Síntese de piretróides e estudo de sua atividade inseticida
Autor(a) principal: | |
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Data de Publicação: | 2006 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | LOCUS Repositório Institucional da UFV |
Texto Completo: | http://locus.ufv.br/handle/123456789/2177 |
Resumo: | The term pyrethroid is used to designate synthetic insecticides derived structurally of pyrethrins. Decades of researches done by the industry agrochemistry and for government and academic laboratories have been resulting in a wide change of structure of pyrethroids and in a multiplicity of uses in the agriculture, veterinary and control of domestic plagues. It is known that the prolonged use of agricultural defensives takes the development of resistance mechanisms for several species, besides the toxicant effects caused to the environment. These disadvantages justify the need of search for agricultural chemicals more specific and with larger insecticide action. In that way, the first part of this work had as objective the pyrethroids synthesis containing several aromatic groups in substitution to the group dimethylvinyl presents in the structure of several pyrethroids and pyrethrins. The synthetic route shown in the first chapter used as first material D-mannitol (1.1), that was submitted to a reaction with ketone in presence of zinc chloride, taking the formation of 1,2:5,6-di-O- isopropylidene-D-mannitol (1.2) in 87% of yielding. The diacetal (1.2) was broken with sodium periodate for the formation of 2,3-O-isopropylidene-D-glyceraldehyde (1.3). The aldehyde (1.3) was submitted to the reaction of Wittig being used methoxycarbonyl(triphenyl)phosphonium in methanol for the formation of esters methyl (S)-(Z)-4,5-O-isopropylidenepent-2-enoate (1.4) and methyl (S)-(E)-4,5-O- isopropylidenepent-2-enoate (1.5) (8: 1) in 24% of yielding starting from the diacetal (1.2). The ester (1.4) was used in the synthesis of methyl (1S,3S)-3-[(S)-2,2-dimethyl- 1,3-dioxolan-4-il]-2,2-dimethylcyclopropane-1-carboxylate (1.6) in 50% of yielding, with Wittig salt. The product (1.6) was hydrolyzed with perchloric acid in THF and broken with sodium periodate that resulted the methyl (1S,3S)-3-formil-2,2- dimethylcyclopropane-1-carboxylate (1.7) in 80% of yielding (and 40% of yielding starting from 1.4). The esters (1.5) was submitted to the same sequence of reactions of esters (1.4) taking the formation of methyl (1R,3R)-3-[(R)-2,2-dimethyl-1,3-dioxolan-4- il]-2,2-dimethylcyclopropane-1-carboxylate (1.8) and later on of methyl (1R,3R)-3- formil-2,2-dimethylcyclopropane-1-carboxylate (1.9) in 10% of yielding starting from (1.5). Finally, the pyrethroids methyl (1S,3S)-3-[2-(2-methoxyphenyl)eten-1-il]-2,2- dimethylcyclopropane-1-carboxylate (1.10), methyl methoxyphenyl)eten-1-il]-2,2-dimethylcyclopropane-1-carboxylate (1S,3S)-3-[2-(3- (1.11), methyl (1S,3S)-3-[2-(2-chlorophenyl)eten-1-il]-2,2-dimethylcyclopropane-1-carboxylate (1.12), methyl (1S,3S)-3-[2-(pentafluorophenyl)eten-1-il]-2,2-dimethylcyclopropane-1- carboxylate (1.13) and methyl (1S,3S)-3-[2-(4-ethoxyphenyl)eten-1-il]-2,2- dimethylcyclopropane-1-carboxylate (1.14) were produced through the reaction of Wittig, starting from the aldehyde (1.7) with yielding of 46, 45, 64, 50 and 65%, respectively. The second chapter is about an alternative route for pyrethroids synthesis that has as intermediary stage a reaction photochemistry of photoadition of isopropylic alcohol. This route uses the phurphural (2.1) as first material that was initially submitted to an oxidation reaction to give the 5H-furan-2-one (2.2a) in 40% of yielding. This last one was irradiated being used low-pressure mercury lamp (= 254 nm) in the presence of isopropylic alcohol, resulting 4-(1'-hydroxy-1'-methylethyl)tetrahydrofuran-2-one (2.3) in 92% of yielding. This alcohol was dehydrated being used phosphorus pentachloride in DCM for formation of alkenes 4-isopropeniltetrahydrofuran-2-one (2.4a) and 4-(1- methylethylideno)tetrahydrofuran-2-one (2.4b) in 90% of yielding. These alkenes were submitted to the reaction with phosphorus tribromide in DCM in the presence of silicon oxide for formation of bromide 4-(1'-bromide-1'-methylethyl)tetrahydrofuran-2-one (2.5) in 39% of yielding. This bromide was treated with potassium tert-butoxide in THF dry, taking the formation of 6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one (2.6) in 40% of yielding. The lactone (2.6) is an important middleman for synthesis of acid trans- chrysanthemic and several pyrethroids. The esters (1.4) was treated with sulfuric acid in methanol for the formation of (S)-5-hydroxymethyl(5H)furan-2-one (2.7) in 73% of yielding. Later on, the group hydroxyl of lactone (2.7) was protected being used tert- butyldimethylsilyl chloride in DCM in the presence of the imidazole, resulting (S)-5-O- tert-butyldimethylsiloxymethyl(5H)furan-2-one (2.8) in 60% of yielding. The lactones (2.8) and (2.7) were irradiated in the presence of isopropylic alcohol taking the formation of alcohols (4S,5S)-5-O-tert-butyldimethylsiloxymethyl-4-(1'-hydroxy-1'- methylethyl)tetrahydrofuran-2-one (2.9) and (4S,5S)-5-hydroxymethyl-4-(1'-hydroxy-1'- methylethyl)tetrahydrofuran-2-one (2.10) in 66 and 90% of yielding, respectively. The alcohol (2.10) was transformed into the (4S,5S)-5-benzoiloxymethyl-4-(1'-hydroxy-1'- methylethyl)tetrahydrofuran-2-one (2.11) in 90% of yielding, being used benzoil chloride in pyridine dry. In the Chapter 3, the results of irradiation are shown (= 254 nm) of esters (1.4) and of (2E,4E)-hexa-2,4-dienoic acid (3.2) in the presence of isopropylic alcohol. In the beginning, the potassium sorbate (3.1) was treated with hydrochloric acid to form the (2E,4E)-hexa-2,4-dienoic acid (3.2) in 87% of yielding. This acid was dissolved in isopropylic alcohol and irradiated by 96h, taking the formation of 2-methyl-3-oxo-1-cyclobutanecarboxylic acid (3.3) in 10% of yielding. This last one was reduced with lithium aluminum hydride to form the 3-hydroxymethyl- 2-methylcyclobutan-1-one (3.4) in 74% of yielding. The irradiation of acid (3.2) being used acetonitrile took the formation of (2Z,4E)-hexa-2,4-dienoic acid (3.5). After irradiation of esters (1.4), during 1h, was observed the formation of methyl 5-hydroxy- 4-oxopentanoate (3.6) in 85% of yielding. Finally, were made biological tests with the objective of evaluating the insecticide action of compositions (1.7), (1.9) to (1.14) and (2.6). Adults of Acanthoscelides obtectus (Say) (Coleoptera: Bruchidae) and Sitophilus zeamais Mots. (Coleoptera: Curculionidae), larvas of Ascia monuste orseis (Godart) (Lepidoptera: Pieridae) and nymphs of Periplaneta americana (L.) (Blattaria: Blattidae) were used to carry out these tests. All pyrethroids, were tested, presented significant insecticide action for the four species, 48h after its application. |
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Carneiro, Vânia Maria Teixeirahttp://lattes.cnpq.br/5262926983667807Rubinger, Mayura Marques Magalhãeshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4784203T8Picanço, Marcelo Coutinhohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4786700U4Alvarenga, Elson Santiago dehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4784664Y6Virtuoso, Luciano Sindrahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4760236Y3Paula, Vanderlúcia Fonseca dehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723796T62015-03-26T13:00:41Z2015-02-052015-03-26T13:00:41Z2006-07-28CARNEIRO, Vânia Maria Teixeira. Pyrethroids synthesis and study of its insecticide activity. 2006. 205 f. Dissertação (Mestrado em Agroquímica analítica; Agroquímica inorgânica e Físico-química; Agroquímica orgânica) - Universidade Federal de Viçosa, Viçosa, 2006.http://locus.ufv.br/handle/123456789/2177The term pyrethroid is used to designate synthetic insecticides derived structurally of pyrethrins. Decades of researches done by the industry agrochemistry and for government and academic laboratories have been resulting in a wide change of structure of pyrethroids and in a multiplicity of uses in the agriculture, veterinary and control of domestic plagues. It is known that the prolonged use of agricultural defensives takes the development of resistance mechanisms for several species, besides the toxicant effects caused to the environment. These disadvantages justify the need of search for agricultural chemicals more specific and with larger insecticide action. In that way, the first part of this work had as objective the pyrethroids synthesis containing several aromatic groups in substitution to the group dimethylvinyl presents in the structure of several pyrethroids and pyrethrins. The synthetic route shown in the first chapter used as first material D-mannitol (1.1), that was submitted to a reaction with ketone in presence of zinc chloride, taking the formation of 1,2:5,6-di-O- isopropylidene-D-mannitol (1.2) in 87% of yielding. The diacetal (1.2) was broken with sodium periodate for the formation of 2,3-O-isopropylidene-D-glyceraldehyde (1.3). The aldehyde (1.3) was submitted to the reaction of Wittig being used methoxycarbonyl(triphenyl)phosphonium in methanol for the formation of esters methyl (S)-(Z)-4,5-O-isopropylidenepent-2-enoate (1.4) and methyl (S)-(E)-4,5-O- isopropylidenepent-2-enoate (1.5) (8: 1) in 24% of yielding starting from the diacetal (1.2). The ester (1.4) was used in the synthesis of methyl (1S,3S)-3-[(S)-2,2-dimethyl- 1,3-dioxolan-4-il]-2,2-dimethylcyclopropane-1-carboxylate (1.6) in 50% of yielding, with Wittig salt. The product (1.6) was hydrolyzed with perchloric acid in THF and broken with sodium periodate that resulted the methyl (1S,3S)-3-formil-2,2- dimethylcyclopropane-1-carboxylate (1.7) in 80% of yielding (and 40% of yielding starting from 1.4). The esters (1.5) was submitted to the same sequence of reactions of esters (1.4) taking the formation of methyl (1R,3R)-3-[(R)-2,2-dimethyl-1,3-dioxolan-4- il]-2,2-dimethylcyclopropane-1-carboxylate (1.8) and later on of methyl (1R,3R)-3- formil-2,2-dimethylcyclopropane-1-carboxylate (1.9) in 10% of yielding starting from (1.5). Finally, the pyrethroids methyl (1S,3S)-3-[2-(2-methoxyphenyl)eten-1-il]-2,2- dimethylcyclopropane-1-carboxylate (1.10), methyl methoxyphenyl)eten-1-il]-2,2-dimethylcyclopropane-1-carboxylate (1S,3S)-3-[2-(3- (1.11), methyl (1S,3S)-3-[2-(2-chlorophenyl)eten-1-il]-2,2-dimethylcyclopropane-1-carboxylate (1.12), methyl (1S,3S)-3-[2-(pentafluorophenyl)eten-1-il]-2,2-dimethylcyclopropane-1- carboxylate (1.13) and methyl (1S,3S)-3-[2-(4-ethoxyphenyl)eten-1-il]-2,2- dimethylcyclopropane-1-carboxylate (1.14) were produced through the reaction of Wittig, starting from the aldehyde (1.7) with yielding of 46, 45, 64, 50 and 65%, respectively. The second chapter is about an alternative route for pyrethroids synthesis that has as intermediary stage a reaction photochemistry of photoadition of isopropylic alcohol. This route uses the phurphural (2.1) as first material that was initially submitted to an oxidation reaction to give the 5H-furan-2-one (2.2a) in 40% of yielding. This last one was irradiated being used low-pressure mercury lamp (= 254 nm) in the presence of isopropylic alcohol, resulting 4-(1'-hydroxy-1'-methylethyl)tetrahydrofuran-2-one (2.3) in 92% of yielding. This alcohol was dehydrated being used phosphorus pentachloride in DCM for formation of alkenes 4-isopropeniltetrahydrofuran-2-one (2.4a) and 4-(1- methylethylideno)tetrahydrofuran-2-one (2.4b) in 90% of yielding. These alkenes were submitted to the reaction with phosphorus tribromide in DCM in the presence of silicon oxide for formation of bromide 4-(1'-bromide-1'-methylethyl)tetrahydrofuran-2-one (2.5) in 39% of yielding. This bromide was treated with potassium tert-butoxide in THF dry, taking the formation of 6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one (2.6) in 40% of yielding. The lactone (2.6) is an important middleman for synthesis of acid trans- chrysanthemic and several pyrethroids. The esters (1.4) was treated with sulfuric acid in methanol for the formation of (S)-5-hydroxymethyl(5H)furan-2-one (2.7) in 73% of yielding. Later on, the group hydroxyl of lactone (2.7) was protected being used tert- butyldimethylsilyl chloride in DCM in the presence of the imidazole, resulting (S)-5-O- tert-butyldimethylsiloxymethyl(5H)furan-2-one (2.8) in 60% of yielding. The lactones (2.8) and (2.7) were irradiated in the presence of isopropylic alcohol taking the formation of alcohols (4S,5S)-5-O-tert-butyldimethylsiloxymethyl-4-(1'-hydroxy-1'- methylethyl)tetrahydrofuran-2-one (2.9) and (4S,5S)-5-hydroxymethyl-4-(1'-hydroxy-1'- methylethyl)tetrahydrofuran-2-one (2.10) in 66 and 90% of yielding, respectively. The alcohol (2.10) was transformed into the (4S,5S)-5-benzoiloxymethyl-4-(1'-hydroxy-1'- methylethyl)tetrahydrofuran-2-one (2.11) in 90% of yielding, being used benzoil chloride in pyridine dry. In the Chapter 3, the results of irradiation are shown (= 254 nm) of esters (1.4) and of (2E,4E)-hexa-2,4-dienoic acid (3.2) in the presence of isopropylic alcohol. In the beginning, the potassium sorbate (3.1) was treated with hydrochloric acid to form the (2E,4E)-hexa-2,4-dienoic acid (3.2) in 87% of yielding. This acid was dissolved in isopropylic alcohol and irradiated by 96h, taking the formation of 2-methyl-3-oxo-1-cyclobutanecarboxylic acid (3.3) in 10% of yielding. This last one was reduced with lithium aluminum hydride to form the 3-hydroxymethyl- 2-methylcyclobutan-1-one (3.4) in 74% of yielding. The irradiation of acid (3.2) being used acetonitrile took the formation of (2Z,4E)-hexa-2,4-dienoic acid (3.5). After irradiation of esters (1.4), during 1h, was observed the formation of methyl 5-hydroxy- 4-oxopentanoate (3.6) in 85% of yielding. Finally, were made biological tests with the objective of evaluating the insecticide action of compositions (1.7), (1.9) to (1.14) and (2.6). Adults of Acanthoscelides obtectus (Say) (Coleoptera: Bruchidae) and Sitophilus zeamais Mots. (Coleoptera: Curculionidae), larvas of Ascia monuste orseis (Godart) (Lepidoptera: Pieridae) and nymphs of Periplaneta americana (L.) (Blattaria: Blattidae) were used to carry out these tests. All pyrethroids, were tested, presented significant insecticide action for the four species, 48h after its application.O termo piretróide é usado para designar inseticidas sintéticos derivados estruturalmente das piretrinas. Décadas de pesquisas feitas pela indústria agroquímica e por laboratórios governamentais e acadêmicos têm resultado numa ampla mudança da estrutura dos piretróides e numa multiplicidade de usos na agricultura, veterinária e controle de pestes domésticas. Sabe-se que o uso prolongado de defensivos agrícolas acarreta o desenvolvimento de mecanismos de resistência por várias espécies, além dos efeitos tóxicos causados ao meio ambiente. Estas desvantagens justificam a necessidade da busca por compostos mais específicos e com maior ação inseticida. Dessa forma, a primeira parte deste trabalho teve como objetivo a síntese de piretróides contendo variados grupos aromáticos em substituição ao grupo dimetilvinil presente na estrutura de vários piretróides e piretrinas. A rota sintética mostrada no primeiro capítulo utilizou como material de partida o D-manitol (1.1), que foi submetido a uma reação com acetona em presença de cloreto de zinco, levando a formação do 1,2:5,6-di-O- isopropilideno-D-manitol (1.2) em 87% de rendimento. O diacetal (1.2) foi clivado com periodato de sódio para a formação do 2,3-O-isopropileno-D-gliceraldeído (1.3). O aldeído (1.3) foi submetido à reação de Wittig utilizando-se metoxicarbonilmetileno(trifenil)fosforano em metanol produzindo os ésteres (S)-(Z)- 4,5-O-isopropilidenopent-2-enoato de metila (1.4) e (S)-(E)-4,5-O-isopropilidenopent-2- enoato de metila (1.5) (8 : 1) em 24% de rendimento a partir do diacetal (1.2). O éster (1.4) foi utilizado na síntese do (1S,3S)-3-[(S)-2,2-dimetil-1,3-dioxolan-4-il]-2,2- dimetilciclopropano-1-carboxilato de metila (1.6) em 50% de rendimento, utilizando-se sal de Wittig. O composto (1.6) foi hidrolisado com ácido perclórico em THF e clivado com periodato de sódio originando o (1S,3S)-3-formil-2,2-dimetilciclopropano-1- carboxilato de metila (1.7) em 80% de rendimento (e 40% de rendimento a partir de 1.4). Já o éster (1.5) foi submetido à mesma seqüência de reações do éster (1.4) produzindo o (1R,3R)-3-[(R)-2,2-dimetil-1,3-dioxolan-4-il]-2,2-dimetilciclopropano-1- carboxilato de metila (1.8) e posteriormente o (1R,3R)-3-formil-2,2- dimetilciclopropano-1-carboxilato de metila (1.9) em 10% de rendimento a partir de (1.5). Finalmente, os piretróides (1S,3S)-3-[2-(2-metoxifenil)eten-1-il]-2,2- dimetilciclopropano-1-carboxilato de metila (1.10), (1S,3S)-3-[2-(3-metoxifenil)eten-1- il]-2,2-dimetilciclopropano-1-carboxilato de metila (1.11), (1S,3S)-3-[2-(2- clorofenil)eten-1-il]-2,2-dimetilciclopropano-1-carboxilato de metila (1.12), (1S,3S)-3- [2-(pentafluorofenil)eten-1-il]-2,2-dimetilciclopropano-1-carboxilato de metila (1.13) e (1S,3S)-3-[2-(4-etoxifenil)eten-1-il]-2,2-dimetilciclopropano-1-carboxilato de metila (1.14) foram produzidos por meio de reação de Wittig, a partir do aldeído (1.7) com rendimentos de 46, 45, 64, 50 e 65%, respectivamente. Já o segundo capítulo trata de uma rota alternativa para a síntese de piretróides tendo como etapa intermediária uma reação fotoquímica de adição de álcool isopropílico. Esta rota utiliza o furfural (2.1) como material de partida que foi inicialmente submetido a uma reação de oxidação originando o 5H-furan-2-ona (2.2a) em 40% de rendimento. Este último foi irradiado utilizando-se lâmpada de mercúrio de baixa pressão (λ = 254 nm) na presença de álcool isopropílico, levando a formação da 4-(1 -hidroxi-1 -metiletil)tetraidrofuran-2-ona (2.3) em 92% de rendimento. Este álcool foi desidratado utilizando-se pentacloreto de fósforo em DCM originando os alquenos 4-isopropeniltetraidrofuran-2-ona (2.4a) e 4-(1- metiletilideno)tetraidrofuran-2-ona (2.4b) em 90% de rendimento. Estes alquenos foram submetidos à reação com tribrometo de fósforo em DCM na presença de óxido de silício, produzindo o brometo 4-(1 -bromo-1 -metiletil)tetraidrofuran-2-ona (2.5) em 39% de rendimento. Este brometo foi tratado com tert-butóxido de potássio em THF anidro, levando a formação da 6,6-dimetil-3-oxabiciclo[3.1.0]hexan-2-ona (2.6) em 40% de rendimento. A lactona (2.6) é um importante intermediário para síntese do ácido trans-crisantêmico e vários piretróides. O éster (1.4) foi tratado com ácido sulfúrico em metanol originando a (S)-5-hidroximetil(5H)furan-2-ona (2.7) em 73% de rendimento. Posteriormente, o grupo hidroxila da lactona (2.7) foi protegido utilizando-se cloreto de tert-butildimetilsilano em DCM na presença de imidazol, levando a formação do (S)-5- O-tert-butildimetilsiloximetil(5H)furan-2-ona (2.8) em 60% de rendimento. As lactonas (2.8) e (2.7) foram irradiadas na presença de álcool isopropílico produzindo os álcoois (4S,5S)-5-O-tert-butildimetilsiloximetil-4-(1 -hidroxi-1 -metiletil)tetraidrofuran-2-ona (2.9) e (4S,5S)-5-hidroximetil-4-(1 -hidroxi-1 -metiletil)tetraidrofuran-2-ona (2.10) em 66 e 90% de rendimento, respectivamente. O álcool (2.10) foi convertido na (4S,5S)-5- benzoiloximetil-4-(1 -hidroxi-1 -metiletil)tetraidrofuran-2-ona (2.11) em 90% de rendimento, utilizando-se cloreto de benzoíla em piridina anidra. No Capítulo 3, são mostrados os resultados da irradiação (λ = 254 nm) do éster (1.4) e do ácido (2E, 4E)- hexa-2,4-dienóico (3.2) na presença de álcool isopropílico. Primeiramente o sorbato de potássio (3.1) foi tratado com ácido clorídrico para formar o ácido (2E, 4E)-hexa-2,4- dienóico (3.2) em 87% de rendimento. Este ácido foi dissolvido em álcool isopropílico e irradiado por 96h, levando a formação do ácido 2-metil-3-oxo-1-ciclobutanocarboxílico (3.3) em 10% de rendimento. Este último foi reduzido com hidreto de lítio e alumínio para formar o 3-hidroximetil-2-metilciclobutan-1-ona (3.4) em 74% de rendimento. A irradiação do ácido (3.2) utilizando-se acetonitrila levou a formação do ácido (2Z,4E)- hexa-2,4-dienóico (3.5). Após irradiação do éster (1.4), durante 1h, foi observada a formação do 5-hidroxi-4-oxopentanoato de metila (3.6) em 85% de rendimento. Finalmente, foram feitos ensaios biológicos com o objetivo de avaliar a ação inseticida dos compostos (1.7), (1.9) a (1.14) e (2.6). Para realização destes testes foram utilizados adultos de Acanthoscelides obtectus (Say) (Coleoptera: Bruchidae) e Sitophilus zeamais Mots. (Coleoptera: Curculionidae), larvas de segundo instar de Ascia monuste orseis (Godart) (Lepidoptera: Pieridae) e ninfas de segundo instar de Periplaneta americana (L.) (Blattaria: Blattidae). Todos os piretróides testados apresentaram ação inseticida significativa para as quatro espécies, 48h após sua aplicação.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de ViçosaMestrado em AgroquímicaUFVBRAgroquímica analítica; Agroquímica inorgânica e Físico-química; Agroquímica orgânicaPiretróides - SínteseInseticidasQuímica orgânicaFotoquímicaPyrethroids - SynthesisInsecticidesOrganic ChemistryPhotochemistryCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICASíntese de piretróides e estudo de sua atividade inseticidaPyrethroids synthesis and study of its insecticide activityinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/embargoedAccessreponame:LOCUS Repositório Institucional da UFVinstname:Universidade Federal de Viçosa (UFV)instacron:UFVORIGINALtexto completo.pdfapplication/pdf3091831https://locus.ufv.br//bitstream/123456789/2177/1/texto%20completo.pdf4c2bae0aee804f81c56030f7a142e42dMD51TEXTtexto completo.pdf.txttexto completo.pdf.txtExtracted texttext/plain205031https://locus.ufv.br//bitstream/123456789/2177/2/texto%20completo.pdf.txt78ad3f698410ac65331693eb1216032dMD52THUMBNAILtexto completo.pdf.jpgtexto completo.pdf.jpgIM Thumbnailimage/jpeg3611https://locus.ufv.br//bitstream/123456789/2177/3/texto%20completo.pdf.jpg82bb75f578813f3100a1f9a82697d775MD53123456789/21772016-04-08 23:01:35.829oai:locus.ufv.br:123456789/2177Repositório InstitucionalPUBhttps://www.locus.ufv.br/oai/requestfabiojreis@ufv.bropendoar:21452016-04-09T02:01:35LOCUS Repositório Institucional da UFV - Universidade Federal de Viçosa (UFV)false |
dc.title.por.fl_str_mv |
Síntese de piretróides e estudo de sua atividade inseticida |
dc.title.alternative.eng.fl_str_mv |
Pyrethroids synthesis and study of its insecticide activity |
title |
Síntese de piretróides e estudo de sua atividade inseticida |
spellingShingle |
Síntese de piretróides e estudo de sua atividade inseticida Carneiro, Vânia Maria Teixeira Piretróides - Síntese Inseticidas Química orgânica Fotoquímica Pyrethroids - Synthesis Insecticides Organic Chemistry Photochemistry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA |
title_short |
Síntese de piretróides e estudo de sua atividade inseticida |
title_full |
Síntese de piretróides e estudo de sua atividade inseticida |
title_fullStr |
Síntese de piretróides e estudo de sua atividade inseticida |
title_full_unstemmed |
Síntese de piretróides e estudo de sua atividade inseticida |
title_sort |
Síntese de piretróides e estudo de sua atividade inseticida |
author |
Carneiro, Vânia Maria Teixeira |
author_facet |
Carneiro, Vânia Maria Teixeira |
author_role |
author |
dc.contributor.authorLattes.por.fl_str_mv |
http://lattes.cnpq.br/5262926983667807 |
dc.contributor.author.fl_str_mv |
Carneiro, Vânia Maria Teixeira |
dc.contributor.advisor-co1.fl_str_mv |
Rubinger, Mayura Marques Magalhães |
dc.contributor.advisor-co1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4784203T8 |
dc.contributor.advisor-co2.fl_str_mv |
Picanço, Marcelo Coutinho |
dc.contributor.advisor-co2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4786700U4 |
dc.contributor.advisor1.fl_str_mv |
Alvarenga, Elson Santiago de |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4784664Y6 |
dc.contributor.referee1.fl_str_mv |
Virtuoso, Luciano Sindra |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4760236Y3 |
dc.contributor.referee2.fl_str_mv |
Paula, Vanderlúcia Fonseca de |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4723796T6 |
contributor_str_mv |
Rubinger, Mayura Marques Magalhães Picanço, Marcelo Coutinho Alvarenga, Elson Santiago de Virtuoso, Luciano Sindra Paula, Vanderlúcia Fonseca de |
dc.subject.por.fl_str_mv |
Piretróides - Síntese Inseticidas Química orgânica Fotoquímica |
topic |
Piretróides - Síntese Inseticidas Química orgânica Fotoquímica Pyrethroids - Synthesis Insecticides Organic Chemistry Photochemistry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA |
dc.subject.eng.fl_str_mv |
Pyrethroids - Synthesis Insecticides Organic Chemistry Photochemistry |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA::QUIMICA ORGANICA |
description |
The term pyrethroid is used to designate synthetic insecticides derived structurally of pyrethrins. Decades of researches done by the industry agrochemistry and for government and academic laboratories have been resulting in a wide change of structure of pyrethroids and in a multiplicity of uses in the agriculture, veterinary and control of domestic plagues. It is known that the prolonged use of agricultural defensives takes the development of resistance mechanisms for several species, besides the toxicant effects caused to the environment. These disadvantages justify the need of search for agricultural chemicals more specific and with larger insecticide action. In that way, the first part of this work had as objective the pyrethroids synthesis containing several aromatic groups in substitution to the group dimethylvinyl presents in the structure of several pyrethroids and pyrethrins. The synthetic route shown in the first chapter used as first material D-mannitol (1.1), that was submitted to a reaction with ketone in presence of zinc chloride, taking the formation of 1,2:5,6-di-O- isopropylidene-D-mannitol (1.2) in 87% of yielding. The diacetal (1.2) was broken with sodium periodate for the formation of 2,3-O-isopropylidene-D-glyceraldehyde (1.3). The aldehyde (1.3) was submitted to the reaction of Wittig being used methoxycarbonyl(triphenyl)phosphonium in methanol for the formation of esters methyl (S)-(Z)-4,5-O-isopropylidenepent-2-enoate (1.4) and methyl (S)-(E)-4,5-O- isopropylidenepent-2-enoate (1.5) (8: 1) in 24% of yielding starting from the diacetal (1.2). The ester (1.4) was used in the synthesis of methyl (1S,3S)-3-[(S)-2,2-dimethyl- 1,3-dioxolan-4-il]-2,2-dimethylcyclopropane-1-carboxylate (1.6) in 50% of yielding, with Wittig salt. The product (1.6) was hydrolyzed with perchloric acid in THF and broken with sodium periodate that resulted the methyl (1S,3S)-3-formil-2,2- dimethylcyclopropane-1-carboxylate (1.7) in 80% of yielding (and 40% of yielding starting from 1.4). The esters (1.5) was submitted to the same sequence of reactions of esters (1.4) taking the formation of methyl (1R,3R)-3-[(R)-2,2-dimethyl-1,3-dioxolan-4- il]-2,2-dimethylcyclopropane-1-carboxylate (1.8) and later on of methyl (1R,3R)-3- formil-2,2-dimethylcyclopropane-1-carboxylate (1.9) in 10% of yielding starting from (1.5). Finally, the pyrethroids methyl (1S,3S)-3-[2-(2-methoxyphenyl)eten-1-il]-2,2- dimethylcyclopropane-1-carboxylate (1.10), methyl methoxyphenyl)eten-1-il]-2,2-dimethylcyclopropane-1-carboxylate (1S,3S)-3-[2-(3- (1.11), methyl (1S,3S)-3-[2-(2-chlorophenyl)eten-1-il]-2,2-dimethylcyclopropane-1-carboxylate (1.12), methyl (1S,3S)-3-[2-(pentafluorophenyl)eten-1-il]-2,2-dimethylcyclopropane-1- carboxylate (1.13) and methyl (1S,3S)-3-[2-(4-ethoxyphenyl)eten-1-il]-2,2- dimethylcyclopropane-1-carboxylate (1.14) were produced through the reaction of Wittig, starting from the aldehyde (1.7) with yielding of 46, 45, 64, 50 and 65%, respectively. The second chapter is about an alternative route for pyrethroids synthesis that has as intermediary stage a reaction photochemistry of photoadition of isopropylic alcohol. This route uses the phurphural (2.1) as first material that was initially submitted to an oxidation reaction to give the 5H-furan-2-one (2.2a) in 40% of yielding. This last one was irradiated being used low-pressure mercury lamp (= 254 nm) in the presence of isopropylic alcohol, resulting 4-(1'-hydroxy-1'-methylethyl)tetrahydrofuran-2-one (2.3) in 92% of yielding. This alcohol was dehydrated being used phosphorus pentachloride in DCM for formation of alkenes 4-isopropeniltetrahydrofuran-2-one (2.4a) and 4-(1- methylethylideno)tetrahydrofuran-2-one (2.4b) in 90% of yielding. These alkenes were submitted to the reaction with phosphorus tribromide in DCM in the presence of silicon oxide for formation of bromide 4-(1'-bromide-1'-methylethyl)tetrahydrofuran-2-one (2.5) in 39% of yielding. This bromide was treated with potassium tert-butoxide in THF dry, taking the formation of 6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one (2.6) in 40% of yielding. The lactone (2.6) is an important middleman for synthesis of acid trans- chrysanthemic and several pyrethroids. The esters (1.4) was treated with sulfuric acid in methanol for the formation of (S)-5-hydroxymethyl(5H)furan-2-one (2.7) in 73% of yielding. Later on, the group hydroxyl of lactone (2.7) was protected being used tert- butyldimethylsilyl chloride in DCM in the presence of the imidazole, resulting (S)-5-O- tert-butyldimethylsiloxymethyl(5H)furan-2-one (2.8) in 60% of yielding. The lactones (2.8) and (2.7) were irradiated in the presence of isopropylic alcohol taking the formation of alcohols (4S,5S)-5-O-tert-butyldimethylsiloxymethyl-4-(1'-hydroxy-1'- methylethyl)tetrahydrofuran-2-one (2.9) and (4S,5S)-5-hydroxymethyl-4-(1'-hydroxy-1'- methylethyl)tetrahydrofuran-2-one (2.10) in 66 and 90% of yielding, respectively. The alcohol (2.10) was transformed into the (4S,5S)-5-benzoiloxymethyl-4-(1'-hydroxy-1'- methylethyl)tetrahydrofuran-2-one (2.11) in 90% of yielding, being used benzoil chloride in pyridine dry. In the Chapter 3, the results of irradiation are shown (= 254 nm) of esters (1.4) and of (2E,4E)-hexa-2,4-dienoic acid (3.2) in the presence of isopropylic alcohol. In the beginning, the potassium sorbate (3.1) was treated with hydrochloric acid to form the (2E,4E)-hexa-2,4-dienoic acid (3.2) in 87% of yielding. This acid was dissolved in isopropylic alcohol and irradiated by 96h, taking the formation of 2-methyl-3-oxo-1-cyclobutanecarboxylic acid (3.3) in 10% of yielding. This last one was reduced with lithium aluminum hydride to form the 3-hydroxymethyl- 2-methylcyclobutan-1-one (3.4) in 74% of yielding. The irradiation of acid (3.2) being used acetonitrile took the formation of (2Z,4E)-hexa-2,4-dienoic acid (3.5). After irradiation of esters (1.4), during 1h, was observed the formation of methyl 5-hydroxy- 4-oxopentanoate (3.6) in 85% of yielding. Finally, were made biological tests with the objective of evaluating the insecticide action of compositions (1.7), (1.9) to (1.14) and (2.6). Adults of Acanthoscelides obtectus (Say) (Coleoptera: Bruchidae) and Sitophilus zeamais Mots. (Coleoptera: Curculionidae), larvas of Ascia monuste orseis (Godart) (Lepidoptera: Pieridae) and nymphs of Periplaneta americana (L.) (Blattaria: Blattidae) were used to carry out these tests. All pyrethroids, were tested, presented significant insecticide action for the four species, 48h after its application. |
publishDate |
2006 |
dc.date.issued.fl_str_mv |
2006-07-28 |
dc.date.accessioned.fl_str_mv |
2015-03-26T13:00:41Z |
dc.date.available.fl_str_mv |
2015-02-05 2015-03-26T13:00:41Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
CARNEIRO, Vânia Maria Teixeira. Pyrethroids synthesis and study of its insecticide activity. 2006. 205 f. Dissertação (Mestrado em Agroquímica analítica; Agroquímica inorgânica e Físico-química; Agroquímica orgânica) - Universidade Federal de Viçosa, Viçosa, 2006. |
dc.identifier.uri.fl_str_mv |
http://locus.ufv.br/handle/123456789/2177 |
identifier_str_mv |
CARNEIRO, Vânia Maria Teixeira. Pyrethroids synthesis and study of its insecticide activity. 2006. 205 f. Dissertação (Mestrado em Agroquímica analítica; Agroquímica inorgânica e Físico-química; Agroquímica orgânica) - Universidade Federal de Viçosa, Viçosa, 2006. |
url |
http://locus.ufv.br/handle/123456789/2177 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/embargoedAccess |
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application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Viçosa |
dc.publisher.program.fl_str_mv |
Mestrado em Agroquímica |
dc.publisher.initials.fl_str_mv |
UFV |
dc.publisher.country.fl_str_mv |
BR |
dc.publisher.department.fl_str_mv |
Agroquímica analítica; Agroquímica inorgânica e Físico-química; Agroquímica orgânica |
publisher.none.fl_str_mv |
Universidade Federal de Viçosa |
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UFV |
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UFV |
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LOCUS Repositório Institucional da UFV |
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LOCUS Repositório Institucional da UFV |
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