This document summarizes a research project on the synthesis, characterization, and biological activity of piperonal-based Schiff bases and their metal complexes. The objectives were to synthesize Schiff bases from piperonal and various amines, form complexes by adding metals, and test the complexes for antibacterial activity. Key steps included preparing the Schiff bases and their metal adducts, using various techniques to characterize the compounds, and evaluating the complexes against gram-positive and gram-negative bacteria to determine antibacterial potential. The research aims to contribute to the development of new antibacterial agents.

2. SYNTHESIS, CHARACTERIZATION AND BIOLOGICAL
ACTIVITY OF PIPERONAL BASED SCHIFF BASE AND
ITS METALADDUCTS.
28 Jan 2016
Aziz Ahmad
Department of Chemistry
Hazara University, Mansehra

3. Research outline
 Introduction..
 Importance
 Aims and Objectives.
 Experimental
 Results and discussion.
 Acknowledgment.

4. 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.

5. INTRODUCTION
 SOURCES OF ULTRASONIC RADIATIONS.
 Ultrasonic Bath (37Hz)
 Ultrasonic immersion probe (20Hz)
 Acoustic Cavitation
The formation of bubbles its growth and collapse.

6. 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.

7. INTRODUCTION
 Piperonal.
1. Heliotropin
2. 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

8. 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
N
H
H
R'''
B :
First Step Second step

9. 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.

10. IMPORTANCE
ANTIBACTERIAL ACTIVITY.  ANTICANCER ACTIVITY
ANTIOXIDANT ACTIVITY.
These complexes show 10 time
greater activity than Schiff base.
S
N
OM
O
M= Co, Ni and Fe
O N
OO
M
M= Cu (II), Co (II), Ni (II) or Mn (II)
O N
N
N +
O
O -
OC u
N
N
H
O
O
N
M
M = C u , Z n , an d C d
N
O
HO
O
O
HO
M

11. 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
OH
O
N N
O OMn

12. OBJECTIVES

13. EXPERIMENTALEXPERIMENTAL

14. Preparation of Schiff base
EXPERIMENTAL
•1

15. Preparation of Schiff base Complexes
EXPERIMENTAL
• 1

16. EXPERIMENTAL
O
O
O
(a) O
O
N
Metal adducts
(b)
(a) Methnol, acetic acid
(b) MOH, water/ Methanol, NEt3, MX2
COOH
NH2
COOH
M= Na, K, Ag, Ca, Ni, Co, Cu, Mn, Sn
SYNTHETIC SCHEME

17. O
O
N
COOH
O
O
N
COOAg
O
O
N
COONa
O
O
N
COOK
O
O
N O
Cu
O
O
O
NO
O
O
O
N O
Pb
O
OAc
O
O
N O
Co
O
Cl
O
O
N O
Sn
O
Cl
O
O
N O
Ca
O
Cl
O
O
N O
Mn
O
Cl
O
O
N O
Ni
O
NO3 O
O
N O
Fe
O
SO4
O
O
N O
Sn
O
O
O
N
O
O
N O
Sn
O
O
O
C4H9
C4H9
O
O
N O
Sn
O
Ph
Ph Ph
EXPERIMENTAL
• SYNTHESIED COMPOUNDS

19. 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
O
N
COOH

20. CHARACTERIZATION
sliver (Z)-2-(benzo[d][1,3]dioxol-5 ylmethyleneamino)benzoate
Physical appearance: Dark Yellow Solid
Molecular weight: 376
M.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
O
N
COOAg

21. CHARACTERIZATION
potassium (Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate
Physical appearance: Dark Yellow Solid
Molecular weight: 307
M.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
O
N
COOK

22. CHARACTERIZATION
copper (Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate
Physical appearance: Greenish white Solid
Molecular weight: 600
M.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 O
Cu
O
O
O
NO
O

23. CHARACTERIZATION
tin (Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate chloride
Physical appearance: light brown color solid
Molecular weight: 422
M.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 O
Sn
O
Cl

24. CHARACTERIZATION
O
O
N O
Mn
O
Cl
manganese (Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate chloride
Physical appearance: brown color solid
Molecular weight:358
M.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).

25. CHARACTERIZATION
cobalt (Z)-2-(benzo[d][1,3]dioxol-5-ylmethyleneamino)benzoate chloride
 Physical appearance: cream color solid
Molecular weight: 362
M.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 O
Co
O
Cl

26. CHARACTERIZATION
O
O
N O
Sn
O
Ph
Ph 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:

27. 1
Biological Activities
• Antibacterial Activity

28. 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

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)

30. 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