A síntese eficiente de novas 1,1,1-tricloro-4-metoxi-3-alquen-2-onas graxas [Cl3CC(O)C(R²)=C(R¹)OMe, onde R¹ = n-hexil, heptil, nonil, undecil, tridecil e R² = H] e 1,1,1-tricloro-2,4-alkanediones [Cl3CC(O)CHR²C (O) R¹, onde R¹ = n-pentil e R² = Me, R¹ = Et e R² = n-butil, R¹ = n-butil e R² = n-propil] é apresentada, com bons rendimentos (85-95%) a partir da acilação dos respectivos acetais com cloreto de tricloroacetila. As 1,1,1-tricloro-4-metoxi-3-alquen-2-onas e 1,1,1-tricloro-2,4-alkanediones graxas reagem com cloridrato de hidrazina produzindo os respectivos 1H-pirazol-5-carboxilatos, uma classe de novos ésteres metílicos (FAMEs) e etílicos (FAEEs) graxos não comuns. As estruturas moleculares dos compostos sintetizados foram confirmadas por análise elementar e ressonância magnética nuclear (NMR) de ¹H e 13C. As 1,1,1-tricloro-4-metoxi-3-alquen-2-onas graxas e seus derivados 1H-pirazol-5-carboxilatos são novos oleoquímicos com propriedades diferenciadas e potencialmente interessantes.

The efficient synthesis of new fatty 1,1,1-trichloro-4-methoxy-3-alken-2-ones [Cl3CC(O)C(R²)=C(R¹)OMe, where R¹ = n-hexyl, heptyl, nonyl, undecyl, tridecyl and R² = H] and 1,1,1-trichloro-2,4-alkanediones [Cl3CC(O)CHR²C(O)R¹, where R¹ = n-pentyl and R² = Me, R¹ = Et and R² = n-butyl, R¹ = n-butyl and R² = n-propyl] in good yields (85-95%) from acetal acylation with trichloroacetyl chloride is reported. The fatty 1,1,1-trichloro-4-methoxy-3-alken-2-ones and 1,1,1-trichloro-2,4-alkanediones were reacted with hydrazine hydrochloride, leading to respective 1H-pyrazole-5-carboxylates, unusual class of fatty acid methyl (FAMEs) and ethyl (FAEEs) esters. Their structures were confirmed by elemental analysis and ¹H and 13C nuclear magnetic resonance (NMR). The fatty 1,1,1-trichloro-4-methoxy-3-alken-2-ones and 1H-pyrazole derivatives are new oleochemicals with potentially interesting and differential properties.

Neste trabalho, a ciclocondensação dos precursores 7,7,7-trifluoro-4-metoxi-6-oxo-4 heptenoato de metila e 7,7,7-trichloro-4-metoxi-6-oxo-4-heptenoato de metila, a partir do ácido levulínico com amidinas [NH2CONH2, NH2CR(NH) (R = H, Me, Ph, NH2, SMe e 1H-pirazol-1-il), 5-amino-3-metil-1H-pirazol e 2-aminotiazol] para obtenção de 3-(6-trifluormetilpirimidina-4-il) propanoatos de metila com estrutura análoga a mediadores glutamatérgicos é relatada. A síntese de 3-(6-trifluormetilpirimidina-4-il)propanohidrazidas também é relatada. A versatilidade desse método foi demostrada através da síntese de quatorze 3(pirimidinil)propanoatos inéditos em rendimentos razoáveis a bons (38-92%). As estruturas moleculares dos produtos foram atribuídas com base nos dados de ressonância magnética nuclear (NMR) de ¹H e 13C e cromatografia de gases acoplada à espectrometria de massas (GC-MS).

The cyclocondensation of methyl 7,7,7-trifluoro-4-methoxy-6-oxo-4-heptenoate and methyl 7,7,7-trichloro-4-methoxy-6-oxo-4-heptenoate, derived from levulinic acid with amidines [NH2CONH2, NH2CR(NH) (R = H, Me, Ph, NH2, SMe and 1H-pyrazol-1-yl), 5-amino-3-methyl1H-pyrazol and 2-aminothiazole] into pyrimidine and pyrimidine-like derivatives as a new type of glutamate-like 3-(trihalomethylatedpyrimidinyl)propanoate is reported. Preparation of 3-(trihalomethylatedpyrimidinyl) propanohydrazides is also described. The synthetic potential of this straightforward protocol was established by the synthesis of fourteen new 3-(pyrimidinyl) propanoates in regular to good yields (38-92%). The structural assignments were based on the analysis of their ¹H and 13C nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC-MS) data.