Reaction of monocyclic ferrocenyl-4,5-dihydropyrazoles with β-dicarbonyl compounds

Monocyclic 3- and 5-ferrocenyl-4,5-dihydropyrazoles with a free NH group in the molecule react with acetylacetone to form the corresponding enaminocarbonyl compounds. The latter were isolated as a single isomer, presumably E. 3-Ferrocenyldihydropyrazoles and 5-ferrocenyl-3-(p-methoxyphenyl)-4,5-dihydropyrazole analogously react with acetoacetic ester. 5-Ferrocenyl-3-phenyl-, 3-(p-bromophenyl)-5-ferrocenyl, and 3,5-diferrocenyl-4,5-dihydropyrazoles react with acetoacetic ester to form acetoacetylpyrazolides.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004, pp. 1942–1947.Original Russian Text Copyright © 2004 by E. Klimova, Vazquez Lopez, T. Klimova, Martinez Garcia, Meleshonkova, Ruiz Ramirez.This revised version was published online in April 2005 with a corrected cover date.     

Non-Born-Oppenheimer treatment of the H2 Hookean molecule

We show that the exact non-Born-Oppenheimer Schrodinger equation for the Hookean diatomic molecule H2 (a two-proton, two-electron system where the electron-proton interaction is harmonic while the proton-proton and electron-electron interactions are Coulombic) can be decoupled into equations describing the relative motion of the electrons, the relative motion of nuclei, the motion of a collective mode representing a three-dimensional harmonic oscillator, and the motion of a free particle expressed as a linear combination of the individual center-of-mass coordinates of the nuclei and electrons. Analytic solutions to the relative motion of electrons can be readily obtained for the given values of the harmonic coupling constant. However, exact analytic solutions to the equation for the relative motion of the nuclei cannot be obtained simultaneously due to the fact that the harmonic constants in these two equations are coupled. For this reason, we present for the relative nuclear motion approximate analytic wave functions, one of them obtained variationally and the other by a series solution where the coefficients are determined recursively. We also explore a variational solution to the Taylor-series expansion of the nuclear interaction potential. Properties of the electronic and nuclear intracule densities are examined at different values of the coupling constant. An interesting result of the present non-Born-Oppenheimer treatment of this harmonic model is the fact that the relative nuclear motion occurs in a highly correlated regime. This leads in a natural way to a spatial localization of the nuclei akin to Wigner electronic crystallization.     

The Radical Cations of 4,5,7,13,15,16-Hexamethyl- and 4,5,7,8,12,13,15,16-Octamethyl [2.2]paracyclophane

4,5,7,13,15,16-Hexamethyl- (3) and 4,5,7,8,12,13,15,16-octamethyl[2.2]paracyclophane (4) have been oxidized to their radical cations in solution under relatively mild conditions. Substantial hyperfine splittings in the ESR. spectra of 3⊕. and 4⊕. arise from the methyl protons, whereas those from methylene protons are very small. This result indicates that the ethano bridges, unlike the methyl substituents, are rather ineffective in delocalizing the positive charge in 3⊕. and 4⊕. It is in line with the interpretation proposed previously to rationalize the gas-phase ionization potentials of multiply bridged [2_N]cyclophanes and methyl derivatives of [2.2]paracyclophane. The π-spin distributions in 3⊕. and 4⊕. are discussed in terms of a simple model in which the singly occupied orbitals are represented as the antibonding combinations of two benzene HOMO's.     

Why copper is intrinsically more selective than silver in alkene epoxidation: ethylene oxidation on Cu(111) versus Ag(111)

The heterogeneously catalyzed epoxidation of alkenes is experimentally challenging, theoretically interesting, and technologically important. Although large-scale ethylene epoxidation is universally carried out with Ag catalysts, recent laboratory studies on single crystal surfaces show that Cu is intrinsically much more selective than Ag in the epoxidation of a variety of terminal alkenes. The reasons for this striking difference between Ag and Cu have been investigated by means of density functional theory. It is found that the fundamental cause is the inversion in the ordering of activation barriers for the competing pathways to epoxide formation versus acetaldehyde formation (the latter being the first step on the route to combustion). On Cu, epoxide formation is less activated than aldehyde formation; the opposite is true on Ag. This behavior is associated with a late transition state to epoxidation on Cu (i.e., product-like) compared to an early (reactant-like) transition state to epoxidation on Ag.     

Diastereoselective synthesis of cularine alkaloids via enium ions and an easy entry to isoquinolines by aza-Wittig electrocyclic ring closure

In preliminary communications, we reported the diastereoselective synthesis of cularine and sarcocapnine via the intramolecular ring closure of nitrenium and oxenium ions, a new highly diastereoselective reductive methylation with (+)-8-phenylmenthyl chloroacetate followed by reduction with sodium borohydride, and a facile entry to the isoquinoline precursors by aza-Wittig electrocyclic ring closure. We now report the full details of the syntheses of (+)-O-demethylcularine, (+)-cularine, (+)-sarcocapnidine, (+)-sarcocapnine, and (+)-crassifoline and describe different methods of synthesis of their precursors.     

Ion chromatography-electrospray mass spectrometry for the identification of low-molecular-weight organic acids during the 2,4-dichlorophenol degradation

End-product identification of organic pollutants during oxidation water treatments is of environmental concern due to their potential toxicity. In this work the coupling of ion chromatography (IC), equipped with a membrane ion suppressor, and electrospray ionization mass spectrometry (ESI-MS) has been successfully exploited for the identification of novel low molecular weight organic acids formed as final by-products of 2,4-dichloro-phenol (DCP) degradation by Fenton's reagent, an oxidation method widely employed to degrade recalcitrant organic pollutants in industrial wastewater. The IC-ESI-MS analytical set-up not only allowed the detection of known organic acids but also the identification of 13 new low molecular weight organic acids as a result of extensive oxidation of the parent organic pollutant. Some of the novel organic acids were shown to be chlorine containing by-products and, consequently, of environmental concern. The analytical set-up could be used for characterizing the unknown organic carbon fraction arising from oxidation water treatments.     

New cup-shaped α-cyclodextrin derivatives and a study of their catalytic properties in oxidation reactions

A series of new α-cyclodextrin derivatives with a substituted propylene bridge attached to the 6-O's of the A,D-glucose units are reported. The compounds were prepared from the known 6^A,6^D-di-O-(prop-2-methylidene-1,3-dienyl)-hexadeca-O-benzyl-α-cyclodextrin, which was transformed into 6^A,6^D-di-O-(prop-2-methyl-1,3-dienyl)-α-cyclodextrin, 6^A,6^D-di-O-(prop-2-formyl-2-hydroxy-1,3-dienyl)-α-cyclodextrin, 6^A,6^D-di-O-(prop-2-aminomethyl-2-hydroxy-1,3-dienyl)-α-cyclodextrin, 6^A,6^D-di-O-(prop-2-hydroxymethylidene-1,3-dienyl)-α-cyclodextrin, 6^A,6^D-di-O-(prop-2-formyl-1,3-dienyl)-α-cyclodextrin, 6^A,6^D-di-O-(prop-2-carboxy-1,3-dienyl)-α-cyclodextrin and 6^A,6^D-di-O-(prop-2-methoxycarbonyl-1,3-dienyl)-α-cyclodextrin. The new compounds were evaluated for their ability to affect amine and alcohol oxidations in the presence of hydrogen peroxide.