Natural Products. Proceedings of the 5th International Congress of Pesticide Chemistry, Kyoto, Japan, 29 August – 4 September 1982

360 Pages·1983·26.269 MB·English

by  N. Takahashi, H. Yoshioka and T. Misato (Eds.)

Some Other IUPAC Titles of Interest from Pergamon Press
IUPAC Symposium Series
BENOIT & REMPP: Macromolecules
BRITTON & GOODWIN: Carotenoid Chemistry and Biochemistry
BROWN & DA VIES: Organ-Directed Toxicity — Chemical Indices and Mechanisms
CIARDELLI & GIUSTI: Structural Order in Polymers
FREIDLINA & SKOROVA: Organic Sulfur Chemistry
LAIDLER: Frontiers of Chemistry (Proceedings of the 28th IUPAC Congress)
NOZAKI: Current Trends in Organic Synthesis
ST-PIERRE & BROWN: Future Sources of Organic Raw Materials (CHEMRAWN I)
SHEMILT: Chemistry & World Food Supplies (CHEMRAWN II)
STEC: Phosphorus Chemistry Directed Towards Biology
TROST & HUTCHINSON: Organic Synthesis — Today and Tomorrow
IUPAC Nomenclature Guides
IRVING, FREISER & WEST: Compendium of Analytical Nomenclature
IUPAC: Nomenclature of Inorganic Chemistry & How to Name an Inorganic
Substance (2-part set)
RIGAUDY & KLESNEY: Nomenclature of Organic Chemistry
WHIFFEN: Manual of Symbols & Terminology for Physicochemical Quantities
and Units
Journals
CHEMISTRY INTERNATIONAL — IUPAC's international news magazine.
PURE AND APPLIED CHEMISTRY — IUPAC's official journal, featuring proceedings
of IUPAC conferences, nomenclature rules and technical reports.
INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY
(Applied Chemistry Division)
PESTICIDE CHEMISTRY:
HUMAN WELFARE
AND THE ENVIRONMENT
Proceedings of the 5th International Congress of Pesticide Chemistry,
Kyoto, Japan, 29 August - 4 September 1982
Editors-in-Chief
J. MIYAMOTO
Pesticides Division, Sumitomo Chemical Co., Ltd.
Takarazuka, Hyogo, Japan
and
P. C. KEARNEY
Agricultural Environmental Quality institute, US Department of Agriculture,
Beltsville, Maryland, USA
Volume 2
NATURAL PRODUCTS
Volume Editors
N. TAKAHASHI
Department of AgricuituraJ Chemistry, University of Tokyo, Japan
H. YOSHIOKA
Sumitomo Chemical Co., Ltd., Takarazuka, Japan
T. MISATO
institute of Physical & Chemical Research, Wako, Japan
and
S. MATSUNAKA
Kobe University, Japan
PERGAMON PRESS
OXFORD · NEW YORK · TORONTO · SYDNEY · FRANKFURT
U.K. Pergamon Press Ltd., Headington Hill Hall,
Oxford 0X3 OBW, England
U.S.A. Pergamon Press Inc., Maxwell House, Fairview Park,
Elmsford, New York 10523, U.S.A.
CANADA Pergamon Press Canada Ltd., Suite 104,
150 Consumers Road, Willowdale, Ontario M2J 1P9, Canada
AUSTRALIA Pergamon Press (Aust.) Pty. Ltd., P.O. Box 544,
Potts Point, N.S.W. 2011, Australia
FEDERAL REPUBLIC Pergamon Press GmbH, Hammerweg 6,
OF GERMANY D-6242 Kronberg-Taunus, Federal Republic of Germany
Copyright © 1983 International Union of Pure and
Applied Chemistry
All Eights Reserved. No part of this publication may be
reproduced, stored in a retrieval system or transmitted in
any form or by any means: electronic, electrostatic,
magnetic tape, mechanical, photocopying, recording or
otherwise, without permission in writing from the
copyright holders.
First edition 1983
Reprinted 1985
Library of Congress Cataloging in Publication Data
International IUPAC Congress of Pesticide Chemistry
(5th: 1982: Kyoto, Japan)
Pesticide chemistry, human welfare and the environ
ment.
(IUPAC symposium series)
At head of title: International Union of Pure and
Applied Chemistry. Applied Chemistry Division.
Congress organized by The Science Council of Japan,
Pesticide Science Society of Japan, and the Japan
Plant Protection Association.
Includes bibliographical references.
1. Pesticides—Congresses. I. Miyamoto, J.
(Junshi) II. Kearney, P. C. (Philip C), 1932-
III. International Union of Pure and Applied Chemistry.
Applied Chemistry Division. IV. Nihon Gakujutsu
Kaigi. V. Nihon Noyaku Gakkai. VI. Nihon Shokubutsu
Boeki Kyokai. VII. Title. VIII. Series. [DNLM:
1. Pesticides—Congresses. 2. Pesticide—Residues—
Congresses. 3. Toxicology—Congresses. 4. Pest
control—Congresses. WA 240 P4738)
SB950.93.I57 1982 632'.95 82-24602
British Library Cataloguing in Publication Data
International Congress of Pesticide Chemistry: {5th:
1982: Kyoto) Pesticide chemistry.
1. Pesticides. Environmental aspects—Congresses
I. Title II. Miyamoto, J. III. Keaney, P. C.
IV.International Union of Pure and Applied Chemistry.
Applied Chemistry Division
632'.95042 QH545.P4
ISBN 0 08 029219 4 (4 vol set)
ISBN 0 08 029223 2 (volume 2)
in order to make this volume available as economically
and as rapidly as possible the authors' typescripts have
been reproduced in their original forms. This method
unfortunately has its typographical limitations but it is
hoped that they in no way distract the reader.
Printed in Great Britain by A. Wheaton & Co. Ltd., Exeter
Organizing Committee
Chairman: M. Nakajima
Vice Chairman: H. Fukami
Secretary General: T. Misato
Members: T. Endo, M. Eto, T. Fujita, S. Goto, T. Hosotsuji, W. Iida, T. Iwata,
A. Kawana, K. Koshimizu, N. Kurihara, S. Kuwatsuka, S. Matsunaka, T. Mitsui,
J. Miyamoto, J. Mizutani, K. Munakata, M. Saito, T. Saito, N. Takahashi,
S. Takahashi, T. Tanaka, M. Uchiyama, K. Ueki, T. Ueno, I. Yamamoto,
K. Yamashita, K. Yasutomi
Scientific Programme Committee
Chairman: J. Miyamoto
Vice Chairman: P. C. Kearney
Members: P. Doyle, N. Drescher, T. Fujita, S. Goto, R. Greenhalgh, D. H. Hutson,
S. Kuwatsuka, S. Matsunaka, S. D. Murphy, N. Takahashi
Congress Organizers
The Science Council of Japan
Pesticide Science Society of Japan
Japan Plant Protection Association
INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY
IUPAC Secretariat: Bank Court Chambers, 2-3 Pound Way,
Cowley Centre, Oxford 0X4 3YF, UK
PREFACE
The Fifth international Congress of Pesticide Chemistry, sponsored by the International
Union of Pure and Applied Chemistry, and organized jointly by the National Science Council
of Japan, Pesticide Science Society of Japan and Japan Plant Protection Association, was
held at Kyoto International Conference Hall in Kyoto, Japan, 29 August - 4 September
1982. The opening of the Congress culminated four years of intensive planning by the
Scientific Programme Committee, the Organizing Committee, and a host of internationally
recognized scientists dedicated to pesticide chemistry. The main theme of the Congress,
Human Welfare — Environment — Pesticides, was intended to encompass current research
topics in pesticide chemistry, not only for increased agricultural production, but also
for public health purposes. Xenobiotics other than pesticides were also included. One
thousand, six hundred scientists from 55 countries attended the Congress.
Two distinguished scientists, Professor Dr. K. H. Büchel, Bayer AG, Leverkusen, FRG, and
Dr. I. J. Graham-Bryce, East Mailing Research Station, UK, presented plenary lectures
dealing with political, economic and philosophical aspects of pesticide use, as well as
future pesticide research for improving human welfare. A number of distinguished invitees
also addressed the Congress participants, including the President of IUPAC, Professor
S. Nagakura.
Eight main topics were selected as the subjects of the Congress, either because of their
timely nature or because the area needs critical review. They included: Synthesis of
Pesticides and Growth Regulators; Chemical Structure and Biological Activity; Bioactive
Natural Products: Chemistry, Biochemistry and Physiology; Biochemistry of Pests and Mode
of Action of Pesticides (including Mechanism of Resistance and Phytotoxicity); Metabolism
and Degradation of Pesticides and Xenobiotics; Toxicology of Pesticides and Xenobiotics;
Pesticide Residues and Methodology; and Formulation Chemistry. Each main topic included
one symposium and several poster-discussion sessions.
Each symposium consisted of several invited presentations, providing the participants with
current and provocative overviews on important aspects of the respective topics.
Poster-discussion sessions constituted the main body of presentations to the Congress and
were intended to cover a wide variety of areas. Each included a few invited papers in
addition to the contributed papers. Invited scientists served as leaders during the
follow-up discussion after the poster presentations. Overall the Congress was organized
into 49 sessions under the eight main topics with 694 submitted papers, including 236
invited papers.
In addition to the eight main topics encompassed by the Congress, three complementary
symposia dealing with related subjects were held simultaneously, with 31 invited
presentations: Pyrethroid Insecticides — Biological Activity, Mode of Action, Metabolism
and Toxicology; Antibiotics for Agricultural Use; and Herbicides and Plant Growth
Regulators for Rice Culture.
The proceedings of the Congress, entitled Pesticide Chemistry: Human Welfare and the
Environment, comprise four volumes containing over 250 invited papers presented at the
symposia, complementary symposia, and poster-discussion sessions. Specifically, the
contents are: Volume 1: plenary lectures, synthesis, structure-activity; Volume 2: natural
products, complementary symposia; Volume 3: mode of action, metabolism and degradation,
toxicology; and Volume 4: residue analysis, formulation chemistry. It is sincerely hoped,
by this overview of the present status of chemical and biochemical pest control, that
readers gain an appreciation of how pesticide science continues to contribute to human
welfare.
Junshi Miyamoto
Philip C. Kearney
IX
Bioactive Natural Products: Recent Status of Research
RECENT PROGRESS IN RESEARCH ON
AGRICULTURAL ANTIBIOTICS IN JAPAN
Noboru Ötake
institute of Applied Microbiology, University of Tokyo, Japan
Abstract - The current status and most recent works on agricultural
antibiotics developed in Japan are reviewed primarily in connection with
the control of plant disease, but also briefly with the livestock disease
and promotion of growth.
The use of antibiotics as protectants against plant pathogen was considered a rather novel
idea around 1953-195*+, however, the discovery since then of blasticidin S (Ref, 1,2,3) and
its successful use for control of rice blast disease has stimulated extensive investigations
by many research organizations in Japan for new antibiotics effective against various kind of
plant disease. As a result, more than twenty new compounds have been developed as protec­
tants against plant pathogen during the past twenty years. In this area, Japan has played a
pioneering role in the world in development of antibiotics used specifically for the control
of individual plant pathogens. Eventually, in this relatively short time, the term
"agricultural antibiotics" was used to refer to such compounds used for the control of pests
in the field of agricultural production.
This talk, in which the current status and most recent works on the new antibiotics are
reviewed, deals primarily with the control of plant disease, but also refers briefly to
compounds used in a broad sense in agrigultural production,
It should be emphasized here that the extensive progress in agricultural antibiotics, in
Japan is closely related to the feature of agricultural production namely, type of intensive
farming in this country. Therefore, it is natural that in the first instance, a great
stimulus to this type of research arose from the need to control the three big pathogens
in rice production, namely, rice blight disease caused by Pyrioularia oryzae, rice sheath
blight caused by Rhizoctonia solani and bacterial leaf blight caused by Xanthomonas oryzae.
Inevitably, unless the cost of using antibiotics for disease control will allow a normal
profit margin to farmers, their use will be restricted: the success of blasticidin S as the
first case indicated that they can economically be used in practice,
It is necessary to consider the background and progress on the discovery of agricultural
antibiotics in Japan.
Screening for antibiotics that can be applied in plant disease control is a problem of
considerable difficulty. Although screening tests in vitro have indicated effectiveness
against the target pathogen of a number of antibiotics in vivo tests have usually failed to
?
coroborate the foregoing results. In the past, the screening tests used have consisted of
determing the MIC of the antibiotic materials in vitro by a disc-plate method against fungal
pathogens, The use of usual tests have, in many cases, resulted in the detection of a number
of known antifungal antibiotics such as polyene macrolides, antimycins and oligomycins which
have no practical value for the use of plant disease control because of their phytotoxicity
or instability,
Fig. 1. By use of direct-spray tests of antibiotic samples against rice plants infected
with Pyrioularia oryzae.
3
4 N. Otake
It is noteworthy that improvement in screening procedures have been of great importance in
discovery of antibiotics having satisfactory effects against target pathogens. For example,
blasticidin S was discovered by a direct-spraying method in the green house, shown in Fig, 1,
which was developed for the first time by the pioneering researchers, Professors Y. Sumiki
and H. Yonehara of Tokyo University in collaboration with Drs. K. Fukunaga and T. Misato of
the National Institute for Agricultural Science. In the same way, kasugamycin could never
have been discovered by the usual in vitro tests because this compound showed only a weak
activity against Pyricularia oryzae by the plate-assay method, thus, no discernible inhi­
bitory zone was observed, (Ref, U,5,6)
In practice, considerable amounts of both blasticidin S and kasugamycin are used in treatment
of rice blast disease in Japan as well as in Korea and South America.
NH2
N^
.0O^N
"00C , HOJ
HOOC— C — HN
* r*
NH HoifV
NH IMH2 0
Blasticidin S Kasugamycin
Despite the enormous efforts made up to the present time, nothing has been evaluated as
better than these two antibiotics as an eradicant against rice blast disease, although a
number of new antibiotics have been isolated.
Next, I would like to talk about the control of rice sheath blight. This blight caused by
infection with the pathogen Rhizoctonia solani is widespread in Japan as well as in various
rice cultivating areas of South Asia, and brings about severe economic losses among rice
producers.
ROC
2
COHNCH/0^1
"y*3 OH ό
HOCH 9
•
CH4000NH2 Ri R2 R3 ΗΝ^γ-ΟΗίΟΗ
Polyoxin A CH2OH X OH
*°9 Ο^Ν^
B CH 0H HO OH 1
2 HzNCH/O.
D COOH HO OH
Vf
E COOH HO H
F COOH X OH OH OH
G CH OH HO H Pölyoxin C R = HO
2
H CH X OH 1 R=X
3
J CH HO OH
3
COOH
K H X OH
L H HO OH ( X
Fig, 2. The Structures of Polyoxin Complex
Progress in Agricultural Antibiotics Research in Japan 5
The first success was attained by the discovery of the polyoxin complex from Streptomyoes
eacaoi var. asoensis by Suzuki et al. (Ref. 7,8,9) of the Institute of Physical and Chemical
Research, who initiated early attempts to develop control agents for this blight. The
polyoxin complex contained a numbered of active components whose structures were shown to be
unique nucleosides as depicted in Fig. 2. Among these, polyoxin D has been used in the
field as the zinc chelate to control rice sheath blight. Other components will be discussed
later such as polyoxin A and polyoxin B, which are also used to control brown spot in
tobacco and leaf spot in apple caused by Altemaria pathogens.
In 1970, Iwasa et al, (Ref. 11,12,13,1*0 were led to the discovery of validamycin by direst
-spray tests of cultured broths from a strain of Streptomyoes hygro»scopious. Validamycins
drastically reduced sheath blight infections on rice plant and this agent has been used in
Japan under the trade name of "validacin". Chemical studies revealed that validamycins were
a complex mixture containing a number of active congeners closely related in structure.
CH,
J—c\ 9CH3
I—INN H-^JV
HOCH2 0 HO" N'
H
SF-1917
Among these validamycin A is a major component. It is of great interest that validamycins
belong to a new class of aminoglycoside antibiotics found for the first time in nature.
They are characterized by their very low toxicity and high specificity against a wide range
of plant diseases caused by R. solani and more than 8700 tons of formulated preparations are
used each year in Japan so far.
More recently, Niida et al. (Ref. l6,17) have detected by screening a new antifungal antibio­
tic SF-1917, produced by a strain of Micromonospora sp., which shows very promising effects
in control of rice sheath blight. The structure of SF-1917 was shown to belong to an
unusual class of nucleoside containing the 7-desazaguanine nucleus. SF-1917 exhibits potent
activity against sheath blight disease of rice plants and is in the process of development.
The third blight of rice plant, bacterial leaf blight, is caused by infection with
Xanthomonas oryzae. This blight causes withering of leaves at the time of fruiting and rice
producing areas have been infected by this blight all over the world,
Although various agents were found to be active in vitro so far, none of them has been shown
HOH2C
OH OH
Laurusin (Formycin B)
6 N. Otake
to be effective both in vivo and in the field. Although laurusin (formycin B) were discover­
ed during the search for control agents for this blight, their practical use is not possible
due to its toxicity (Ref. l8), thus an antibiotic effective against bacterial leaf blight is
still greatly to be desired and earnest efforts to find one continue in many research
organizations in Japan.
So far, I have been discussing mainly the diseases of rice plant, but now I wish to extend
my comments to diseases of fruit trees, vegetables, various garden and decorative plants.
Polyoxin B (Fig, 2) is effective against various kinds of blasts in fruit trees, vegetables
and tobacco plant caused by pathogens of the Alternaria species and it is now in commercial
use.
Powdery mildew is a troublesome disease which attacks various plants closely involved with our
daily life. In the rainy season of early Summer, we can often see rose trees and other Rosa
plants covered with white powder: This is actually caused by an Asoomycetes fungi,
Sphaerotheca pannosa, and the artificial cultivation of this pathogen has not yet been achiev­
ed.
A substance effective against this fungus was discovered by Iwasa et al, (Ref, 19,20) in
mildiomycin, This agent is also a new antibiotic containing the 5-hydroxymethylcytosine
nucleus in the molecule. It should be emphasized here that this agent is highly effective
against a wide range of powdery mildew in more than 150 kinds of plants including fruit
trees, vegetables, wheat etc. Its development as a new agricultural antibiotic is eagerly
awaited,
NH
t
-CH0H
2
OH °:f
.or
H3N-1V
NH
HOC^HCONhN-^"
NH
2
Mildiomycin
It is important to note here that the knowledge we have so far obtained from investigations
on the action mechanisms of new antibiotics has revealed to us the presence of many metabolic
pathways involving participation by many enzyme systems of which we were previously unaware
or which were completely unknown before. These systems can be used as new assay systems,
thus leading to further discovery of new compounds. Some examples of such use are discussed
below,
COOH
I
HOOC CH2 CH2OH
I CH OC ■HN-CH-CO-NH-CH-CO-NH
0=C-HNCH 3 L L I
I f CHsCHgCHiCh^oCO-HN-CH L L CI H-CH2OH
H2N-CH H3C-CH CO
I I
HC-CH3 0 N-CH3
HC-OH I CH-CH2-CONH2
CO CO
HOOC- CH2CH2-HC^^^K)C-HC--HN--CO-CH-N-CH3
CHOH CH2
I
CH2
I
CONH2
Neopolyoxin A·'
Neopolyoxin B: Lipopeptin A
Progress in Agricultural Antibiotics Research in Japan 7
In a search for inhibitors of cell wall biosynthesis, Isono et al. (Ref. 22,23,2*+,25) have
discovered a number of active compounds by using an assay of a chitin-synthetase system.
Neopolyoxins are produced by Streptomyoes oaoaoi var, asoensis (the same organism as produces
polyoxins) and of these, neopolyoxin A is effective against Sphaerotheoa fuliginea in green
house tests. In a similar way, use of a proteo-heteroglycan enzyme system led to the
detection and isolation of lipopeptins from Streptomyoes violaceoohromogenes, which showed an
effect against powdery mildew in cucumber. Moreover, they have discovered neopeptins recently
from a strain of unidentified Streptomyoes sp., which are also effective against Sf fulginea,
Omura et al, (Ref, 26) have discovered irumamycin from Streptomyoes sp., which was elucidated
as a new member of macrolide antibiotics effective against gray mold disease caused by
Botritis oinera,
Capsimycin discovered by Aizawa et al. (Ref, 27) is active against damping-off of cucumber by
Phytophtora oaps-isoi. Its structure has been elucidated as a unique polyketide containing
the tetramic acid nucleus as chromophore. (Ref. 28)
Capsimycin _> Hygrolidin
OH
Among the damage to fruit trees, apple canker disease caused by invasion of the pathogenic
fungi, Valsa oeratosperma is one of the most severe economic loss in Japan, We have
recently discovered hygrolidin which inhibits germination of the pathogen at a concentration
as low as 5 meg/ml,