Conselho Nacional de Desenvolvimento Científico e Tecnológico / Chemoselective synthesis of ethyl 4-pirimidinecarboxylates and/or ethyl 5-pirimidineoxalates via cyclocondensation reaction of b-dimethylaminoenones [R1C(=O)C(=CNMe2)C(=O)CO2Et, where R1 = Ph, 4-MeC6H4, 4-MeOC6H4, 4-BrC6H4,
4-ClC6H4, 4-FC6H4, 4-O2NC6H4, 2-thienyl, benzo[b]furan-2-yl and CF3] with NCN 1,3- dinucleophiles such as benzamidine hydrochloride or 1H-1-pyrazolyl-carboxamidine
hydrochloride (50-86%); utilization of ethyl 4-pirimidinecarboxylates (when R1 = Ph, 4-MeOC6H4, 4-FC6H4 and 2-thienyl) in the cyclization reaction with hydrazine
monohydrate, leading to 7,8-dihydropyrimido[4,5-d]pyridazin-8-ones (81-92%). In this work it was also studied the condensation reaction of (3,5-dimethyl-1H-1-
pyrazolyl)alkylketones with N,N-dimethylformamide dimethylacetal, with the aim to obtain b-dimethylaminoenones [PhC(=O)C(=CNMe2)(3,5-dimethyl-1H-1-pyrazolyl), PhC(=O)C(=CNMe2)(3,5-dimethyl-1H-1-pyrazolylmethyl) and MeC(=O)C(=CNMe2)(3,5-dimethyl-1H-1-pyrazolyl)] (92-98%); and synthesis of 1,4 -biazoles via cyclocondensation reaction of b-dimethylaminoenones with different 1,2-dinucleophiles such as hydrazine monohydrate, terc-butylhydrazine hydrochloride,phenylhydrazine hydrochloride, carboxymethylhydrazine or hydroxylamine
hydrochloride (50-80%). The X-ray diffraction technique was used in the elucidation of the stereochemistry of PhC(=O)C(=CNMe2)(3,5-dimethyl-1H-1-pyrazolylmethyl)
and regiochemistry of the cyclocondensation reactions. / Síntese quimiosseletiva de 4-pirimidinocarboxilatos de etila e/ou 5-pirimidinoxalatos de etila via reação de ciclocondensação de b-dimetilaminoenonas [R1C(=O)C(=CNMe2)C(=O)CO2Et, onde R1 = Ph, 4-MeC6H4, 4-MeOC6H4, 4-BrC6H4, 4-ClC6H4, 4-FC6H4, 4-O2NC6H4, 2-tienil, benzo[b]furan-2-il e CF3] com 1,3-dinucleófilos do tipo NCN, tais como cloridrato de benzamidina ou cloridrato de 1H-1-pirazolil-carboxamidina (50-86%); utilização de 4-pirimidinocarboxilatos de etila (quando R1 = Ph, 4-MeOC6H4, 4-FC6H4 e 2-tienil) na reação de ciclização com monoidrato de hidrazina, levando a 7,8-diidropirimido[4,5-d]piridazin-8-onas (81- 92%). Neste trabalho, também foi estudada a reação de condensação de (3,5-dimetil-1H-1-pirazolil)alquilcetonas com N,N-dimetilformamida dimetilacetal, visando
a obtenção de b-dimetilaminoenonas [PhC(=O)C(=CNMe2)(3,5-dimetil-1H-1-pirazolil), PhC(=O)C(=CNMe2)(3,5-dimetil-1H-1-pirazolilmetil) e MeC(=O)C(=CNMe2)(3,5-dimetil-1H-1-pirazolil)] (92-98%); e síntese de 1,4 -biazóis via reação de ciclocondensação de b-dimetilaminoenonas com diferentes 1,2-dinucleófilos, tais como monoidrato de hidrazina, cloridrato de terc-butilidrazina, cloridrato de fenilidrazina, carboximetilidrazina ou cloridrato de hidroxilamina (50-
80%). A técnica de difração de raios-X foi utilizada na elucidação da estereoquímica de PhC(=O)C(=CNMe2)(3,5-dimetil-1H-1-pirazolilmetil) e regioquímica das reações
de ciclocondensação.
| Identifer | oai:union.ndltd.org:IBICT/oai:repositorio.ufsm.br:1/4175 |
| Date | 06 March 2009 |
| Creators | Fiss, Gabriela Fehn |
| Contributors | Martins, Marcos Antonio Pinto, Zoch, Alana Neto, D'oca, Marcelo Gonçalves Montes, Flores, Alex Fabiani Claro, Dalcol, Ionara Irion |
| Publisher | Universidade Federal de Santa Maria, Programa de Pós-Graduação em Química, UFSM, BR, Química |
| Source Sets | IBICT Brazilian ETDs |
| Language | Portuguese |
| Detected Language | Portuguese |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/doctoralThesis |
| Format | application/pdf |
| Source | reponame:Repositório Institucional da UFSM, instname:Universidade Federal de Santa Maria, instacron:UFSM |
| Rights | info:eu-repo/semantics/openAccess |
| Relation | 100600000000, 400, 300, 300, 300, 300, 300, 300, c28419d9-6027-4f9c-acd2-76e8067a85d1, cc64d879-43d2-4db5-baf6-6834db3f6de1, a5d677e5-2cb0-4552-a4bb-750f18fc2f0f, 61a36a31-d5bd-4c07-aa71-3077a561271f, ef88f877-9177-4caf-ba05-4129d89287e1, 7feddb12-8bec-4266-9132-ae56cfe5ce9e |
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