Handbook of Natural Pesticides: Pheromono, Part B, Volume IV 9780429945274, 0429945272, 978-1-138-59700-6, 978-0-429-48720-0

Table of contents :
Content: Cover
Title Page
Copyright Page
INTRODUCTION
FOREWORD
PREFACE
THE EDITORS
Table of Contents
Part B
Pheromones of Diptera
Pheromones of Hymenoptera and Isoptera
Pheromones of Hemiptera, Blattodea, Orthoptera, Mecoptera, Other Insects, and Acari
Index

Citation preview

CRC Series in Naturally Occurring Pesticides Series Editor-in-Chief

N. Bhushan Mandava

Handbook of Natural Pesticides: Methods Volume I: Theory, Practice, and Detection Volume II: Isolation and Identification Editor

N. Bhushan Mandava

Handbook of Natural Pesticides Volume III: Insect Growth Regulators Volume IV: Pheromones Editors E. David Morgan

N. Bhushan Mandava

Future Volumes

Handbook of Natural Pesticides Insect Attractants, Deterrents, and Defensive Secretions Editors E. David Morgan

N. Bhushan Mandava

Plant Growth Regulators Editor

N. Bhushan Mandava

Microbial Insecticides Editors

Carl M. Ignoffo

CRC Handbook of Natural Pesticides V olum e IV

Pheromones Part B Editors

E. D avid M organ, D .P h il.

N . Bhushan M andava, P h .D .

Reader Department of Chemistry University of Keele Staffordshire, England

Senior Partner Todhunter, Mandava and Associates Washington, D.C.

CRC Series in Naturally Occurring Pesticides Series Editor-in-Chief N . Bhushan M andava, P h .D .

Boca Raton London New York

CRC Press is an imprint of the Taylor & Francis Group, an informa business

First published 1988 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 Reissued 2018 by CRC Press © 1988 by Taylor & Francis Group. CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www. copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Publisher's Note The publisher has gone to great lengths to ensure the quality of this reprint but points out that some imperfections in the original copies may be apparent. Disclaimer The publisher has made every effort to trace copyright holders and welcomes correspondence from those they have been unable to contact. ISBN 13: 978-1-138-59700-6 (hbk) ISBN 13: 978-0-429-48720-0 (ebk) Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com

CRC Handbook Series in Naturally Occurring Pesticides INTRODUCTION The United States has been blessed with high quality, dependable supplies of low cost food and fiber, but few people are aware of the never-ending battle that makes this possible. There are at present approximately 1,100,000 species of animals, many of them very simple forms, and 350,000 species of plants that currently inhabit the planet earth. In the U.S. there are an estimated 10,000 species of insects and related acarinids which at sometime or other cause significant agricultural damage. Of these, about 200 species are serious pests which require control or suppression every year. World-wide, the total number of insect pests is about ten times greater. The annual losses of crops, livestock, agricultural products, and forests caused by insect pests in the U.S. have been estimated to aggregate about 12% of the total crop production and to represent a value of about $4 billion (1984 dollars). On a world-wide basis, the insect pests annually damage or destroy about 15% of total potential crop production, with a value of more than $35 billion, enough food to feed more than the population of a country like India. Thus, both the losses caused by pests and the costs of their control are considerably high. Insect control is a complex problem for there are more than 200 insects that are or have been subsisting on our main crops, livestock, forests, and aquatic resources. Today, in the U.S., conventional insecticides are needed to control more than half of the insect problems affecting agriculture and public health. If the use of pesticides were to be completely banned, crop losses would soar and food prices would also increase dramatically. About 1 billion pounds of pesticides are used annually in the U.S. for pest control. The benefits of pesticides have been estimated at about $4/$l cost. In other words, chemical pest control in U.S. crop production costs an estimated $2.2 billion and yields a gross return of $8.7 billion annually. Another contributing factor for increased crop production is the effective control of weeds, nematodes, and plant diseases. Crop losses due to unwanted weed species are very high. Of the total losses caused by pests, weeds alone count for about 10% of the agricultural production losses valued at more than $12 billion annually. Farmers spend more than $6.2 billion each year to control weeds. Today, nearly all major crops grown in the U.S. are treated with herbicides. As in insect pest and weed control programs, several chemicals are used in the disease programs. Chemical compounds (e.g., fungicides, bactericides, nematicides, and viracides) that are toxic to pathogens are used for controlling plant diseases. Several million dollars are spent annually by American farmers to control the diseases of major crops such as cotton and soybeans. Another aspect for improved crop efficiency and production is the use of plant growth regulators. These chemicals that regulate the growth and development of plants are used by farmers in the U.S. on a modest scale. The annual sale of growth regulators is about $130 million. The plant growth regulator market is made up of two distinct entities — growth regulators and harvest aids. Growth regulators are used to increase crop yield or quality. Harvest aids are used at the end of the crop cycle. For instance, harvest aids defoliate cotton before picking or desiccate potatoes before digging. The use of modem pesticides has accounted for astonishing gains in agricultural production as the pesticides have reduced the hidden toll exacted by the aggregate attack of insect pests, weeds, and diseases, and also improved the health of humans and livestock as they control parasites and other microorganisms. However, the same chemicals have allegedly posed some serious problems to health and environmental safety, because of their high toxicity and severe persistence, and have become a grave public concern in the last 2 decades. Since the general public is very much concerned about their hazards, the U.S. Environmental

Protection Agency enforced strong regulations for use, application, and handling of the pesticides. Moreover, such toxic pesticides as DDT, 2,4,5-T and toxaphene were either completely banned or approved for limited use. They were, however, replaced with less dangerous chemicals for insect control. Newer approaches for pest control are continuously sought, and several of them look very promising. According to a recent study by the National Academy of Sciences, pesticides of several kinds will be widely used in the foreseeable future. However, newer selective and biode­ gradable compounds must replace older highly toxic persistent chemicals. The pest control methods that are being tested or used on different insects and weeds include: (1) use of natural predators, parasites, and pathogens, (2) breeding of resistant varieties of species, (3) genetic sterilization techniques, (4) use of mating and feeding attractants, (5) use of traps, (6) development of hormones to interfere with life cycles, (7) improvement of cultural practices, and (8) development of better biodegradable insecticides and growth regulators that will effectively combat the target species without doing damage to beneficial insects, wildlife, or man. Many leads are now available, such as the hormone mimics of the insect juvenile and molting hormones. Synthetic pyretheroids are now replacing the conventional insecticides. These insecticides, which are a synthesized version of the extract of the pyrethrum flower, are much more attractive biologically than the traditional insecticides. Thus, the application rates are much lower in some cases, one tenth the rates of more traditional insecticides such as organophosphorus pesticides. The pyrethroids are found to be very specific for killing insects and apparently exhibit no negative effects on plants, livestock, or humans. The use of these compounds is now widely accepted for use on cotton, field com, soybean, and vegetable crops. For the long term, integrated pest management (IPM) will have tremendous impact on pest control for crop improvement and efficiency. Under this concept, all types of pest control — cultural, chemical, inbred, and biological — are integrated to control all types of pests and weeds. The chemical control includes all of the traditional pesticides. Cultural controls consist of cultivation, crop rotation, optimum planting dates, and sanitation. Inbred plant resistance involves the use of varieties and hybrids that are resistant to certain pests. Finally, the biological control involves encouraging natural predators, parasites, and microbials. Under this system, pest-detection scouts measure pest populations and determine the best time for applying pesticides. If properly practiced, IPM could reduce pesticide use up to 75% on some crops. The naturally occurring pesticides appear to have a prominent role for the development of future commercial pesticides not only for agricultural crop productivity but also for the safety of the environment and public health. They are produced by plants, insects, and several microorganisms, which utilize them for survival and maintenance of defense mech­ anisms, as well as for growth and development. They are easily biodegradable, often times species-specific and also sometimes less toxic (or nontoxic) on other non-target organisms or species, an important consideration for alternate approaches of pest control. Several of the compounds, especially those produced by crop plants and other organisms, are consumed by humans and livestock, and yet appear to have no detrimental effects. They appear to be safe and will not contaminate the environment. Hence, they will be readily accepted for use in pest control by the public and the regulatory agencies. These natural compounds occur in nature only in trace amounts and require very low dosage for pesticide use. It is hoped that the knowledge gained by studying these compounds is helpful for the development of new pest control methods such as their use for interference with hormonal life cycles and trapping insects with pheromones, and also for the development of safe and biodegradable chemicals (e.g., pyrethroid insecticides). Undoubtedly, the costs are very high as compared to the presently used pesticides. But hopefully, these costs would be compensated for by the benefits derived through these natural pesticides from the lower volume of pesticide use

and reduction of risks. Furthermore, the indirect or external costs resulting from pesticide poisoning, fatalities, livestock losses, and increased control expenses (due to the destruction of natural enemies and beneficial insects as well as the environmental contamination and pollution from chlorinated, organophosphorus, and carbamate pesticides) could be assessed against benefits vs. risks. The development and use of such naturally occurring chemicals could become an integral part of IPM strategies. As long as they remain endogenously, several of the natural products presented in this handbook series serve as hormones, growth regulators, and sensory compounds for growth, development, and reproduction of insects, plants, and microorganisms. Others are useful for defense or attack against other species or organisms. Once these chemicals or their analogs and derivatives are applied by external means to the same (where produced) or different species, they come under the label “ pesticides” because they contaminate the environment. Therefore, they are subject to regulatory requirements, in the same way the other pesticides are handled before they are used commercially. However, it is anticipated that the naturally occurring pesticides would easily meet the regulatory and environmental requirements for their safe and effective use in pest control programs. A vast body of literature has been accumulated on natural pesticides during the last 2 or 3 decades; we have been assembling this information in these handbooks. We have limited our attempts to chemical and a few biological aspects concerned with biochemistry and physiology. Wherever possible, we tried to focus attention on the application of these compounds for pesticidal use. We hope that the first two volumes which dealt with theory and practice served as introductory volumes and will be useful to everyone interested in learning about the current technology that is being adapted from compound identification to the field trials. The subsequent volumes deal with the chemical, biochemical, and phys­ iological aspects of naturally occurring compounds, grouped under such titles as insect growth regulators, plant growth regulators, etc. In a handbook series of this type with diversified subjects dealing with plant, insect, and microbial compounds, it is very difficult to achieve either uniformity or complete coverage while putting the subject matter together. This goal was achieved to a large extent with the understanding and full cooperation of chapter contributors who deserve my sincere appreciation. The editors of the individual handbooks relentlessly sought to meet the deadlines and, more importantly, to bring a balanced coverage of the subject matter, but, however, that seems to be an unattainable goal. Therefore, they bear full responsibility for any pitfalls and deficiencies. We invite comments and criticisms from readers and users as they will greatly help to update future editions. It is hoped that these handbooks will serve as a source book for chemists, biochemists, physiologists, and other biologists alike — those engaged in active research as well as those interested in different areas of natural products that affect the growth and development of plants, insects, and other organisms. The editors wish to acknowledge their sincere thanks to the members of the Advisory Board for their helpful suggestions and comments. Their appreciation is extended to the publishing staff, especially Amy Skallerup, Melanie Mortellaro, and Sandy Pearlman for their ready cooperation and unlimited support from the initiation to the completion of this project. N. Bhushan Mandava Editor-in-Chief

FOREWORD Pests of crops and livestock annually account for multi-billion dollar losses in agricultural productivity and costs of control. Insects alone are responsible for more than 50% of these losses. For the past 40 years the principal weapons used against these troublesome insects have been chemical insecticides. The majority of such materials used during this period have been synthetic organic chemicals discovered, synthesized, developed, and marketed by commercial industry. In recent years, environmental concerns, regulatory restraints, and problems of pest resistance to insecticides have combined to reduce the number of materials available for use in agriculture. Replacement materials reaching the marketplace have been relatively few due to increased costs of development and the general lack of knowledge about new classes of chemicals having selective insecticidal activity. In response to these trends, it is gratifying to note that scientists in both the public and private sectors have given significant attention to the discovery and evaluation of natural products as fertile sources of new insecticidal agents. Not only are these materials directly useful as insect control agents, but they also serve as models for new classes of chemicals with novel modes of action to attack selective target sites in pest species. Such new control agents may also be less susceptible to the cross resistance difficulties encountered with most classes of currently used synthetic pesticide chemicals to which insects have developed immunity. Natural products originating in plants, animals, and microorganisms are providing a vast source of bioactive substances. The rapid development and application of powerful analytical instrumentation, such as mass spectrometry, nuclear magnetic resonance spectroscopy, gas chromatography, high performance liquid chromatography, immuno- and other bioassays, have greatly facilitated the identification of miniscule amounts of active biological chemicals isolated from natural sources. These new scientific approaches and tools are addressed and reviewed extensively in these volumes. Some excellent examples of success in this research involve the discovery of insect growth regulators, especially the so-called juvenoids, which are responsible for control of insect metamorphosis, reproduction, and behavior. Pheromones which play essential roles in insect communication, feeding, and sexual behavior represent another important class of natural products holding great promise for new pest insect control technology. All of these are discussed in detail in Volumes dealing with insects. It is hoped that the scientific information provided in these volumes will serve researchers in industry, government, and academia, and stimulate them to continue to seek even more useful natural materials that produce effective, safe, and environmentally acceptable materials for use against insect pests affecting agriculture and mankind.

Orville G. Bentley Assistant Secretary Science and Education U.S. Department of Agriculture

PREFACE The end of the Second World War was a time of great hopes; hopes of a new organization of governments that would settle disputes between nations peacefully; new nations with high intentions of feeding their growing populations adequately, and new insecticides like DDT that would make those promises of abundant food possible. There were great hopes of eliminating the insect pests that destroyed or damaged so much food, and there was promise of removing the scourges of malaria and other insect-transmitted diseases. Today these hopes and many others of that time seem tarnished by reality. The goals were not so easily achieved as we then thought, and we see now that more thought and effort and more strategy must be put into their achievement. The idea too of a pancratic insecticide is less prominent. No one would seriously suggest today a single pharmaceutical product to treat all infectious diseases. We must recognize also that insect control will be most efficacious if it is directed towards a specific pest or group of pests. One of our best hopes in finding such means of control is to look again at how nature controls insect populations, and the natural substances of insects themselves. Volume III in this series has dealt with the natural substances affecting insect growth and development. This volume concerns itself with pheromones, another apsect of insect regulation. Insects make use of all their senses, to varying degrees, for their communication, mating, food-seeking, regulation of maturity, and survival. Research in recent decades has shown they make particular use of the chemical sense of “ smell” if that is an appropriate term to use by extension from our human sense. The term pheromone is now widely accepted for those substances emitted by one member of a species, conveying some message to another member of the species. The appeal of breaking into this message system to block or disrupt it, to send false messages, is immediate and obvious. The use of pheromones has the advantages of specificity, economy in the use of material, the air to transmit them, and few problems of persistence and residues. Pheromone strategies need not be confined to the natural substances. Sometimes an unnatural isomer or enantiomer of a pheromone can effectively suppress the message of the natural substance. This is frequently found for geometric isomers of lepidopteran phero­ mones. We know very little as yet of the avoidance by one species of an area marked with the pheromone of another species. Although considerable experience has been gained in the use of pheromones for attraction and disruption, and there are now a number of effective uses for pheromones in agriculture and silviculture, the possibilities of the use of pheromones and their mimics or antagonists are far from being thoroughly examined. Sometimes, a too limited view of insects in agriculture is uppermost, and we lose sight of the damage done by insects in stored products and in packaging, or the spoilage of food by insect filth. There, is, also, the importance of insects as parasites and vectors of pathogens in medical and veterinary practice. The curious and powerful attraction of the copulatory pheromone for the male tsetse fly is just one example that should be capable of exploitation. In this volume, the first chapter introduces the subject of perception of odor and the function of molecular structure. The current theories linking molecular structure and odor are considered, to help in the understanding of odor perception. In the following chapters, the major insect orders are considered in turn, by international experts in each speciality. Our knowledge is certainly greatest at present for the Lepidoptera, but there it is limited largely to the subject of sexual attraction. Among Coleoptera the use of pheromones is perhaps more varied and still more so with Diptera. The greatest and most varied use of pheromones is among the social insects, so that the Hymenoptera and Isoptera are considered together in one chapter. Finally the other insect orders where our knowledge, as yet, is still but fragmentary are gathered together by B. S. Fletcher and T. E. Bellas.

The reader is commended to the wealth of information collected and tabulated here, both to extend further our knowledge of insects and their communication and to find those more effective, selective, and acceptable methods of control that a hard-pressed natural world requires. The contributors must have our deepest thanks for their labors with a difficult and ever­ growing task. Our thanks also to Mrs. Margaret Furnival and Mrs. Christine Owen for their considerable secretarial help.

E. D. M. N. B. M.

THE EDITORS E. David Morgan, D.Phil., is a Chartered Chemist, a Fellow of the Royal Society of Chemistry, and a Fellow of the Royal Entomological Society of London. He received his scientific training in Canada and England, and has worked for the National Research Council of Canada, Ottawa, The National Institute for Medical Research, London, the Shell Group of Companies and is now Reader in Chemistry at the University of Keele, Staffordshire, England. He is co-author of a textbook on aliphatic chemistry with the Nobel prizewinner, Sir Robert Robinson, and with him is a co-inventor of a number of patents. Dr. Morgan has contributed to over 130 papers, most of them on aspects of insect chemistry and has written a number of reviews on insect hormones and pheromones.

N. Bhushan Mandava, holds B.S., M.S., and Ph.D. degrees in chemistry and has published over 140 papers including two patents, several monographs and reviews, and books in the areas of pesticides and plant growth regulators and other natural products. As editorial advisor, he has edited three special issues on countercurrent chromatography for the Journal o f Liquid Chromatography. He is now a consultant in pesticides and drugs. Formerly, he was associated with the U.S. Department of Agriculture and the Environmental Protection Agency as Senior Chemist. He has been active in several professional organi­ zations, was President of the Chemical Society of Washington, and serves as Councilor of the American Chemical Society.

ADVISORY BOARD E. David Morgan N. Bhushan Mandava Editors

Members Murray S. Blum Research Professor Department of Entomology The University of Georgia Athens, Georgia

J. F. Bertil Kullenberg Professor, Institute of Zoology Uppsala University Uppsala, Sweden and Director, the Ecological Stations Olands Skogsby Farjestaden, Oland, Sweden

CONTRIBUTORS Thomas E. Bellas, Ph.D.

Brian S. Fletcher, Ph.D.

Principal Research Scientist Division of Entomology CSIRO Canberra, Australia

Senior Principal Research Scientist Division of Entomology CSIRO Canberra, Australia

Hans Jurgen Bestmann, Ph.D.

Yoshio Tamaki, Ph.D.

Professor and Head Institute of Organic Chemistry University of Erlangen-Nuremburg Erlangen, W. Germany

Chief Insect Biochemistry Laboratory National Institute of Agricultural Sciences Nannondai, Ibaraki, Japan

Richard Duffield, Ph.D.

Otto Vostrowsky, Dr. Phil.

Department of Zoology Howard University Washington, D.C.

Institute of Organic Chemistry University of Erlangen-Nuremburg Erlangen, W. Germany

Richard P. Evershed, Ph.D.

James W. Wheeler, Ph.D.

Senior Experimental Officer Department of Biochemistry University of Liverpool Liverpool, England

Professor Department of Chemistry Howard University Washington, D.C.

TABLE OF CONTENTS Part A Insect Olfaction and Molecular Structure.................................................................................... 1

Richard P. Evershed Pheromones of the Lepidoptera.................................................................................................. 35

Yoshio Tamaki Pheromones of the Coleoptera....................................................................................................95

Hans Jurgen Bestmann and Otto Vostrowsky Index.............................................................................................................................................185

Part B Pheromones of D iptera................................................................................................................ 1

B. S. Fletcher and T. E. Bellas Pheromones of Hymenoptera and Isoptera............................................................................... 59

Janies W. Wheeler and Richard M. Duffield Pheromones of Hemiptera, Blattodea, Orthoptera, Mecoptera, Other Insects, and Acari............................................................................................................207

B. S. Fletcher and T. E. Bellas Index

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Volume IV: Pheromones, Part B

1

PHEROMONES OF DIPTERA B. S. Fletcher and T. E. Bellas

INTRODUCTION In recent years considerable progress has been made in the study of Dipteran pheromones, not only in determining the roles they play in intraspecific communication, but also in the identification of the compounds involved. Even so, the information available about phero­ mone systems in this group is much less extensive than that relating to pheromone com­ munication in Lepidoptera, Coleoptera, and Hymenoptera, the other major groups of endopterygote insects. In part, this is because in Diptera the roles pheromones play in regulating behavior differ considerably from group to group as a result of the different life history strategies evolved by specific groups or even individual species. Also pheromone cues are frequently combined with other types of signaling, including auditory and visual stimuli, making precise analysis of the contribution of the pheromone to the overall behavioral response difficult. The situation is further complicated because in the majority of species investigated the pheromones are mixtures of several components. Most of this chapter is devoted to the biological and chemical data currently available about releaser pheromones involved in sexual and oviposition behavior and possible appli­ cations these pheromones might have in pest management programs. A section on mosquito overcrowding factors is also included, even though there is some indication that bacteria may play an intermediary role in the elaboration of some of the active components, because their intraspecific action is analogous at least to that of certain pheromones and they appear to have considerable potential as control agents. It was decided, however, not to include data on male accessory gland secretions because although they act intraspecifically and are thus sometimes referred to as pheromones, what is known about their chemistry suggests that they are large proteinaceous molecules and their mode of action resembles that of hormones rather than typical pheromones.1

PHEROMONES INVOLVED IN SEXUAL BEHAVIOR As discussed by Fletcher,2 the importance of sex pheromones in promoting sexual behavior in Diptera varies considerably from group to group, and there are a variety of ways in which species use pheromones to enhance mating success. A few species use pheromones to recruit mates from a distance, but in the majority the two sexes aggregate either at emergence, feeding, or oviposition sites in response to nonsexual stimuli, or use other nonpheromonal cues to locate a mate. In many species, sex pheromones, if used at all, only operate at short range or after initial contact has been made and their principal functions are to elicit copulatory behavior from conspecific partners and to serve as sex recognition factors. In some species of Drosophila there is evidence that short range pheromonal cues may indicate strain or genetic differences between prospective mates and influence the female’s choice of a partner. Pheromones may also play other roles related to sexual behavior. The oviposition-deterring pheromones, deposited on fruit by the females of certain tephritid fruit flies after egg laying, serve the additional role of arresting males in the vicinity of the marked fruit for a period, thereby increasing the chance of sexual encounters. In at least one species of swarming midge, swarm cohesion appears to be maintained, to some extent at least, by a pheromone and there is circumstantial evidence that pheromones influence the lek behavior that occurs in certain male tephritid fruit flies and Hawaiian Drosophila.

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Some species of Diptera use pheromones as mating deterrents, either to deter copulation attempts by prospective mates, or to prevent homosexual advances.

Occurrence and Function of Sex Pheromones Species of Diptera known to use pheromones as part of the mating process are listed in Table 1. Because in the majority of cases the precise role of the sex pheromone in the different steps of the mating process has not been determined, attractants, mating stimulants, and sex recognition compounds have been grouped under the general heading of sex pher­ omones. When available, more precise information about their roles in individual species is included in the text. In the suborder Nematocera the involvement of pheromones in the mating process has been reported from species belonging to the families Ceratopogonidae, Chironomidae, Culicidae, Sciaridae, and Tipulidae. Studies employing a T-shaped olfactometer indicated that females of the biting midge, Culicoides nubeculosusf release a pheromone(s) which acts both as an attractant and a mating stimulant for the males. In the related species C. melleusf bioassays in which males were observed manipulating small pieces of cork treated with extracts, indicated that the cuticular wax of females contains a contact sex pheromone which stimulates the copulatory response of males. In the Culicidae, females of Deinocerites cancer and Culiseta inornata have been reported to release volatile pheromones which attract males.6-910 In D. cancer, the pharate female, prior to emergence, releases the pheromone through the pupal spiracles, which project above the water surface. Attracted males alight on the water surface and remain in attendance until the female emerges, when copulation takes place. A recent attempt to isolate an attractant from female C. inornata was unsuccessful but the presence of a nonvolatile heat-stable contact pheromone which enabled the males to identify conspecific females was demon­ strated.7,8 The males of certain species of Culex mosquitoes have also been reported to release pheromones during swarming which at high concentrations act as short range at­ tractants and excitants for females.15 In Aedes aegypti and some members of the genus Stegomyia, the males locate the females using auditory cues but appear to rely on contact sex pheromones for the final stage of mate recognition. If the pairs are separated prior to the completion of mating, the pheromone also stimulates search behavior.5 In Tipula paludosa, females have a pheromone which acts as a short range excitant for males.14 In the sciarid flies, Lycoriella mali and Bradysia impatiens, olfactometer studies indicate that females release sex pheromones which, over short distances at least, act as attractants for males.1113 In Chironomus riparius the males appear to release a pheromone during swarming that helps maintain swarm cohesion. It was found in laboratory experiments that when air, which had previously been drawn across a swarm, was recirculated, the swarming continued but if fresh air was passed across the swarm, swarming stopped.16 In the suborder Brachycera, sex pheromones have been reported from species belonging to nine different families of Cyclorrhapha: Calliphoridae, Chloropidae, Drosophilidae, Glossinidae, Muscidae, Phoridae, Sarcophagidae, Syrphidae, and Tephritidae (Table 1). As yet, no pheromones have been reported from the Orthorrhapha. Olfactometer studies with the eye gnat, Hippelates collusor,19 indicated that virgin females release a sex pheromone that attracts males. Field tests with newly emerged virgin females of the syrphid Microdon cothurnatus also indicated that males were attracted to the females by a sex attractant pheromone.47 In the majority of muscoid flies, sex pheromones are produced by the females and influence male behavior only at short range or once contact has been made. A notable exception to

Volume IV: Pheromones, Part B

Table 1 DIPTERA THAT PRODUCE PHEROMONES INVOLVED IN MATING Family and species

Ref.

NEMATOCERA Female Produced Sex Pheromones Ceratopogonidae Culicoides me Ileus C. nubeculosus Culicidae Aedes aegypti A. albopictus A. mascarensis A. polynesiensis Culiseta inornata Deinocerites cancer Sciaridae Bradysia impatiens Lycoriella mail Tipulidae Tipula paludosa

3 4

11 12,13 14

Culicidae Culex pipiens C. quinquefasciatus C. tarsalis

15 15 15

Swarm Cohesion Pheromone

16

BRACHYCERA: CYCLORRHAPHA Female Produced Sex Pheromones Calliphoridae Cochliomyia hominivorax Lucilia cuprina Chloropidae Hippelates collusor Drosophilidae Drosophila melanogaster D. pseudoobscura Glossinidae Glossina austeni G. morsitans morsitans G. pallidipes G. palpalis palpalis Muscidae Fannia canicularis F. femoralis F. pusio Haematobia irritans Musca autumnalis M. domestica Stomoxys calcitrans

Phoridae Megaselia halterata Syrphidae Microdon cothurnatus Tephritidae Dacus oleae

Ref.

46 47 48—53

Male Produced Sex Pheromones 5 5 5 5 6—8 9,10

Male Produced Sex Pheromones

Chironomidae Chironomus riparius

Family and species

Calliphoridae Cochliomyia hominivorax Drosophilidae Drosophila grimshawi Sarcophagidae Sarcophaga bullata Tephritidae Anastrepha suspensa A. ludens Ceratitis capitata Dacus aquilonus D. cucurbitae D. dorsalis D. neohumeralis D. opiliae D. tryoni D. zonatus Rhagoletis cerasi R. pomonella Rioxia pornia

54 55,56 57 58—60 59—61 62—65 66 67—69 67,68 70 66 70—74 75 76 77 78

Male Strain Recognition Pheromones Drosophilidae Drosophila melanogaster D. pseudoobscura

79 80

Male Aggregation Pheromones 17 18 19 20,21 22 23 24,25 26—28 29 30 31 32 33 34,35 36—42 43— 45

Tephritidae Anastrepha suspensa Ceratitis capitata Dacus oleae

81 64,82 83

Female Site Marking Arrestant Pheromones Tephritidae Ceratitis capitata Rhagoletis cerasi R. pomonella

84 85 86

Male Site Marking Arrestant Pheromones Tephritidae Rhagoletis completa Urophora cardui

87 87

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CRC Handbook o f Natural Pesticides

this is the male fleshfly, Sarcophaga bullata, which uses a sex pheromone to attract females from a distance prior to copulation.57 In contrast, in the tsetse flies (Glossinidae) there does not appear to be any involvement of pheromones in mating until the male actually makes contact with a female, which he does using visual cues. Once contact has been made, pheromone components present in the female’s cuticular waxes aid in conspecific sex rec­ ognition and promote the successive steps in the male’s mating behavior, which include orientation on the female and extension and engagement of the genitalia.23 26,29 In muscid flies, the principal roles of the female sex pheromone are to stimulate nearby males to make copulatory advances towards females (or objects which have the same general characteristics as females) and to act as conspecific sex recognition compounds once contact has been made.30'39 In the house fly, Musca domestica, the pheromone also acts as a relatively short range and weak attractant for males and possibly as an aggregation pheromone for both sexes.88,89 A male stimulant and sex recognition pheromone, similar in effect to those of muscid flies, has been reported from the female screwworm, Cochliomyia hominivorax.17 Earlier studies also indicated that unmated male screwworm flies produce a volatile pheromone which acts as a sexual excitant for females, inducing them to become more active and make physical contact with nearby individuals.54 In the Australian sheep blowfly, Lucilia cuprina, the only other calliphorid fly so far studied, mature virgin females release a volatile pher­ omone which increases the sexual excitement of males and stimulates them to attempt copulation with nearby flies of either sex.18 The sexual behavior of drosophilids shows a considerable amount of species diversity with each species having a specific repertoire of signals involving visual, auditory, and chemical cues. In many species, mating occurs at the feeding and breeding sites, with males making advances towards any object which resembles a prospective mate. Studies on Dro­ sophila melanogaster and D. pseudoobscura have shown that the female produces a pher­ omone that acts only at short range and stimulates males to orient towards and contact nearby individuals with their front tarsi and mouthparts.20 22 Until contact has been made, however, interspecific and conspecific discrimination by the males is lacking. In contrast, a number of Hawaiian Drosophila species have evolved highly specialized types of mating behavior, analogous in many respects to those observed in certain tephritid fruit flies, with the males displaying lek behavior away from the food mass. Courtship signaling varies from species to species, but the production of pulsating anal-droplets or marking of the substrate at the lek by dragging the tip of the abdomen, plus observations on female behavior, indicate that the males release volatile pheromones during courtship.55,56 The sexual behavior of tephritid fruit flies varies considerably from group to group. Some species, particularly those that infest flowerheads and use the host as a rendezvous site, have evolved elaborate and highly ritualized courtship dances which involve visual signaling with their distinctly patterned wings, and do not appear to use pheromones to recruit partners. In a number of the fruit-infesting species, however, including many of the pest species belonging to the genera Anastrepha, Ceratitis, and Dacus, lek formation by males is an important component of the premating phase, and females are attracted to the lek by a combination of auditory, visual, and pheromonal cues.90'92 It is also possible that in some species males are attracted to lek sites by the pheromone released by males already in attendance, because traps baited with pheromone extracts of male Ceratitis capitata and live males of Anastrepha suspensa caught both males and females during field trials.64,81 With the exception of the olive fly, Dacus oleae, in all species of fruit fly in which sex attractant pheromones have so far been demonstrated the pheromones are released by males. In D. oleae, the female uses a sex pheromone to attract males, even though the males appear to produce a pheromone which acts as an attractant for other males.48'51 Besides releasing a sex attractant pheromone,62,76,77 males of the apple maggot, Rhagoletis

Volume IV: Pheromones, Part B

5

pomonella, the European cherry fly, R. cerasi, and the Mediterranean fruit fly, C. capitata, are arrested by the oviposition deterring pheromone that females deposit on fruit.84'86 In the related species R. completa and the flower-head infesting tephritid, Urophora cardui, the males mark larval foodplants with a pheromone that acts as an arrestant for females.87

The Chemistry of Dipteran Sex Pheromones Extraction Procedures In studies on short range excitants and sex recognition pheromones as found in the Muscidae and Glossinidae, crude extracts have been obtained by surface washing mature virgin females with hexane or diethyl ether and then separating the lipids into their respective classes by column chromatography, using Florisil or activated silica gel and hexane/benzene or hexane/diethyl ether mixtures to elute the different fractions.24,38 The hydrocarbons eluted in hexane were then separated into saturated and unsaturated fractions by column chroma­ tography using silver nitrate impregnated Florisil or silica gel and into unbranched and branched fractions by the use of molecular sieves. Except that the starting material was a hexane extract of homogenized females, similar procedures were used to isolate the sex pheromones of female Lycoriella mali and Drosophila melanogaster, once it was established that they were hydrocarbons present in the cuticular waxes.13 21 For studies on the sex pheromone of male Sarcophaga bullata, crude extracts were obtained by homogenizing 2-day-old adult males in ethyl acetate.57 After filtration and removal of solvent the residue was re-extracted in hexane and separated into fractions by gel permeation chromatography and the active component further purified by preparative GC, prior to mass spectrometry. In investigations on tephritid fruit fly sex pheromones, because the pheromones are pro­ duced in specialized glands and are not incorporated into the cuticular waxes, various extraction procedures have been employed. In the Caribbean fruit fly, Anastrepha suspensa, active material was obtained by extracting the bodies of mature males with ether, or by extracting with hexane the aqueous washing of cages that had contained males, and then fractionating the material on silica gel columns.58'60 In the case of the Mexican fruit fly, A. ludens, the presumptive pheromone components were extracted from whole abdomens into hexane, fractionated on Florisil columns, and then further purified by repeated chromatog­ raphy on small columns of silica gel, Florisil, and silver nitrate impregnated Florisil, prior to gas chromatography-mass spectrometry (GC-MS) and spectroscopic and X-ray analyses.93 For the Mediterranean fruit fly, Ceratitis capitata, active material was obtained by cold­ trapping the air passed over caged mature males. The condensate was collected in methylene chloride, chromatographed on silica gel, and two active peaks separated by preparative GC.64 In the Queensland fruit fly, Dacus tryoni, the rectum and associated pheromone glands were dissected out. The contents were collected directly into micropipettes and stored in ether prior to fractionation using preparative GC.70 In D. oleae, active fractions were obtained by cold trapping the air passed over batches of mature virgin females, or by dissecting out the glands and extracting them with ether or subjecting them to solid sample GC.50,53 A solid sampling technique was also used in studies on the rectal gland secretions of D. cucurbitae .69 Bioassay Techniques In their pioneering work on the sex pheromone of the housefly, Musca domestica, Carlson et al.38 used a two-port olfactometer containing up to 200 mature males to determine the activity of test materials applied in hexane solutions to strips of filter paper in the outer end of one of the ports. Olfactometers have also been used to test responses of two other muscid flies, the horn fly, Haematobia irritans and the stable fly, Stomoxys calcitrans.94,95 In more recent studies on Musca domestica and other species of muscid flies, the number of copulatory

6

CRC Handbook o f Natural Pesticides

attempts or “ strikes” by males toward pseudoflies (made from black shoe lace knots or washed dead flies attached to straws) treated with the test materials has been used as a bioassay for female-produced pheromones. Usually, up to ten males are used in each test and observations are carried out for 3- to 5-min periods. The results are expressed as strikes per hour or as an activity quotient obtained by dividing the number of strikes directed at the treated pseudoflies by the number of strikes towards test females or pseudoflies treated with solvent only.35’96 The bioassays used to check test materials for pheromonal activity in Glossinidae were developed by Carlson et al.24 and Huy ton et al.25 Hexane solutions were loaded onto small glass beads or sol vent-washed male flies which acted as decoys. These were then attached individually to the inside of lids of tubes which contained individual mature males and the tubes inverted or tapped to bring the males into contact with the decoys. Activity was assessed on a three-point scale depending upon the extent of the copulatory response displayed by the male. Arrestment on the decoy scored 1 point, orientation to the copulatory position 2 points, and a full mating response with attempted engagement of the genitalia 3 points. In studies on the pheromone of Drosophila melanogaster, bioassays were carried out by applying 3 to 6 |xg of the test material to a freshly killed hexane washed male, which was placed into a small container with a test male. Activity was determined by the duration of wing vibration (a component of male courtship behavior) displayed by the male during a 5min observation period.21 In the sciarid, L. mali13 and the phorid, Megaselia halterata46 the response of males to candidate compounds and blank controls in olfactometers was used as a bioassay to determine the activity of compounds isolated from females. Similarly, during studies on the sex attractant pheromone of male S. bullata, candidate compounds were tested in an olfactometer containing females. A number of different bioassays have been used in tests with tephritid fruit flies. In A. suspensa, bioassays were carried out in a multiple-choice olfactometer, with blank and test materials loaded into the distal end of trap tubes attached to the ports which opened into the main chamber, containing 20 mature virgin females.58 In C. capitata, laboratory bioassays were carried out by placing the candidate materials loaded onto strips of filter paper inside small sticky cups which were suspended in a cage containing 100 mature virgin females. The numbers caught were compared with blank control cups and a standard containing a filter paper which had been exposed to 2000 males for 17 to 18 hr. Tests of a similar type were also conducted in a large outdoor cage containing around 1500 females, with the cups attached to a slowly revolving wheel.97 In studies on Dacus tryoni, laboratory bioassays were carried out by exposing groups of five females to candidate compounds loaded on small filter paper disks in a series of glass activity chambers and recording the number that showed a copulatory response toward the pheromone source.98 Field tests for attractant activity were carried out in large field cages placed over fruit trees and containing around 500 virgin females. Cylindrical sticky traps containing cotton wool wicks loaded with test materials or solvent controls were placed into the cages just before the start of the dusk mating period.2 For D. oleae, laboratory bioassays of candidate pheromone components have been carried out by loading the test materials and solvent controls onto squares of filter paper which were hung in the upwind part of a cage containing 100 5- to 8-day-old males during the last 2 hr of the photophase.51 In other studies, the test materials were loaded onto paper rolls placed in an olfactometer containing 3- to 5-day-old males.52 The number of males responding during a fixed period, ranging from 10 min to 1 hr, was used to compare the activity of test materials with controls. Bioassays have also been carried out in field cages containing 300 to 400 males, by placing the test materials in solvent in small glass vials which were placed inside cylindrical sticky traps that were suspended from the cage roof. The tests were

Volume IV: Pheromones, Part B

7

conducted during the optimal mating period in the late afternoon.51 In field trials carried out in Spain to determine the activity of synthetic samples of the major pheromone component isolated from the rectal glands of females, up to 50 mg of the test material were loaded onto rubber sleeve stoppers and then exposed in triangular sticky traps in olive groves.50 In field studies carried out in Italy, the activity of compounds identified in cold-trap condensate of females was determined by loading 5 mg quantities of the candidate compounds onto cellulose pads which were placed into yellow triangular sticky traps. The traps were hung out in olive groves, along with uncharged traps of the same design, and the numbers of wild male and female olive flies responding to the two types of traps compared.52 In studies with D. cucurbitae, the responses of females to excised male glands and gland extracts in an olfactometer, or a specially constructed wind tunnel have been used as bioassays for sex pheromone activity.67 69 Techniques Used to Identify the Cuticular Hydrocarbons The long chain hydrocarbons which form part of the cuticular lipids of insects fall into several homologous series. The chemical and physical properties of these hydrocarbons vary systematically with the chain length, the position of unsaturation and the substitution pattern (if any) on the chain. The techniques which have been employed for the identification of hydrocarbons of the several series include the retention index (RI) in GC, MS, GC-MS, and spectroscopic methods — infrared and nuclear magnetic resonance (IR, NMR).94,99,100,101 The location of the position of double bonds can be accomplished by oxidative cleavage or MS after chemical modification of the double bond. The aldehydes produced by ozonolysis,102 or by oxidation of epoxides,103 or of vicinal diols (see Table 3), may be identified by GC retention time or by MS.94,104 Acid products of cleavage are usually identified as methyl esters. Functionalization of the double bond may be achieved by epoxidation,105,106 hydroxylation,107 or methoxymercuration.108 The products, or derivatives of them, give mass spectra with characteristic fragmentation patterns allowing the position of the double bond to be determined.

The Identity and Chemical Properties of Dipteran Sex Pheromones Most of the Dipteran sex pheromones so far investigated have turned out to be multicom­ ponent systems. Because of the varying levels of activity of the different compounds present, it is often difficult to decide which compounds should be classed as pheromone components. This is particularly true in the case of the short range, or contact, excitant, and conspecific sex recognition pheromones which appear to consist largely of mixtures of hydrocarbons incorporated into the cuticular waxes.109 Even in the case of the longer range sex attractant pheromones, some, at least, contain a number of different components and the precise roles of the individual compounds are poorly understood. Compounds which have been isolated from various species of Diptera and have been shown by bioassay to elicit some kind of sexual response from conspecific individuals are listed in Table 2. The chemical and spectral data relating to compounds that have been identified as com­ ponents of Dipteran sex pheromones are given in Tables 3 and 4 and their structures are shown in Figure 1.

The Biological Activity of Sex Pheromone Components Sciaridae Olfactometer tests with 1 p,g quantities of a series of synthetic /i-alkanes using 1- to 3day-old males of Lycoriella mali indicated that most showed some activity, but that heptadecane (1) elicited the greatest response.13 As its retention time corresponded to that of the most active fraction from the female extract, it was concluded that it was the major component of the pheromone, although some of the other /i-alkanes (e.g., C15, C16, C18,

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CRC Handbook o f Natural Pesticides

Table 2 COMPOUNDS WHICH HAVE BEEN IDENTIFIED AS COMPONENTS OF DIPTERAN SEX PHEROMONES ON THE BASIS OF THEIR ACTIVITY IN BIOASSAYS Species Sciaridae Lycoriella mali Drosophilidae Drosophila melanogaster Glossinidae Glossina m. morsitans

Sex

Compounds

Ref.

F

(1) Heptadecane

13

F

(2) (Z,Z)-6,9-heptacosadiene

21

F

(3) (4) (5) (6) (7)

15,19,23-Trimethylheptatriacontane 17,21 -Dimethylheptatriacontane 15,19-Dimethylheptatriacontane 13,23-Dimethylpentatriacontane 15,19-Dimethyltritriacontane

24 24 24 28 23

(Z)-9-tricosene 4,8-Dimethylheptacosane 13-Methylnonacosane 13-Methylheptacosane 11-Methylnonacosane cis-9,10-Epoxytricosane (Z)-l 4-tricosen-10-one (Z)-14-nonacosene (Z)-13-nonacosene (Z)-13-heptacosene (Z)-9-pentacosene (Z)-9-heptacosene (Z)-l 1-hentriacontene (Z)-13-hentriacontene (Z)-13-tritriacontene (Z)-11-hentriacontene Tricosane Pentacosane (Z)-9-hentriacontene (Z)-9-tritriacontene 11,15-Dimethylhentriacontane 15-Methylhentriacontane 15,19-Dimethyltritriacontane 13-Methyl-1-hentriacontene 13-Methyl-1-tritriacontene 11 -Methylhentriacontane (Z)-9-pentacosene (Z)-9-heptacosene (Z)-5-tricosene

38 42 42 41 41 40 40 35 35 35 30 30 32 32 32 31 31 31 45 45 44 44 44 45 45 45 33 33 33

G. pallidipes G. austeni Muscidae Musca domestica

F

M. autumnalis

F

Fannia canicularis

F

F. pusio

F

F. femoralis

F

Stomoxys calcitrans

F

Haematobia irritans

F

F F

(8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (20) (23) (24) (25) (26) (27) (28) (7) (29) (30) (31) (18) (19) (32)

Phoridae Megaselia halterata Sarcophagidae Sarcophaga bullata Tephritidae Anastrepha suspensa A. ludens

F

(33) 3,6-Dimethylheptane-2,4-dione

46

M

(34) Hexanal

57

M M

Ceratitis capitata

M

Dacus oleae

F

(35) (Z)-3-nonen-1-ol (36) (Z,Z)-3,6-nonadien-l-ol (37) Anastrephin (38) Epianastrephin (39) (£>6-nonen-1-ol (40) Methyl (£)-6-nonenoate A mixture of fatty acids (41)1,7-Dioxaspiro[5.5]undecane

59 59 60 60 65 65 66 50

9

Volume IV: Pheromones, Part B

Table 2 (continued) COMPOUNDS WHICH HAVE BEEN IDENTIFIED AS COMPONENTS OF DIPTERAN SEX PHEROMONES ON THE BASIS OF THEIR ACTIVITY IN BIOASSAYS Species

Sex

D. oleae

M

D. tryoni D. neohumeralis

M

D. cucurbitae D. dorsalis

_M M

Compounds

Ref.

(39) (£>6-nonen-l-ol (42) p-Cymene (41) l,7-Dioxaspiro[5.5]undecane (43) Diethyl 5-oxononanedioate (44) A^-3-methylbutylpropanamide (45) A^-3-methylbutylacetamide (46) N-(3-methylbutyl)-2methylpropanamide (47) N-2-methylbutylpropanamide (48) N-2-methylbutylacetamide (49) A^-(2-methylbutyl)-2methylpropanamide (45) N-3-methylbutylacetamide (47) N-2-methylbutylpropanamide

52 52 83 83 70 70 70 70 70 70 69 68

Table 3 OXIDATION PRODUCTS OF ALKENES AND RELATED COMPOUNDS

Name

Structure

(Z)-5-tricosene (Z)-9-tricosene (Z)-9-pentacosene (Z)-9-heptacosene (Z)-13-heptacosene (Z)-13-nonacosene (Z)-14-nonacosene (Z)-9-hentriacontene (Z)-11-hentriacontene (Z)-13-hentriacontene 13-Methyl-1-hentriacontene (Z)-9-tritriacontene (Z)-13-tritriacontene 13-Methyl-1-tritriacontene (Z,Z)-6,9-heptacosadiene

(32) (8) (18) (19) (17) (16) (15) (25) (20) (21) (29) (26) (22) (30) (2)

(Z)-14-tricosen-10-one cis-9,10-Epoxytricosane

(14) (13)

Retention index (SE30) 2292 2272 2477 2677

Products Octadecanal (pentanal)3 Nonanal, tetradecanal Nonanal, hexadecanal Nonanal, octadecanal Tridecanal, tetradecanal Tridecanal, hexadecanal Tetradecanal, pentadecanal Nonanal (docosanal)b Undecanal, eicosanal Tridecanal, octadecanal 12-Methyltriacontanal Nonanal, tetracosanal Tridecanal, eicosanal 12-Methyldotriacontanal Hexanoic acid,c octadecanoic acidc Nonanal Nonanal,d tetradecanald

Ref. 94 94 94 94 35 35 35 43 32 32 45 43 32 45 110 40 40

a Pentanal was not seen. b Docosanal was obscured in GC by triphenylphosphine reactant. c Oxidation was achieved by 0 s 0 4 followed by periodate/permanganate. The acids were identified as the methyl esters. d Oxidation by periodate.

and C20) which had retention times corresponding to other active fractions seem likely to function as minor components of the pheromone. Bioassays using quantities of (1) ranging from 10“ 4 to 10-11 g indicated that males showed two peak responses, to 10” 6 and 10“ 9 g respectively. The significance of this bimodal response curve is uncertain. Drosophilidae The major sex pheromone component of Drosophila melanogaster, which stimulates the male wing vibration component of courtship behavior, was identified as heptacosadiene (2),

Heptadecane

629-78-7 (1)

(3)

67979-80-0

c 27h 52

5145-36-8 (2)

15,19,23Trimethylheptatriacontane C40H82 562

376

Heptacosadiene [(Z,Z)-6,9-heptacosadiene]

26050-34-0

240

C17H36

Name Formula Mol wt

C.A.S. registry number (Compound)" 22 301.8/760 129/2

mp bp °C

Film 2920(s) 2850(s) 1470(m) 1380(m) 730(w)

(117)

[0.9; 1.3]b

2920 (s) 2865 (s) 1468 (s) 1378 (m) 1303 (w) 890 (w) 721 (m)

(112)

(117)

'H 100 MHz CCI4 0.82—0.94 (15H, 5 x CH0; 1.26 (67H, br s)

(116)

,3C 25 MHz CDCI3 13.9 (Cl, C27); 22.8 (C2,C26); 25.8 (C8);27.4 (C5,C11); 29.5 (C4,C24); 29.8 (C12— C23); 31.7 (C3); 32.1 (C25); 128.1 (C7,C9); 130.3 (C6,C10)

(114,115)

'H 0.90, (6H,t,Cl,C27); 1.25 (br s); 2.00 (4H); 2.78 (2H,t,C8); 5.36 (4H,J = 6 Hz, vinylic)

'H CC14

NMR (ppm)

Liquid

anr

IR (cm" ')

UV (nm), other spectral properties

(2 4)

E.I. 547 (M - CH, +); 365 (M C,4H29+); 295 (M - C19H39+); 225; 224 (M C23H47+)

240 (3,M +°); 127 (4); 113 (5); 99 (8); 85 (36); 71 (54); 57 (94); 56 (15); 55 (26); 43 (100); 42 (15); 41 (56) (113)

E.I.

Mass spectrum m/z (%)

24, 117

Synthesis reference

Table 4 DIPTERAN PHEROMONES INVOLVED IN SEXUAL BEHAVIOR: CHEMICAL AND SPECTRAL PROPERTIES

o CRC Handbook o f Natural Pesticides

56987-80-5 (7)

85046-06-6 (6)

56987-91-8 (5)

67979-79-7 (4)

492

C35H72

15,19Dimethyltritriacontane

520

13,23Dimethylpentatriacontane C37H76

548

C39H80

15,19Dimethylheptatriacontane

C39H80 548

17,21Dimethylheptatriacontane

4 5 ^ 6 .5 2960 (m,sh) 2930 (vs) 2850 (s) 1470 (m) 1380 (w) 720 (w)

CC14

(27)

10.2)

(C H C I 3 ,

-0.26°

(R,R) [a]$?

c = (27)

351; 196

0.7— 1.0 (12H,m, 4 x CH3); 1.24 (64H,br s)

295

E.I.

'H 60 MHz CC14

(27)

295

(43)

(119)

(M — ); 281; 280 (M — C,gH3V+); 225; 224 (M C23H47+) (24)

— E -u H 2g + );

E.I. 533 (M CH,+ ); 351 (M

E.I. 533 (M - CH3+); 323 (M C|6Hu +); 253 (M - C21H43); 252 (24)

44, 120

27,119

24,44

118

Volume IV; Pheromones, Part B 11

( 1 1)

15689-72-2

( 10 )

7371-98-4

61295-60-1 (9)

27519-02-4 (8)

C.A.S. registry number (Compound)8

394

C28H58

13-Methylheptacosane

C3(,H62 422

13-Methylnonacosane

408

C29H60

4,8-Dimethylheptacosane

322

C23H46

(Z)-9-tricosene

Name Formula Mol wt 150—154/.35

mp bp °C

3010 2930 2850 1460 720 (121)

IR ( c m 1)

UV (nm), other spectral properties

129.98

(121)

322 (11 ,M + ’); 83 ( 100) (121)

0.88 (6H,t,J = 5 Hz); 1.27 (34H, br s); 2.00 (4H,m); 5.29 (2H,t,J = 5 Hz) (121) 13C

121)

E.I. 394;379;365; 225; 224(M - C,2H25H) +; 197; 196(M - C14H29-H) +; 169; 168

(42,138)

E.I. 422; 253; 225; 297; 169

(42)

E.I. 365 (M - C-,H7) \ 295; 141 ;71

(

379 (89, M + C4H9+); 323 (94, M + H +); 321 ( 100,M - H +)

C.I. C4Hlfl 200 eV

E.I.

Mass spectrum m/z (%)

'H 100 MHz CDCI3

NMR (ppm)

42

42

42

38, 121— 127

Synthesis reference

Table 4 (continued) DIPTERAN PHEROM ONES INVOLVED IN SEXUAL BEHAVIOR: CHEM ICAL AND SPECTRAL PRO PERTIES

12 CRC Handbook of Natural Pesticides

(Z)-14-tricosen-10-one C ^O 336

66640-78-6 (14)

(Z)-14-nonacosene C29H58 406

(Z)-13-nonacosene C29H58 506

(Z)-13-heptacosene C27H54 378

54863-80-8 (15)

54863-79-5 (16)

54863-75-1 (17)

QtfH^O 338

Tricosan-10-one (dihydroketone)

c/s-9,10-Epoxy tricosane C23H460 338

422

C3 oH 62

11-Methylnonacosane

66640-79-7 (13)

7371-99-5 (12)

39—40

378 (M +*)

E.I.

406 (M+ )

E.I.

406 (M+ )

E.I.

(35)

(35)

(35)

E.I. 226 (10); 211 (41); 183 (9); 170 (14); 155 (45); 127 (8) (40)

(138,42)

E.I. 422; 281; 253; 169; 141

(139) C.I. 200 eV CH4 393(100,M - H +) (139)

35, 129, 141

35, 129, 141

35, 129, 141

40, 140

40

42

Volume IV: Pheromones, Part B 13

(Z)-9-heptacosene

36258-12-5 (19)

462

(Z)-13-tritriacontene

66648-67-/

( 22)

(Z)-13-hentriacontene C3,H62 434

434

c 3,h 62

(Z)-\ 1-hentriacontene

394

C27 H54O

cis-9,10-Epoxyheptacosane (epoxide)

378

66648-66-6 (21)

66648-68-8 (20)

(Z)-9-pentacosene C25H50 350

51865-00-0 (18)

C27H54

Name Formula Mol wt

C.A.S. registry number (Compound)1

mp bp °C

730 (Z ene)

730 (Z) ene)

(107)

(142)

IR (cm* ')

UV (nm), other spectral properties

5.47 (t,J = 5 Hz) (on mixture) (145)

'H CDC13

NMR (ppm)

(116)

E.I. 394 (M +‘); 376 (M - H20 + ); 281 (M - C8H17+); 155 (M C|?H35+) (145)

350 (M + ’)

E.I.

Mass spectrum m/z (%)

32

32

31, 32

30

30, 143, 144

Synthesis reference

Table 4 (continued) DIPTERAN PHEROMONES INVOLVED IN SEXUAL BEHAVIOR: CHEMICAL AND SPECTRAL PROPERTIES CRC Handbook o f Natural Pesticides

15

45

45

Co

r\ 'in

4 m r-

in ON ■

9

W

Monomorium pharaonis3033

F orm icidae: p oison g lan d o f

Monomorium lati­ node, M. subopacum31

F orm icidae : p o iso n glan d o f

Monomorium lati­ node, M. subopacum,31 Solenopis fugax, S. punctaticops27

F o rm icidae: po iso n g lan d o f

Solenopsis molesta, S. texanus32

F orm icidae: p o iso n g la n d o f

F o rm icid ae:

w orkers

h =c h ,

C ,5H 29N

M o l w t 223

m /z (E l) 2 2 3 (2 ), 2 2 2 (1 ), 153(9), 1 52(100), 150(3), 14 1 (5 6 ), 140 (6 4 ), 122(2), 110(2), 109(3), 1 0 8 (3 ), 9 6 (4 ), 8 2 (1 5 ), 8 1 (5 ), 7 0 (3 ), 6 9 (5 ), 6 8 (6 ), 6 7 (1 0 ), 5 7 (3 ), 5 6 (8 ), 5 5 (1 3 ), 4 4 (3 ), 4 3 (5 ), 4 1 (1 3 ) F o rm icid ae:

5 -B u ty l-2 -h e p ty l-1-p y tro lin e

w orkers

CH,(CH,)r ( ~ ^ - ( c H J),CH1 C I5H 29N

M ol w t 223

m /z (E l) 2 2 3 (1 ), 2 2 2 (2 ), 2 0 8 (2 ), 194(4), 180(6), 1 6 6 (1 0 ), 15 2 (3 0 ), 1 39(50), 12 6 (1 2 ), 110 (1 0 ), 9 6 (1 2 ), 8 3 (2 0 ), 8 2 (1 0 0 ), 5 5 (2 5 ), 4 3 (1 0 ), 4 1 (2 5 )31 /ra rt$ -2 -B u ty l-5 -h ep ty lp y rro lid in e

HJ

Vih

CH,(CH1) P - N '^ ( C H J 1CH> C ,5H 31N

h

F o rm icid ae:

w orkers

M o l w t 225

m /z (E l) 2 2 5 (1 ), 2 2 4 (3 ), 168 (8 5 ), 126(100) /ra n j-2 -H e x y l-5 -p e n ty lp y rro lid in e

y CH ,(CH C 15H 31N

y ^ N / 3 (c H,) jCH , h

M ol w t 225

m /z(EI) 2 2 5 (2 ), 2 2 4 (3 ), 1 5 5 (1 3 ), 154(97), 141 (1 3 ), 1 4 0 (1 0 0 ), 8 2 (1 3 ), 6 9 (1 6 ), 6 8 (1 1 ), 5 5 (2 4 ), 4 1 (1 6 )

F o rm icid ae:

w orkers

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Table 2 (continued) PYRROLES, PYRROLIDINES, AND PYRROLINES, FOUND IN HYMENOPTERA

Compound rrans-2-Butyl-N-methyl-5-heptylpyrrolidine

Family Species References

Biological information

Formicidae: la tin o d e 31

M o n o m o r iu m

Formicidae: poison gland of workers

Formicidae:

M o n o m o r iu m p h a r -

Formicidae: poison gland of workers

H' T \ H CH.fCHj.^N^CH^CH, C 16H„N ch> Mol wt 239 (El) 239(1), 183(9), 182(71), 141(9), 140(100), 82(6), 42(5)21 ;ra«.v-2-Heptyl-5-(5-hexenyl)pyrrolidine

m /z

a o n is , M . s u b o p a c u m 31

CH2=CH(CH2h ) ^> NO^ CchH 2),CH, C 17H33N h Mol wt 251 m/z (El) 251, 152(100) 2(5-Hexenyl)-5-(8-nonenyl)-1-pyrroline

Formicidae:

M o n o m o r iu m e b e n -

in u m , M . v irid u m , M . C H i = C H (C H 1) j- ( ^ - ( C H !) C H = C H ,

C 19H„N Mol wt 275 m/z (El) no spectra reported 5(5-Hexenyl)-2-(8-nonenyl)-1-pyrroline CH,=CH(CH^r 43-(CH,),CH=CH1 N C 19H33N Mol wt 275 m/z (El) no spectra reported f/Ym.s-2(5-Hexenyl)-5(8-nonenyl)pyrrolidine V VH CH2=CH(CH2) f SsN ^C H ?)4CH=CHl CI9H35N h Mol wt 277 m i l (El) 277(3), 276(2), 234(12), 220(14), 195(15), 194(100), 178(10), 153(9), 152(83), 150(4), 136(3), 124(2), 122(2), 110(2), 109(1), 108(2), 96(5), 95(3), 94(2), 83(7), 82(30), 81(5), 70(2), 69(4), 68(10), 67(18) 57(1), 56(4), 55(20), 54(3), 53(2)28 fran.s-2-(5-Hexenyl)-5-nonylpyrrolidine

sp.

(Georgia)28

Formicidae:

M o n o m o r iu m e b en -

in u m , M . v irid u m , M .

sp.

(Georgia)28

Formicidae;

M o n o m o r iu m c a r-

b o n a r iu m , M . e b en in u m , M . m in im u m , M . m in u tu m , M .

,(c h , ) K ^ \ c h 1), c h = c h i

CI9H37N h Mol wt 279 m/z (El) 279(4), 278(3), 222(11), 197(20), 196(83), 178(10), 165(7), 153(2), 152(100), 150(5), 124(5), 110(5), 109(3), 108(3), 97(6), 96(10), 95(9), 94(4), 84(4), 83(13), 81(10), 70(9), 69(18), 68(15), 67(23), 57(7), 56(14), 54(6), 43(19), 41(19)28 2-Hwxyl-5-nonylpyrrolidine HJ VH CH,(CH2)r^N^(CH 2)5CH, C 19H39N h Mol wt 281 m/z (El) 281(1), 280(3), 197(13), 196(80), 155(10), 154(100), 82(12), 69(19), 56(10), 55(17)

Formicidae: whole body ex­ tracts of workers; presumed poison gland product

Formicidae: whole body ex­ tracts of workers; presumed poison gland product

v irid u m , M . sp. (Georgia), M . sp. (N. Mexico, Texas), M . n. sp. (Florida)28

Formicidae:

M o n o m o r iu m c y -

a n e u m , M . e b en in u m , M . m in ­ ch

Formicidae: whole body ex­ tracts of workers; presumed poison gland product

u tu m ,28 M . p h a r a o n is ,30 M .

Formicidae: poison gland product of workers/whole body extracts

sp. (Georgia), M . sp. (N. Mexico, Texas), M . n. sp. (Florida)28 v irid u m , M .

Formicidae:

M o n o m o r iu m e b e n ­

in u m , M . f lo r ic o la , M . v ir i­ dum , M .

sp. (Georgia)28

Formicidae: whole body ex­ tracts; presumed poison gland product

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Table 2 (continued) PYRROLES, PYRROLIDINES, AND PYRROLINES, FOUND IN HYMENOPTERA

Compound frart.s-2(5-Hexenyl)-,/V-methyl-5-(8nonenyl)pyrrolidine Ijr^CH J 4CH=CH, CH C20H37N 1 Mol wt 291 m/z (El) no spectra reported frart.s-2(5-Hexenyl)-,/V-methyl-5nonylpyrrolidine

Family Species References

Biological information

Formicidae: Monomorium mini­ mum, M. viridum28

Formicidae: whole body ex­ tracts; presumed poison gland product

Formicidae: Monomorium cyaneum, M. viridum, M. sp. (Georgia), M. sp. (N. Mexico, Texas)28

Formicidae: whole body ex­ tracts; presumed poison gland product

CH,=CH(CH

vry

CH,(CH0,

N/N (CH04CH=CH1

C20H39N CHj Mol wt 293 m/z (El) 293(1), 211(8), 210(100), 167(5), 166(55)

are secondary amines. The analytical data are very sparse on some of the bicyclic bases reported in Monomorium, making it difficult to evaluate the work. M ISCELLA N EO U S N ITRO G EN -C O N TA IN IN G COM POUNDS

Introduction Besides the alkaloids derived from pyrazines, pyrroles, pyridines, indolizidines, and pyrrolizidines described previously, a few other nitrogen-containing compounds occur in Hymenoptera and Isoptera. Since these compounds are so diverse they are included here for lack of a better arrangement.

Source A terminal nitroalkene was the first compound identified from the frontal gland secretion of soldier termites (Prorhinotermes simplex).50 2-Piperidone and its N-methyl homolog have been identified recently from the frontal gland of another termite (Cornitermes weberi).52 Skatole (3-methylindole) is present in the poison glands of two species of myrmicine ants (Pheidole spp.)42 and in the mandibular gland secretion of stingless bees (Trigona).262 Indole3-acetic acid, a known plant hormone, has been identified in the worker metapleural glands of two species of leafcutting ants (Atta spp.).48 Methyl anthranilate is much more widespread, though it is strictly a mandibular gland product. In two formicine ant genera (Camponotus, eight species;23,44 Myrmecocystus, two species47) it is found specifically in the male man­ dibular glands. In two myrmicine ant genera (Aphaenogaster and Xenomyrmex) it occurs in the mandibular gland secretions of queens and workers.46 It is difficult to miss the grape­ like odor when the mandibular glands are crushed and smelled; the mass spectrum is unique as well. 0-Aminoacetophenone is a mandibular gland product in the myrmicine ant Mycocepurus goeldii.293 A large number of amines have been identified in two Mesoponera ant species but their source is unknown; analyses were performed on total extracts of thoraces and gasters.330

Chemistry The mass spectrum of 1-nitro- 1-pentadecene is unusual in that the major losses are hydroxyl

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Table 3 PYRIDINES, PIPERIDEINES, AND PIPERIDINES FOUND IN HYMENOPTERA Family Species References

Compound Actinidine CH, u

Biological information

Formic idae: two C o n o m y rm a spp. #1 (Texas), #2 (Geor­ gia),34 I r id o m y r m e x h u m ilis 217

Formicidae: anal gland of workers

Formicidae: S o le n o p s is (D ip lo r h o p tr u m ) sp. (Puerto Rico)31

Formicidae: poison gland of workers

p

CH C 10H13N 3 Mol wt 147 m/z (El) 147(50), 146(26), 132(100), 131(20), 130(18), 117(42), 105(5), 103(17), 91(15), 89(6), 77(33), 65(18), 55(17), 53(22), 51(22)M 2-(4-Penten-1-yl)-1-piperideine C ^ C chJ jCh ^ch, C 10H17N Mol wt 151 m/z (El) 151(10), 150(10), 136(20), 110(10), 108(5), 97(100), 96(30)31 'H NMR 8 5.6(1H,doublet of t), 4.96(lH,brd), 4.87(lH,brd) 3.46(2H,brm), 2.05(6H,m), 1.6(6H,m)

Formicidae:

Formicidae: poison gland of workers; functions as an attractant

A p h a e n o g a s te r

f u lv a , A . te n n e s s e e n s is 35

C 10H 12N2 Mol wt 160 m/z (El) 160(85), 159(84), 156(81), 155(68), 145(53), 131(97), 105(51), 104(100), 78(47), 77(40), 51(58), 50(40), 41(30)35 *H NMR (220 MHz) 8 8.95(lH,s), 8 .6 (lH,brs), 8.1(lH,d), 3.85(2H,t), 2.62(2H,t), 1.85(2H,m), 1.70(2H,m) 2-Methyl-6-nonylpiperidine

Formicidae:

S o le n o p s is

(D ip lo r -

h o p tr u m ) c a r o lin e n s is 31 S .( D .)

CHfCji^CHj.CH, C 15H31N ” Mol wt 225 m/z (El) 225(0.5), 224(2), 210(5), 99(10), 98(100), N, 2-Dimethy 1-6-nonylpiperidine

(both isomers),309 S. sp. (Puerto Rico),31 5. g e n in a ta , S. r ic h te r i (venom of alate females)37 c o n ju r a ta ,

Formicidae:

S o le n o p s is (D ip lo r -

h o p tr u m ) c a r o lin e n s is 31 S.

ch/

C ^ ch^ ch,

C16H„N CH' Mol wt 239 m /z (El) 239(0.5), 238(1), 225(1), 224(2), 113(8), 112(100)

c o n ju r a ta

(D .)

(both isomers)309

Formicidae: whole body ex­ tracts of workers; presumed poison gland product

Formicidae: whole body ex­ tracts of workers; presumed poison gland product

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Table 3 (continued) PYRIDINES, PIPERIDEINES, AND PIPERIDINES FOUND IN HYMENOPTERA Family Species References

Compound 2-Methyl-6-undecyl- 1 -piperideine

CHf^N^(CH 2)1tCH, C 17H33N Mol wt 251 m /z (El) 251(15), 236(12), 222(3), 208(4), 194(3), 180(10), 156(10), 152(30), 138(17), 124(15), 111(16), 110(100), 107(32), 97(95), 96(75), 82(18), 55(23), 43(23), 41(40)38 2-Methyl-6-undecylpiperidine

Formicidae:

Formic idae:

S o le n o p s is x y lo n i38

S o le n o p s is a u r e a ,

S. e d u a r d i ,310 S . g e m in a ta ,37 3*

CHfCr^(CHOi.CH> C,7H35N H Mol wt 253 m/z (El) 253(1), 252(1), 238(3), 99(10), gsaoo)3*

N , 2-Dimethyl-6-undecylpiperidine

S. in v ic ta 36 3* 39 S . r ic h te r i ,37-3*

(Brazil),310 S. x y ­ (D ip lo r h o p tr u m ) p e r g a n d e i,31 S. ( D . ) c o n ju r a ta (c is isomer)309

S. s a e v is s im a

Biological information Formicidae: poison gland extracts of workers

Formicidae: poison gland of workers; in some cases alate female venom; whole body extracts of workers

lo n i ,3* S .

Formicidae: S o le n o p s is (D ip lo r ­ h o p tr u m ) p e r g a n d e i 31

Formicidae: poison gland of workers

Formicidae:

Formicidae: poison gland of workers

CHrCi^fCHOHCH, C 18H37N ’ Mol wt 267 m/z (El) 267(1), 266(1), 253(1), 252(2), 113(6), 112(100)31 2-Methyl-6-(4-tridecenyl)piperidine

S o le n o p s is g e m i-

n a ta ,38 S . in v ic ta ,36 S. r i ­

CHrC^X(cH 2),CH=CH(CH2) 7CHJ H C 19H37N Mol wt 279 m /z (El) 279(2), 278(2), 264(3), 250(1), 236(1), 180(4), 125(20), 111(20), 98(100)38 2-Methyl-6-tridecylpiperidine

c h te r i ,310 S . s a e v is s im a

(Brazil),310 S.

Formicidae:

x y lo n i.3*

S o le n o p s is a u r e a ,310

S . g e m in a ta ,31 S . in v ic ta ,36 S.

ch^ C k ^ ( chO,2ch,

H C 19H39N Mol wt 281 m /z (El) 280(1), 266(2), 99(5), 98(100)38 2-Methyl-6-(6-pentadecenyl)piperidine CHJ^K^(CHJ 5CH=CH(CH2)7CHj H C2,H4IN Mol wt 307 m/z (El) 307(1), 306(2), 292, 278, 264, 208, 206, 154, 152, 124, 111, 99(7), 98(100), 55(15), 43(13), 41(21) (intensi­ ties of other ions not reported)

Formicidae: poison gland of workers

(E u o p h th a lm a ) litto r a lis ,31 S. r ic h te r i,37 310 S . s a e v is s im a

(Brazil),310 S.

x y lo n i 38

Formicidae: S o le n o p s is in ­ v ic ta ,36,38 S. r ic h te r i, S. s a e v is s m a (Brazil)310

Formicidae: poison gland of workers

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Table 3 (continued) PYRIDINES, PIPERIDEINES, AND PIPERIDINES FOUND IN HYMENOPTERA

Compound 2-Methyl-6-pentadecylpiperidine C H fCi^(C H ,) 1.CHl H C21H43N Mol wt 309 m/z (El) 309(1), 308(2), 294, 280, 266, 99(7), 98(100), 55(15), 43(13), 41(21) (intensities of other ions not reported) 2-Methyl-6-(8-heptadecenyl)piperidine chj^ C k

Family Species References

Biological information

Formicidae: Solenopsis geminata,37 S. invicta,36-38 S. richteri37

Formicidae: poison gland of workers

Formicidae: Solenopsis spp.31

Formicidae: poison gland of workers

^( ch ,)7ch=ch(ch J 7ch,

|!| C23H45N Mol wt 335 m/z (El) 335, 334, 320, 306, 292, 98(100) (intensities of other ions not reported)

and then water leaving C 15H26N + . There is no loss of N 0 2(M-46) or oxygen from the molecular ion. The only other major fragment reported is m/z 30 measured as NO + . All of the mass spectra of the amines found in Mesoponera are dominated by alpha cleavage adjacent to the nitrogen just as in the alkaloids found in Tables 2, 3, and 4. The mass spectra of 2-piperidone and N-methyl-2-piperidone are dominated by ions at m/z 30 and 44 respectively probably corresponding to CH2NH2+ and CH3NHCH2+. The mass spectra of skatole and methyl anthranilate are unique. The former shows a base peak at M-l and the latter loses methanol to form a base peak at m/z 119. Indole 3-acetic acid exhibits unique cleavage as well as losing the entire side chain to form a base peak at m/z 130. 0-Aminoacetophenone shows cleavage on both sides of the carbonyl group losing the methyl and acetyl group.

Summary Most of the nitrogen-containing compounds listed in this section can be easily recognized from their mass spectra. Again, it is possible to detect the presence of many of these compounds by the human nose (e.g., methyl anthranilate) when nothing can be seen in the mass spectrometer. They are much less widely distributed than the alkaloids listed earlier, many being limited to one or two species.

ESTERS Introduction Esters are the most widely distributed class of compounds in Hymenoptera (over 170 out of the 600 total). Although acetates and propionates of diterpenes have been identified in Isoptera, they will be discussed later. The esters found in Hymenoptera can be classified into three types: (1) those formed from even carbon-containing acids and even carboncontaining alcohols, (2) those formed from even carbon-containing acids and terpenoid alcohols, and (3) those formed from terpenoid acids and terpenoid alcohols. The compounds which do not fall into these classifications consist of odd carbon-containing esters (two propanoates, three nonanoates, and an undecanoate), and a few aromatic esters and esters related to type 1 above but containing an odd number of carbons in the alcohol moiety.

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Table 4 PYRROLIZIDINES AND INDOLIZIDINES FOUND IN HYMENOPTERA

Compound (5Z,9Z)-3-ethyl-5methyloctahydroindolizidine

Family Species References Formicidae: Solenopsis (Diplorhoptrum) conjurata309

Formicidae: whole body ex­ tracts; presumed poison gland product

Formicidae: Monomorium pharaonis2930

Formicidae: poison gland of workers

Formicidae: Monomorium pharaonis41

Formicidae: poison gland of workers

Formicidae: Solenopsis sp .40

Formicidae: whole body extract

Qp ch

3

c h 2c h

3

C„H2IN Mol wt 167 m/z (El) 167(1), 166(3), 152(6), 139(10), 138(100), 124(2), 122(1), 110(2), 96(2), 95(5), 84(1), 82(2), 70(3), 69(3), 68(3), 67(3), 56(2), 55(5), 42(2), 41(6) ■H NMR 8 3.56(lH,m), 3.36(lH,m), 3.23(lH,m), 1.58(3H,d,J = 6.2), 1.13(3H,t,J = 6 . 8) 13C NMR 8 67.3(CH), 64.4(CH), 60.1(CH), 35.8(CH2), 32.1(CH2), 30.8(CH2), 30.3(CH2), 29.2(CH2), 24.9(CH2), 22.7(CH3), and 11.0(CH3) 3-Butyl-5-methyloctahydroindolizidine

QP CH,

(CH2),C H ,

C 13H25N Mol wt 195 m/z(EI) 195, 194, 180, 138(100)29(intensities of other ions not reported) ■H NMR(CDC13) 8 2.52(lH,br), 2.27(lH,br), 2.13(lH,br), 1.18(3H,d), 0.88(3H,t) 3-(3-Hexen-l-yl)-5methyloctahydroindolizidine

CH,

Biological information

(C H 2) 2C H = C H C H 2CH ,

C,5H27N Mol wt 221 m/z (El) no data reported (5Z,8£)-3-Heptyl-5-methylpyrrolizidine

m CH,

(C H 2),C H ,

C 15H29N Mol wt 223 m/z (El) 223(4), 222(2), 208(8), 194(3), 180(3), 166(2), 139(1), 138(2), 136(2), 125(10), 124(100), 110(9), 98(1), 97(1), 84(2), 82(1), 81(5), 69(3), 68(2), 67(2), 56(3), 55(7), 54(1), 43(4), 4K8 )40 IR 2790, 2690, 1460, 1370, 1355, 1180, 1130, 1105, 120 c m -1 'H NMR(CDC13) 8 3.66(lH,m), 2.78(lH,m), 2.66(lH,m), 1.8(4H,m), 1.6 — 1.3(16H,m), 1.12(3H,d,J = 6.2), 0.88(3H,brt)

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Table 4 (continued) PYRROLIZIDINES AND INDOLIZIDINES FOUND IN HYMENOPTERA

Compound ,3C NMR (C6D6) 8 66.29, 64.99, 61.81, 37.46, 35.13, 32.59, 32.40(2C), 32.20, 30.20, 30.45. 29.93, 27.33, 23.11, 22.59, 14.35 (5Z,9Z)-3-hexyl-5-methylindolizidine

CO

Family Species References

Formicidae: Solenopsis (Diplorhoptrum) sp. (Florida)309

Biological information

Formicidae: whole body ex­ tracts; presumed poison gland product

CHj (PH,)sCH3

C 15H29N Mol wt 223 m/z (El) 223(1), 222(2), 208(3), 139(12), 138(100), 136(3), 95(3), 82(2), 70(2), 69(2), 68(2), 67(3), 55(5), 41(6) IR 2835, 2790, 2720, 2590, 1455, 1380, 1320, 1305, 1263, 1205, 1170, 1135, 1110,1015 cm - 1 'H NMR (CF3C 0 2H) 5 3.65(lH,m), 3.36(lH,m), 3.22(lH,m), 1.58(3H,d,J = 6 .8 ), 0.92(3H,brt) ,3C NMR 8 67.3(CH), 63.0(CH), 60.3(CH), 39.7(CH2), 35.7(CH2), 31.9(CH2), 30.8(CH2), 30.2(CH2), 29.7(2CH2), 29.4(CH2), 27.0(CH2), 24.9(CH2), 22.7(CH3) and 14.0(CH3)

Source Acetates constitute the most extensive category (35 compounds) and they are the most diverse in their occurrence. They occur as venom gland components in the European hornet, as sting-shaft gland components of the honeybee, in the Dufour’s gland of many ants, in cephalic extracts of bees and wasps, and in the frontal gland of one species of termite soldiers. Although they are common Dufour’s products in ants, they are very uncommon in bee Dufour’s secretions but are found in both the labial and mandibular glands of other bee species. Acetates are not present in ant mandibular glands. Although butanoates have been identified as both Dufour’s and cephalic gland products, hexanoates have only been found in Dufour’s extracts. Octanoates and decanoates are fairly common both as cephalic secretions and Dufour’s secretions. The higher acid residues C 12, C 14, C 16, C 18, C20, C22, and C24 are much less common, those above C 18 being found only as Dufour’s products while the other three residues occur both as Dufour’s and cephalic products. Many of the acid moieties mentioned above occur in conjuction with terpenoid alcohols of 5, 10, 15, and 20 carbons. The C5 alcohols are restricted to esters found in halictid and nomiine bees containing aliphatic acids beginning at 14 carbons and occur in the Dufour’s gland. These same C5 alcohols have been found associated with C5 acids as venom com­ ponents in the European hornet. The monoterpenoid alcohol moieties (C10) occur more widely: in a termite frontal gland, in the cephalic extracts of carpenter bees, in the European hornet venom gland, and extensively in andrenid bee mandibular glands as well as their Dufour’s glands.364 Sesquiterpenoid (C15) alcohol residues are much more restricted. Famesyl esters are the

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Table 5 MISCELLANEOUS NITROGEN-CONTAINING COMPOUNDS FOUND IN HYMENOPTERA AND ISOPTERA

Compound

- P

2-Piperidone

C5H9NO Mol wt 99 mlz (El) 99(65), 98(10), 71(5), 70(15), 58(1), 56(10), 55(21), 43(60), 42(61), 41(59), 30(100) A-Methyl-2-piperidone

Family Species References

Biological information

Isoptera Termitidae: Cornitermes weberi52

Termitidae: frontal gland of soldiers

Isoptera Termitidae: Cornitermes weberi52

Termitidae: frontal gland of soldiers

Hymenoptera Apidae: Melipona interrupta triplaridis262 Formicidae: Neivamyrmex nigrescens,43 Pheidole fallcud2

Apidae: mandibular gland of workers Formicidae: cephalic secre­ tions; P. fallax; poison gland of major workers

Hymenoptera Formicidae: Mycocepurus goeldii293

Formicidae: mandibular gland of workers

Hymenoptera Formicidae: Aphaenogaster fulva,46 Camponotus an­ thrax, C. nearcticus, C. pavidus, C. rasilis, C. sayi, C. subbarbatus, C. vafer, C. n. sp. 23M Myrmecocystus romainei, M. semirufus,47 Xenomyrmex floridanus46

Formicidae: A. fulva, mandi­ bular gland of workers; Camponotus, male mandi­ bular gland; Myremecocystus, male mandibular gland; Xenomyrmex worker man­ dibular gland

Hymenoptera Formicidae: Atta sexdens, Acromyrmex, Myrmica48

Formicidae: worker metapleural gland

1 CH

Q H l NO ’ Mol wt 113 mlz (El) 113(35), 112(10), 85(3), 84(3), 70(11), 57(37), 55(26), 44(100), 43(15), 42(70), 41(30) Skatole (3-methylindole)

1

H

C ^N Mol wt 131 mlz (El) 131(50), 130(100), 103(8), 102(5), 77(18), 65(10), 63(5), 51(10), 50(5) o-Aminoacetophenone CO C H ,

P v nh> l^ s ji

C8H9NO Mol wt 135 mlz (El) 135(100), 120, 92, 65, no intensi­ ties given Methyl anthranilate nh

2

^ k ^ C 0 2CH ,

u C8H9N 0 2 Mol wt 151 mlz (El) 151(1), 120(30), 119(100), 92(55), 91(10), 90(2), 65(20), 64(5), 63(5), 52(3), 39(10)

Indole-3-acetic acid

11

C 10H,NO2 h Mol wt 175 mlz (El) 175(35), 130(100), 103(5), 102(4), 77(10), 44(10)

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Table 5 (continued) MISCELLANEOUS NITROGEN-CONTAINING COMPOUNDS FOUND IN HYMENOPTERA AND ISOPTERA

Compound N-Acetyl nonylamine 0 c h ,c n h (c h

2), c h ,

CnH23NO Mol wt 185 m/z (El) 185(27), 170(8), 150(9), 142(13), 128(12), 114(23), 100(31), 87(15), 86(34), 73(70), 72(69), 60(27), 58(7), 57(5), 56(7), 55(14), 44(22), 43(52), 42(7), 41(23), 39(4), 30(100), 29(11), 27(6) AMsoamyl nonenylamine CH , ^ C H (C H 2) 2N H ( c H 2),C H , CH,

(c=c) CI4H29N Mol wt 211 m/z (El) 211(0.1), 210(0.2), 209(0.2), 196(0.4), 194(0.3), 154(4), 142(1), 126(2), 114(1), 105(1), 100(75), 91(5), 83(1), 71(1), 70(1), 69(2), 67(1), 57(1), 56(1), 55(3), 45(2), 44(100), 43(12), 42(2) N-Isoamyl nonylamine CH , ^ c h (c h J 2n h (c h ,), c h , CH,

C 14H31N Mol wt 213 m/z (El) 213(12), 198(4), 184(1), 170(4), 156(98), 142(5), 100(75), 70(5), 57(6), 56(4), 55(6), 44(100), 43(30), 42(5), 41(15) AMsovaleroyl nonenylamine CH , ^ c h c h 2c n h (c h 2), c h , CH, II

C 14H29NO Mol wt 227 m/z (El) 227(25), 212(20), 208(10), 185(30), 170(25), 156(20), 142(10), 128(30), 115(40), 114(38), 102(20), 101(18), 100(30), 85(83), 73(60), 57(100), 44(40), 43(60), 41(62), 30(70), 29(30) N-Formyl AMsoamylnonylamine CH O CH, | ^ c h (c h J 2n (c h 2), c h , CH]

C 15H31NO Mol wt 241 m/z (El) 241(2), 240(1), 226(3), 212(1), 198(5), 184(30), 172(3), 170(4), 156(5), 142(3), 128(25), 114(5), 100(7), 86(3), 73(20), 72(100), 60(8), 58(8), 55(8), 44(10), 43(17), 41(10)

Family Species References

Biological information

Hymenoptera Formicidae: Mesoponera castanea, M. castaneicolor330

Formicidae: total extract of gasters and thoraces of workers

Hymenoptera Formicidae: Mesoponera castanea, M. castaneicolor330

Formicidae: total extracts of thoraces and gasters of workers

Hymenoptera Formicidae: Mesoponera castanea, M. castaneicolor330

Formicidae: total extracts of thoraces and gasters of workers

Hymenoptera Formicidae: Mesoponera castanea, M. castaneicolor330

Formicidae: total extracts of thoraces and gasters of workers

Hymenoptera Formicidae: Mesoponera castanea, M. castaneicolor330

Formicidae: total extracts of thoraces and gasters of workers

Volume IV: Pheromones, Part B

19

Table 5 (continued) MISCELLANEOUS NITROGEN-CONTAINING COMPOUNDS FOUND IN HYMENOPTERA AND ISOPTERA

Compound iV-Heptyl nonylamine C H ,(C H ,),N H (C H l)tC H ,

C 16H35N Mol wt 241 m/z (El) 241(0.5), 182(7), 156(85), 128(100), 98(7), 84(9), 70(14), 57(20), 56(18), 55(18), 44(61), 43(30), 42(6), 41(7) 1-Nitro-1-pentadecene ch

,(c h 1) 12c h = c h n o ,

C 15H28NO Mol wt 255 m/z (El) 255(0), 238, 220, 30 (no intensi­ ties reported) IR 3095, 1646, 1522, 1350, 960, 725 cm -1 *H NMR(CC14) 5 7.17(lH,dt,J = 13.4,6.6,6.6), 6.87(lH,dt,J = 13.4,1.0,0.9), 2.25(2H,brq), 1.15— 1.70(22H,brs), 0.88(3H,t,J = 6.5). /V,/V-Diisoamyl nonylamine rcH j n ^ C H C H jC H j N (C H 2),CH , |C H 3 _J2

Family Species References

Biological information

Hymenoptera Formicidae: Mesoponera castanea, M. castaneicolor330

Formicidae: total extracts of thoraces and gasters of workers

Isoptera Rhinotermitidae: Prorhinotermes simplexi50

Soldier frontal gland LDjq = 13 |xg/fly (Musca domestica)51

Hymenoptera Formicidae: Mesoponera castanea, M. castaneicolor330

Formicidae: total extracts of thoraces and gasters of workers

C 19H41N Mol wt 283 m/z (El), 283(7), 268(1), 226(100), 170(96), 156(4), 114(27), 100(4), 58(18), 44(8), 43(7)

only compounds found to date and all but one of these are restricted to andrenid Dufour’s products. The one exception, 2,3-dihydrofamesyl acetate, is found in labial glands of male Bombus and in the Dufour’s gland of one species of Melissoides bee.274 Although the hexanoate has been identified in only 45 species of andrenids, the only other Hymenoptera having it are two species of cleptoparasitic Nomada that are associated with species of Andrena.270 The butanoate, octanoate, and decanoate are also restricted to andrenids. Only famesyl acetate has been identified elsewhere, in labial glands of male bumblebees,60 Du­ four’s glands of Melissoides 274 cephalic extracts of Ceratina77 and Dufour’s glands of ants.6!’63 ?! Only two diterpenoid (C20) alcohol residues have been identified, both from bees. Geranylgeranyl octanoate is an Andrena Dufour’s gland product65 and geranylgeranyl acetate is found in the Dufour’s gland of Formica ants70 as well as the labial glands of male bumblebees.60 Terpenoid acid residues are restricted to C5 and C 10 and these are found in the European hornet, the former compounds from the venom gland and the latter from the seventh sternal glands. Geranyl geranate, famesyl geranate, and famesyl famesate have recently been re­ ported in Protandrena Dufour’s glands,364 but the reported molecular weights are incorrect for all three and no spectral documentation is provided. The only other odd carbon-containing acid residues are two propanoates (one from female mandibular glands of Andrena265 and the other from pine sawflies286), three nonanoates (two from Camponotus male mandibular glands66 and the other of whole body extracts of Notoncus ants).9

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Odd carbon-containing alcohol residues are more common, methyl, heptyl, nonyl, undecyl, tridecyl, and heptadecyl being found in addition to semi- and sesquiterpenes. Aromatic (benzene derivatives) have been found in the queen mandibular glands of Apis,229 worker sting apparatus of Apis,250 mandibular glands of male Camponotus,66 as well as male mandibular glands of other formicine ants.23 45 53 296

Chemistry Homologous series of aliphatic esters are easily recognized by ions in their mass spectra corresponding to RCO+, R C 02H2+, and CnH2n of the corresponding alcohol. Mixtures of esters having the same molecular weight can be characterized using these ions. Even if the molecular ions are very weak the combination of alcohol (minus water) and acid (RCO+, R C 02H2+) ions allows identification.

Summary Several trends are apparent in the appearance of esters in Hymenoptera. From the highest molecular weight reported (mol wt 526) down to a molecular weight of 320 (famesyl hexanoate) all but three compounds are Dufour’s gland products. Many of these are reported to be used to line the brood cells in solitary and eusocial species of bees representing approximately six families and numerous genera. In contrast, compounds with molecular weights under 200 are found primarily in the poison glands (presumably alarm pheromones), sting apparatus Apis workers, and mandibular glands of both ants and bees. The compounds isolated from the sting apparatus of honeybee queens are all high mol wt (mostly decanoates) (284 to 424) whereas those from honeybee workers are all of low mol wt (i-Hexyl acetate 0 CH ,CO (CH jCH j

C8H 160 2 Mol wt 144 m/z (El) 84(15), 73(8), 69(10), 61(18), 56(32), 55(18), 43(100), 42(15), 41(13) Benzyl acetate c h ,c o c h

y

2- ^

C9H 10O2 Mol wt 150 m/z (El) 150(15), 108(60), 107(10), 106(20), 105(20), 91(30), 90(25), 79(15), 77(30), 65(10), 63(5), 60(25), 51(20), 45(40), 43(100) Methyl p-hydroxybenzoate HO—

y- COCH,

C8H80 3 Mol wt 152 m/z (El) 152(38), 122(10), 121(100), 93(20), 65(15), 39(10) Methyl anthranilate C8H9N 0 2 Mol wt 151 2-Heptyl acetate O

,

^

H

C Hj(c H j)4CH O C C H j CH

C9H,g0 2 1 Mol wt 158 m/z (El) 143(1), 116(1), 102(5), 98(20), 87(35), 70(15), 69(20), 61(10), 56(45),

See Table 5 Hymenoptera Apidae: Apis mellifera3,8

Apidae: sting-shaft gland of workers

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CRC Handbook o f Natural Pesticides

Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA F a m ily S p e c ie s C om pound

Methyl 3-isopropyl pentanoate (methyl 3ethyl-4-methylpentanoate)

y

___ OH V c O .C H ,

' ---(

CH,

QH^C^ Mol wt 166 m/z (El) 166(40), 135(20), 134(100), 106(25), 105(10), 78(15), 77(8)

Methyl 5-methylsalicylate OH

Hymenoptera Formicidae: Formica polyc-

Formicidae: extraction of heads and thoraces

Hymenoptera Formicidae: Bothroponera soror , 296 Camponotus americanus, C. castaneus, C. dumetorum, C. ferruginus,23 C. herculeanus,45 C. ligniperda,45 C. nearcticus, C. novaeboracensis,44 C. pavidus, C. planatus ,23 C. pennsylvanicus,44 C. quercicola, C. rasilis , C. sayi,23 C. subbarbatus,44 C. ulcerosus, C. vafer,23 Gnamptogenys pleurodon,53 Polyergus lucidus (Georgia)23

Hymenoptera Formicidae: Bothroponera

o

Formicidae: Camponotus, male mandibular gland; Gnamptogenys, mandibular gland of workers; Polyer­ gus, mandibular gland of females and workers

Formicidae: mandibular gland of workers

soror296

COCH* QH^C^

B io lo g ic a l in f o r m a t io n

tena, F. rufanf>

COjCH,

Q H ^O j Mol wt 158 m/z (El) 158(1), 127(15), 115(16), 111(8), 109(11), 101(10), 97(15), 87(35), 85(46), 83(32), 74(100), 69(41), 43(55), 41(43) Methyl 6 -methylsalicylate C

R e fe r e n c e s

Mol wt 166

m/z (El) 166(51), 134(100)351 3-Methyl-3-buten- 1 -yl 3-methyl-2-

butenoate

Hymenoptera Vespidae: Vespa crabro 54

Vespidae: poison gland of workers

Hymenoptera Vespidae: Vespa crabro54

Vespidae: poison gland of workers

ch,

ll ^ ch2 ^C=CHCOCHjCH,C CH, V CH,

CIOH 160 2 Mol wt 168 m/z (El) 113(0.7), 101(5), 83(100), 68 (66 ), 67(20), 55(34), 53(22), 41(37) 3-Methyl-2-buten-1-yl 3-methyl-2butenoate CH, ■;c = CH,

H

^CH ,

chcoch,ch= c

CH,

C,oH i60 2 Mol wt 168 m /z (El) 168(1), 153(1), 123(3), 109((1), 101(5), 100(17), 83(100), 69(53), 68(50), 67(48), 55(47), 53(42), 41(64)

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83

Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA Family Species References

Compound 3-Methyl-3-buten-1-yl 3-methylbutanoate CH, ft CM, ^ C H C H 2COCH2CH2C ^CHj

Biological information

Hymenoptera Vespidae: V e s p a

c r a b r o 54

Vespidae: poison gland of workers

Hymenoptera Vespidae: V e s p a

c r a b r o 54

Vespidae: poison gland of workers

Hymenoptera Vespidae: V e s p a

c r a b r o 54

Vespidae: poison gland of workers

CHj

C10H180 2 Mol wt 170 (El) 128(0.5), 110(1), 103(2), 85(37), 68(100), 67(33), 57(66), 53(11), 41(78) 3-Methyl-2-buten-1-yl 3-methylbutanoate

m /z

CH, || /C H , ^ C H C H 2COCH2CH = C CH, X CH,

C10H18O2 Mol wt 170 (El) 170(0.8), 128(0.5), 103(1), 85(43), 69(60), 68(58), 67(52), 60(37), 57(59), 53(29), 43(26), 41(100) 3-Methyl-1-butyl 3-methyl-2-butenoate

m /z

CH,

ft

/H ,

^:c = c h c o c h 2c h 2c h

CH,

>VCH,

C10H180 2 Mol wt 170 (El) 170(2), 126(0.4), 101(18), 100(38), 83(100), 71(18), 70(22), 55(56), 53(11), 43(54), 41(32) Oct-2-en-l-yl acetate 0 C H ,(c H j,C H = CH C H 2O C C H, m /z

C10H18O2 Mol wt 170 m /z (El) no spectral data reported 3-Methyl-1-butyl 3-methylbutanoate

Hymenoptera Apidae: A p is

m e llife r a 318

Hymenoptera Vespidae: V e s p a

c r a b r o 54

Apidae: sting-shaft gland ol workers

Vespidae: poison gland of workers

CH, ,-C H , ^ C H C H 2COCH2CH 2CH CH, ^ CH,

C10H20O2 Mol wt 172 (El) 130(1), 129(2), 115(3), 104(14), 85(71), 70(100), 60(7), 57(60), 55(47), 43(83), 41(74)M Octyl acetate m /z

o c h ,c o (c h

0 7c h ,

C10H20O2 Mol wt 172 m /z (El) 130(1), 129(1), 112(5), 84(15), 83(12), 70(20), 69(18), 61(18), 57(10), 56(21), 55(20), 43(100), 42(17), 41(30) Non-2-enyl acetate o ch

,(c h 2) sc h = c h c h 2o c c h ,

C uH20O2 Mol wt 184 (El) no spectral data reported

m /z

Hymenoptera Andrenidae:

A ndren a

n ig r o a e n e a 216

Apidae:

A p is c e r a n a ,55 56 A .

Andrenidae: mandibular gland product Apidae: sting-shaft gland ol workers

d o r s a ta 55 56 A . f l o r e a 56 A . m e llife r a 56 250311

Hymenoptera Apidae: A p is

m e llife r a 318

Apidae: worker-sting shaft gland

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Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA

Compound

Family Species References Hymenoptera Formicidae:

n-Nonyl acetate o C H jC O fC H j.C H ,

C uH220 2 Mol wt 186 m/z (El) 126(5), 98(25), 97(20), 84(25), 83(28), 82(10), 70(35), 69(30), 68(10), 61(30), 57(18), 56(45), 55(35), 43(100), 42(18), 41(25) 2-Nonyl acetate o II

F o r m ic a s a n g u i-

Biological information Formicidae: Dufour’s gland of females

n e a ,51 G ig a n tio p s d e s tr u c to r 182

Hymenoptera Apidae: A p is

m e llife r a 318

Apidae: sting-shaft gland of workers

CH ,(C H f),C H O C C H , CH ,

CnH20O2 Mol wt 186 m/z (El) no spectral data reported c/s-Pin-3-en-2-yl acetate o II ^ . .O C C H ,

Isoptera Termitidae:

C o r ta r ite r m e s

Termitidae: Frontal gland of soldiers

s ilv e s tr i229.

ltfj| C12H180 2 Mol wt 194 m/z (El) 166(3,M + ( s ic ) ) , 134(38), 132(39), 119(100), 117(44), 115(23), 91(76), 44(64), 36(51) ‘H NMR(CDC13) 8 5.3—5.4(2H,m), 2.06(3H,s), 1.76(3H,s), 1.34(3H,s), 0.92(3H,s) Geranyl acetate ?

i

A n d r e n a c a ra n -

to n ic a , A . h a e m o r r h o a ,216 A . la b i a t a , 139 A . n ig r o a e n e a 216

L

X

Anthophoridae:

C12H20O2 Mol wt 196 m/z (El) 196(0.5), 181(2), 136(10), 121(12), 119(2), 109(2), 107(3), 105(2), 95(15), 93(30), 81(10), 69(100), 68(40), 67(15), 55(10), 53(8), 43(90), 41(80)

2-Decen-l-yl acetate 0 c h ,c o c h ,c h

Hymenoptera Andrenidae:

= c h (c h ,)#c h ,

C12H220 2 Mol wt 198 m/z (El) 156(5), 138(9), 43(100) Methyl 9-oxodec-2-enoate o o II, . II CH ,C (C H ,)5CH = C H C O C H , CMH180 3 Mol wt 198 m/z (El) no spectral data available

C e r a tin a

s tr e n u a ,11 P ith itis s m a r a g d u la 58 Apidae: B o m b u s p r a to r u m 259 Specidae: S c e lip h r o n

Andrenidae: mandibular gland of females Anthophoridae: female ce­ phalic extracts Apidae: male labial gland Sphecidae: female cephalic extracts

c a e m e n ta r iu m 59

Hymenoptera Apidae: A p is

d o r s a ta , A .

Apidae: sting-shaft gland of workers

m e llife r a 329

Apidae: mandibular gland of queens

f l o r e a 5556

Hymenoptera Apidae: A p is

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85

Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA Family Species References

Compound Citronellyl acetate 1

0

p ^ ^ O -C C H ,

C12H220 2 Mol wt 198 m lz (El) 138(13), 123(24), 109(15), 95(29), 81(42), 69(59), 67(43), 57(38), 55(43), 43(100), 41(87)

Methyl 9-oxodecanoate o

0

Hymenoptera Andrenidae:

A n d r e n a o c r e a ta ,

A . w ilk e lla 265

Anthophoridae: P ith itis s m a r a g d u la 58 Apidae: B o m b u s p r a to r u m 60259

Vespidae:

Biological information Andrenidae: mandibular gland of females Anthophoridae: female ce­ phalic extracts Apidae: male labial gland Vespidae: poison gland of workers

V e s p a c r a b r o 54

Hymenoptera Apidae: A p is

m e llife r a 329

Apidae: mandibular gland of queens

Hymenoptera Apidae: A p is

m e llife r a 329

Apidae: mandibular gland of queens

C H 3C (C H 2) 7C O C H j

CnH20O3 Mol wt 200 (El) no spectral data reported !H NMR 8 3.66(3H,s), 2.1 l(3H,s)356 Methyl 9-hydroxydec-2-enoate o

m lz

c h 3c h o h (c h

2) , c h = c h c o c h 3

C hH2o0 3 Mol wt 200 m lz (El) no spectral data reported; however see Ref. 359 for a A-4 compound Ethyl decanoate 0 ch

,(c h 2) , c o c h 2c h ,

C12H2402 Mol wt 200 m lz (El) 200(2), 171(1), 157(15), 155(18), 115(10), 101(25), 88(100), 44(20), 43(55)

o 3(c h 2) 2c o (c h 2) 7c h 3

C12H240 2 Mol wt 200 m lz (El) similar to hexadecyl hexanoate but diagnostic ions at 112, 71, and 89 n-Decyl acetate 0 c h ,c o (c h

2) , c h 3

C12H240 2 Mol wt 200 m lz (El) 129(1), 128(1), 127(1), 112(8), 111(3), 98(5), 97(5), 84(10), 83(12), 70(20), 69(18), 61(20), 57(18), 56(20), 55(20), 43(100), 42(18), 41(30)

E x o n e u ra b i-

c in c ta , E . b ic o lo r , E . r ic h a r d s o n i261

Apidae:

Anthophoridae: mandibular gland of females Apidae: labial gland of males

B o m b u s te r r e s tr is , B .

lu c o r u m 60

Hymenoptera Andrenidae:

Octyl butanoate ch

Hymenoptera Anthophoridae:

A ndren a

Andrenidae: mandibular gland product

c a r a n to n ic a 276

Hymenoptera Andrenidae:

A n dren a

c a r a n to n ic a 276

Apidae: A p is m e llife r a 250317 Formicidae: C a m p o n o tu s lig n ip e r d a ,63 F o r m ic a p e r g a n d e i62 F . r u fib a r b is , F . s a n g u in e a ,57 F . s ch a u f u s s i , 285 F . s u b in te g r a ,62 G ig a n tio p s d e s tr u c to r , 182 L a s iu s n ig e r 61

Andrenidae: mandibular gland product Apidae: worker sting-shaft gland Formicidae: Dufour’s gland of the workers and females

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Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA

Compound Methyl 9-Hydroxydecanoate oII ch, choh(ch,)7coch, CnH220 3 Mol wt 202 m /z (El) 200(5), 169(10), 143(35), 125(5), 111(55), 98(5), 97(10), 87(20), 83(35), 74(15), 71(12), 69(20), 58(35), 55(40), 43(100), 41(15) 8-Acetoxy-2,6-dimethyl-2-octenal 1 9 p Ss/NsO-CCH, ^C H O C12H20O3 Mol wt 212 m /z (El) 212(1), 170(2), 152(4), 137(2), 123(6), 109(8), 95(27), 81(28), 67(25), 61(3), 55(31), 43(100) •H NMR 8 9.40(lH,s), 6.49(lH,t,J = 7.2), 4 .12(2H,t,J = 7.2), 2.38(2H,m), 2.05(3H,s), 1.76(3H,s), 1.55(5H,m), 0.97(3H,d,J = 6.5) Citronellyl propanoate 1

0

C13H240 2 Mol wt 212 (El) 138(20), 123(55), 109(25), 95(70), 82(60), 81(100), 69(75), 68(30), 67(40), 57(40), 55(20), 41(15) Methyl dodecanoate 0 CHj(CH2)1#COCHj C13H260 2 Mol wt 214 m /z (El) 214(5), 183(5), 171(5), 143(10), 129(3), 101(2), 87(55), 75(10), 74(100), 69(5), 59(5), 57(10), 55(15), 43(20), 41(15) /i-Undecyl acetate o CHjCO(chJ„CH, C13H260 2 Mol wt 214 m /z (El) similar to decyl acetate with diag­ nostic ions at 154, 61, and 43 Geranyl butanoate o IL ,

Family Species References Hymenoptera Apidae: A p is

Hymenoptera Andrenidae:

m e llife r a 329

P a n u r g in u s

Biological information Apidae: mandibular gland of queens

Andrenidae; mandibular gland of males and females

a tr a m o n te n s is 64

Hymenoptera Andrenidae:

A n dren a

Andrenidae: mandibular gland of females

o c r e a ta 265

m /z

Hymenoptera Anthophoridae:

Anthophoridae: mandibular gland of females

c in c ta , E . b ic o lo r , E . r ic h a r d s o n i261

Hymenoptera Formicidae:

C a m p o n o tu s lig -

Formicidae: Dufour’s gland of workers and females

n ip e r d a ,63 F o r m ic a r u fib a rb is , F . s a n g u in e a ,51 L a s iu s n ig e r 61

Hymenoptera Andrenidae:

A ndren a

c a r a n to n ic a 216

C14H240 2 ^ Mol wt 224 m tz (El) 136(10), 121(20), 107(5), 105(10), 93(100), 92(20), 91(22), 79(25), 77(25), 71(10), 69(80), 68(25), 60(20), 55(20), 53(22), 43(25), 41(85)

E x o n e u r a b i-

Andrenidae: mandibular gland product

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87

Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA

Compound Ethyl dodecanoate

Hymenoptera Anthophoridae:

0 C H ,(C H j)10C O C H 2CH,

C14H280 2 Mol wt 228 m/z (El) similar to ethyl dodecanoate with diagnostic ions at 88 and 101

n - Dodecyl

acetate 0 c h jc o (c h

Family Species References

a d a n i , 268 E x o n e u r a b ic in c ta , E . b ic o lo r , E . r ic h a r d s o n i 261

Apidae:

C14H280 2 Mol wt 228 m/z (El) similar to decyl acetate with diag­ nostic ions at 168, 61, and 43

Anthophoridae: mandibular gland of females Apidae: labial gland of males

B o m b u s lu c o r u m , 60,326

B . p a ta g ia tu s , B . s p o r a d ic u s, B . te r r e s tr is 60

Hymenoptera Andrenidae: 2) 11c h j

C e n tr is

Biological information

A n dren a h aem or-

r h o a ,216 A . l a b ia ta 139

Apidae:

T r ig o n a (O x y tr ig o n a )

ta ta ir a 246

Formicidae:

F o r m ic a p e r g a ti-

d e i ,62 F . r u fib a r b is , F . s a n ­ g u i n e d 51 F . s u b in te g r a ,62

Andrenidae: mandibular gland of females Apidae: cephalic extracts of workers Formicidae: Dufour’s gland of workers Melittidae: Dufour’s gland product

L a s iu s n ig e r 6163

Melittidae;

M e litta

h a e m o r r h o id a lis 315

Hymenoptera Andrenidae:

Decyl butanoate 0 CHj(CH2)2CO(CH2),CH j

C14H280 2 Mol wt 228 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 140, 89, and 71 Octyl hexanoate 0 c

H j(c h J , c o (c h J 7c h ,

C14H280 2 Mol wt 228 m/z (El) 228(0.1), 185(0.1), 172(0.5), 157(1), 117(53), 112(20), 99(41), 83(30), 71(42), 70(44), 61(16), 55(45), 43(100), 41(64) Citronellyl 3-methylbutanoate ? ^CH, ^ 0 -C C H ,C H

f

5

Andrenidae: mandibular gland product

c a r a n to n ic a 276

Hymenoptera Andrenidae:

A n d r e n a c a r lin i,

A . p e r p le x a 65

Halictidae:

D u fo u re a

Andrenidae: Dufour’s gland of females Halictidae: Dufour’s gland of females

n o v a e a n g lia e 15

Hymenoptera Vespidae: V e s p a

c r a b r o 54

Vespidae: poison gland of workers

Hymenoptera Vespidae: V e s p a

c r a b r o 54

Vespidae: poison gland of workers

T

C15H280 2 Mol wt 238 m/z (El) 138(15), 123(31), 109(15), 95(49), 85(23), 81(62), 69(59), 67(37), 57(48), 55(41), 43(23), 4K100)54 3-Methyl-1-butyl citronellate 0

r

A n dren a

J U v

l

^ CH3

^ o - c h , c h 2c h

Mol w t 238 m/z (El) 153(1), 152(9), 138(2), 123(7), 110(22), 95(31), 81(19), 69(74), 55(52), 41(100)”

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Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA Family Species References

Compound Methyl tetradecanoate

Hymenoptera Anthophoridae:

0 ch

c in c ta , E . b ic o lo r , E . r i-

,(c h , ) „ c o c h ,

C Mol wt 242 m/z (El) 242(5), 211(5), 199(5), 143(8), 87(60), 75(10), 74(100), 69(10), 59(8), 57(12), 55(20), 43(35), 41(25) rt-Tridecyl acetate 0

2) i c o c H|Ch 2— ^

Anthophoridae: mandibular gland of females; X y lo c o p a Dufour’s gland

c h a r d s o n i ,261 X y lo c o p a v ir g in ic a te x a n a 314

Hymenoptea Formicidae:

C a m p o n o tu s

Formicidae: Dufour’s gland of workers

lig n ip e r d a 63

CHjCO(CH2) 12CH,

C,5H30O2 Mol wt 242 m /z (El) similar to decyl acetate with diag­ nostic ions at 182, 61, and 43 2-Phenylethyl octanoate 0 c h j(c h

E x o n e u r a b i-

Biological information

y

Hymenoptera Formicidae:

C a m p o n o tu s

Formicidae: mandibular gland of males

c la r ith o r a x 66

C16H240 2 Mol wt 248 m/z (El) 104(100), 127 (no intensity given) Geranyl hexanoate 1 o r ^ ^ O - C ( C H j 4CH3

Hymenoptera Andrenidae:

A n dren a ac-

Andrenidae: Dufour’s gland secretions

c e p t a ,364 A . c a r b o n a r ia ,68 A . c o n fe d e r a ta ,65 A . d e n tic u l a t a A . f l e x a , 65 A . lo n g ifa -

C16H280 2 Mol wt 252 m /z (El) 252(0.1), 183(0.5), 136(10), 121(20), 107(5), 99(5), 93(45), 80(25), 69(100), 68(60), 57(15), 43(30), 41(80)

Tetradecenyl acetate 0

A . n i g r o a e n e a A . s p ir a e n a , A . tr id e n s 65

Hymenoptera Apidae: T r ig o n a

d e p ilis , T.

tu b ib a , T. x a n th o tr ic h a 69

CH jC O fcH jn CH j

Formicidae:

(VC = c )J

C16H3o0 2 Mol wt 254 m/z (El) 95(50), 82(78), 81(65), 68(60), 67(75), 55(55), 54(50), 43(100)

C a m p o n o tu s lig ­

C H j(CH2) jC H = C H ( C H 2) 7C O C H 1C H j

C,6H3o0 2 Mol wt 254 m/z (El) 254(7), 209(13), 208(12), 191(1), 166(16), 155(4), 137(7), 124(11), 110(14), 101(32), 88(55), 69(47), 61(10), 60(8), 55(100), 43(22), 41(60) Ethyl tetradecanoate 0

F o r m ic a n ig r ic a n s , F . p o ­ ly c te n a , F . ru fa 70

lu c o r u m ,326

Mol wt 256

Apidae: labial gland of males

B . te r r e s tr is , P s ith y r u s g lo b o s u s , P . s ilv e s tr is 60'72

Hymenoptera Anthophoridae:

E x o n e u r a b i-

c in c ta , E . b ic o lo r , E . ri-

C H ,(CH j12CO CH2CHj

Apidae: mandibular gland of workers Formicidae: Dufour’s gland of workers and females

n ip e r d a ,63 C . h e r c u le a n u s ,71

Hymenoptera Apidae: B o m b u s

Ethyl ris-9-tetradecenoate 0

C16H320 2 m/z (El)

c i e s ,61 A . m ilk w a u k e e n s is ,65

c h a r d s o n i,261 P ith itis s m a r a g d u la 58

Anthophoridae: mandibular gland of females

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Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA Family Species References

Compound Octyl octanoate 0 C H ,(C H ,),C O (C H ^ C H ,

C,6H3202 Mol wt 256 m /z (El) 256(0.1), 213(0.1), 200(0.1), 185(0.5), 157(1), 145(45), 127(28), 112(30), 83(40), 70(45), 61(25), 57(100), 55(60), 43(90), 41(80)

Hymenoptera Andrenidae:

A n d r e n a c a r lin i,

A ilic is , A . p e r p le x a , A . v ic in a 65

Anthophoridae:

S v a s tr a 0 .

o b liq u a 74

Biological information Andrenidae, Anthophoridae, Halictidae: Dufour’s gland Apidae: mandibular gland of workers Formicidae: mandibular gland of males

Apidae: T r ig o n a f iilv iv e n tr is 73 Formicidae: M y r m e c o c y s tu s d e p ilis , M . r o m a in e i41

Halictidae:

D u fo u re a

n o v a e a n g lia e 75

w-Tetradecyl acetate 0

CHjCOfCH^jCH, Mol wt 256 (El) 196(10), 168(12), 140(2), 125(15), 111(30), 97(60), 83(90), 69(95), 61(20), 57(90), 43(100), 41(80)

m /z

Hymenoptera Andrenidae:

A n d ren a h aem or-

r h o a ,276 P e r d ita s p h a e r a lc e a e , P . u ta h e n sis 364 Anthophoridae: M e lis s o id e s d e s p o n s a 274 Apidae: B o m b u s s p o r a d ic u s T r ig o n a ta ta ir a 246

Formicidae:

C a m p o n o tu s lig -

Andrenidae: mandibular gland product Anthophoridae: Dufour’s gland product Apidae: B o m b u s , labial gland of males; cephalic extracts in T r ig o n a Formicidae: Dufour’s gland of workers and females

n ip e r d a ,62 C . h e r c u le a n u s ,7x F o r m ic a p e r g a n d e i, F . su b in te g r a ,62 F . n ig r ic a n s , F . p o ly c te n a , F . r u fa ,70 L a s iu s n ig e r 61

Dodecyl butanoate 0 C H ^ C H ^ C O tC H ^ .C H ,

C16H320 2 Mol wt 256 m /z (El) similar to hexadecyl hexanoate but diagnostic ions at 168, 89, and 71

Decyl hexanoate 0 ch

,(c h J 4c o (c h J#c h ,

C16H3202 Mol wt 256 m /z (El) 256(0.3), 185(1.5), 172(0.5), 140(15), 117(65), 99(45), 97(20), 83(30), 73(8), 70(35), 61(20), 55(50), 43(100), 41(62) 2-Phenylethyl nonanoate Q ___ C H,(c Ht), CO C H,C H

C17H260 2 Mol wt 262 (El) 104(100), 141 (no intensity given)

m /z

Hymenoptera Andrenidae:

A n dren a

c a r a n to n ic a 276

Anthophoridae:

M e lis s o d e s

d e n tic u la ta 274

Melittidae:

M e litta

Andrenidae: mandibular gland product Anthophoridae: male ce­ phalic product Melittidae: Dufour’s gland product

h a e m o r r h o id a lis 315

Hymenoptera Andrenidae:

A n d r e n a c a r lin i,

Andrenidae: Dufour’s gland Halictidae: Dufour’s gland

A . p e r p le x a , A . v ic in a 65

Halictidae:

D u fo u r e a

n o v a e a n g lia e 75

Hymenoptera Formicidae:

C a m p o n o tu s

c la r ith o r a x 66

Formicidae: mandibular gland of males

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Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA Family Species References

Compound Famesyl acetate

s, }— C,7H280 2 Mol wt 264 m/z (El) 264(0.1), 204(1), 189(2), 161(1), 136(9), 121(6), 93(23), 81(26), 69(100), 43(80), 41(64)

2,3-Dihydrofamesyl acetate -C C H ,

Mol wt 266 m/z (El) no spectral data reported 2,6-Dimethyl-5-hepten-1-yl octanoate C , 7H 3o0 2

,

%0II

?1h3

C H j(C H 2) ,C O C H i C H C H 2C H jC H = C

Hymenoptera Andrenidae: Andrena accepta,364 A. bicolor,68 A. bisalicis, A. carlini, A. con­ federatei, A. cressonii,65 A. d en tic u la ta A . erigeniae,61 A. fenningeri, A. flexa,65 A. haemorrhoa68 A. imitatrix, A. milkwaukeensis, A. nasonii,65 A. nigroaenea,68 A. nuda, A. pruni, A. rugosa, A. spiraena, A. vicina,65 A. w-scripta61 Anthophoridae: Ceratina strenua,11 Melissodes desponsa274 Apidae: Bombus cullumanus,60 B. pratorum,60,259 Psithyrus barbutellus60 Formicidae: Camponotus ligniperda,63 C. herculeanus,71 Lasius niger61 Hymenoptera Anthophoridae: Melissodes desponsa274 Apidae: Bombus terrestris60 Hymenoptera Formicidae: Camponotus clarithorax66

Biological information Andrenidae: Dufour’s gland of females Anthophoridae: Dufour’s gland product Ceratina, ce­ phalic extracts Apidae: labial gland of males Formicidae: Dufour’s gland of workers

Anthophoridae: Dufour’s gland product Apidae: labial gland of males Formicidae: mandibular gland product of males

^CH, CHj

C,7H320 2 Mol wt 268 m/z (El) 145, 127, 109, 95, 82, 69, 67, 55, 41 (no intensities given) Methyl n-hexadecanoate 0 ch

,(c h J „ c o c h ,

C17H340 2 Mol wt 270 m/z (El) 270(2), 239(3), 227(10), 143(20), 129(5), 101(3), 87(85), 74(100), 69(10), 57(10), 55(15), 43(15), 41(10) /i-Pentadecyl acetate 0 c h ,c o (c h

J„ch ,

C,7H340 2 Mol wt 270 m/z (El) similar to decyl acetate with diag­ nostic ions at 210, 61, and 43

Hymenoptera Anthophoridae: Xylocopa virginica texana258 Formicidae: Lasius alienus (W)61

Anthophoridae: Dufour’s gland product Formicidae: Dufour’s gland product

Hymenoptera Formicidae: Camponotus ligniperda,63 C. herculeanus71

Formicidae: Dufour’s gland product of workers

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91

Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA

Compound Ethyl hexadecatrienoate 0

Family Species References Hymenoptera Apidae: lu c o ru m 60

Biological information B om bus

Apidae: labial gland of males

C H 3(CH2) m CO CH,CH,

C18H30O2 (3 C = c ) Mol wt 278 m/z (El) no spectral data reported Ethyl hexadecadienoate 0

Hymenoptera Apidae: B o m b u s

la p id a r iu s 60

Apidae: labial gland of males

C H j(C h J m C O C H 2CH,

C18H320 2 ( 2 C = c) Mol wt 280 m/z (El) no spectral data reported Geranyl octanoate

Hymenoptera Andrenidae:

A n dren a a c ­

Andrenidae: Dufour’s gland product

c e p t o r A . b is a lic is ,65 A . b r a d le y i,61 A . c a r b o n a r ia ,6S A . c o n f e d e r a ta ,65 A . d e n tic u -

C18H320 2 Mol wt 280 m/z (El) 280(0.1), 211(0.5), 136(10), 127(15), 121(20), 107(5), 93(50), 80(25), 69(100), 68(60), 57(15), 43(30), 41(80)

la ta ,68 A . f l e x a , 65 A . h e lv o la ,68 A . lo n g if a c ie s ,61 A . m a n d ib u la r is , A . m ilk w a u k e e n sis , A . m is e r a b ilis , A . n iv a lis ,65 A . p r a e c o x , 16 A . s p ir a e n a 65

2,6-Dimethyl-5-hepten-1-yl nonanoate o ch3 ru II 1 / CHi C H 3f C H l C O C H 2C H C H 2C H 2C H = C CH3 Mol wt 282 m/z (El) 159, 141, 109, 95, 82, 69, 67, 55, 41 (no intensities given) Ethyl hexadecenoate 0 ch

,(c h J 14c o c h 2c h ,

C,sH340 2 ^c = c ^ Mol wt 282 m/z (El) no spectral data reported 9-Hexadecenyl acetate c h 3c o (c h

J , c h = c h (c h J sc h 3

CigH^Oz Mol wt 282 m/z (El) 282(1), 222(28), 194(6), 180(3), 179(4), 166(6), 152(8), 138(15), 124(22), 110(28), 109(27), 96(78), 82(100), 67(62), 61(12), 55(70), 43(97), 41(58)

Hymenoptera Formicidae:

C a m p o n o tu s

Formicidae: mandibular gland of males

c la rith o r a x 66

Hymenoptera Apidae: B o m b u s B . lu c o r u m 60

Hymenoptera Apidae: T r ig o n a

h y p n o ru m ,

d e p ilis , T.

tu b ib a , T. x a n th o tr ic h a 69 Formicidae: C a m p o n o tu s h e r c u le a n u s ,7‘ C. lig n ip e r d a 63 F o r m ic a n ig r ic a n s , F . p o ly c te n a , F . ru fa 10

Apidae: labial gland of males

Apidae: mandibular gland of workers Formicidae: Dufour’s gland of workers

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Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA

Compound Hexadecenyl acetate o CH,CO (CH,)„CH,

Family Species References Hymenoptera Apidae: B o m b u s

Biological information Apidae: labial gland of males

s c a n d in a v ic u s 259

(C = C )

(double bond position unknown) C 18H3402 Mol \vt 282 m/z (El) no spectral data reported Tetradecenyl butanoate o

Hymenoptera Anthophoridae:

M e lis s o d e s

Anthophoridae: male ce­ phalic product

d e n tic u la ta 214

(c = c )

(double bond position unknown) C 18H34O2 Mol \vt 282 m/z (El) no spectral data reported Decyl octanoate 0 c h j(c h

?) i c o (c h J i c h ,

Hymenoptera Andrenidae:

A n d r e n a ca rli, ni,

A . ilic is , A . p e r p le x a , A . v ic in a 65

Anthophoridae: CjgH^Oz Mol \vt 284 m/z (El) 284(0.1), 213(1), 185(0.3), 145(55), 140(50), 127(35), 111(10), 97(20), 83(30), 69(35), 61(10), 57(5 55(50), 43(100), 41(60)

o ch

o b liq u a 74 Apidae: A p is m e llif e r a 251 Halictidae: D u fo u r e a n o v a e a n g lia e 15

Hymenoptera Andrenidae:

Dodecyl hexanoate

,(c h J , c o (c h J )Ic h j

0 C H jfC H j.C o fC H ^ C H ,

A n d r e n a carlii ni,

A . ilic is , A . p e r p le x a , A . v ic in a 65

Halictidae: Cjgl^^Oj Mol vvt 284 m/z (El) 284(0.1), 213(1), 185(0.5), 168(6), 117(48), 111(10), 99(25), 9'7(20), 83(30), 69(35), 61(10), 57(55), 55(5 0 ), 43(100), 41(60) Octyl decanoate

C e n tr is an-

a l i s , 366 S v a s tr a o b liq u a

Andrenidae: Dufour’s gland of females Anthophoridae: Dufour’s gland product Apidae: sting-shaft gland of queens Halictidae: Dufour’s gland product

Andrenidae: Dufour’s gland product Halicitidae: Dufour’s gland product

D u fo u r e a

n o v a e a n g lia e 75

Hymenoptera Anthophoridae:

C e n tr is a n -

Anthophoridae: Dufour’s gland product

a l i s , 366 S v a s tr a o b liq u a o b liq u a 74

CisH^Oz Mol vvt 284 m/z (El) similar to hexadecyl hexanoa te but diagnostic ions at 173, 155, and 112 Tetradecyl butanoate o C Hj(C HJ 2CO(c HJ „C Hj

^lgHjgOz Mol Vvt 284 m/z (El) similar to hexadecyl hexanoalte with diagnostic ions at 196, 89, and 7 1

Hymenoptera Andrenidae:

A n dren a

o c r e a ta 265

Anthophoridae: M e lis s o d e s d e n tic u la ta 274 Melittidae: M e litta h a e m o r r h o id a lis , M . le p o r in a 315

Andrenidae: mandibular gland of females Anthophoridae: male ce­ phalic product Melittidae: Dufour’s gland of females

Volume IV: Pheromones, Part B

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Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA Family Species References

Compound Ethyl hexadecanoate 0 ch

Hymenoptera Anthophoridae:

Anthophoridae: mandibular gland of females

c in c ta , E . r ic h a r d s o n i261

3(c h 2),4c o c h 2c h 3

C18H360 2 Mol wt 284 m /z (El) 284(5), 239(3), 157(8), 143(3), 101(55), 89(15), 88(100), 74(5), 73(10), 70(10), 69(8), 61(10), 60(10), 57(10), 55(20), 43(35), 41(25) /i-Hexadecyl acetate 0 c h 3c o (c h

E x o n e u r a b i-

Biological information

Apidae:

M e lip o n a in te r ru p ta

tr ip la r id is 262

Apidae: mandibular gland of workers Hymenoptera Andrenidae:

P e r d ita c a llic e r -

a ta , P . s p h a e r a lc e a e 364

,))Sc h 3

C18H360 2 Mol wt 284 m lz (El) 224(3), 196(3), 140(3), 139(3), 125(10), 111(20), 97(40), 83(50), 69(38), 61(38), 57(45), 55(55), 43(100), 41(40)

Anthophoridae:

C e r a tin a

c u c u r b itin a 77

Apidae: B o m b u s s c a n d in a v ic u s ,259.327 g s p o r a d ic u s ,60 T r ig o n a ta ta ir a 246

Formicidae:

C a m p o n o tu s lig -

n ip e r d a ,63 C . h e r c u le a n u s ,71 F o r m ic a n ig r ic a n s , F . p o ­

Andrenidae: Dufour’s glanc product Anthophoridae: mandibular gland of males Apidae: B o m b u s , labial gland of males; T r ig o n a , cephalic extracts Formicidae: Dufour’s gland of workers Melittidae: Dufour’s gland product

ly c te n a , F . r u f a ,70 L a s iu s a lie n u s, L . n ig e r * {

Melittidae:

M e litta

h a e m o r r h o id a lis 315

Hymenoptera Andrenidae:

Famesyl butanoate 1

1

°

A n dren a a c ­

Andrenidae: Dufour’s glanc of females

c e p t o r A . a r a b i s , 67 A . b i­ c o lo r ,68 A . b is a lic is ,65 A . b r a d le y i,67 A . c a r lin i, A .

C19H320 2 Mol wt 292 (El) 292(0.1), 189(2), 161(7), 136(10), 121(15), 93(21), 81(21), 71(43), 69(100), 41(76)

m /z

c o n fe d e r a ta ,65 A . d e n tic u la ta ,68 A . e r ig e n ia e 67 A . fe n n in g e r i, A . f le x a , A . g a r d in e r i,65 A . h a e m o r r h o a ,68 A . h ip p o te s , A . im ita tr ix ,65,67 A . n a s o n ii, A . n iv a lis , A . n u d a , A . p r u n i, A . r u g o sa , A . s p ir a e n a ,65 A . v io la e ,67 A . v ic in a ,65 A . w ilk e lla 65 67

3-Methyl-2-buten-1-yl tetradecanoate ch

,

o , H

u

3(c h 2) 11c o c h ,c h = c

/ CH’ CH3

C,9H360 2 Mol wt 296 (El) 296(0.2), 253(0.1), 219(0.2), 211(10) 69(88), 68(100)

m /z

Hymenoptera Halictidae: N o m ia n e v a d e n s is 78

Halictidae: Dufour’s gland product

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CRC Handbook o f Natural Pesticides Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA Family Species References

Compound 3-Methyl-3-buten-1-yl tetradecanoate o C H,(C h A jCOC HjC H,C

CH.

II

CH,

l

Hymenoptera Halictidae: Nomia nevadensis78

Halictidae: Dufour’s gland product

Hymenoptera Diprionidae: Diprion similis, Neodiprion sertifer■286-287

Diprionidae: source unknown

Hymenoptera Andrenidae: Protandrena mexicanorum, P. verbesinae364

Andrenidae: Dufour’s gland product

Hymenoptera Vespidae: Vespa crabro79

Vespidae: seventh sternal gland of workers

Hymenoptera Andrenidae: Panurginus potentillae140 Vespidae: Vespa crabro79

Andrenidae: Dufour’s gland product Vespidae: Seventh sternal gland of workers

CH,

C 19H360 2 Mol wt 296 m/z (El) 296(0.2), 253(0.1), 219(0.2), 211(10), 69(45), 68(100) erytho-Z ,7-Dimethylpentadecan-2-yl acetate O

Biological information

1

c h , c o c h c h (c h ,),c h (c h J 7c h ,

CH

C 19H380 2 Mol wt 298 m iz (El) 254, 238, 154, 140, 125, 116, 96, 86 (no intensities given) IR 1742, 1468, 1375, 1250, 950 cm -' 'H NMR(benzene d6) 8 4.88(lH,brp,J = 6 ), 1.75(3H,s), 1.06(3H,d,J = 6.4) ,3C NMR(benzene d6) 8 169.3, 73.8, 37.6, 33.1, 32.3, 30.4, 30.1, 29.8, 27.5, 24.9, 23.0, 20.9, 19.9, 15.8, 14.7, 14.3 Geranyl geranate i

u

i

\ 2 C2oH320 2 Mol wt 304 m/z (El) no spectral data reported; mol wt reported incorrectly Citronellyl geranate

d

^

S k

2 x

Mol wt 306 m/z (El) 306(0.5), 169(1), 168(1), 151(18), 138(15), 123(31), 109(8), 100(5), 95(24), 82(28), 81(30), 69(100), 55(20), 41(93) Citronellyl citronellate o

A

A . C2oH360 2 Mol wt 308 m/z (El) 308(0.5), 171(0.6), 170(1), 153(5), 152(6), 138(18), 123(25), 109(28), 95(35), 81(42), 69(100), 55(38), 41(88)

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Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA

Compound Geranyl decanoate JL i^

4s^

0 o

- c (c h J 1c h 1

X C20H36O2 Mol wt 308 m/z (El) 308(0.1), 239(0.5), 155(5), 136(10), 121(20), 107(5), 93(50), 80(25), 69(100), 68(60), 57(15), 43(30), 41(80) 9-Octadecenyl acetate 0 c h ,c o (c h

Biological information

Hymenoptera Andrenidae: Andrena confederata,65 A. helvola,68 A. Iongifacies,67 A. milkwaukeensis, A. tridens65

Andrenidae: Dufour’s gland product

Hymenoptera Apidae: Bombus muscorum60

Apidae: labial gland of males

Hymenoptera Anthophoridae: Melissodes denticulata274

Anthophoridae: male head extracts

Hymenoptera Andrenidae: Perdita albipennis, P. callicerata, P. coreopsidis, P. latior, P. mentzeliae, P. sphaeralceae. P. utahensis364 Anthophoridae: Centris analis, C. ruthannae366 Apidae: Bombus lapponicus,259 Psithyrus barbutell u s T r i g o n a tataira246 Formicidae: Camponotus ligniperda,63 Formica nigri­ cans, F. polyctena, F. rufa,10 Lasius nigerM Melittidae: Melitta americana364

Andrenidae: Dufour’s gland product Apidae: labial gland of males; Trigona, cephalic extracts of workers Anthophoridae: Dufour’s gland product Formicidae: Dufour’s gland of workers Melittidae: Dufour’s gland product

Hymenoptera Anthophoridae: Melissodes denticulata274 Melittidae: Melitta haemorrhoidalis, M. leporina315

Anthophoridae: male head extracts Melittidae: Dufour’s gland product

J, c h = c h (c h J 7c h 1

C20H380 2 Mol wt 310 m/z (El) no spectral data reported Hexadecenyl butanoate (double bond posi­ tion unknown) 0 ch

Family Species References

,(c h O,c o (c h ,),sc h ,

(c -c ) C20H380 2 Mol wt 310 m/z (El) no spectral data reported n-Octadecyl acetate 0 CHjCOfCH^CH, C2oH4o0 2 Mol wt 312 m/z (El) similar to decyl acetate with diag­ nostic ions at 252, 61, and 43

Hexadecyl butanoate o C H,(c H2) jCO ( c H2) ISC H, C2oH4o0 2 Mol wt 312 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 280, 89, and 71

96

CRC Handbook o f Natural Pesticides Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA

Compound ^^^•^^-Dimethylpentadecan-Z-yl propanoate O

CH,

CH,

Species References

Biological information

Hymenoptera Diprionidae: Diprion similis, Neodiprion sertifer286287

Diprionidae: source undetermined

Hymenoptera Andrenidae: Andrena carlini, A. ilicis, A. perplexa, A. vicina65 Halictidae: Dufourea novaeangliae75

Andrenidae: Dufour’s gland product Halictidae: Dufour’s gland product

Hymenoptera Andrenidae: Andrena carlini, A. ilicis, A. perplexa, A. vicina65 Anthophoridae: Svastra obliqua obliqua74 Halictidae: Dufourea novaeangliae75

Andrenidae: Dufour’s gland product Anthophoridae: Dufour’s gland product Halictidae: Dufour’s gland product

Hymenoptera Andrenidae: Andrena carlini, A. ilicis, A. perplexa, A. vicina65 Anthophoridae: Centris analis,366 Svastra obliqua obliqua74 Apidae: Apis mellifera251 Hymenoptera Anthophoridae: Centris analis,366 Svastra obliqua obliqua74

Andrenidae: Dufour’s gland product Anthophoridae: Dufour’s gland product Apidae: sting-shaft gland of queens

c h ,c h 2c o c h c h (c h J ,c h (c h 2) 7c h , CH,

C20H4o0 2 Mol wt 312 m/z (El) no spectral data reported •H NMR (CDC13) 5 4.82(1H, brp, J = 6 ), 2.28(2H, q, J = 7) Tetradecyl hexanoate o ch

,(c h J 4c o (c h 2), jc h ,

C20H4o0 2 Mol wt 312 m/z (El) 312(0.2), 241(1), 213(1), 196(3), 117(50), 111(18), 99(25), 97(30), 83(40), 69(45), 61(10), 57(80), 55(60), 43(100), 41(65) Dodecyl octanoate 0 ch

,(c h J , c o (c h J i )c h ,

Mol wt 312 m/z (El) 312(0.2), 241(1), 213(1), 168(8), 145(70), 127(35), 111(15), 97(30), 83(35), 69(42), 62(10), 61(10), 57(80), 55(60), 43(100), 41(65) Decyl decanoate o C Hj(c H2),CO(C H 2) jC Hj Mol wt 312 m/z (El) 312(0.2), 241(1), 213(1), 173(5), 155(3), 140(30), 111(18), 97(30), 83(38), 69(40), 61(10), 57(80), 55(60), 43(100), 41(65) Octyl dodecanoate 0 c h j(c h

2) „ c o (c h j) 7c h ,

C20H4o0 2 Mol wt 312 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 201, 183, and 112 Ethyl octadecanoate 0 C Hj(C H2)|gCO C H,C Hj

C2oH4o0 2 Mol wt 312 m/z (El) 312(10), 269(5), 267(5), 157(15), 143(5), 115(5), 101(60), 89(20), 88(100), 73(15), 70(10), 69(12), 61(15), 60(12), 57(15), 55(20), 45(5), 43(35), 41(20)

Hymenoptera Colletidae: Crawfordapis luctuosa,116 Hylaeus modestus,97 Ptiloglossa jonesi116

Anthophoridae: Dufour’s gland product

Colletidae: Dufour’s gland product

Volume IV: Pheromones, Part B

97

Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA F a m ily S p e c ie s R e fe r e n c e s

C om pound

Famesyl hexanoate l

Hymenoptera Andrenidae: Andrena ac0

X CziH^Oz Mol wt 320 m /z (El) 320(0.1), 259(0.1), 204(2), 189(2), 161(3), 136(10), 121(10), 107(14), 99(16), 93(35), 81(34), 69(100), 68(35), 55(15), 43(55), 41(84)

3-Methyl-2-buten-1-yl hexadecanoate H

c h i (c h J I4c o c h 1c h = c

v

s CH> CH,

C21H4o0 2 Mol wt 324 m /z (El) 324(0.25), 281(0.1), 257(0.25), 239(10), 69(88), 68(100) 3-Methyl-3-buten-1-yl hexadecanoate ° , . H ^ CH2 C HjfC H.1..COC H,C H,C 1 '"CH,

C2iH4o0 2 Mol wt 324 m/z (El) 324(0.1), 281(0.05), 257(0.25), 239(10), 69(40), 68(100) Dodecyl nonanoate o c h ,(c h 3 , c o (c h J„ c h ,

C2iH420 2 Mol wt 326 m /z (El) 326(5), 269(10), 241(15), 168(50), 159(100)

cepta , 364 A. andrenoides,65 275 A. arabis,67 A. bicolor , 68 A . bim aculata , 76 A. bisalicis,65 A. carantonica 76 A. carbonaria , 68 A. c a r lin i65 A. ceanothi,67 A. confederata,65 A. crataegi,67 A. cressonii , 65,275 A. denticulata,68 A. erigeniae,67 A. erythronii,65 275 A. fenningeri,65 A. fle x a ,65 A. forbesii 76 275 A. fucata, A. fu lva g o ,76 A. gardineri,65 A. gelri,76 A. haem orrhoa,68 96 A. hattorfia n a ,76 A. helvola 68 A. hilaris,67 A. hippotes 65 67 275 A. ilicis,65 A. imitatrix 65 67 275 A. marginata,96 A. m ariae,65 A. nasonii,65 A. nigroaenea,68 A. nivalis 65 A. n u d a 65'67 275 A. ovatula,76 A. pru n i,65 A. robertsonii,67 A. rugosa,65 A. russula,80 A. spiraena,65 A. tibilais 76 A. tridens 65 A. vaga,76 A. vicina,65 A. violae,67 A. wilkella, A. w-scripta67 Anthophoridae: Nomada bi­ fid a , N. marshamella270

Hymenoptera Halictidae: Dialictus coeru-

B io lo g ic a l in f o r m a t io n

Andrenidae: Dufour’s gland product Anthophoridae: male mandi bular gland product

Halictidae: Dufour’s gland product

leus,81 Nom ia nevadensis, N. triangulifera 78

Hymenoptera Halictidae: Dialictus coeru-

Halictidae: Dufour’s gland product

leus , 81 Nom ia nevadensis, N. triangulifera 78

Hymenoptera Formicidae: Notoncus ectatommoides9

Formicidae: whole body extracts

CRC Handbook o f Natural Pesticides

98

Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA Family Species References

Compound Geranylgeranyl acetate 1

1

ft

1

C22H360 2 Mol wt 332 m/z (El) no spectral data reported Geranyl dodecanoate o c h jc o (c h

Hymenoptera Apidae: Bombus cullum a n u s B . hypnorum,60-259 B. lucorum,60 B. pratorum,60 259 B. sorocensis, Psithyrus rupestris Formicidae: Formica nigri­ cans, F. polyctena, F. rufa70 Hymenoptera Andrenidae: Andrena tridens65

Biological information Apidae: labial gland of males Formicidae: Dufour’s gland of workers

Andrenidae: Dufour’s gland product

J„c h ,

(c=c) C22H4o0 2 Mol wt 336 m/z (El) 336(0.1), 267(0.5), 183(5), 136(10), 121(20), 107(5), 93(50), 80(25), 69(100), 68(60), 57(15), 43(30), 41(80) Eicosenyl acetate . o Jk * |i „

C22H420 2 Mol wt 338 m/z (El) no spectral data reported Tetradecenyl octanoate 0 c h j(c h

Hymenoptera Andrenidae: Perdita albipennis, P. callicerata, P. coreopsidis, P. mentzeliae, P. sphaeralceae, P. utahensis364

Anthophoridae: Centris analis366

Andrenidae: Dufour’s gland product Apidae: male labial gland

Anthophoridae: Dufour’s gland product

J i c o (c h J „ c h ,

(c=c) C22H420 2 Mol wt 338 m/z (El) no spectral data reported Ethyl eicosanoate 0 C H j(CH2)„ C O C H 2C H 3

C22H4402 Mol wt 340 m/z (El) similar to ethyl decanoate with di­ agnostic ions at 101 and 88 /i-Eicosyl acetate 0 C H jC O (C H 2)„CH3

C22H4402 Mol wt 340 m/z (El) similar to decyl acetate with diag­ nostic ions at 280, 61,, and 43

Octadecyl butanoate 0

c Hj(ch 2)2c o (c HjJjjCHj C22H4402 Mol wt 340 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 252, 89, and 71

Hymenoptera Colletidae: Crawfordapis luctuosa,U6 Hylaeus modestus,91 Ptiloglossa jonesi116 Oxaeidae: Protoxaea gloriosa1,6

Colletidae: Dufour’s gland product Oxaeidae: Dufour’s gland of females

Hymenoptera Andrenidae: Perdita albipennis, P. coreopsidis, P. latior, P. mentzeliae, P. sphaeralceae, P. utahensis364 Apidae: Bombus lucorum B. /. lapponicus327

Andrenidae: Dufour’s gland product Apidae: labial gland of males

Hymenoptera Andrenidae: Perdita latior364 Anthophoridae: Melissoides denticulata214 Nomada flavopicta3,5 Melittidae: Melitta americana,364 M. haemorrhoidalis, M. leporina315

Andrenidae: Dufour’s gland product Anthophoridae: Melissoides, male cephalic extracts; No­ mada, male head extracts Melittidae: Dofour’s gland product

Volume IV: Pheromones, Part B

99

Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA

Compound Hexadecyl hexanoate 0 CHjfCHj^COfCHj.jCH, C22H4402 Mol wt 340 m/z (El) 340(0.1), 269(1), 241(0.3), 224(6), 117(75), 111(15), 99(25), 97(30), 83(40), 69(45), 61(8), 57(65), 55(55), 43(100), 41(55); diagnostic ions are at 224, 117, and 99 Tetradecyl octanoate 0 c h j(c h

J, c o (c h 2)„ c h 1

C22H4402 Mol wt 340 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 196, 145, and 127 Dodecyl decanoate 0 CHjtCHj.COfcHjnCH, C22H4402 Mol wt 340 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 168, 173, and 155 Decyl dodecanoate 0 c h j(c h

JI0c o (c h J , c h j

C22H4402 Mol wt 340 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 140, 201, and 183 Octyl tetradecanoate 0 ch

,(c h 2) 12c o (c h 2) 7c h ,

C22H4402 Mol wt 340 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 229, 211, and 112 Famesyl octanoate 1 |

^

1 ^

A^

S - o - c (c h 2) i c h j

X C23H4o0 2 Mol wt 348 m/z (El) 348(0.1), 279(0.5), 204(2), 189(2), 161(3), 136(10), 127(20), 121(10), 107(15), 93(35), 81(33), 69(100), 68(35), 55(15), 43(55), 41(80)

Family Species References

Biological information

Hymenoptera Andrenidae: Andrena carlini, A. ilicis, A. perplexa65 Halictidae: Dufourea novaeangliae15

Andrenidae: Dufour’s gland product Halictidae: Dufour’s gland product

Hymenoptera Andrenidae: Andrena carlini, A. ilicis, A. perplexa65 Anthophoridae: Svastra obliqua obliqua74

Andrenidae: Dufour’s gland product Anthophoridae: Dufour’s gland product

Hymenoptera Andrenidae: Andrena perplexa65 Anthophoridae: Svastra obli­ qua obliqua74 Apidae: Apis mellifera,251 Trigona tataira246 Hymenoptera Andrenidae: Andrena perplexa65 Anthophoridae: Centris analis,366 Svastra obliqua obliqua74

Andrenidae: Dufour’s gland product Anthophoridae: Dufour’s gland product Apidae: queen sting-shaft product

Hymenoptera Anthophoridae: Svastra obli­ qua obliqua14

Anthophoridae: Dufour’s gland product

Hymenoptera Andrenidae: Andrena ac­ c e p to r A. arabis,61 A. bi­ c o l o r A . bisalicis,65 A. bradleyi,61 A. carbonaria,68 A. carlini, A. confederata, A. cressonii,65 A. denticul a t a A . erigeniae,61 A. erythronii,215 A. flexa, A. gardineri,65 A. haemorrhoa, A. helvola,6* A. hilaris,61 A. imitatrix,215 A. ilicis,65 A. longifacies61 A. mandibularis 215 A. milkwaukeensis,65 A. miserabilis,65 A. nigroaenea,6* A. nivalis 65 A. placida, A. pruni, A. spiraena, A. tridens65 A. violae, A. wilkella, A. w-scripta61

Andrenidae: Dufour’s gland product

Andrenidae: Dufour’s gland product Anthophoridae: Dufour’s gland product

CRC Handbook of Natural Pesticides

100

Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA Family Species References

Compound 3-Methyl-2-buten-1-yl octadecanoate ,

, «

C H ,( C H ,) „ C O C H ,C H = C

' CH> CH,

C23H44O2 Mol wt 352 m/z (El) 352(0.25), 285(0.25), 267(10), 69(90), 68(100)

3-Methyl-3-buten-1-y 1 octadecanoate °II

C H J(C H l) „ C O C H lC H l C v J

^ rw CH2 CH j

C23H44O2 Mol wt 352 m/z (El) 352(0.1), 285(0.1), 267(3), 69(40), 68(100)

Dodecyl undecanoate 0 C H ^ C H jjC O t C H ^ C H ,

Q 3H46O2 Mol wt 354 m/z (El) 354(10), 297(15), 241(15), 187(100), 168(70) Tetradecenyl decanoate 0|| C H jt C H j.C O fC H j.jC H ,

Biological information

Hymenoptera Halictidae: Agapostemon radiatus, A. texanus, Augochlorella striata, Dialictus coeruleus, D. cressonii, D. pilosus, D. versatus, Halictus confusus, Lasioglossum coriaceum, L. fuscipenne,81 Nomia heteropoda, N. nevadensis, N. triangulifera, N. t. tetrazonata78

Halictidae: Dufour’s gland product

Hymenoptera Halictidae: Agapostemon radiatus, A. texanus, Augochlorella striata, Dialictus coeruleus, D. cressonii, D. pilosus, D. versatus, Halictus confusus, Lasioglossum fuscipenne, L. coriaceum,81 Nomia heteropoda, N. nevadensis, N. triangulifera, N. t. tetrazonata78

Halictidae: Dufour’s gland product

Hymenoptera Formicidae: Notoncus ectatommoides9

Formicidae: whole body extracts

Hymenoptera Anthophoridae: Centris analis366

Anthophoridae: Dufour’s gland product

Hymenoptera Andrenidae: Perdita albipennis, P. callicerata, P. latior, P. utahensis364 Apidae: Bombus lucorum60 Melittidae: Melitta americana364

Andrenidae: Dufour’s gland product Apidae: labial gland of males Melittidae: Dufour’s gland product

Hymenoptera Andrenidae: Perdita callicerata364 Melittidae: Melitta ameri­ cana,364 M. haemorrhoidalis, M. leporina315

Andrenidae: Dufour’s gland product Melittidae: Dufour’s gland product

(c = c )

C2411^ 0 2 Mol wt 366 m/z (El) no spectral data reported n-Docosyl acetate 0 C H jC O f C H ^ .C H ,

C24H4802 Mol wt 368 m/z (El) similar to decyl acetate with diag­ nostic ions at 308, 61, and 43

Eicosyl butanoate 0 c h ,(c h !), c o (c h !)„ c h ,

C24H4802 Mol wt 368 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 280, 89, and 71

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101

Table 6 (continued) ESTERS FOUND IN HYMENOPTERA AND ISOPTERA Family Species References

Compound Octadecyl hexanoate 0

CHJ(CH,),CO(CH,)„CHl

C24H40O2 Mol wt 368 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 252, 117, and 99

Hexadecyl octanoate 0 c h 3(c h 1), c o (c h J isc h j

C24H4A Mol wt 368 m/z (El) similar to hexadecyl hexanoate but diagnostic ions at 224, 145, and 127 Tetradecyl decanoate 0 c h ,(c h ,), 0

C10H18O2 Mol wt 170 m/z (El) 128(5), 100(3), 85(100), 70(3), 69(3), 57(5), 56(10), 55(12), 43(15), 41(18) Mellein (3,4-Dihydro-8-hydroxy-3methylisocoumarin OH

O

L Xx C10H10O3 Mol wt 178 m/z (El) 178(88), 160(43), 148(18), 134(100), 132(20), 106(28), 104(26), 78(42), 77(35), 63(18), 51(55)

Tetrahydro-3,5-dimethyl-6-( 1-methylbutyl)2H-pyran-2-one

YY^

C,2H2 20 2 C i2H220 Mol wt 198 m/z (El) 198(0.3), 156(18), 127(100), 99(43), 83(8), 69(24), 56(53)

,45

237

Formicidae: extracts of queens; part of the of the queen recognition pheromone

Volume IV: Pheromones, Part B

113

Table 7 (continued) LACTONES FOUND IN HYMENOPTERA AND ISOPTERA

Compound

IR(CS2) 2954, 1749, 1380, 1189, 1091, 1022, 988 cm -' 'H NMR(benzene-d6) 8 3.44(lH,d,J = 10), 2.03(lH,ddq,J = 7,8,7), 1.49(lH,dddq,J = 7,7,10,6.5), 1.44— 1.10(6H), 1.07(3H,d,J = 7), 0.97(1 H,ddd,J = 7,8,13), 0.87(3H,t,J = 7), 0.81(3H,brd,J = 6), 0.45(3H,d,J = 6.5) 4-Hexadec-9-enolide

Family Species Reference

Biological information

Hymenoptera Formicidae: Lasius flavus61

Formicidae: Dufour’s gland of workers

Hymenoptera Colletidae: Colletes cunicularius,9' C. thoracicus92 Halictidae: Evylaeus albipes,93 E. calceatus9X93M1

Colletidae: Dufour’s gland products Halictidae: Dufour’s gland products

Hymenoptera Vespidae: Vespa orientalis241

Vespidae: mandibular gland of queens

Hymenoptera Formicidae: Iridomyrmex humilis217

Formicidae: whole body ex­ tract of workers

Hymenoptera Colletidae: Colletes cunicularius,91’96 C. cunicularius celticus 95 C. inaequalis," 6 C. succinctus 95 C. thoracicus9293 Halictidae: Augochloropsis metallica, Dialictus cressonii, D. rohweri, D. versa-

Colletidae: Dufour’s gland product Halictidae: Dufour’s gland product

ch,(ch,),ch =ch(ch

C16H280 2 Mol wt 252 m/z (El) spectrum similar to 4-octadec-9enolide but no details 16-Hexadecanolide ^c= o (CH,)„ | 0 C16H3o0 2 Mol wt 254 m/z (El) 254(12), 236(15), 194(8), 166(7), 152(8), 138(9), 124(11), 110(15), 97(30), 83(41), 69(55), 60(8), 55(100), 41(93) 5-Hexadecanolactone

ii CH \,

o n

\ i