MICROWAVE ASSISTED SYNTHESIS OF

BENZYLIDENE MALANONITRILE DERIVATIVES BY

KNOEVENAGEL CONDENSATION

Report on a project carried out as a part of curriculum for the degree of “Master of Science
in Organic Chemistry” at Department of Chemistry, Agasti Arts, Commerce & Dadasaheb
Rupwate Science College, Akole. Tal. - Akole, Dist.- Ahmednagar, (422 601).

Submitted by
Torkad Bharti Babasaheb
M. Sc. II (Organic Chemistry)
Department of Chemistry

Agasti Arts, Commerce & Dadasaheb Rupwate Science College, Akole

Tal. - Akole, Dist.- Ahmednagar 422601

2024-2025

Under the guidance of

Dr. Pankaj Haribhau Naikwadi

Assistant Professor, Department of Chemistry,
Agasti Arts, Commerce & Dadasaheb Rupwate Science College, Akole Tal. - Akole,
Dist.- Ahmednagar 422 601

SAVITRIBAI PHULE PUNE UNIVERSITY

October / November 2024
1|Page
 CANDIDATES DECLARATION

I hereby declared that, project entitled “Microwave Assisted Synthesis of Benzylidene

Malanonitrile Derivatives by Knoevenagel Condensation,” submitted to the

Department of Chemistry, Agasti Arts, Commerce & Dadasaheb Rupwate Science College,
and Akole. Tal. - Akole, Dist. - Ahmednagar 422 601, in partial fulfillment of degree of
Master of Science, has not been submitted to any other University or institution. This
Work carried out at the Department of Chemistry, Agasti Arts, Commerce & Dadasaheb
Rupwate Science College, and Akole. Tal. - Akole, Dist. - Ahmednagar, 422 601.

Miss. Torkad Bharti Babasaheb

M. Sc. II (Organic Chemistry)

Department of Chemistry,

Agasti Arts, Commerce & Dadasaheb Rupwate Science College, Akole

Tal. - Akole, Dist.- Ahmednagar, 422 601.

2|Page
 CERTIFICATE

This is to certify that the work incorporated in this project entitled

“Microwave Assisted Synthesis of Benzylidene Malanonitrile Derivatives by
Knoevenagel Condensation” being submitted to Department of Chemistry, Agasti
Arts, Commerce And Dadasheb Rupwate Science College, Akole as partial fulfillment
of requirement for the degree of Master of Science in Organic Chemistry by Miss.
Bharti Babasaheb Torkad is carried out under my supervision at Department of
Chemistry, Agasti Arts, Commerce And Dadasaheb Rupwate Science College, Akole.
Tal. - Akole, Dist.- Ahmednagar, (422 601) during the academic year 2024-2025.

Dr. Pankaj Haribhau Naikwadi

Assistant Professor, Department of Chemistry,
Agasti Arts, Commerce & Dadasheb Rupwate Science College, Akole
Tal. - Akole, Dist. – Ahmednagar, 422 601.

3|Page
 Department of Chemistry
Agasti Arts, Commerce & Dadasaheb Rupwate Science College, Akole.

Tal. - Akole, Dist. - Ahmednagar, 422 601.

CERTIFICATE
This is to certified that, the work incorporated in the project report entitled
“Microwave Assisted Synthesis of Benzylidene Malanonitrile Derivatives by
Knoevenagel Condensation” being submitted by Miss. Torkad Bharti Babasaheb for
the award of the degree of Master of Science in Organic Chemistry to Department
of Chemistry, Agasti Arts, Commerce and Dadasaheb Rupwate Science College Akole,
was carried out by the candidate under the supervision of Dr. Pankaj Haribhau
Naikwadi, Assistant Professor, Department of Chemistry, Agasti Arts, Commerce and
Dadasaheb Rupwate Science College, Akole. Tal. - Akole, Dist. - Ahmednagar, (422
601) during the academic year 2024-2025.

Dr. S. M. Sonawane Examiner

4|Page
 Acknowledgment
It is my great pleasure to thank many people who have assisted me through
this short journey. First and foremost, I wish to thank my advisor Dr. Pankaj
H. Naikwadi, for his guidance, support, encouragement, and inspiration to my
project studies. He is a fantastic mentor who was influential for my interest, and
my ability to grasp the essence of organic chemistry. He teaches me everything
he knows and always encourages me to think creatively and be prepared to learn
new scientific method . I am grateful to him for all the way in which he has
prepared me to move forward in my career and life

I was very fortunate to work with a fantastic group of Chemistry Department, Akole
College. My thanks to Dr. S. M. Sonawane, Prof. Mrs. S. M. Bangal, Prof. S. G. Muthe,
Prof. A. L. Wakchaure, Prof. Mrs. J. S. Shinde, Prof. Miss. A. B. Akaram, for
devoting their precious time and made much valuable suggestion which indeed helped me
during this project work. A special thank goes to Kotkar Vaishnavi and Pawar Sakshi
for their help and friendship.

I also take this opportunity to thank all respected teachers from the department
who always helped me to move ahead and were always source for motivation and spiritual
energy. Along with them I sincerely thanks to all my friend, colleagues in M. Sc- I, Lab
asst. Mr. K. D. Bhalerao, Lab. Attendant Mrs. S. A. Shewale, Mrs. P. B. Nawale, Mr.
V. P. Deshmukh for their constant support and continuous motivation. My apologies to all
those who have helped me but I forgot to acknowledge.

Torkad Bharti Babasaheb

5|Page
 INDEX

Page No.
Sr.no. Title

1 Abbreviation 07

2 Introduction 08

3 Literature Review 10

4 Scheme 14

5 Experimental section 18

6 Results 23

7 Thin Layer Chromatofraphy 24

8 IR Spectrum 26

9 Conclusion 29

10 References 30

6|Page
 1. List of Abbreviations

Unit
0
C Degree Celsius

min Minute

mL Milliliter

mmol Millimole

gm Gram

Chemical group
Aq. Aqueous

D.W Distilled water

Other Notations
Cat. Catalytic

Equal Equivalent

M.P. Melting point

M.W. Molecular weight

% Percentage

R.T. Room temperature

TLC Thin layer chromatography

IR Infrared Spectroscopy

M.W. Microwave

7|Page
 2. INTRODUCTION

This is an example of Knoevenagel condensation. It is the coupling reaction between

aldehyde/ketone with activated methylene compound in presence of base or Lewis acid as catalyst.
In the present experiment, ZnCl2 is used as Lewis’s catalyst or coupling of benzaldehyde and
malononitriles. Benzaldehyde coordinates with Lewis acid ZnCl2 which make carbonyl carbon
more electrophilic. The tautomeric form of malononitrile then shows nucleophilic attack on a
carbonyl carbon of aldehyde or ketone. The ẞ-hydroxyl compound generates when the negative
charge over oxygen picks up one proton from the protonated nitrile group. The B-hydro compound
thus forms of-unsaturated dicyano compound, benzylidene malononitrile phenyl methylene
malononitrile), through the elimination of one water molecule.
The Knoevenagel condensation is one of the most important methodologies for carbon–carbon
double bond formation in synthetic organic chemistry and allows the production of various α, β-
unsaturated acids, commonly referred to as cinnamic acids. These cinnamic acids are key
intermediates for the synthesis of natural and therapeutic drugs, polymer, cosmetic, and perfumes.
Generally, Knoevenagel reactions are carried out by the condensation of an active methylene
compound with an aldehyde using large amounts of pyridine as a solvent and piperidine as an
organcatalyst .For a variety of reasons, the use of pyridine as a solvent is not desirable and should
be significantly reduced or eliminated. Pyridine is toxic and represents a significant health risk
above a vapor concentration of 3500 ppm .The use of ionic liquids has been examined as an
alternative because of their unique properties, e.g. good solubility, non-flammability, negligible
vapor pressure, and recyclability However, their industrial application is limited due to their high
cost (11). Another possibility is to exclude the solvent completely from the reaction medium .These
so-called solvent-free conditions can lead to additional improvements such as the reduced amount
of catalyst needed, increased reaction rate and higher.

8|Page
 3. LITERATURE REVIEW

1. B.P. Koli and R. P. Gore (2023) Alum catalyzed an Eco-Friendly Synthesis of

Benzylidene Malononitrile and banzylidine Barbituric Acid Derivatives in Aqueous
medium. Vol.16 No.3 ISSN: 0974-1496 Rasayn J. Chem., 16(3), 1734-1740.

CHO
CN
CN

20 mol% Alum
+

H2O, 60 0C CN
CN R
R

2. Swareena Jain, Tavleen Maidh & Madhavi Badole. (2020) Enhanced reaction rate by
using N, N-dimethylformamide as a catalyst in Knoevengel condensation Vol. 59B,
July, pp.1025-1029.

O
CN
C N
C DMF
H + H2 C
300W,20sec
C N CN

3. Nader Noroozi Pesyan, Mohammad Ali Kimia, Mohammad Jalilazadeh and Ertan
Sahin (2013) ‘A New Fast and Easy Strategy for One-pot Synthhesis of Full Substituted

9|Page
Cyclopropane: Direct Transformation of Aldehydes to 3-Aryl-1,1,2,2-
tetracyanocyclopropanes’ J. Chin. Chem. Soc. 60, 35-44

R H
R H CN CN

O NC CN

4. Siddheshwar W. Kshirsagar, Nitin R. Patil, Shriniwas D. Samant (2010) One-pot

Synthesis of 2-amino-5-nitro-4,6-diarylcyclohex-1-ene-1,3,3-tricarbonitriles by
condensation of aldehyde , malononitrile, and nitromethane in the presence of Mg-Al HT
under – free condition, 2924-2927.

NH2
CN
CHO CN
NC
CN

CH3NO2 MgAl-HT
+ +
r.t.
NO2
R
CN R
R

5. Anirban Karmkar, Anup Paul, Karmakar T. Mahmudov, M. Fatima c. Guedes da ailva

and Armando J. L. Pombeiro “pH dependent synthesis of Zn (II) coordination polymers
with dicarboxyl-functionalized arylhydrazone of barbituric acid: photoluminescence
properties and catalysts for Knoevenagel condensation” 20-21

10 | P a g e
 CN

CHO NC

[Zn (kN-H3L) (H2O)3].3H2O

+ CN CN + H2O
THF, 500C, 4h

6. Amarsinh L Jadhav and Ganapati D Yadav. (2019) “Clean synthesis of benzylidene-

malononitrile by Knoevenagel condensation of benzaldehyde and malononitrile : effect
of combustion fuel on activity and selectivity of Ti-hydrotalcite and Zn-Hydrotalcite
catalysts” J. Chem. Sci. 131: 79

N N
C C

O
H
C
+ Ti-HT-Glycine
H C C
+ H2O
N N 0
60 C

7. Abdul Ahad and Maqdoom Farooqui (2016) “Access to arylmethylidene-isoxazol-

5(4H)-ones and benzylidenemalononitriles promoted by imidazole as an efficient
organocatalyst” Vol. 8, No. 1 1685-1691

CHO
CN
NC

+ Imidazole (10 mol%)

EtOH:H2O CN

CN R.T R
R

8. Leena Sarkar and Ajaykumar Ramkumar Nishad (2016) “Novel Methods of

Knoevenagel Condensation” Vol. 65, issue 8.
11 | P a g e
 O

CN
C C N
H
+ H2 C
Ammonium Acetate
CN
C N R.T,5-7 min
X
X -H2O

9. N. Mase, T Horibe suggested that carbamic acid ammonium salt used as an

organocatalyst give the desired knovenagel reaction between aldehyde and active
methylene group and give 98% yield.

CO2R CO2R CO2R

O
0.5 eq . catalyst
+
solvent free
Ar H CO2R 25 0C, 14 -24h
Ar

12 | P a g e
 4. SCHEME

General Reaction:
CN
O N N
M.W. 10 min R
+ C C
ZnCl2 CN
R H C
H2
H
Aldehyde Malononitrile
Akylidene Malononitrile
Scheme 1: Synthesis of benzylidenemalanonitrile (2-phenylmethylene malononitrile) from
benzaldehyde and malononitrile"

Reaction:

CN
O N N
M.W. 10 min H
+ C C CN
C ZnCl2
Ph H
H2
Ph
Benzaldehyde Malononitrile 2-benzylidenemalononitrile

Scheme 2: Synthesis of P-methoxy benzylidenemalanonitrile (2-phenylmethylene malononitrile)

from Anisaldehyde and malononitrile"
Reaction:
CHO
CN

N N H
M.W. 10 min CN
+ C C
ZnCl2
C
H2
Malononitrile
OCH3

OCH3
2-(4-methoxybenzylidene)malononitrile

13 | P a g e
Scheme 3: Synthesis of 4-hydroxy benzylidenemalononitrile (2-phenylmethylene malononitrile)
from 4- hydroxy benzaldehyde and malononitrile"

Reaction:
CHO

N N CN
M.W. 10 min
C C H
+ C ZnCl2 CN
H2

Malononitrile
OH
4-hydroxybenzaldehyde

OH
2-(4-hydroxybenzylidene)malononitrile

Scheme 4: Synthesis of P-Chloro benzylidenemalononitrile (2-phenylmethylene malononitrile)

from P-Chloro benzaldehyde and malononitrile"

Reaction:
CHO

N N CN

M.W. 10 m in
C C H
+ CN
C ZnCl2
H2

Malononitrile
Cl
4- chlorobenzaldehyde

Cl
2-(4-chlorobenzylidene)malononitrile

14 | P a g e
Scheme 5: Synthesis of 3, 4 Dimethoxy benzylidenemalononitrile (2-phenylmethylene
malononitrile) from 3, 4 Dimethoxy benzaldehyde and malononitrile"

Reaction:

CHO
N N CN

M.W. 10 min
C C H
+ C ZnCl2 CN
H2
OCH3
Malononitrile
OCH3

3,4-dimethoxybenzaldehyde
H3CO

OCH3
2-(3,4-dimethoxybenzylidene)malononitrile

15 | P a g e
4.1 OPTIMIZATION OF REACTION CONDITION
Synthesis of 2-(Phenylmethylidene) propanedinitrile

O N

M.W. 10 min
+ ZnCl2 CN

Ph H
N CN
H

Benzaldehyde Malononitrile 2-(Phenylmethylidene )

propanedinitrile

Place a mixture benzaldehyde (0.5g 4.71mmol) malononitrile (0.31g 4.71mmol) and

zinc chloride (catalytic amount) in a conical flask and microwave irradiation at 1200C for
10 min. Then cool the mixture to room temperature and add 5 ml of 1% aqueous ethanol
in the flask to obtain the product benzylidenemalononitrile as solid good purity. Filter the
product, dry and record yield, M. P., TLC and IR spectrum.

Catalytic amount Temperature Yield

Entry No. Catalyst
(0.47 mmol) (oC) (%)
20 mg
1 LiOH 50 64
(0.47 mmol)
25 mg
2 NH4Cl 60 72
(0.47 mmol)
64 mg
3 AlCl3 60 82
(0.47 mmole)
64 mg
4 BF3 80 78
(0.47 mmole)

64 mg
5 ZnCl2 90 94.78
(0.47 mmole)

After optimizing reaction condition entry no. 5 catalyst are used for the further synthesis

16 | P a g e
 4. EXPERIMENTAL SECTION

General Reaction:

CN
O N N
Microwave , 10 min R
+ C C
ZnCl2 CN
R H C
H2
H
Aldehyde Malononitrile
Akylidene Malononitrile

Procedure:
Place a mixture of aldehyde (0.5 gm, 4.71mmol), malononitrile (0.31gm,
4.71mmol) & zinc chloride (0.1gm, 0.47mmol) in a conical flask and microwave irradiation at
1200C for 10 min. Then cool the reaction mixture to room temperature and add 5ml of 1%
aqueous ethanol in the flask to obtain the product, benzylidenemalononitrile as solid in good
purity. Filter the product, dry and record the yield, M.P. TLC and IR spectrum.

Scheme 1: Synthesis of benzylidenemalononitrile (2-phenylmethylene malononitrile) from

benzaldehyde and malononitrile" (D1)

Reaction:

CN
O N N
M.W. 10 min H
+ C C
ZnCl2 CN
Ph H C
H2
Ph
Benzaldehyde Malononitrile 2-benzylidenemalononitrile

Procedure:
Place a mixture of benzaldehyde (0.5 gm, 4.71mmol), malononitrile
(0.31gm,4.71mmol) & zinc chloride (0.1gm,0.47mmol) in a conical flask and microwave
irradiation at 1200C for 10 min. Then cool the reaction mixture to room temperature and add
5ml of 1% aqueous ethanol in the flask to obtain the product, benzylidenemalononitrile as solid
in good purity. Filter the product, dry and record the yield, M.P., TLC and IR spectrum.

17
Result Table:
Sr. No. Particulars (D1) Result
1. Colour of the product White
2. Practical yield of the product 0.50 gm
3. % practical yield of the product 85.42%
4. Physical constant (M.P) 830 C
5. Rf of Reactant 0.66
6. Rf of Product 0.50
7. Solvent for TLC n-hexane+ Ethyl acetate (8:2)
8. Solvent for Recrystallization Alcohol

Scheme 2: Synthesis of P-methoxy benzylidenemalononitrile (2-phenylmethylene

malononitrile) from Anisaldehyde and malononitrile"
Reaction:

CHO
CN

N N H
M.W. 10 min CN
+ C C
ZnCl2
C
H2
Malononitrile
OCH3
4- Methoxy benzaldehyde

OCH3
2-(4-methoxybenzylidene)malononitrile
Procedure:

Place a mixture of Anisaldehyde (0.5 gm, 4.71mmol), malononitrile (0.31gm,

4.71mmol) & zinc chloride (0.1gm, 0.47mmol) in a conical flask and microwave irradiation at
1200C for 10 min. Then cool the reaction mixture to room temperature and add 5ml of 1%
aqueous ethanol in the flask to obtain the product, P-Methoxy benzylidenemalononitrile as
solid in good purity. Filter the product, dry and record the yield, M.P., TLC and IR spectrum.

18
Result Table:
Sr. No. Particulars (D2) Result
1. Colour of the product Light green
2. Practical yield of the product 0.45gm
3. % practical yield of the product 87.16%

4. Physical constant (M.P) 1100 C

5. Rf of Reactant 0.42
6. Rf of Product 0.74
7. Solvent for TLC n-hexane+ Ethyl acetate (8:2)
8. Solvent for Recrystallization Alcohol

Scheme 3: Synthesis of 4-Hydroxy benzylidenemalononitrile (2-phenylmethylene

malononitrile) from 2-Hydroxy benzaldehyde and malononitrile"
Reaction:

CN

H
CN
CHO
N N
M.W. 10 min
C C
+ ZnCl2
C
H2

Malononitrile OH
OH 2-(4-hydroxybenzylidene)malononitrile
4- Hydroxybenzaldehyde

Procedure:

Place a mixture of 4-Hydroxy benzaldehyde (0.5 gm, 4.71mmol), malononitrile (0.31gm,

4.71mmol) & zinc chloride (0.1gm,0.47mmol) in a conical flask and microwave irradiation at
1200C for 10 min. Then cool the reaction mixture to room temperature and add 5ml of 1%
aqueous ethanol in the flask to obtain the product, 2-Chloro benzylidenemalononitrile as solid
in good purity. Filter the product, dry and record the yield, M.P., TLC and IR spectrum.

19
Result Table:
Sr. No. Particulars (D3) Result
1. Colour of the product Faint Yellow
2. Practical yield of the product 0.43gm
3. % practical yield of the product 89.16 %
4. Physical constant (M.P) 860 C
5. Rf of Reactant 0.70
6. Rf of Product 0.58
7. Solvent for TLC n-hexane+ Ethyl acetate (6:4)
8. Solvent for Recrystallisation Alcohol

20
Scheme 4: Synthesis of p-Chloro benzylidenemalononitrile (2-phenylmethylene
malononitrile) from P-Chloro benzaldehyde and malononitrile"
Reaction:
CHO

N N CN

Microwave, 10 min
C C H
+ C ZnCl2 CN
H2

Malononitrile
Cl
4-chlorobenzaldehyde

Cl
2-(4-chlorobenzylidene)malononitrile

Procedure:
Place a mixture of p-Chloro benzaldehyde (0.5 gm, 4.71mmol), malononitrile
(0.31gm,4.71mmol) & zinc chloride (0.1gm,0.47mmol) in a conical flask and microwave
irradiation at 1200C for 10 min. Then cool the reaction mixture to room temperature and add
5ml of 1% aqueous ethanol in the flask to obtain the product, P-Chloro
benzylidenemalononitrile as solid in good purity. Filter the product, dry and record the yield,
M.P., TLC and IR spectrum.
Result Table:
Sr. No. Particulars (D4) Result
1. Colour of the product White
2. Practical yield of the product 0.48gm
3. % practical yield of the product 91.64%
4. Rf of Reactant 0.77
5. Rf of Product 0.61
6. Physical constant (M.P) 1420 C
7. Solvent for TLC n-hexane+ Ethyl acetate (8:2)
8. Solvent for Recrystallisation Alcohol

21
Scheme 5: Synthesis of 3, 4 Dimethoxy benzylidenemalononitrile (2-phenylmethylene
malononitrile) from 3,4 Dimethoxy benzaldehyde and malononitrile"
Reaction:
CHO

N N CN

M.W. 10 min
C C H
+ ZnCl2 CN
C
H2
OCH3
Malononitrile
OCH3

3,4-dimethoxybenzaldehyde
H3CO

OCH3
2-(3,4-dimethoxybenzylidene)malononitrile

Procedure:

Place a mixture of p-Chloro benzaldehyde (0.5 gm, 4.71mmol), malononitrile (0.31gm,

4.71mmol) & zinc chloride (0.1gm, 0.47mmol) in a conical flask and microwave irradiation at
1200C for 10 min. Then cool the reaction mixture to room temperature and add 5ml of 1%
aqueous ethanol in the flask to obtain the product, 3, 4 Dimethoxy benzylidenemalononitrile
as solid in good purity. Filter the product, dry and record the yield, M.P., TLC and IR
spectrum.
Result Table:
Sr. No. Particulars (D5) Result
1. Colour of the product Dark Yellow
2. Practical yield of the product 0.51gm
3. % practical yield of the product 88.68 %
4. Physical constant (M.P) 1380 C
5. Solvent for TLC n-hexane+ Ethyl acetate (8:2)
6. Rf of Reactant 0.78
7. Rf of Product 0.68
8. Solvent for Recrystallisation Alcohol

22
5. Results

Comparative Data

Sr. Derivatives
Particulars
No. D1 D2 D3 D4 D5
Colour of the Light Faint
1. White White Dark Yellow
product green Yellow
Practical yield of
2. 0.75 gm 0.85gm 0.93gm 0.88gm 0.81gm
the product
% practical yield
3. 85.42% 87.16% 89.16 % 91.64% 88.68 %
of the product
Physical constant
4. 830 C 1100 C 860 C 1420 C 1380 C
(M.P)
5. Rf of Reactant 0.66 0.42 0.70 0.77 0.78
6. Rf of Product 0.50 0.74 0.58 0.61 0.68
n-hexane+ n-hexane+ n-hexane+ n-hexane+ n-hexane+ Ethyl
Solvent used for Ethyl Ethyl Ethyl Ethyl acetate
7.
TLC acetate acetate acetate acetate
(8:2) (8:2) (6:4) (8:2) (8:2)

Solvent for
8. Alcohol Alcohol Alcohol Alcohol Alcohol
Recrystallization

23
 6. THIN LAYER CHROMATOGRAPHIC DATA

Sr.
Name of the Product TLC Product
No.

1. Benzylidenemalononitrile

P-methoxy
2. benzylidenemalononitrile

4-Hydroxy
3. Benzylidenemalononitrile

24
 P-Chloro
4. benzylidenemalononitrile

3,4 Dimethoxy
5. benzylidenemalononitrile

25
 7. SPECTRAL ANALYSIS

IR Spectrum
1. IR spectrum of 3, 4 Dimethoxy benzylidenemalononitrile (2-phenylmethylene
malononitrile)
99.5
99.0
Transmittance [%]
97.0 98.097.5 98.5

3840.27

3684.54
3625.82

3443.62
3406.89
3342.22
3273.39

3058.41

2924.58
2853.32

2731.16
2669.64

2384.37
2346.26
2308.67
2213.67

1948.86

1737.04

1560.24
1499.88
1463.98
1415.25
1339.28
1264.29
1205.08
1135.01
1007.43

892.25
955.77
929.62

844.82
815.24
767.61
723.06
699.30
624.10
3500 3000 2500 2000 1500 1000
Wavenumber cm-1
-1
The - C-O-C- ether stretching frequency at 1000-1300 cm , whereas –C=C- alkene stretching
frequency at 2900-3000 cm-1 , -CN cyanide group shows stretching frequency at 2200-2260
cm-1 , Benzene shows IR stretching frequency at 1500-1600 cm-1 .

2. IR spectrum of P-Chloro benzylidenemalononitrile (2-phenylmethylenemalononitrile)

3500 3000 2500 2000 1500 1000

Wavenumber cm-1

The –C=C alkene stretching frequency at 2900-3000 cm-1 , whereas –CN cyanide group shows
stretching frequency at 2200-2260 cm-1 . The aromatic ring stretching frequency at 1500-1600
cm-1. Ar-Cl shows IR stretching frequency 736-821 cm-1.

26
3. IR spectrum of P-methoxy benzylidenemalononitrile (2-phenylmethylene
malononitrile)
99
98 97
Transmittance [%]
94 95 96
93
92

2924.11

2213.46

1562.34
1502.73

1312.89
1270.33
1176.11

1012.86

827.59
3500 3000 2500 2000 1500 1000
Wavenumber cm-1

The –C-O-C- ether stretching frequency at 1000-1300 cm-1 , Whereas aromatic region
stretching frequency at 1500-1600 cm-1 , also the –CN cyanide group shows stretching
frequency at 2200-2260 cm-1 .

4. IR spectrum of 4-Hydroxy Benzylidenemalononitrile

3500 3000 2500 2000 1500 1000

Wavenumber cm-1

The –OH stretching frequency at 3100-3200cm-1 , where as aromatic ring stretching

frequency at 1500-1600 cm-1 , also –CN cyanide group stretching frequency at 2200-2260
cm-1, The –C=C- alkene stretching frequency at 2900-3000 cm-1.

27
 9. CONCLUSION

 In conclusion, we have reported an efficient procedure for the synthesis of

Benzylidenethiazolidine-2, 4-dione derivatives under microwave irradiation using zinc
chloride solvent.

 The final compounds are filtered and purified just by simple crystallization.

 The current methodology has the advantages of operational simplicity, mild reaction
conditions and good to high yield of the products (84–91%).

 Therefore, microwave irradiation reducing the reaction time and improving the reaction
yields.

28
 10. REFERENCES

[1] List, B. Emil Knoevenagel and the Roots of Aminocatalysis.bAngew. Chem. (Int. ed. in
English). 2010, 49, 1730–1734.

[2] Cho, H.; Ueda, M.; Tamaoka, M.; Hamaguchi, M.; Aisaka, K.; Kiso, Y.; Inoue, T.; Ogino,
R.; Tatsuoka, T.; Ishihara, T. Novel Caffeic Acid Derivatives: Extremely Potent Inhibitors of
12-Lipoxygenase. J. Med. Chem. 1991, 34, 1503–1505.

[3] Kwak, G.; Fujiki, M. Colored and Luminous Aliphatic Polyester via One-Pot Intra- and
Intermolecular Knoevenagel Reactions. Macromolecules . 2004, 37, 2021–2025.

[4] Nokami, J.; Kataoka, K.; Shiraishi, K.; Osafune, M.; Hussain, I.; Sumida, S. Convenient
Formation of 4-Hydroxyalk-2-en-1- One Functionality Via A Knoevenagel-Type Carbon
Chain Elongation Reaction of Aldehyde With 1- Arylsulfinylalkan-2-One. J. Org. Chem. 2001,
66, 1228– 1232.

[5] De, P.; Koumba Yoya, G.; Constant, P.; Bedos-Belval, F.; Duran, H.; Saffon, N.; Daffé,
M.; Baltas, M. Design, Synthesis, and Biological Evaluation of New Cinnamic .Derivatives as
Antituberculosis Agents. J. Med. Chem. 2011, 54, 1449–1461.

[6] Knoevenagel, E. Ueber eine Darstellungsweise der Glutarsäure. Berichte der deutschen
chemischen Gesellschaft 1894, 27, 2345–2346.

[7] Alfonsi, K.; Colberg, J.; Dunn, P.J.; Fevig, T.; Jennings, S.; Johnson, T.A.; Kleine, H.P.;
Knight, C.; Nagy, M.A.; Perry, D.A.; et al . Green Chemistry Tools to Influence a Medicinal
Chemistry and Research Chemistry Based Organisation. Green Chem. 2008, 10, 31–36.

[8] Kerton, F.; Marriott, R.; Clark, J.H.; Seidl, P.; Clark, J.H. Alternative Solvents for Green
Chemistry;Green Chemistry Series;Royal Society of Chemistry: Cambridge, 2013.

[9] Pawar, H.S.; Wagh, A.S.; Lali, A.M. Triethylamine: A Potential N-Base Surrogate for
Pyridine in Knoevenagel Condensation of Aromatic Aldehydes and Malonic Acid. New J.
Chem. 2016, 40, 4962–4968.

[10] Ranu, B.C.; Jana, R. Ionic Liquid as Catalyst and Reaction Medium – A Simple, Efficient
and Green Procedure for Knoevenagel Condensation of Aliphatic and Aromatic Carbonyl
Compounds Using a Task-Specific Basic Ionic Liquid. Eur. J. Org. Chem. 2006, 2006, 3767–
3770.

[11] Hangarge, R.V.; Jarikote, D.V.; Shingare, M.S. Knoevenagel Condensation Reactions in
an Ionic Liquid. Green Chem. 2002, 4, 266–268.

[12] Kaupp, G.; Reza Naimi-Jamal, M.; Schmeyers, J. SolventFree Knoevenagel

Condensations and Michael Additions in the Solid State and in the Melt with Quantitative
Yield. Tetrahedron. 2003, 59, 3753–3760.

29
[13] Pinxterhuis, E.B.; Giannerini, M.; Hornillos, V.; Feringa, B.L. Fast, Greener and Scalable
Direct Coupling of Organolithium Compounds with No Additional Solvents. Nat. Commun.
2016, 7, 11698.

[14] Martins, M.A.P.; Frizzo, C.P.; Moreira, D.N.; Buriol, L.; Machado, P. Solvent-Free
Heterocyclic Synthesis. Chem. Rev. 2009, 109, 4140–4182.

[15] Jawor, M.L.; Ahmed, B.M.; Mezei, G. Solvent- and CatalystFree, Quantitative Protection
of Hydroxyl, Thiol, Carboxylic Acid, Amide and Heterocyclic Amino Functional Groups.
Green Chem. 2016, 18, 6209–6214.

[16] Lu, J.; Toy, P. Organocatalytic Decarboxylative DoebnerKnoevenagel Reactions Between

Arylaldehydes and Monoethyl Malonate Mediated by a Bifunctional Polymeric Catalyst.
Synlett. 2011, 2011, 1723–1726.

[17] Kasinathan, P.; Seo, Y.; Shim, K.; Hwang, Y.; Lee, U.; Hwang, D.; Hong, D.; Halligudi,
S.B.; Chang, J. Effect of Diamine in Amine-Functionalized MIL-101 for Knoevenagel
Condensation. Bull. Korean Chem. Soc. 2011, 32, 2073–2075.

[18] Gu, X.; Tang, Y.; Zhang, X.; Luo, Z.; Lu, H. Organocatalytic Knoevenagel Condensation
by Chiral C2-Symmetric Tertiary Diamines. New J. Chem. 2016, 40, 6580 6583.

[19] Hoskins, T.J.C. Carbon-Carbon Bond Forming Reactions of Biomass Derived Aldehydes,
Georgia Institute of Technology: Atlanta, 2008.

[20] Pasha, M.A.; Manjula, K. Lithium Hydroxide: A Simple and an Efficient Catalyst for
Knoevenagel Condensation Under Solvent-Free Grindstone Method. J. Saudi Chem. Soc.
2011, 15, 283–286.

[21] Leelavathi, P.; Kumar, SR. Niobium (V) Chloride Catalyzed Knoevenagel Condensation:
An Efficient Protocol for the. Preparation of Electrophilic Alkenes. J. Mol. Catal. A

[22] Ogiwara, Y.; Takahashi, K.; Kitazawa, T.; Sakai, N. Indium(III)- Catalyzed Knoevenagel
Condensation of Aldehydes and Activated Methylenes Using Acetic Anhydride as a Promoter.
J. Org. Chem. 2015, 80, 3101–3110.
[23] Jackson, T.; Clark, J.H.; Macquarrie, D.J.; Brophy, J.H. Base Catalysts Immobilised on
Silica Coated Reactor Walls for Use in Continuous Flow Systems. Green Chem. 2004, 6, 193–
195.
[24] Nageswara Rao, R.; Kumar Talluri, M.V.N. An Overview of Recent Applications of
Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) in Determination of Inorganic
Impurities in Drugs and Pharmaceuticals. J. Pharmaceut. Biomed. 2007, 43, 1–13.
[25] Gupta, M.; Wakhloo, B.P. Tetrabutylammoniumbromide Mediated Knoevenagel
Condensation in Water: Synthesis of Cinnamic Acids. Arkivoc. 2007, 2007, 94.
[26] Bhuiyan, M.M.H.; Hossain, M.I.; Ashraful Alam, M.; Mahmud, M.M. Microwave
Assisted Knoevenagel Condensation: Synthesis and Antimicrobial Activities of Some
Arylidene-malononitriles, 02.

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