Insecticidal Properties of Monoterpenoids and Their Derivatives As a New Natural Means of Crop Protection Sang Kyun Lee Iowa State University
Total Page：16
File Type：pdf, Size：1020Kb
Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1997 Insecticidal properties of monoterpenoids and their derivatives as a new natural means of crop protection Sang Kyun Lee Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Agricultural Science Commons, Agriculture Commons, Agronomy and Crop Sciences Commons, Entomology Commons, and the Toxicology Commons Recommended Citation Lee, Sang Kyun, "Insecticidal properties of monoterpenoids and their derivatives as a new natural means of crop protection " (1997). Retrospective Theses and Dissertations. 11478. https://lib.dr.iastate.edu/rtd/11478 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. TJMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter fiice, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely aflfect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. UMI A Bell & Howell Infonnation Company 300 North Zed) Road, Ann Aibor MI 48106-1346 USA 313/761-4700 800/521-0600 Insecticidal properties of monoterpenoids and their derivatives as a new natural means of crop protection by Sang Kyun Lee A dissertation submitted to the graduate faculty in partial fulfilment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major; Toxicology Major Professor: Joel R. Coats Iowa State University Ames, Iowa 1997 UMX Number: 9725429 UMI Microform 9725429 Copyright 1997, by UMI Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. UMI 300 North Zeeb Road Ann Arbor, MI 48103 ii Graduate CoUege Iowa State University This is to certify that the Doctoral dissertation of Sang Kyun Lee has met the dissertation requirements of Iowa State Univeristy Signature was redacted for privacy. Major Professor Signature was redacted for privacy. For the Major Program Signature was redacted for privacy. For the Graduate College iii TABLE OF CONTENTS LIST OF FIGURES v LIST OF TABLES vii ACKNOWLEDGMENTS x ABSTRACT xii CHAPTER 1. GENERAL INTRODUCTION 1 Introduction 1 Pest Damage and the Agrochemical Market 2 Natural Products as Pesticides 3 Terpenoids and Monoterpenoids 6 Dissertation Objectives 11 Dissertation Organization 13 CHAPTER 2. DSrSECTICIDAL ACTIVITY OF MONOTERPENOIDS TO WESTERN CORNROOTWORM(COLEOPTERA: CHRYSOMELIDAE), TWO- SPOTTED SPIDER MITE (ACARI; TETRANYCHIDAE), AND HOUSE FLY (DIPTERA: MUSCIDAE) 15 Abstract 15 Introduction 16 Materials and Methods 18 Results and Discussion 23 Acknowledgment 45 References Cited 45 CHAPTER 3. INSECTICEDAL ACTIVITIES OF MONOTERPENOID DERIVATIVES AGAINST SEVERAL INSECT PESTS 51 Abstract 51 Introduction 52 Materials and Methods 55 Results and Discussion 63 Conclusions 72 Acknowledgment 73 References Cited 74 iv CHAPTER 4. COMPARISON OF THE FUMIGATION TOXICITY OF MONOTERPENOIDS AGAINST THE RED FLOUR BEETLE (COLEOPTERA: TENEBRIONIDAE) 79 Abstract 79 Introduction 80 Materials and Methods 83 Results and Discussion 87 Conclusions 98 Acknowledgment 99 References Cited 99 CHAPTER 5. INFLUENCE OF DIETARY MONOTERPENOIDS AND DERIVATIVES ON SURVIVAL AND GROWTH OF THE EUROPEAN CORN BORER, OSTRINIA NUBILALIS (LEPIDOPTERA; PYRALIDAE) 105 Abstract 105 Introduction 106 Materials and Methods 108 Results 114 Discussion and Conclusions 131 Acknowledgment 135 References Cited 136 GENERAL CONCLUSIONS 141 APPENDIX L QUANTTTATTVE STRUCTURE-ACTIVITY RELATIONSHIPS (QSAR) WITH CALCULATED PARTITION COEFHCIENTS (CLOG-P) FORMONOTEREPNOID STRUCTURES WITH INSECTICIDAL ACTIVITIES 143 APPENDIX n. A TIMESAVING RESPIRATION BIOASSAY MEASURING THE CO2 PRODUCTION IN THE SOYBEAN CYST NEMATODE AND THE AMERICAN COCKROACH 189 GENERAL REFERENCES 198 V LISTOFHOURES CHAPTER 1. GENERAL INTRODUCTION Figure 1. World agrochemical market split by region (1995, Wood Mackenzie) 4 Figure 2. World agrochemical market split by key group (1995, Wood Mackenzie) 4 Figure 3. World agrochemical market split by crops (1995, Wood Mackenzie) 5 Figure 4. Terpenoid pathway in plants 7 Figure 5. Monoterpenoid structures 10 CHAPTERS. INSECTICIDAL ACTIVITIES OF MONOTERPENOID DERIVATIVES AGAINST SEVERAL INSECT PESTS Figure I. Ten parent monoterpenoid structures 56 Figure 2. The synthesis of monoterpenoid ester and ether derivative compounds. X = CI, Br, or I; R, see Fig. 3; M = monoterpenoid parent compounds; DCC, dicyclohexylcarbodiimide; DMAP, 4-(dimethylamino)pyridine; BTAB, benzyltributylammonium bromide 57 Figure 3. Monoterpenoid derivative types. " Refers to R in Fig. I 59 CHAPTER 4. COMPARISON OF THE FUMIGATION TOXICITY OF MONOTERPENOIDS AGAINST THE RED FLOUR BEETLE (COLEOPTERA: TENEBRIONIDAE) Figure 1. Structures of three monoterpenoids 85 Figure 2. Comparison of the toxic eflfect of acetone as a solvent, vi depending on the air-drying time intervals at 24 and 37 °C 90 CHAPTER 5. INFLUENCE OF DIETARY MONOTERPENOIDS AND DERIVATIVES ON SURVIVAL AND GROWTH OF THE EUROPEAN CORN BORER, OSTRINIA NUBILAUS (LEPIDOPTERA: PYRALIDAE) Figure 1. Monoterpenoid structures 109 Figure 2. Monoterpenoid derivative structures 110 vii UST OF TABLES CHAPTER 1. GENERAL INTRODUCTION Table I. Classification of terpenoids and subgroups 8 CHAPTER 2. INSECTICIDAL ACTIVITY OF MONOTERPENOIDS TO WESTERN CORNROOTWORM(COLEOPTERA: CHRYSGMELIDAE), TWO- SPOTTED SPIDER MITE (ACARI: TETRANYCHIDAE), AND HOUSE FLY (DIPTERA: MUSCIDAE) Table 1. Mortality of adult M domestica and D. virgifera virgifera 24 h after topical application of monoterpenoids 25 Table 2. Acaricidal activity of monoterpenoids fi'om the primary screening against T. urticae at 24 and 72 h by leaf-dip application 29 Table 3. Acaricidal activity of some selected monoterpenoids against T urticae at 48 h by leaf-dip application 33 Table 4. Mortality of 3rd instar D. virgifera virgifera at 48 h by soil application of monoterpenoids 34 Table 5. Com root protection effect of selected monoterpenoids against D. virgifera virgifera in greenhouse tests when 500 eggs were added per pot 38 Table 6. Phytotoxicity of monoterpenoids to com roots (expressed by dry weight) 40 Table 7. Phytotoxicity of selected monoterpenoids to com leaves and roots by visual inspection 10 d after treatment 42 CHAPTER 3. INSECTICIDAL ACTIVITIES OF MONOTERPENGID DERIVATIVES AGAINST SEVERAL INSECT PESTS Table 1. Insecticidal activity of monoterpenoids and their derivatives against M. domestica by topical application 64 Table 2. Larvicidal activity of monoterpenoids and their derivatives against D. virgifera virgifera by soil bioassay 69 vm••• Table 3. Fumigation toxicity of monoterpenoids and their derivatives against some public health and stored grain insects (14 hours after initial exposure at 50 ^g/ml) 71 CHAPTER 4. COMPARISON OF THE FUMIGATION TOXICITY OF MONOTERPENOIDS AGAINST THE RED FLOUR BEETLE (COLEOPTERA: TENEBRIONIDAE) Table I. Preliminaiy fumigation toxicity of twenty monoterpenoids against some public health and stored insects (14 hours after initial exposure at SO ^g/ml) 88 Table 2. Fumigation activity of several monoterpenoids and temperatures against 71 castaneum 91 Table 3. Efifect of temperature and concentration on the fumigation toxicity of several monoterpenoids against T. castaneum at 24 hours 95 Table 4. Efifect of temperature and concentration on the fumigation toxicity of several monoterpenoids against T castaneum at 48 hours 96 Table 5. Efifect of temperature and concentration on the fumigation toxicity of several monoterpenoids against T. castaneum at 96 hours 97 CHAPTER 5. INFLUENCE OF DIETARY MONOTERPENOIDS AND DERIVATIVES ON SURVIVAL AND GROWTH OF THE EUROPEAN CORN BORER, OSTRINIA NUBILAUS (LEPIDOPTERA: PYRALIDAE) Table 1. Larvicidal toxicity (6-day mortality data) of selected monoterpenoids and derivatives applied on the diet the 1st instar Ostrinia nubilalis 115 Table 2. Larvicidal mortality of four organic solvents incorporated into the dietof the 1st instar Ostrinia nubilalis 118 Table 3. Larvicidal toxicity of some selected monoterpenoids incorporated into the diet against the 2nd instar Ostrinia nubilalis after six days