Thesis (Ph. D.)--University of Wisconsin--Madison, 1960. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 104-108).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (M.S.)--University of Wisconsin--Madison, 1963. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 82-94).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1967. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (M.S.)--University of Wisconsin--Madison, 1967. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1981. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 139-146).

Thesis (M.S.)--University of Wisconsin--Madison, 1961. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 95-98).

Thesis (Ph. D.)--Oregon State University, 2008. / Printout. Includes bibliographical references (leaves 168-181). Also available on the World Wide Web.

Made available in DSpace on 2014-06-11T19:28:36Z (GMT). No. of bitstreams: 0 Previous issue date: 2004-08-27Bitstream added on 2014-06-13T18:35:00Z : No. of bitstreams: 1 silva_rf_me_botfca.pdf: 206090 bytes, checksum: d0288cc28838f575fdd2b8c666897008 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Universidade Estadual Paulista (UNESP) / A localização das lagartas de Spodoptera frugiperda no interior do cartucho-do-milho, muitas vezes, dificulta a absorção da dose de inseticida necessária a sua morte, de tal forma que uma porcentagem significativa de insetos absorvem doses subletais, sofrendo evidentemente alterações na sua biologia e capacidade reprodutiva. Dessa forma, esse trabalho se propôs a verificar a ação de diferentes concentrações de clorpirifós, deltametrina e lufenuron no desenvolvimento larval e performance biológica de S. frugiperda em dieta artificial e natural (folhas de milho) sob condições controladas (em temperatura de 25 +/- 2ºC, umidade relativa de 70 % e fotofase de 14 horas). Folhas de milho foram mergulhadas em soluções contendo clorpirifós nas concentrações 0,15; 0,25; 0,35; 0,50; 0,75; 1,00; 2,00; 4,00; 8,00; 16,00 e 32,00 ppm, deltametrina nas concentrações 0,20 e 0,40 ppm e lufenuron nas concentrações 0,20; 0,50 e 1,00 ppm, em seguida fornecidas para as lagartas, 48 horas após a eclosão. Também foram preparadas dietas artificiais específicas para S. frugiperda contendo os mesmos inseticidas nas respectivas concentrações, onde foram inoculadas lagartas com 48 horas de idade. As observações de mortalidade e desenvolvimento foram realizadas em dias alternados e os dados comparados ao tratamento testemunha, sem tóxico. Verificou-se que as lagartas que se alimentaram tanto em dieta artificial quanto no alimento natural contaminado pelos inseticidas deltametrina e lufenuron não atingiram a fase de pupa, no entanto, muitas lagartas permaneceram vivas por mais tempo do que o período de duração da fase larval da testemunha. Os tratamentos com clorpirifós, apesar de provocarem uma alta mortalidade de lagartas só inviabilizaram a obtenção de adultos a partir da concentração 8,00 ppm. Mesmo nas doses menores,... / The localization of Spodoptera frugiperda larvae in the inner part of maize whorl, turns difficult the absorption of the necessary insecticide dosage to provoke insect mortality, what means that in field conditions, a significant percentage of the insects absorbs sub-lethal dosages, showing evident modifications on their biology and reproduction capacity. This way, the aim of this research was to verify the action of concentrations chlorpyrifos, deltamethrin and lufenuron on larval development and on the biological performance of S. frugiperda fed on artificial and natural diets. Maize leaves were dip in solutions of clorpyrifos at 0.15, 0.25, 0.35, 0.50, 0.75, 1.00, 2.00, 4.00, 8.00, 16.00 and 32.00 ppm, deltamethrin at 0.2 and 0.4 ppm and lufenuron at 0.2, 0.5 and 1.00 ppm. These leaves were immediately offered to 48 hours larvae. Artificial diets, specially developed for S. frugiperda, were also prepared containing the same insecticides at the same concentrations to receive larvae with 48 hours old. The observations of mortality and development were obtained every other day and the data were compared to a check treatment, with no insecticide. It was possible to verify that the larvae fed on artificial or natural diets containing deltamethrin and lufenuron, did not reach the pupal stage, however, many of them stayed alive for a period superior than that observed for the check treatment. The clorpyrifos treatment, dispite its high larval mortality, turned difficult the obtaining of adults from concentration of 8.00 ppm on. Even at low dosages, many survival larvae died during the pupal phase; only for 16.00 and 32.00 ppm the larval mortality reached 100%. When insects are exposed to sub-lethal dosages of insecticides during their larval period of development, they can increase their life cycle, even when they do not afford the insecticide action, nevertheless, those insects that reach the adult stage, do not show any life cycle modifications.

The work presented in this thesis is concerned with the evaluation of potential synthetic routes for the diacylhydrazine group of compounds, and particularly, unsymmetrical diacylhydrazines. Diacylhydrazines form the basis for a relatively new group of insecticides that have molt accelerating properties, and which are considered to offer substantial advantages over other insecticides used for the control of certain insects. The overall objective for this study is to evaluate different potential synthetic routes for a model diacylhydrazine with the view to define potentially scaleable routes. The compound selected for this study was the unsymmetrical diacylhydrazine, N-[N-(tertbutyl) phenylcarbonylamino](4-methylphenyl)-carboxamide since it offers the same range of challenges that would be expected for the synthesis of other similar unsymmetrical diacylhydrazines. Thus, the synthesis of unsymmetrical diacylhydrazines require two reaction steps: The first step is the synthesis of the intermediate mono-acylhydrazine, while the second step is the synthesis of the desired diacylhydrazine from the intermediate mono-acylhydrazine. The most important factor in the two-step reaction sequence is to obtain a high degree of selectivity for the desired mono-acylhydrazine isomer. Acylation of t-butylhydrazine using 4-methylbenzoyl chloride can produce the desired product N-[(tert-butyl)amino](4-methylphenyl)carboxamide in yields above 90 percent, but this reaction produces a variety of by-products, including the “wrong” isomer (N-amino-N- (tert-butyl)(4-methylphenyl)carboximide). Unexpected byproducts for this particular acylation reaction, not previously reported in the literature have also been identified during this investigation. This includes a de-butylated diacylhydrazine, (4-methylphenyl)- N-[(4-methylphenyl)carbonylamino] carboxamide. Although the reaction between tert-butylhydrazine and 4-methylbenzaldehyde is very selective giving near quantitative yields of the desired hydrazone, the subsequent conversion of the hydrazone into the desired mono-acylhydrazine is problematic. The most promising route appears via bromination to form the hydrazidic bromide, followed by hydrolysis of the hydrazidic bromide. Yields for the bromination reaction during this investigation were somewhat higher than that reported previously in literature. Hydrolysis of the hydrazidic bromide, apparently also results in the hydrolysis of the reaction product to give an ester of the free acid (when an ester solvent is used). The synthesis of N-[N-(tert-butyl)phenylcarbonylamino](4-methyl phenyl)carboxamide was only briefly considered to evaluate essentially two approaches, namely: · The conversion of the monoacylhydrazine, N-[(tert-butyl)amino](4- methylphenyl)carboxamide, by acylating with either benzoyl chloride or methylbenzoate (gave 86 percent N-[N-(tert-butyl)phenylcarbonylamino](4-methyl phenyl)carboxamide when benzoyl chloride was used as acylating agent); and · The one-pot conversion of the hydrazone, [(1E)-2-(4-methylphenyl)-1- azavinyl](tert-butyl)]amine, by bromination/hydrolysis and acylation. In this case, benzoyl chloride (2 percent N-[N-(tert-butyl)phenylcarbonylamino](4-methyl phenyl)carboxamide), benzoic acid (80.67 percent N-[N-(tertbutyl) phenylcarbonylamino](4-methylphenyl)carboxamide) were evaluated as potential acylating agents.