalysis in organic chemistry. Free
salen ligand is often written as SalenH2 to emphasize its diprotic character.
3.1.1. Salen Complexes
Salen conjugate base forms complexes with most transition metals. These complexes are usually
prepared by the reaction of the diprotic pro-ligand with metal precursors containing built-in bases, such as
alkoxides, metal amides, or metal acetates. The pro-ligand may also be treated with metal hallides, with or
without an added base. Lastly, the pro-ligand may be deprotonated by a non-nucleophilic base,
e.g. Sodium hydride, before treatment with the metal halide.

(a) Copper Salen ligand complex

(b) Nickel Salen ligand complex

3.2 AG-1
AG-1 is produced by reaction between amino-phrnol and glyoxal.
+
4. Unknown Complexes

4.1. L1
L1 is produced by the reaction of 2-Aminophenol and acetyl acetone in
presence of rectified spirit at room temperature for 12 hours.

2-Aminophenol + Acetyl acetone L1

(a) Copper L1 Complex

1. Synthesis
(i) 6mM of L1 is weighed out in a round bottom flask and dissolved in
methanol.
(ii) To this solution 15mM KOH is added.
(iii) Weigh out 6 mM of copper sulphate in another beaker and dissolve it in
methanol.
(iv) This solution is now added in the round bottom flask containing the
solution of L1 and KOH.
(v) Let the solution stir for 4-6 hours on magnetic stirrer.
(vi) Filter out the precipitate and keep it for drying at room temperature.

2.Characterization
Colour of precipitate is green.

(b)Nickel L1 complex
 1. Synthesis
(i) 2mM of L1 is weighed out in a round bottom flask and dissolved in
methanol.
(ii) To this solution 6mM KOH is added.
(iii) Weigh out 2mM of Nickel Sulphate in another beaker and dissolve it in
methanol.
(iv) This solution is now added in the round bottom flask containing the
solution of L1 and KOH.
(v) Let the solution stir for 4-6 hours on magnetic stirrer.
(vi) Filter out the precipitate and keep it for drying at room temperature.

2.Characterization
Colour of precipitate is blackish brown.

(c)Iron L1 complex
(i) 5mM of L1 is weighed out in a round bottom flask and dissolved in
methanol.
(ii) To this solution 15mM KOH is added.
(iii) Weigh out 5mM of Ferrous Sulphate in another beaker and dissolve
it in methanol.
(iv) This solution is now added in the round bottom flask containing the
solution of L1 and KOH.
(v) Let the solution stir for 4-6 hours on magnetic stirrer.
(vi) Filter out the precipitate and keep it for drying at room
temperature.

2.Characterization
 Colour of precipitate is brown.

4.2. L2

(a)Copper L2 Complex

(i) 2mM of L2 is weighed out in a round bottom flask and dissolved in

methanol.
(ii) To this solution 5mM KOH is added.
(iii) Weigh out 2mM of copper sulphate in another beaker and dissolve
it in methanol.
(iv) This solution is now added in the round bottom flask containing the
solution of L2 and KOH.
(v) Let the solution stir for 4-6 hours on magnetic stirrer.
(vi) Filter out the precipitate and keep it for drying at room
temperature.

2.Characterization
Colour of precipitate is blackish green.

(b)Nickel L2 complex

2. Synthesis
(i) 2mM of L2 is weighed out in a round bottom flask and dissolved in
methanol.
(ii) To this solution 6mM KOH is added.
(iii) Weigh out 2mM of Nickel Sulphate in another beaker and dissolve it in
methanol.
(iv) This solution is now added in the round bottom flask containing the
solution of L2 and KOH.
(v) Let the solution stir for 4-6 hours on magnetic stirrer.
(vi) Filter out the precipitate and keep it for drying at room temperature.

2.Characterization
Colour of precipitate is blackish brown.

(c)Iron L2 complex
(vii) 2mM of L1 is weighed out in a round bottom flask and dissolved in
methanol.
(viii) To this solution 5mM KOH is added.
(ix) Weigh out 2mM of Ferrous Sulphate in another beaker and dissolve
it in methanol.
(x) This solution is now added in the round bottom flask containing the
solution of L2 and KOH.
(xi) Let the solution stir for 4-6 hours on magnetic stirrer.
(xii) Filter out the precipitate and keep it for drying at room
temperature.

2.Characterization
Colour of precipitate is brown.