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Previous issue date: 2004-03-25 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / O objetivo deste trabalho foi sintetizar compostos potencialmente inseticidas análogos às piretrinas a partir do D-manitol [1] em 7 etapas. A primeira reação foi de proteção das hidroxilas do D-manitol fornecendo o 1,2:5,6- di-O-isopropilideno-D-manitol [2] com rendimento quantitativo. O acetal [2] foi convertido no aldeído 2,3-O-isopropilideno-D-gliceraldeÍdo [3] por meio de clivagem oxidativa com NaIO4 em 70% de rendimento. O aldeído [3] com metoxicarbonilmetileno(trifenil)fosforano por reação de Wittig produzindo os isômeros (S)-(Z)-4,5-O-isopropilidenopent-2-enoato de metila [4] e (S)-(E)-4,5-O- isopropilidenopent-2-enoato de metila [5] em 65 % de rendimento na proporção de 8:2, respectivamente. (1S,3R)-2-[(S)-2,2-dimetil-1,3-dioxolan-4-il]-3,3- dimetilciclopropano-1-carboxilato de metila [6] foi sintetizado a partir do éster [4] e iodeto de isopropiltrifenilfosfônio/Butilítio em 81% de rendimento. O produto obtido na etapa anterior foi submetido a uma hidrólise utilizando ácido perclórico. O diol obtido foi submetido à clivagem oxidativa utilizando NaIO4 obtendo 3- formil-2,2-dimetilciclopropano-1-carboxilato de metila [8]. Por meio de reações de Wittig o aldeído [8] obtido na etapa anterior foi transformado nos piretróides (1S,3S)-2,2-dimetil-3-[2-metilprop-1-en-1-il]ciclopropano-1-carboxilato de metila [9] (23% de rendimento), (1S,3S)-2,2-dimetil-3-[(Z)-2-(4-nitrofenil)eten-1- il]ciclopropano-1-carboxilato de metila [10] e (1S,3S)-2,2-dimetil-3-[(E)-2-(4- nitrofenil)eten-1-il]ciclopropano-1-carboxilato de metila [11] (80% de rendimento), (1S,3S)-3-[(Z)-2-(4-bromofenil)eten-1-il]-2,2-dimetilciclopropano-1-carboxilato de metila [12] e (1S,3S)-3-[(E)-2-(4-bromofenil)eten-1-il]-2,2-dimetilciclopropano-1- carboxilato de metila [13] (83% de rendimento), (1S,3S)-3-[(Z)-2-(4- clorofenil)eten-1-il]-2,2-dimetilciclopropano-1-carboxilato de metila [14] e (1S,3S)- 3-[(E)-2-(4-clorofenil)eten-1-il]-2,2-dimetilciclopropano-1-carboxilato [15] (95% de rendimento), dimetilciclopropano-1-carboxilato de metila (1S,3S)-3-[(Z)-2-(4-fluorofenil)eten-1-il]-2,2- de metila [16] e (1S,3S)-3-[(E)-2-(4- fluorofenil)eten-1-il]-2,2-dimetilciclopropano-1-carboxilato de metila [17] (66% de rendimento), (1S,3S)-3-[(Z)-2-fenileten-1-il]-2,2-dimetilciclopropano-1-carboxilato de metila [18] e (1S,3S)-3-[(E)-2-fenileten-1-il]-2,2-dimetilciclopropano-1- carboxilato de metila [19] (60% de rendimento).Os compostos sintetizados[10], [14], [15], [18] e [19] foram submetidos a ensaios de atividade inseticida sobre: larvas de 2o ínstar de Musca domestica (L.) (Diptera: Muscidae) e dos Lepidoptera Ascia monuste orseis (Godart) (Pieridae), Leucoptera coffeella (Guérin-Mèneville) (Lyonetiidae) e Tuta absoluta (Meyrick) (Gelechiidae); ninfas de 2o ínstar de Periplaneta americana (L.) (Dictyoptera: Blattidae) e adultos de Sitophilus zeamais Mots. (Coleoptera: Curculionidae). Utilizando doses de 1 e 5 μg de cada substância/ mg de massa corporal do inseto e avaliação após 4, 12, 24 e 48 horas de aplicação. Não foi detectada toxicidade dos piretróides a M. domestica e S. zeamais. Os piretróides apresentaram toxicidade a A. monuste orseis, P. americana e T. absoluta. Apenas o piretróide [15] não apresentou toxicidade a L. coffeella. L. coffeella e T. absoluta foram mais suscetíveis aos piretróides [10], [14], [18] e [19] que A. monuste orseis e P. americana. A. monuste orseis, P. americana e T. absoluta apresentaram suscetibilidade semelhante ao piretróide [15]. A mortalidade de T. absoluta pelos piretróides ocorreu até quatro horas após a aplicação. Para A. monuste orseis a mortalidade ocorreu até 12 horas após a aplicação. Já para P. americana a mortalidade ocorreu até 24 horas após a aplicação, com exceção do piretróide [15] para o qual a mortalidade foi verificada até 12 horas após a aplicação. Os piretróides tenderam a apresentar maiores toxicidades na maior dose. / The current study had the purpose to synthesize compounds analog to pyrethrins with potential insecticide activity. The compounds were obtained in seven steps starting with D-Manitol [1]. The first step of the synthetic route corresponded to the protection of the hydroxyl groups present in D-Manitol [1] affording the acetal 1,2:5,6-di-O-isopropylidene-D-manitol [2] in quantitative yield. The oxidative cleavage of [2] utilizing NaIO4 gave 2,3-O-isopropylidene-D- gliceraldehyde in 70% yield. The Wittig reaction between [3] and (methyl(triphenylphosphoranylidene) acetate produced a mixture (65% yield) of two isomers namely methyl (S)-Z-4,5-O-isopropylidenepent-2-enoate [4] and methyl (S)-E-4,5-O-isopropylidenepent-2-enoate [5] respectively. The reaction between in the ratio of 8:2 compound [4] and isopropyltriphenylphosphonium iodide / buthyl lithium afforded methyl (1S,3S)-3- [(S)-2,2-dimethyl-1,3-dioxolan-4-il]-2,2-dimethyl cyclopropane-1-carboxylate [6] in 81% yield. The hydrolysis of [6] with perchloric acid resulted in a diol that was submitted to oxidative cleavage with NaIO4 affording the aldehyde methyl (1S,3S)-3-formyl-2,2-dimethylcyclopropane-1-carboxylate [8]. This aldehyde, through Wittig reactions with different ylides, was converted to the pyrethrins mehtyl carboxylate (1S,3S)-2,2-dimethyl-3-[2-methylprop-1-en-1-il]cyclopropane-1- [9] (23% yield), methyl (1S,3S)-2,2-dimethyl-3-[(Z)-2-(4- nitrophenyl)ethen-1-il]cyclopropane-1-carboxylate [10] and methyl (1S,3S)-2,2- dimethyl-3-[(E)-2-(4-nitrophenyl)ethen-1-il]cyclopropane-1-carboxylate [11] (80% yield), methyl (1S,3S)-2,2-dimethyl-3-[(Z)-2-(4-bromophenyl)ethen-1- il]cyclopropane-1-carboxylate [12] and methyl (1S,3S)-2,2-dimethyl-3-[(E)-2-(4- bromophenil)ethen-1-il]cyclopropane-1-carboxylate [13] (83% yield), methyl (1S,3S)-2,2-dimethyl-3-[(Z)-2-(4-chlorophenyl)ethen-1-il]cyclopropane-1- carboxylate [14] and methyl (1S,3S)-2,2-dimethyl-3-[(E)-2-(4-nitrophenyl)ethen-1- il]cyclopropane-1-carboxylate [15] (95% yield), methyl (1S,3S)-2,2-dimetil-3-[(Z)- 2-(4-fluorophenyl)ethen-1-il]cyclopropane-1-carboxylate [16] and (1S,3S)-2,2- dimethyl-3-[(E)-2-(4-fluorophenyl)ethen-1-il]cyclopropane-1-carboxylate [17] (66% yield), methyl (1S,3S)-2,2-dimethyl-3-[(Z)-2-phenilethen-1-il]cyclopropane- 1-carboxylate [18] and methyl (1S,3S)-2,2-dimethyl-3-[(E)-2-phenylethen-1- il]cyclopropane-1-carboxylate [19] (60% yield). Biological tests were conducted in laboratory using second instar larvae of Musca domestica (L.) (Diptera: Muscidae), Ascia monuste orseis (Godart) (Peridae), Leucoptera cofeela (Guérin-Mèneville) (Lyonetiidae) and Tuta absoluta (Meyrick) (Gelechiidae). Second instar nymphs of Periplaneta americana (L.) and adult insects of Sitophilus zeamais Mots (Coleoptera: Curculionidae) were also used to evaluate the potential insecticide activity of the synthesized pyrethrins. Doses ranging from 1 to 5 μg of each pyrethrin/mg of insect corporal mass were used to perform the testes and the effect of the compounds over the insects were evaluated after 4, 12, 24 and 48 hours after the application of the pyrethrins. The tests revealed that the pyrethrins are ineffective against M. domestica and S. zeamais. All of the pyrethrins showed activity against A. monuste oreseis, P. Americana and T. absoluta. Only the compound [15] did not show any activity against L. coffeella and T. absoluta. L. coffeella and T. absoluta were more susceptible to pyrethrins [10], [14], [18] and [19] than A. monuste orseis and P. Americana. A. monuste orseis, P. Americana and T. absoluta showed similar susceptibility to the pyrethrin [15]. The death of the insects T. absoluta happened after four hours of the pyrethrins application. Regarding P. Americana, the death was observed after 24 hours of the pyrethrins application, except for the pyrethrin [15] that led to death after 12 hours of application. The toxicity of the pyrethrins against the insects was superior when the compounds were applied in higher doses.
| Identifer | oai:union.ndltd.org:IBICT/oai:localhost:123456789/8756 |
| Date | 25 March 2004 |
| Creators | Silvério, Flaviano Oliveira |
| Contributors | Rubinger, Mayura Marques Magalhães, Picanço, Marcelo Coutinho, Alvarenga, Elson Santiago de |
| Publisher | Universidade Federal de Viçosa |
| Source Sets | IBICT Brazilian ETDs |
| Language | Portuguese |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/masterThesis |
| Source | reponame:Repositório Institucional da UFV, instname:Universidade Federal de Viçosa, instacron:UFV |
| Rights | info:eu-repo/semantics/openAccess |
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