Síntese de novas azinas trifluormetil substituídas e derivados a partir de reações de heterociclização de trifluoracetil enol éteres com diamino arenos
Ano de defesa: | 2013 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , , |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
|
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
BR
|
Palavras-chave em Português: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/4258 |
Resumo: | The present research describes the study of synthetic strategies for obtaining of polyheterocyclic systems trifluoromethyl substituted from simple precursors: 4-alkoxy-1,1,1-trifluoroalk-3-en-2-ones (1), of formula F3C-C(O)-CH=C(R1)-OR, where R1 = H, CH3, C6H5, 4-FC6H4, 4-BrC6H4, 4-CH3C6H4, 4-OCH3C6H4, 2-furyl, 2-thienyl and R = Me, Et, and three diamino arenes: 1,3-phenylenediamine (1,3-FDA), 2,6-diaminopyridine (2,6-DAP) and 2,6-diaminotoluene (2,6-DAT). Considering the biological importance and employment of amino-quinolines as the starting material for the synthesis of new heterocycles, as well as, it is known that there is difficulty in relation to the control of regiochemistry reactions involving the synthesis of pyridine ring structures with aryl-geminal CF3- substituted, studies were directed to establish protocols for cyclocondensation reactions of [3+3] type. Was evaluated the synthesis of a new series of 1,7-phenanthrolines, 7-aminoquinolines, acridines, 2-amino-1,8-naphthyridines, antiridines and derivatization reactions. Initially, the reactions between 1 and 1,3-FDA, at a molar ratio of 1:1, were developed. The bis-enaminoneswere preferably obtained, in 32 41 % yields, instead of aminoquinolines 2. Whereas, reactions employing 1 and 2,6-DAP, at a molar ratio of 1:1, produced 2-amino-1,8-naphthyridines 4 (26 73 %). Following, the reactions of 1 and 2,6-DAT, furnished enaminones 9, in 46 70 % yields, which were subjected to reactions carried out in the presence of a strongly acidic medium (PPA), affording the corresponding new series of tetrasubstituted quinolines 10 (86 93 % yields). Finally, was evaluated the behavior of the compounds 4 and 10 in reactions with 1, diazotization, halogenation and N-acylation reactions. C-oxidation side chain reactions demonstrated the possibility of C H allylic bond oxidation (8-Me) when only two non-linked (free) carbonyl groups are attached to the nitrogen atom (7-NR2) at the β-position of the CH3 substituent (8-Me), affording the corresponding carbaldehyde (7-formyl-quinoline) in satisfactory yield (79 %). |
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2017-05-252017-05-252013-12-13ANDRIGHETTO, Rosalia. Synthesis of new trifluoromethyl substituted azines and derivatives from heterocyclization reactions of trifluoroacetyl enol ether with diamino arenes. 2013. 305 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013.http://repositorio.ufsm.br/handle/1/4258The present research describes the study of synthetic strategies for obtaining of polyheterocyclic systems trifluoromethyl substituted from simple precursors: 4-alkoxy-1,1,1-trifluoroalk-3-en-2-ones (1), of formula F3C-C(O)-CH=C(R1)-OR, where R1 = H, CH3, C6H5, 4-FC6H4, 4-BrC6H4, 4-CH3C6H4, 4-OCH3C6H4, 2-furyl, 2-thienyl and R = Me, Et, and three diamino arenes: 1,3-phenylenediamine (1,3-FDA), 2,6-diaminopyridine (2,6-DAP) and 2,6-diaminotoluene (2,6-DAT). Considering the biological importance and employment of amino-quinolines as the starting material for the synthesis of new heterocycles, as well as, it is known that there is difficulty in relation to the control of regiochemistry reactions involving the synthesis of pyridine ring structures with aryl-geminal CF3- substituted, studies were directed to establish protocols for cyclocondensation reactions of [3+3] type. Was evaluated the synthesis of a new series of 1,7-phenanthrolines, 7-aminoquinolines, acridines, 2-amino-1,8-naphthyridines, antiridines and derivatization reactions. Initially, the reactions between 1 and 1,3-FDA, at a molar ratio of 1:1, were developed. The bis-enaminoneswere preferably obtained, in 32 41 % yields, instead of aminoquinolines 2. Whereas, reactions employing 1 and 2,6-DAP, at a molar ratio of 1:1, produced 2-amino-1,8-naphthyridines 4 (26 73 %). Following, the reactions of 1 and 2,6-DAT, furnished enaminones 9, in 46 70 % yields, which were subjected to reactions carried out in the presence of a strongly acidic medium (PPA), affording the corresponding new series of tetrasubstituted quinolines 10 (86 93 % yields). Finally, was evaluated the behavior of the compounds 4 and 10 in reactions with 1, diazotization, halogenation and N-acylation reactions. C-oxidation side chain reactions demonstrated the possibility of C H allylic bond oxidation (8-Me) when only two non-linked (free) carbonyl groups are attached to the nitrogen atom (7-NR2) at the β-position of the CH3 substituent (8-Me), affording the corresponding carbaldehyde (7-formyl-quinoline) in satisfactory yield (79 %).O presente trabalho descreve os estudos desenvolvidos em busca de estratégias sintéticas para a obtenção de compostos heteropolicíclicos trifluormetil substituídos e derivados, envolvendo uma série de reações de 4-alcóxi-4-alquila[arila(heteroarila)]-1,1,1-triflúor-3-alquen-2-onas (1), de fórmula geral F3C-C(O)-CH=C(R1)-OR, onde R = CH3, C2H5 e R1 = H, CH3, C6H5, 4-FC6H4, 4-BrC6H4, 4-CH3C6H4, 4-OCH3C6H4, 2-furila e 2-tienila com três diamino arenos: 1,3-fenilenodiamina (1,3-FDA), 2,6-diaminopiridina (2,6-DAP) e 2,6-diaminotolueno (2,6-DAT). Em vista da importância biológica e do emprego de amino-heterociclos na síntese de diversas moléculas, bem como, a dificuldade de controle regioquímico em reações envolvendo a síntese de estruturas com anéis piridínicos arila-geminados e CF3-substituídos, os estudos foram direcionados ao estabelecimento de protocolos para reações de ciclocondensação regiosseletivas do tipo [3+3]. Avaliou-se a síntese de séries inéditas de 1,7-fenantrolinas, 7-aminoquinolinas, acridinas, 2-amino-1,8-naftiridinas e antiridinas trifluormetil substituídas e reações de derivatização. Inicialmente, as reações de adição/eliminação nucleofílica ciclização/aromatização entre 1 e 1,3-FDA, 1:1 equivalentes, demonstraram que os produtos de dissubstituição (bis-enaminonas) são preferencialmente obtidos (32 41 %), ao invés de aminoquinolinas 2. Enquanto que, as reações entre 1 e 2,6-DAP conduziram a síntese regiosseletiva de 2-amino-1,8-naftiridinas 4 (26 73 %). Posteriormente, as reações entre 1 e 2,6-DAT, forneceram arilenaminonas monossubstituídas 9 (46 70 %), as quais, quando submetidas a reações de termociclização na presença de PPA, forneceram regiosseletivamente quinolinas tetrasubstituídas 10 (86 93 %). Finalmente, foi avaliado o comportamento dos amino-heterociclos 4 e 10 em reações com 1.0 equivalente de 1, bem como, em reações de diazotição, halogenação, N-acilação e reações multicomponentes. Por sua vez, reações de C-oxidação demonstraram que SeO2 oxidou seletivamente a ligação alílica C H em posição α ao sistema insaturado aromático (8-Me) quando dois grupos acetilas estão ligados ao átomo de nitrogênio (7-NR2) em posição β ao substituinte metila, produzindo o respectivo carbaldeído (79 %). Quando na posição 7 do anel quinolínico está ligado um substituinte N-carbocíclico apenas traços dos respectivos 8-carbaldeído derivados foram observados.Conselho Nacional de Desenvolvimento Científico e Tecnológicoapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaQuímicaQuinolinasCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese de novas azinas trifluormetil substituídas e derivados a partir de reações de heterociclização de trifluoracetil enol éteres com diamino arenosSynthesis of new trifluoromethyl substituted azines and derivatives from heterocyclization reactions of trifluoroacetyl enol ether with diamino arenesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisBonacorso, Helio Gauzehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0Frizzo, Clarissa Piccininhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4757171J0Silva Júnior, Eufrânio Nunes dahttp://lattes.cnpq.br/5627593695811199Zeni, Gilson Rogériohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4728651J6Rodrigues, Oscar Endrigo Dorneleshttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4763956Z6http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4131584P0Andrighetto, Rosalia10060000000040030030030030030050006c852ad-d805-43c3-99d6-93a6a86f507c720f190c-d3eb-473d-b34d-464c63eb9580bf4338e5-e87c-4326-93b7-60f8f505f4666b114cab-8e20-4447-bd40-832f2db5dca6135e9ed6-f30a-4f2b-9b09-4aaa65fcc55f9dfccbe0-bd16-4e23-a1fb-8e55f871ce46info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALANDRIGHETTO, ROSALIA.pdfapplication/pdf12129964http://repositorio.ufsm.br/bitstream/1/4258/1/ANDRIGHETTO%2c%20ROSALIA.pdf84ff0659491535b9a720f98cc1bccd3dMD51TEXTANDRIGHETTO, ROSALIA.pdf.txtANDRIGHETTO, ROSALIA.pdf.txtExtracted texttext/plain445463http://repositorio.ufsm.br/bitstream/1/4258/2/ANDRIGHETTO%2c%20ROSALIA.pdf.txt8801cbce195c3ad54c2a9c6d47accc6bMD52THUMBNAILANDRIGHETTO, ROSALIA.pdf.jpgANDRIGHETTO, ROSALIA.pdf.jpgIM Thumbnailimage/jpeg6787http://repositorio.ufsm.br/bitstream/1/4258/3/ANDRIGHETTO%2c%20ROSALIA.pdf.jpg40cb5afd482a9ee75fcd3e0f68fcd3e6MD531/42582017-07-25 11:05:16.312oai:repositorio.ufsm.br:1/4258Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132017-07-25T14:05:16Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese de novas azinas trifluormetil substituídas e derivados a partir de reações de heterociclização de trifluoracetil enol éteres com diamino arenos |
dc.title.alternative.eng.fl_str_mv |
Synthesis of new trifluoromethyl substituted azines and derivatives from heterocyclization reactions of trifluoroacetyl enol ether with diamino arenes |
title |
Síntese de novas azinas trifluormetil substituídas e derivados a partir de reações de heterociclização de trifluoracetil enol éteres com diamino arenos |
spellingShingle |
Síntese de novas azinas trifluormetil substituídas e derivados a partir de reações de heterociclização de trifluoracetil enol éteres com diamino arenos Andrighetto, Rosalia Química Quinolinas CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de novas azinas trifluormetil substituídas e derivados a partir de reações de heterociclização de trifluoracetil enol éteres com diamino arenos |
title_full |
Síntese de novas azinas trifluormetil substituídas e derivados a partir de reações de heterociclização de trifluoracetil enol éteres com diamino arenos |
title_fullStr |
Síntese de novas azinas trifluormetil substituídas e derivados a partir de reações de heterociclização de trifluoracetil enol éteres com diamino arenos |
title_full_unstemmed |
Síntese de novas azinas trifluormetil substituídas e derivados a partir de reações de heterociclização de trifluoracetil enol éteres com diamino arenos |
title_sort |
Síntese de novas azinas trifluormetil substituídas e derivados a partir de reações de heterociclização de trifluoracetil enol éteres com diamino arenos |
author |
Andrighetto, Rosalia |
author_facet |
Andrighetto, Rosalia |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0 |
dc.contributor.referee1.fl_str_mv |
Frizzo, Clarissa Piccinin |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4757171J0 |
dc.contributor.referee2.fl_str_mv |
Silva Júnior, Eufrânio Nunes da |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/5627593695811199 |
dc.contributor.referee3.fl_str_mv |
Zeni, Gilson Rogério |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4728651J6 |
dc.contributor.referee4.fl_str_mv |
Rodrigues, Oscar Endrigo Dorneles |
dc.contributor.referee4Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4763956Z6 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4131584P0 |
dc.contributor.author.fl_str_mv |
Andrighetto, Rosalia |
contributor_str_mv |
Bonacorso, Helio Gauze Frizzo, Clarissa Piccinin Silva Júnior, Eufrânio Nunes da Zeni, Gilson Rogério Rodrigues, Oscar Endrigo Dorneles |
dc.subject.por.fl_str_mv |
Química Quinolinas |
topic |
Química Quinolinas CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The present research describes the study of synthetic strategies for obtaining of polyheterocyclic systems trifluoromethyl substituted from simple precursors: 4-alkoxy-1,1,1-trifluoroalk-3-en-2-ones (1), of formula F3C-C(O)-CH=C(R1)-OR, where R1 = H, CH3, C6H5, 4-FC6H4, 4-BrC6H4, 4-CH3C6H4, 4-OCH3C6H4, 2-furyl, 2-thienyl and R = Me, Et, and three diamino arenes: 1,3-phenylenediamine (1,3-FDA), 2,6-diaminopyridine (2,6-DAP) and 2,6-diaminotoluene (2,6-DAT). Considering the biological importance and employment of amino-quinolines as the starting material for the synthesis of new heterocycles, as well as, it is known that there is difficulty in relation to the control of regiochemistry reactions involving the synthesis of pyridine ring structures with aryl-geminal CF3- substituted, studies were directed to establish protocols for cyclocondensation reactions of [3+3] type. Was evaluated the synthesis of a new series of 1,7-phenanthrolines, 7-aminoquinolines, acridines, 2-amino-1,8-naphthyridines, antiridines and derivatization reactions. Initially, the reactions between 1 and 1,3-FDA, at a molar ratio of 1:1, were developed. The bis-enaminoneswere preferably obtained, in 32 41 % yields, instead of aminoquinolines 2. Whereas, reactions employing 1 and 2,6-DAP, at a molar ratio of 1:1, produced 2-amino-1,8-naphthyridines 4 (26 73 %). Following, the reactions of 1 and 2,6-DAT, furnished enaminones 9, in 46 70 % yields, which were subjected to reactions carried out in the presence of a strongly acidic medium (PPA), affording the corresponding new series of tetrasubstituted quinolines 10 (86 93 % yields). Finally, was evaluated the behavior of the compounds 4 and 10 in reactions with 1, diazotization, halogenation and N-acylation reactions. C-oxidation side chain reactions demonstrated the possibility of C H allylic bond oxidation (8-Me) when only two non-linked (free) carbonyl groups are attached to the nitrogen atom (7-NR2) at the β-position of the CH3 substituent (8-Me), affording the corresponding carbaldehyde (7-formyl-quinoline) in satisfactory yield (79 %). |
publishDate |
2013 |
dc.date.issued.fl_str_mv |
2013-12-13 |
dc.date.accessioned.fl_str_mv |
2017-05-25 |
dc.date.available.fl_str_mv |
2017-05-25 |
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info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
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dc.identifier.citation.fl_str_mv |
ANDRIGHETTO, Rosalia. Synthesis of new trifluoromethyl substituted azines and derivatives from heterocyclization reactions of trifluoroacetyl enol ether with diamino arenes. 2013. 305 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4258 |
identifier_str_mv |
ANDRIGHETTO, Rosalia. Synthesis of new trifluoromethyl substituted azines and derivatives from heterocyclization reactions of trifluoroacetyl enol ether with diamino arenes. 2013. 305 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2013. |
url |
http://repositorio.ufsm.br/handle/1/4258 |
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por |
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Universidade Federal de Santa Maria |
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Universidade Federal de Santa Maria |
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