Synthesis and Chemistry of Agrochemicals II

610 Pages·1991·41.45 MB·English

by  Don R. Baker

A CS S Y M P O S I UM SERIES 443
Synthesis and Chemistry
of Agrochemicals II
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American Chemical Society, Washington, DC 1991
In Synthesis and Chemistry of Agrochemicals II; Baker, D., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
Library of Congress Cataloging-in-Publication Data
Synthesis and chemistry of agrochemicals II / Don R. Baker, editor,
Joseph G. Fenyes, editor, William K. Moberg, editor.
p. cm.—(ACS Symposium Series ; 443)
Includes bibliographical references and index.
ISBN 0-8412-1885-4
1. Pesticides—Synthesis—Congresses. 2. Herbicides—Synthesis—
1
0 Congresses. 3. Fungicides—Synthesis—Congresses. I. Baker, Don R.,
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by e: Copyright © 1991
aded n Dat American Chemical Society
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PRINTED IN THE UNITED STATES OF AMERICA
In Synthesis and Chemistry of Agrochemicals II; Baker, D., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
ACS Symposium Series
M. Joan Comstock, Series Editor
1990 ACS Books Advisory Board
V. Dean Adams John L. Massingill
Tennessee Technological Dow Chemical Company
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s.org 3.fw00 University Robert McGorrin
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s.a04 Paul S. Anderson Kraft General Foods
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10 Alexis T. Bell
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Doubli Imperial Chemical Industries
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Mary A. Kaiser
Ε. I. du Pont de Nemours and
Company Robert A. Weiss
University of Connecticut
Michael R. Ladisch
Purdue University
In Synthesis and Chemistry of Agrochemicals II; Baker, D., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
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, but are reproduced as they are submit
ted by the authors in camera-ready form. Papers are reviewed
under the supervision of the editors with the assistance of the
1
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s.a04 because symposia may embrace both types of presentation.
2 | http://pub21/bk-1991- Hpaopweresv earr,e nvoertb aactcimep terde.p roductions of previously published
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In Synthesis and Chemistry of Agrochemicals II; Baker, D., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
Preface
AGRICULTURAL CHEMISTRY IS A RICH INTERDISCIPLINARY HELD,
drawing on many aspects of fundamental and applied research.
Chemistry—including the synthesis of new molecules, isolation and
analysis of naturally occurring compounds and enzymes, and studies of
physicochemical processes to understand and predict structure-activity
relationships—lies at its center. However, the discipline reaches its
1 greatest heights when chemistry is integrated with biochemistry, biology,
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42 on June 16, 7, 1991 | doi: 1 dfIoner pAeaemdtn dtodhis tetioo nsana r,tme hs eteva ajntulidimddai reccd,io osanu gocsrfe i arcennuffsdlit c utaairbmcaoyleu clatyhn efudoms oseiads fot ersftyay a ff egeftrocyore c ashan nlemdem woeicsn catv hlesiarv.ol elnernymg aeegnsrt.oa Fcl hiqreusmta laiicntyadl.
89.163.35.December mhtaanavrtek cebhte ehemanvi ceian lrt ricosoednnut crdoerdla ,mm aaenttihdco ardlelsys.i satsa nnceew i sp rao dsuecritosu ws itthh riematp rtoov emda npyro ipmerptoiers
ed by Date: creTahtievsitey cthhaallte nbgreosu gahrte aaglsrooc ohpempoicrtaulsn ittioe st,h aenird wpree sdeon tn oletv deol uobft etfhfaicta cthye,
nloadation convenience, and safety will be channeled into making further improve
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cially chemists. Nor has there been a convenient source where interested
scientists outside the field could share in the goals, excitement, and tech
nological sophistication of agricultural chemistry. Much of the best work
in the field is either widely dispersed throughout the scientific literature
or disclosed only in patent applications, and many excellent and informa
tive studies are never published because they are not commercially suc-
xi
In Synthesis and Chemistry of Agrochemicals II; Baker, D., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
cessful. This dearth of published works is especially unfortunate for chem
ists, because most chemists are not trained specifically in agricultural
chemistry but begin their careers with a more specialized background in
one of the field's many component disciplines, particularly organic syn
thesis. Most agricultural chemists must learn on the job, and thus the
experience of others has great value. The greatest value lies in detailed
outlines of individual projects, each of which offers its own important
nuances; by studying these projects, the researcher can develop an instinc
tive feel for the discipline seldom available from general reviews.
In 1984 these considerations prompted us to organize a series of sym
posia sponsored by the American Chemical Society's Division of Agro
chemicals. Titled "Synthesis and Chemistry of New Agrochemicals," these
1 symposia had two primary objectives: to give chemists an ongoing and
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3.35.mber covering the entire spectrum of herbicides, plant growth regulators, insec
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ed by Date: Creative Invention, for choosing to present his award address as part of
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Doubli fonylurea herbicide chemistry.
P In the following chapters, stimulating chemistry is integrated with
discovery strategies, biochemical studies, and biological testing in the
greenhouse and the field. Each story is interesting in itself. Taken
together, however, they show the innovative use of chemistry to solve
important agricultural problems and give the best view available of the
current status of the field
Our ultimate hope for this publication is the same as that stated in the
preface of our earlier volume: to contribute to the successful partnership
between chemistry and agriculture by providing an overview of the chemi
cal and biochemical tools available for agrochemical discovery and by
xii
In Synthesis and Chemistry of Agrochemicals II; Baker, D., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
sharing viewpoints of many scientists from around the world. We thank
the authors and their supporting organizations for making this concept a
reality.
DON R. BAKER
ICI Americas, Inc.
Richmond, CA 94804
JOSEPH G. FENYES
Buckman Laboratories International, Inc.
Memphis, TN 38108
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xiii
In Synthesis and Chemistry of Agrochemicals II; Baker, D., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
Chapter 1
Trends in the Synthesis and Chemistry
of Agrochemicals
William K. Moberg1, Don R. Baker2, and Joseph G. Fenyes3
1E. I. du Pont de Nemours and Company, Stine-Haskell Research Center,
Newark, DE 19714
2ICI Americas, Inc., 1200 South 47th Street, Richmond, CA 94804
3Buckman Laboratories International, Inc., 1256 North McLean Boulevard,
1 Memphis, TN 38108
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42 on 7, 199 iinn crleusdpionngs er etgou rlaaptoidry c hpaonlgicei eisn, ortehseirs tfaonrccee s oafff epcetsintsg itto,
3.35.mber chemical control, and rising standards in the market
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ed by Date: what may be expected in the near future.
oadon
wnlcati In accepting the Nobel Prize for contributions to organic synthesis,
Dobli the late R. B. Woodward expressed the opinion that synthesis "... is
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more readily ~ and I dare say more effectively — exemplified and
epitomized than it is articulated and summarized" (JJ. We feel the
same is true for discovering and optimizing new agrochemicals. No
general discussion can be more than a reflection of the particular
circumstances of each individual adventure. Moreover, only by
studying specific case histories, commercially successful or not,
can agricultural chemists develop the instinctive "feel" that so often
lies behind creative leaps from the known to the new. These con
siderations have inspired the current volume, its predecessor (2),
and the ongoing ACS Agrochemicals Division Symposium Series on
which they are based.
This being said, it is still true that trends can be observed in
agricultural chemistry, and in the forces shaping it. The previous
0097-6156/91/0443-0001$06.00/0
© 1991 American Chemical Society
In Synthesis and Chemistry of Agrochemicals II; Baker, D., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.
2 SYNTHESIS AND CHEMISTRY OF AGROCHEMICALS Π
volume in this series provided an overview of how the field evolved
from reliance on inorganic compounds, through the beginnings of
organic crop protection chemistry in the 1940s, to the complexity
of the mid-1980s (3). In this chapter we discuss developments of
the intervening years, the current state of discovery strategies,
unsolved agronomic problems, and future prospects for agricultural
chemistry.
Developments in Technology
Though this book has synthesis as its central theme, it is evident in
almost every chapter that progress depends on integrating all avail­
able technology. Indeed, this integration is one of the dominant
trends in agrochemistry today. Thus the brief review that follows
1
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org ch0 and selected areas deserving more attention.
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42 on June 16, 7, 1991 | doi: 1 bpMeroectocaTemlhsaeset iaoc cnhpa,e ormwdeiiessnrptafreuly cl ititarsole olnayl,dr g ahuseta otbiedllrlayuoy sa uttroisanemt e-oaddgf i trrohoerrccgohtaueengdmo hmoiclueiattt la htlihldaieicts icsosuonplv efeco(2rinyeJys , l auh(nrSdae)as .
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Of equal potential are stereo-controlled reactions. The impor
tance of relative and absolute stereochemistry in agrochemicals,
first addressed extensively for pyrethroids (15.16). is now well rec
ognized for many classes (17). Indeed, since the activity of most
chiral compounds resides in one enantiomer, a lively debate is
forming over whether the "isomeric ballast" of racemates should be
tolerated in agrochemical registration (18). This, combined with
economic incentives for eliminating inactive isomers, will doubtless
encourage increased use of asymmetric synthesis (19). including
the rapidly developing area of enzymatic and microbial transfor
mations (20-26).
Other significant trends include the "taming" of radical chem
istry (27-29). continuing improvements in protecting group
chemistry (4,30), and new methods for fluorination (31; Haga et âL.
In Synthesis and Chemistry of Agrochemicals II; Baker, D., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1991.