Insecticides of Plant Origin

221 Pages·1989·4.17 MB·English

by  J. T. Arnason

Insecticides of Plant Origin
In Insecticides of Plant Origin; Arnason, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
In Insecticides of Plant Origin; Arnason, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
ACS SYMPOSIUM SERIES 387
Insecticides of Plant Origin
J. T. Arnason,
EDITOR
University of Ottawa
B. J. R. Philogène,
EDITOR
Peter Morand,
EDITOR
University of Ottawa
Developed from a symposium sponsored
by the Division of Agrochemicals
of the American Chemical Society
at the Third Chemical Congress of North America
(195th National Meeting of the American Chemical Society),
Toronto, Ontario, Canada,
June 5-11, 1988
American Chemical Society, Washington, DC 1989
In Insecticides of Plant Origin; Arnason, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
Library of Congress Cataloging-in-Publication Data
Insecticides of plant origin.
(ACS Symposium Series; 387)
"Developed from a symposium sponsored by the
Division of Agrochemicals of the American Chemical
Society at the Third Chemical Congress of North America
(195th National Meeting of the American Chemical
Society, Toronto, Ontario, Canada, June 5-11, 1988)."
Includes bibliographies and indexes.
1. Botanical insecticides—Congress.
I. Arnason, J. T. II. Philogêne
(Peter) IV. American Chemica
Agrocnemicals. V. Series.
SB951.54.I57 1989 632'.951 89-85
ISBN 0-8412-1569-3
CIP
Copyright © 1989
American Chemical Society
All Rights Reserved. The appearance of the code at the bottom of the first page of each
chapter in this volume indicates the copyright owner's consent that reprographic copies
of the chapter may be made for personal or internal use or for the personal or internal
use of specific clients. This consent is given on the condition, however, that the copier
pay the stated per-copy fee through the Copyright Clearance Center, Inc., 27 Congress
Street, Salem, MA 01070, for copying beyond that permitted by Sections 107 or 108 of the
U.S. Copyright Law. This consent does not extend to copying or transmission by any
means—graphic or electronic—for any other purpose, such as for general distribution, for
advertising or promotional purposes, for creating a new collective work, for resale, or for
information storage and retrieval systems. The copying fee for each chapter is indicated in
the code at the bottom of the first page of the chapter.
The citation of trade names and/or names of manufacturers in this publication is not to
be construed as an endorsement or as approval by ACS of the commercial products or
services referenced herein; nor should the mere reference herein to any drawing,
specification, chemical process, or other data be regarded as a license or as a conveyance
of any right or permission to the holder, reader, or any other person or corporation, to
manufacture, reproduce, use, or sell any patented invention or copyrighted work that may
in any way be related thereto. Registered names, trademarks, etc., used in this publication,
even without specific indication thereof, are not to be considered unprotected by law.
PRINTED IN THE UNITED STATES OF AMERICA
In Insecticides of Plant Origin; Arnason, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
ACS Symposium Series
M. Joan Comstock, Series Editor
1989 ACS Books Advisory Board
Paul S. Anderson Mary A. Kaiser
Merck Sharp & Dohme Research Ε I du Pont de Nemours and
Laboratories
Michael R. Ladisch
Alexis T. Bell
Purdue University
University of California—Berkeley
John L. Massingill
Harvey W. Blanch
Dow Chemical Company
University of California—Berkeley
Daniel M. Quinn
Malcolm H. Chisholm
University of Iowa
Indiana University
James C. Randall
Alan Elzerman Exxon Chemical Company
Clemson University
Elsa Reichmanis
John W. Finley AT&T Bell Laboratories
Nabisco Brands, Inc.
C. M. Roland
U.S. Naval Research Laboratory
Natalie Foster
Lehigh University
Stephen A. Szabo
Conoco Inc.
Marye Anne Fox
The University of Texas—Austin Wendy A. Warr
Imperial Chemical Industries
G. Wayne Ivie
U.S. Department of Agriculture, Robert A. Weiss
Agricultural Research Service University of Connecticut
In Insecticides of Plant Origin; Arnason, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
Foreword
The ACS SYMPOSIUM SERIES was founded in 1974 to provide a
medium for publishing symposia quickly in book form. The
format of the Series parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that, in order to save time, the
papers are not typeset
by the authors in camera-ready Paper
the supervision of the Editors with the assistance of the Series
Advisory Board and are selected to maintain the integrity of the
symposia; however, verbatim reproductions of previously pub
lished papers are not accepted. Both reviews and reports of
research are acceptable, because symposia may embrace both
types of presentation.
In Insecticides of Plant Origin; Arnason, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
Preface
ILANT-DERIVED SUBSTANCES have been used as botanical pesticides
since ancient times. They were largely abandoned during the era of
synthetic pesticides, but now the study of natural pesticides contributes
novel approaches in control strategies for pests.
Botanical pesticides are plant natural products that belong to the
group of so-called secondary metabolites, which includes thousands of
alkaloids, terpenoids, phenolics d mino secondar chemicals Thes
substances have no know
basic aspects of plant physiology; however, their biological activity with
insects, nematodes, and phytopathogenic fungi, among other organisms,
is well-documented in the recent explosion of literature in chemical
ecology. Selective pressure exerted by plant pests has probably
contributed to the evolution of natural protective agents designed to
disrupt pest physiology. Apparently, almost every plant species has
developed a unique chemical complex (hat protects it from pests. Thus,
the plant kingdom offers us a diverse group of complex chemical
structures and almost every imaginable biological activity.
The discovery rate for new insecticides from synthetic sources has
declined in recent years. Furthermore, synthetic insecticides that share a
neurotoxic mode of action can lead to the development of cross
resistance in plants. Fortunately, we can find many new alternatives
within the large group of natural substances. In addition, many botanical
pesticides have the advantage of providing novel modes of action that
reduce the risk of cross resistance. Naturally occurring mixtures of
substances provide a multifactoral selective pressure that slows the
development of resistance in pests. More important, researchers in this
area have discovered subtle but effective mechanisms of pest control,
such as the behavior-modifying antifeedants, repellents, and oviposition
deterrents.
The symposium on which this book is based brought together
specialists from Africa and Asia, Europe and North America. Among the
chapters in this volume are historical, ethnobotanical reports about the
use of plants by native North Americans and accounts of traditional use
of plants by African and Asian farmers. Martin Jacobson, who has the
longest association of the authors with the field, describes the modern
history of botanicals and surveys the range of species investigated in
ix
In Insecticides of Plant Origin; Arnason, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
recent years. Among the new botanical pesticides examined in this
volume are acetogenins of the Annonaceae, agarofurans of the
Celastraceae, and limonoids of the Me/iaceoe. The authors deal with the
metabolism and toxicity of acetylchromenes in insects, electro­
physiological bases of antifeedant action of nonprotein amino acids, and
the repellent action of eugenol to stored grain pests.
Several chapters focus on the botanical pesticide, neem, which is
close to registration and has potent antifeedant and molt-inhibiting
properties and can move systemically in plants. Neem is used worldwide
and has a preliminary registration in the United States. Authors evaluate
its mode of action and performance under field conditions. The novel
phototoxic thiophenes, which arc exceptional larvicides of the malaria
mosquito, are described. Pipericides are the subject of a chapter about
synthetic approaches to developing highly active insecticides from a
promising lead. Transgeni
explored.
Acknowledgments
The symposium and book would have been impossible without the
support of a major grant from the Natural Sciences and Engineering
Research Council of Canada and generous support from Cyanamid
Canada Ltd., Safer Canada Ltd., the Chemical Institute of Canada, the
Canadian Society for Chemistry, and the American Chemical Society.
We are especially grateful to the many reviewers who contributed their
time and effort and to J. Pierce, who suggested the project.
J. T. ARNASON
B. J. R. PHILOGENE
PETER MORAND
University of Ottawa
Ottawa, Ontario K1N 6N5, Canada
December 14, 1988
χ
In Insecticides of Plant Origin; Arnason, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
Chapter 1
Botanical Pesticides
Past, Present, and Future
Martin Jacobson1
1131 University Boulevard West
Until the Second World War, the only botanical pesticides used in
the Western Hemisphere were pyrethrum, rotenone, nicotine,
sabadilla, and quassin. Rotenone is presently used only on a limited
number of crops due to its high toxicity to fish, and natural
pyrethrum from chrysanthemum flowers is employed mainly as a
rapid knockdown agent for crawling and flying insects affecting
man and animals. Nicotine, sabadilla, and quassin are seldom used
as pesticides today. Based on my 44 years of personal research
experience with several thousand plants of many families as
pesticides,it is my opinion that the most promising botanicals for
use at the present time and in the future are species of the families
Meliaceae, Rutaceae, Asteraceae, Malvaceae, Labiatae, and
Canellaceae; their research and applicability are reviewed.
From early Roman times to the mid-20th century, only pyrethrum, rotenone,
nicotine, sabadilla and quassin were widely used as insect repellents and toxicants
in the Western Hemisphere. The discovery of DDT, initially believed to be the
universal synthetic panacea from insect attack, proved after prolonged use to be
disastrous. Rachel Carson's "Silent Spring" in 1962 signalled DDT's practical
elimination due to its extreme persistence, toxicity, bioaccumulation, and tendency
to cause malignancy. This led to a frantic search for "safer" synthetics,
culminating in the chlorinated hydrocarbons (aldrin, dieldrin, chlordane, and
heptachlor). These compounds also proved to be unduly toxic, ecologically
disastrous, or induced insect resistance, and their use has either been severely
restricted or banned by the Environmental Protection Agency (EPA). In the search
for safer alternatives, attention has once again turned to botanicals.
Rotenone is presently used only on a limited number of crops due to its
high toxicity to fish, natural pyrethrum from chrysanthemum flowers is employed
mainly as a rapid knockdown agent for crawling and flying insects affecting man
and animals, and nicotine, sabadilla and quassin are rarely used today.
The most promising botanicals for use at the present time and in the future
are species of the families Meliaceae, Rutaceae, Asteraceae, Annonaceae,
Labiatae, and Canellaceae.
Retired from U.S. Department of Agriculture.
0097-6156/89/0387-0001$06.00/0
* 1989 American Chemical Society
In Insecticides of Plant Origin; Arnason, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
2 INSECTICIDES OF PLANT ORIGIN
MELIACEAE
The neem tree, Azadirachta indica A. Juss (synonym Melia azadirachta A. Juss),
also known commonly as "nim" or "margosa." is a sub-tropical tree native to the
arid areas of Asia and Africa. It is presently being cultivated in a number of
Central American and South American countries as well. Extracts of various parts
of the tree, but especially of the seeds, have been shown to possess feeding
deterrency, repellency, toxicity, and growth disruptive properties to numerous
species and stages of insects of many orders, and this has earned for the tree its
reputation as the "wonder tree". A comprehensive review of the entomological
properties of neem has been published (l).
A host of tetranortriterpenoids have been isolated and identified from
various parts of the tree, but the major entomologically active component is
azadirachtin, whose highly complicated structure was first reported by Zanno (2)
and Nakanishi (3) and most recently revised from the stereochemical standpoint
(4,5). Isomeric azadirachtin
et al (7,8).
Azadirachtin is effective as a feeding deterrent, repellent, toxicant, sterilant,
and growth disruptant for insects at dosages as low as 0.1 ppm. Homemade
formulations of neem seeds have been used by farmers in the developing countries
for many years and are receiving even greater use today. Although the molecular
complexity of azadirachtin probably precludes its synthesis in the near future, both
crude and partially purified extracts can be used for pest control and have been
shown to be safe for man and animals (Jacobson, M.; Ed., The Neem Tree, CRC
Press, Boca Raton, Florida, in press).
A commercial patent (9) has been issued describing the neem seed
formulation known as "Margosan-O" for use on nonfood crops and in nurseries, as
approved by EPA, and the improved preparation and marketing of neem
formulations in the United States seems to be assured.
The Chinaberry tree, Melia azedarach L., is frequently mistaken in the
literature for the neem tree. Although it occurs in much the same areas of the
world, its seeds contain several of the limonoids (10,11) common to neem seeds
except azadirachtin (10) and its extracts are insecticidally active (Larson, R.O.,
personal communication), chinaberry does not have a bright future as a pesticide
due to its extreme toxicity to warm-blooded animals.
Cedrela Odorata L., Spanish cedar. Ethanol extracts of the leaves roots, root
bark, or twigs of this tree are reported to prevent feeding by adult striped cucumber
beedes, Acalymma vittatum (Fabricius) in the greenhouse. Also effective in this
regard are extracts of the twigs, leaves, or roots of Ç. Toona Roxb. ex Rottl. &
Willd, the root bark of Carapa guianensis Aubl., and the leaves of Trichilia hispida
(Reed, D.K., personal communication).
Trichilia roka L. Limonoids (trichilins A-F) in the root bark are known to be
antifeedants for larvae of Spodoptera eridania (Cramer)(southern army worm), and
adult Epilachna varivestis Mulsant (Mexican bean beetle) (12). The limonoid
sendanin, isolated from the fruits (13), is a potent growth inhibitor for Heliothis
virescens Fabricius (tobacco budworm), Spodoptera frugiperda (J.E. Smith)(fall
army worm), and H. zea (Boddie)(corn earworm)(14).
Trichilia hispida Penning. Limonoids (hispidins A-C) were isolated from this
species (15-16).
Carapa procera DC. Three tetranortriterpenoids, designated "carapolides A, B, and
In Insecticides of Plant Origin; Arnason, J., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1989.