Synthesis of Schiff Bases of 4-Amino-3-Mercapto-5-Pyridin

135 Pages·2012·5.44 MB·English

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Synthesis of Schiff Bases of 4-Amino-3-Mercapto-5-Pyridin-
4yl-4H-1,2,4-Triazole and Their Evaluation as Resistance
Inducers and Antifungal Agents

By

SUJAN MAJUMDER

DIVISION OF AGRICULTURAL CHEMICALS
INDIAN AGRICULTURAL RESEARCH INSTITUTE
NEW DELHI – 110 012

2013
Synthesis of Schiff Bases of 4-Amino-3-Mercapto-5-Pyridin-
4yl-4H-1,2,4-Triazole and Their Evaluation as Resistance
Inducers and Antifungal Agents

By
SUJAN MAJUMDER

A Thesis Submitted to the Faculty of Post-Graduate School,
Indian Agricultural Research Institute, New Delhi
in partial fulfilment of requirements for the degree of

MASTER OF SCIENCE
IN
AGRICULTURAL CHEMICALS

2013

Approved by:

Chairperson: [Dr. R.L. Gupta]

Members: [Dr. Rajesh Kumar]

[Dr. Aditi kundu]

[Dr. H. K. Sharma]

[Dr. Bishnu Maya Bashyal]
Division of Agricultural Chemicals,
Indian Agricultural Research Institute
New Delhi-110 012, India

Dr. R. L. Gupta
Principal Scientist

CERTIFICATE

This is to certify that the thesis entitled “Synthesis of Schiff Bases of 4-Amino-3-
Mercopto-5-Pyridin-4yl-4H-1,2,4-Triazole and Their Evaluation as Resistance
Inducers and Antifungal Agents” submitted to the Faculty of the Post-Graduate
School, Indian Agricultural Research Institute, New Delhi, in partial fulfillment of
Master of Science in Agricultural Chemicals, embodies the results of bona fide
research work carried out by Mr. Sujan Majumder, Roll No. 20115 under my
guidance and supervision, and that no part of this thesis has been submitted for any
other degree or diploma. The assistance and help availed during the course of
investigation as well as source of information have been duly acknowledged by him.

Place: New Delhi (Dr. R.L. Gupta)
Dated: June 29, 2013 Chairman
Advisory Committee
DEDICATED TO MY P ARENTS
ACKNOWLEDGEMENT

I would like to express my deepest sense of gratitude and indebtedness to
Dr. R. L. Gupta, Principal Scientist, Division of Agricultural Chemicals, Indian
Agricultural Research Institute, New Delhi and chairperson, advisory committee for
his invaluable guidance, constant encouragement, cooperative attitude, immense
patience, useful discussions and peerless criticism during the course of investigation
and preparation of the manuscript. He has been a consistent source of inspiration,
towards the completion of this work.
It is my privilege to express profound sense of gratitude to Dr. Rajesh Kumar,
Senior Scientist and Dr. Aditi Kundu, Scientist, Division of Agricultural Chemicals
and members of my advisory committee for their constructive and valuable
suggestions.
I take pleasure to convey my heartfelt thanks to Dr. Bishnu Maya Bashyal,
Scientist, Division of Plant Pathology, IARI, and member, advisory committee for
her invaluable advice and encouragement endowed during the research work. I
implore my feeling of gratitude to Dr. H. K. Sharma, Principal Scientist, Division
of Nematology, IARI and member advisory committee for his cordial behavior
and guidance. My sincere thanks are to Dr. V. T. Gajbhiye, Head, Division of
Agricultural Chemicals, Indian Agricultural Research Institute, for encouraging
me and providing facilities throughout this study.
My heartiest thanks are to Mrs. Renu Thukral, for her technical assistance in
lab and untiring help in antifungal study. I convey my heartiest thanks to Mr. Yajulu,
Shri P. K. Singh and Dr. R. S. Tanwar, for their help during the entire span of study.
The unceasing affection and support of seniors Anirban da, Suman da, Tilak da,
Prithu da, Abhishek da, Parshant sir and Pradeep sir shall always be in my memory. I
extend my heartfelt thanks to my juniors Vikas and Liton for their special concerns.
I extend my heartfelt thanks to my friends Shailesh, Chandrika, Ali, Ashish,
Sam, Srikanta and Soumya enabled me to pursue my goals and never admit defeat.
The endless love, affection, sacrifice and constant inspiration from parents
have enabled me to reach the foothills of my long cherished aspiration. I would like
to mention the selfless love and emotional support of Moumita who changed my life
forever. Also I would like to convey my love and respect to Mej da and Satya da
who gave me immense support throughout.
Finally, the financial assistance provided by the institute in the form of IARI
fellowship during the tenure of research is gratefully acknowledged.

Place: New Delhi Sujan Majumder

Dated: June 29, 2013
CONTENTS
S. No. Chapter Page No.
1 Introduction 1
2 Background 4
3 Materials and Methods 23
4 Research Paper I 43
5 Research Paper II 63
6 Research Paper III 74
7 General Discussion 80
8 Summary and Conclusion 82
9 Abstract (English and Hindi)
10 Bibliography i-vi
11 Appendix I. 1H NMR spectra
12 Appendix II. 13C NMR spectra
13 Appendix III. IR spectra
LIST OF TABLES
Table Title Page
No. No.
4.1 4-Arylidenamino-3-mercapto-5-pyridin-4-yl-4H-1,2,4-triazoles 46
synthesized
4.2 Preparation and yield data of 4-Arylidenamino-3-mercapto-5- 47
pyridin-4-yl-4H-1,2,4-triazoles using conventional method
4.3 Preparation and yield data of 4-Arylidenamino-3-mercapto-5- 48
pyridin-4-yl-4H-1,2,4-triazoles using Microwave-induced Organic
Reaction Enhancement [MORE] method
4.4 Melting point and TLC data of 4-Arylidenamino-3-mercapto-5- 50
pyridin-4-yl-4H-1,2,4-triazoles
4.5 Elemental analysis data of 4-Arylidenamino-3-mercapto-5- 51
pyridin-4-yl-4H-1,2,4-triazoles
4.6 1H NMR data of 4-Arylidenamino-3-mercapto-5-pyridin-4-yl-4H- 52
1,2,4-triazoles
4.7 53
13C NMR data of 4-Arylidenamino-3-mercapto-5-pyridin-4-yl-
4H-1,2,4-triazoles
4.8 IR data of 4-Arylidenamino-3-mercapto-5-pyridin-4-yl-4H-1,2,4- 55
triazoles
5.1 Resistance inducing effect of 4-Arylidenamino-3-mercapto-5- 68
pyridin-4-yl-4H-1,2,4-triazoles on rice plants (var. Pusa basmati-
1) at 500 ppm concentration
5.2 Effect of potential resistance inducing 4-Arylidenamino-3- 69
mercapto-5-pyridin-4-yl-4H-1,2,4-triazoles on rice plants (var.
Pusa basmati-1) at 250 ppm concentration
5.3 Effect of potential resistance inducing 4-Arylidenamino-3- 69
mercapto-5-pyridin-4-yl-4H-1,2,4-triazoles on rice plants (var.
Pusa basmati-1) at 500 ppm concentration
5.4 Effect of potential resistance inducing 4-Arylidenamino-3- 69
mercapto-5-pyridin-4-yl-4H-1,2,4-triazoles on rice plants (var.
Pusa basmati-1) at 1000 ppm concentration
5.5 Quantitative changes in polyphenol content in rice plants treated 70
with 4-(Arylideneamino)-3-mercapto-5-pyridin-4-yl-4H-1,2,4-
triazoles
5.6 Quantitative changes in phenyl alanine ammonia Lyase (PAL) 71
content in rice plants treated with 4-Arylidenamino-3-mercapto-5-
pyridin-4-yl-4H-1,2,4-triazoles
5.7 Quantitative changes in peroxidase content in rice plants treated 72
with 4-Arylidenamino-3-mercapto-5-pyridin-4-yl-4H-1,2,4-
triazoles
6.1 Fungicidal activity of 4-Arylidenamino-3-mercapto-5-pyridin-4yl- 77
4H-1,2,4-triazoles against Rhizoctonia solani
6.2 Fungicidal activity of 4-Arylidenamino-3-mercapto-5-pyridin-4yl- 78
4H-1,2,4-triazoles against Fusarium moniliforme
8.1 Comparisons of microwave and conventional methods involved in 84
the synthesis
LIST OF FIGURES
Figure Title Page No.
No.
4.1 IR spectra of 4-(4-Methylbenzylidenamino)-3-mercapto- 59
5-pyridin-4-yl-4H-1,2,4-triazole (GS10)
4.2 1H NMR spectra of 4-(4-Methylbenzylidenamino)-3- 60
mercapto-5-pyridin-4-yl-4H-1,2,4-triazole (GS10)
4.3 13C NMR spectra of 4-(4-Methylbenzylidenamino) -3- 61
mercapto-5-pyridin-4-yl-4H-1,2,4-triazole (GS10)
4.4 Thiol-thione forms of 4-Arylidenamino-3-mercapto-5- 62
pyridin-4-yl-4H-1,2,4-triazoles
5.1 Sheath blight symptoms at 5 days after inoculation 65
5.2 Polyphenol content at 3 days after inoculation at 1000 70
ppm
5.3 PAL content at 3 days after inoculation at 1000 ppm 71
5.4 Peroxidase content at 3 days after inoculation at 1000 72
ppm
6.1 Fungicidal activity of 4-(4-Fluorobenzylidenamino)-3- 76
mercapto-5-pyridin-4-yl-4H-1,2,4-triazole against
Rhizoctonia solani
6.2 Fungitoxicity of of 4-Arylidenamino-3-mercapto-5- 78
pyridin-4-yl-4H-1,2,4-triazoles against Rhizoctonia solani
6.3 Fungitoxicity of of 4-Arylidenamino-3-mercapto-5- 79
pyridin-4-yl-4H-1,2,4-triazoles against Fusarium
moniliforme
1

1. INTRODUCTION

Agriculture, as the largest private enterprise in India, has been and will continue to be the
lifeline of the Indian economy at least in the forcible future. Despite great agricultural
advances in the past, million still go hungry, live under constant threat of famine. So, we
have to raise our production to feed the increasing population. Therefore, we should have
concentrated on food production up to 250 million tons by utilizing the untapped potentials.
We must ensure that the agriculture, which is the mainstay of our livelihood and ecological
security, is carried out in such a way that it can produce more but in a sustainable way.
There are two ways to improve the output of food production, by increasing the crop
productivity through adoption of high yielding variety cultivar and avoiding the crop failure
occurrence due to infestation of insect-pests, weeds, disease problem and post-harvest crop
losses. The overall crop losses by insect pests, plant diseases, and weeds in spite of modern
crop protection measures are as high as 50% (Devakumar and Kumar 2007; Dureja and
Gupta 2009). In India, the approximate crop losses due to pests and diseases are about 10-
30%. By taking an average loss of 20% and based on the present gross value of our
agriculture produce, the crop losses due to pests and diseases were estimated to be Rs
2,50,000 crores annually. So, we have to control the diseases, weeds, and insects to get
increased crop production. Use of plant protection chemicals is one of the most effective
control measures to manage the pests. Chemical crop protection therefore, will continue to
play an important role in agribusiness in spite of the emergence of novel biotechnological
solutions. Scientific progress in chemistry, biology, and molecular biology has
revolutionized the way of searching for new agrochemicals over the past decade. The search
for and the development of novel agrochemicals with new modes of action, improved safety
profiles, and adapted to the changing requirement of the food and feed production chain are
more than ever the challenge. Adequate crop protection with green chemicals will contribute
in the future to increase the yield per hectare and help to ensure food, feed, and fiber of high
quality.
Systemic Acquired Resistance (SAR) was first described as a response to pathogen
infection. Subsequently it has been found that treatment of plants with low molecular weight
molecules can also induce SAR. Natural signaling molecules SA (salicylic acid), JA
(Jasmonic acid), systemin and other elicitors, are the components of biological induction.
The use of chemicals to activate SAR provides novel alternatives for disease control in
agronomic system as well tools for the elucidation of the SAR signal transduction cascade
(Neuenschwander et al., 1995).Various chemicals have been discovered that seems to act at
various point in these defense activating networks and mimic all or parts of the biological
activation of resistance (Kessmann et al., 1994). To be considered an activator first, the