Characterization studies of 1-(4-cyano-2-oxo-1,2-dihydro-1-pyridyl)-3-(4-cyano-1,2-dihydro-1-pyridyl)propane formed from the reaction of hydroxide Ion with 1,3-Bis-(4-cyano pyridinium)propane

The aqueous alkaline reaction of 1,3-bis(4-cyanopyridinium)propane dibromide, a reactant constituted of two pyridinium rings linked by a three-methylene bridge, generates a novel compound,1 -(4-cyano-2-oxo-1,2-dihydro-1-pyridyl)-3-(4-cyano-1,2-dihydro-1-pyridyl)propane. The reaction pathway is attributed to the proximity of the OH- ion inserted between two pyridinium moieties, which occurs only in bis(pyridinium) derivatives connected by short methylene spacers, where charge-conformational effects are important.A reação em meio aquoso alcalino do dibrometo de 1,3-bis(4-cianopiridinium)propano, um composto constituído por dois anéis piridínicos conectados por uma ponte metilênica de três carbonos, gerou um novo composto, o 1-(4-ciano-2-oxo-1,2-diidro-1-piridil)-3-(4-ciano-1,2-diidro-1-piridil)propano. O resultado da reação é atribuído à proximidade do íon OH-, encapsulado entre os dois anéis piridínicos, fato este observado apenas em derivados bis-piridínicos conectados por pontes metilênicas de curta extensão, onde imperam efeitos de carga aliados à conformação.CNPqFAPESPFundação Araucári

Abietane diterpenes from Sagittaria montevidensis ssp montevidensis Charm. & Schltdl

Two new abietane-type diterpenes, 3beta-hydroxy-9alpha, 13alpha-epidioxyabiet-8(14)-ene (1) and 3-oxo-9alpha,13alpha-epidioxyabiet-8(14)-ene (2), were isolated from the methanolic crude extract of the petioles of Sagittaria montevidensis ssp montevidensis (Alismataceae). The structures of 1 and 2 were determined on the basis of spectrometric analyses including HREIMS, IR as well as ¹H and 13C 1 and 2D NMR.Dois novos diterpenos do tipo abietano 3beta-hidroxi-9alfa, 13alfa-epidioxiabiet-8(14)-eno (1) e 3-oxo-9alfa,13alfa-epidioxiabiet-8(14)-eno (2) foram isolados do extrato bruto metanólico dos pecíolos de Sagittaria montevidensis ssp montevidensis (Alismataceae). As estruturas de 1 e 2 foram determinadas com base em análises espectrométricas do tipo EM-AR, IV, bem como, RMN de ¹H e 13C uni e bi dimensionais.44444

Atribuição inequívoca de deslocamentos químicos de RMN de ¹H e 13C de plumierídeo isolado da Allamanda cathartica

There are NMR data of ¹H and 13C of the iridoid plumieride, but controversy related to the assignments of the protons H-3 or H-10 and carbons C-6 or C-7 and C-3 or C-10 are described in the literature. There are a little discussion regarding to the resonance assignment of protons of the glycoside unity. Analysis based on 2D shift correlated NMR spectra (COSY, HETCOR, HETCORLR) and NOE difference ¹H NMR spectra allowed to assign unambigously the chemical shift of ¹H and 13C of plumieride which has been found in the literature with non coincident values

Semiempirical and ab initio calculations versus dynamic NMR on conformational analysis of cyclohexyl-N,N-dimethylcarbamate

Axial-equatorial conformational proportions for cyclohexyl-N,N-dimethyl carbamate have been measured, for the first time, by the Eliel method, ¹H and 13C dynamic nuclear magnetic resonance (DNMR). The results were compared against those determined by theoretical calculations. By the Eliel method at least five experimentally independent measureables were used in CCl4, CDCl3 and CD3CN. The ¹H and 13C low temperature experiments were performed in CF2Br2/CD2Cl2 . Semiempirical methods MNDO, AM1 and PM3 and ab initio molecular orbital calculations at the HF/STO-3G and HF/6-31G(d,p) levels have been performed on the axial and equatorial conformers populations. All applied methods correctly predict the equatorial conformer preference over the axial one. The resulting equatorial preferences determined by NMR data and theoretical calculations are in good agreement