SYNTHESIS, CHARACTERIZATION AND BIOLOGICAL

ACTIVITY OF PIPERONAL BASED SCHIFF BASE AND

ITS METAL ADDUCTS.

28 Jan 2016

Aziz Ahmad Department of Chemistry Hazara University, Mansehra

Research outline

Introduction..

Importance

Aims and Objectives.

Experimental

Results and discussion.

Acknowledgment.

INTRODUCTION

Ultrasound: Sound waves having frequency higher, to which human ears can

responds. (µ,>16 KHz). Richards and Loomis in 1927. first time reported the effect of

ultrasonic on the reaction rate. (Fry & Herr,1978), (Luche & Damiano 1980)1. Ultrasonic assisted Reductive dehalogenation of dibromoketones with

mercury.2. sonochemical preparation of organolithium and Grignard

reagents and their coupling with carbonyls.

INTRODUCTION

SOURCES OF ULTRASONIC RADIATIONS. Ultrasonic Bath (37Hz) Ultrasonic immersion probe (20Hz)

Acoustic Cavitation The formation of bubbles its growth and collapse.

INTRODUCTION

The Sound waves passes through liquid medium in the form of refraction and compression

The bubbles life time have great impact on reaction mechanism.Free radical……………….. short life time Ionic Mechanism …………………. Long life time The Temperature and Pressure inside the bubble is very high (5000K, 1000atm). These acts as micro reactor.

INTRODUCTION

Piperonal. 1.Heliotropin2.Organic compound.3.found in fragrances and flavors.

4.structurally related to other aromatic aldehyde.

Uses.1. Aroma therapy tool.2. Flavors & Perfumery Industries.

O

O

O

benzo[d][1,3]dioxole-5-carbaldehyde

INTRODUCTION

SCHIFF BASE. Organic compounds congaing Carbon Nitrogen double bond. They are also called imine.For the first time it was synthesis by Hugo Schiff and that is why the are called Schiff bases.SYNTHESIS Schiff bases are synthesis by the reaction of primary amine and aldehyde or ketone in the presence of acid or base as catalyst.

O

R''R'

H Acid

Base

C R''R'

N

OH

R'''H

H A

C

N

R' R''

R'''

+ H2O

NH

H

R'''B :

First Step Second step

INTRODUCTION SCHIFF BASES COMPLEX. Schiff bases are good ligands.

The lone pair of electron on Nitrogen atom in azomethine group . Play important role in coordination chemistry. CLASSIFICATION OF SCHIFF BASES .

APPLICATIONS OF SCHIFF BASES COMPLEXES. Schiff bases complexes are very versatile in nature and have a large number of applications.

IMPORTANCE ANTIBACTERIAL ACTIVITY.

ANTIFUNGAL ACTIVITY.

ANTICANCER ACTIVITY

ANTIOXIDANT ACTIVITY.These complexes show 10 time

greater activity than Schiff base.

S

NOM

O

M= Co, Ni and Fe

O NOO

MM= Cu (II), Co (II), Ni (II) or Mn (II)

ON NN+

O O-

OCu

NNH

O

O

N

M

M= Cu, Zn, and Cd

NO

HO

OO

HO

M

APPLICATIONS

USE AS CATALYST. In Polymerization Reaction. For reduction of thionylcholride.

For Aldol reaction. For Henry Reaction

• 1

UREASE INHIBITION. Transition metal complexes

show high urease inhibition than the Schiff bases.

N

N

OH

O

OHO

N N

O OMn

OBJECTIVES

Ultrasonic assisted synthesis of piperonal based Schiff base.Ultrasonic assisted synthesis of metal adducts of the synthesized Schiff base.Characterization of the synthesized products by spectroscopic methods.To evaluate the biological activities of synthesized compounds.

EXPERIMENTALEXPERIMENTAL

Preparation of Schiff base

EXPERIMENTAL•1

Preparation of Schiff base Complexes

EXPERIMENTAL

• 1

EXPERIMENTAL

O

O

O

(a) O

O

N

Metal adducts

(b)

(a) Methnol, acetic acid

(b) MOH, water/ Methanol, NEt3, MX2

COOH

NH2COOH

M= Na, K, Ag, Ca, Ni, Co, Cu, Mn, Sn

SYNTHETIC SCHEME

O

ON

COOHO

ON

COOAgO

ON

COONaO

ON

COOK

O

O

N OCu

O

O

O

NOO

O

O

N OPb

O

OAc

O

O

N OCo

O

Cl

O

O

N OSn

O

Cl

O

O

N OCa

O

Cl

O

O

N OMn

O

Cl

O

O

N ONi

O

NO3 O

O

N OFe

O

SO4

O

O

N OSn

O

O

O

N

O

O

N OSn

O

OO

C4H9C4H9

O

O

N OSn

O

PhPh Ph

EXPERIMENTAL

• SYNTHESIED COMPOUNDS

Results and Discussion

CHARACTERIZATION

(Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoic acid Physical appearance: Yellow Solid Molecular weight: 269 M.P= 197

Rf Value: 0.81 n-Hexane: Acetone (2:1)

IR Values: 3340.71 (OH), 1705.07 (C=O), 1616.35 (C=N), 1398-1492 (C=C), 1398.39 (C-O) NMR Values:

O

ON

COOH

CHARACTERIZATION

sliver (Z)-2-(benzo[d][1,3]dioxol-5 ylmethyleneamino)benzoate

Physical appearance: Dark Yellow Solid Molecular weight: 376M.P: 213

Rf Value: 0.48 n-Hexane: Acetone (2:1)

IR: 1708.93 (C=O), 1591.27 (C=N), 1492.90 (C=C), 1396.46 (C-O)

O

ON

COOAg

CHARACTERIZATIONpotassium (Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate

Physical appearance: Dark Yellow Solid Molecular weight: 307M.P: 200

Rf Value: 0.51 n-Hexane: Acetone (2:1)

IR: 1712.72 (C=O), 1589.34 (C=N), 1494.83 (C=C), 1377.17 (C-O),

O

ON

COOK

CHARACTERIZATIONcopper (Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate

Physical appearance: Greenish white Solid Molecular weight: 600M.P: above 300

Rf Value: 0.21 n-Hexane: Acetone (2:1)

IR Values: 1612.42 (C=O), 1537.03 (C=N), 1402.25 (C=C), 1327.03 (C-O), 527.28 (O-Cu), 480.28 (N Cu).NMR Values:

O

O

N OCu

O

O

O

NOO

CHARACTERIZATION

tin (Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate chloridePhysical appearance: light brown color solid Molecular weight: 422M.P: above 300

Rf Value: 0.86 n-Hexane: Acetone (2:1)

IR:1615.49 (C=O), 1587.42 (C=N), 1404.18 (C=C), 1327.03 (C-O), 525.42 (O-Sn), 482.20 (N Sn).

O

O

N OSn

O

Cl

CHARACTERIZATION

O

O

N OMn

O

Clmanganese (Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate chloride

Physical appearance: brown color solid Molecular weight:358M.P: above 300

Rf Value: 0.41 n-Hexane: Acetone (2:1)

IR:1612.49 (C=O), 1587.42 (C=N), 1404.18 (C=C), 1327.03 (C-O), 503.42 (O-Mn), 482.20 (N Cu).

CHARACTERIZATION

cobalt (Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate chloride

Physical appearance: cream color solid Molecular weight: 362M.P: 270

Rf Value: 0.36 n-Hexane: Acetone (2:1)

IR: 1612.42 (C=O), 1589.34 (C=N), 1402.25 (C=C), 1327.03 (C-O), 511.14 (O-Co), 428.20 (N Cu).

O

O

N OCo

O

Cl

CHARACTERIZATION

O

O

N OSn

O

PhPh Ph

(Z)-triphenylstannyl 2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate Physical Appearance: White Solid Molecular weight: 618 M.P: 160 Rf Value: 0.47 n-Hexane: Acetone (2:1) NMR Values:

Biological Activities

• Antibacterial Activity

Antibacterial Activity against Gram Positive bacteria.Vancomycin

S.No Code Inhibition zone in mm Standard Drug

1 AA01 20.6 29

2 AA02 18.3 29

3 AA03 21.6 29

4 AA04 29.9 29

5 AA05 17.8 29

6 AA06 16.8 29

7 AA07 37.9 29

8 AA08 25.2 29

9 AA09 21.1 29

10 AA10 24.3 29

11 AA11 20.1 29

12 AA12 15.0 29

13 AA13 27.1 29

14 AA14 30.5 29

15 AA15 27.4 29

16 AA16 24.5 29

S.No Code Inhibition zone in mm Standard Drug

1 AA01 16.9 36

2 AA02 24.9 36

3 AA03 22.0 36

4 AA04 23.6 36

5 AA05 26.5 36

6 AA06 20.9 36

7 AA07 33.4 36

8 AA08 26.5 36

9 AA09 22.8 36

10 AA10 31.7 36

11 AA11 18.7 36

12 AA12 23.3 36

13 AA13 27.2 36

14 AA14 20.5 36

15 AA15 22.7 36

16 AA16 15.7 36

Antibacterial Activity against Gram Negative bacteria.Vancomycin (E.Coli)

Almighty Allah

Dr. Obaid-ur-Rahman (Supervisor) Dr. Wajid (Co-Supervisor)

• Chairman Prof. Dr Muhsin Nawaz Head of Department

• All teachers • My All Lab Fellows and all my class fellows• Friends• Family Members

ACKNOWLEDGEMENTS