NUCLEOPHILIC AND DIELS ALDER REACTIONS OF

ACTIVE ACETYLENES WITH FEW SELECTED COMPOUNDS

Presented By:

AASHNA PERWIN
GI-2845
17-OCHM-018

DEPARTMENT OF CHEMISTRY
ALIGARH MUSLIM UNIVERSITY ALIGARH
Overview
 Introduction
 Objective
 Active acetylenes
 Synthesis of dibenzoylacetylene
 Reaction of DBA
 Reaction of DPA
 Reaction of DMAD
 Characterization of the products
 Thin layer chromatography
 Column chromatography
 FT-IR of the product
 Conclusion
Introduction

• The Diels Alder reaction of dibenzoylacetylene (DBA) and

dimethyl acetylenedicarboxylate (DMAD) with suitable
dienes has been studied extensively. For example, DBA (1)
and DMAD (2) undergo Diels Alder reaction with anthracene
derivatives to give 9,10-adduct.
DMAD (2) reacts with carbomethoxypyrroles (5) to give Diels
Alder adduct (6).
Objective

An attempt to look into the reaction of l-naphthol, 2-naphthol,

1-naphthylamine with DBA and DPA under neat heating as well
as refluxing in toluene.
 In addition, an attempt has also been made to study the
reaction of 3-cyanoindole with DMAD under different
conditions with an aim to use these reactions for the synthesis of
various adducts and also to examine the mode of addition of
these compounds to acetylene derivatives.
Active Acetylenes

Dibenzoylacetylene (DBA)- synthesized

Diphenylacetylene (DPA)- purchased
Dimethyl acetylenedicarboxylate (DMAD)- purchased
Synthesis of dibenzoylacetylene (DBA)
Reaction of DBA

The Diels Alder reaction of naphthol derivatives such as 1-

naphthol and 2-naphthol with DBA has been carried out by
neat heating and refluxing with toluene.
 Reaction of DPA

The Diels Alder reaction of 1-naphthol and 1-naphthylamine with

DPA was carried out by neat heating under refluxing with
toluene.
 Reaction of DMAD

DMAD was reacted with 3-cyanoindole (33) by neat heating under

refluxing with toluene.
Characterization of the products

The reaction mixture was characterized by

• Thin layer chromatography (TLC)
• Column chromatography
• Melting point analysis
• FT-IR analysis
Thin layer chromatography (TLC)

• TLC was taken for all the

reactions to determine the
purity and progress of the
reaction.
• The TLC of the reaction of
DMAD with 3-cyanoindole
shows the presence of two
extra spots in addition to
the starting materials.
Column Chromatography

To separate and purify

the mixture column
chromatography was
done with 20% eluent.
The separated compound
was recrystallized and
further characterized.
 FT-IR
The confirmation of the separated compound was done by FT-IR
technique by subsequent comparison with the starting reactant.
26

24

22 879.91cm-1, 22.97%T
860.85cm-1, 23.01%T
941.01cm-1, 21.64%T
844.59cm-1, 21.67%T
20

1877.86cm-1, 19.23%T 1019.83cm-1, 19.01%T

18
1911.69cm-1, 17.97%T
1789.49cm-1, 17.74%T 1260.83cm-1, 17.79%T
16 1737.30cm-1, 17.00%T
2309.40cm-1, 16.43%T 1365.37cm-1, 17.05%T
1948.28cm-1, 17.83%T
1064.22cm-1, 15.61%T
14 2490.80cm-1, 14.84%T 1496.27cm-1, 15.14%T 1007.35cm-1, 14.91%T
1149.25cm-1, 14.43%T
%T

2568.82cm-1, 13.96%T 1180.08cm-1, 14.70%T

2606.53cm-1, 14.02%T
12
2676.05cm-1, 12.57%T
2740.89cm-1, 12.05%T
10
1340.24cm-1, 13.27%T
2125.78cm-1, 13.01%T 1311.87cm-1, 15.02%T
2174.82cm-1, 12.11%T 1459.00cm-1, 12.34%T
1134.97cm-1, 11.94%T
1332.01cm-1, 12.03%T
1108.68cm-1, 10.82%T

2856.42cm-1, 9.44%T 1581.91cm-1, 8.94%T

8
2921.95cm-1, 7.92%T
2985.16cm-1, 7.45%T 729.95cm-1, 7.48%T
3932.13cm-1,
6 6.86%T 3004.55cm-1, 7.32%T 681.88cm-1, 7.12%T
2955.55cm-1, 8.12%T
3049.03cm-1, 6.12%T 1525.84cm-1, 6.27%T

4
1431.50cm-1, 4.40%T 502.73cm-1, 4.38%T
3123.26cm-1, 3.90%T 1242.78cm-1, 3.82%T 470.80cm-1, 3.84%T
1638.46cm-1, 3.31%T 755.28cm-1, 3.16%T
2 3235.22cm-1, 0.88%T 1617.54cm-1, 2.64%T 605.11cm-1, 2.66%T
3410.73cm-1, 0.61%T
2228.18cm-1, 1.83%T 422.48cm-1, 1.94%T

-0
4000 3500 3000 2500 2000 1500 1000 500 400
cm-1
Name Description
Conclusion

The reaction of acetylene derivatives such as DBA, DPA and

DMAD has been investigated with different naphthol derivatives
under neat heating. The work up of the reaction mixture and
characterization with IR spectroscopic studies indicate some
formation of nucleophilic and Diels Alder adduct. The complete
separation, purification and characterization is under process.
 Acknowledgement
It is a great pleasure to present this report on the project named NUCLEOPHILIC AND
DIELS ALDER REACTIONS OF ACTIVE ACETYLENES WITH FEW SELECTED
COMPOUNDS undertaken by me as the part of my project work.
First of all I am thankful to almighty ALLAH who gave me the strength and ideas for
implementing the project.
I am immensely grateful to Prof. Sartaj Tabassum, Chairman, Department of Chemistry,
AMU, Aligarh for providing me all the necessary laboratory facilities. I would like to
express my appreciation to the rest of faculty and staff members of our department for
their helpful suggestions and encouragement.
I am bereft of words to thank my mentor and supervisor, Prof. M. Muneer, for introducing
me to the fascinating world of heterocyclic synthesis and gave me the liberty to carry out
this project. Thank you, Sir! For always encouraging, guiding and supporting me
throughout this project.
I would also like to express my sincerest appreciation to my seniors and my lab colleagues
Haider Iqbal, Shubham Kumar and Reesha Fatima.