By means of deuterium-labeling experiments, we have carried out a systematic ESI-MS study to determine the mechanism of ESI ionization of alkenyl and alkynyl group 6 Fischer carbene complexes. These compounds can be ionized under ESI conditions only in the presence of additives such as hydroquinone (HQ) or tetrathiafulvalene (TTF). Our results demonstrate that in the ESI source an anion-radical is formed after the initial HQ- or TTF-mediated electron transfer to the metallic carbene complex. For alkenyl carbene complexes, this species evolves by extrusion of a hydrogen radical to form an allenylchromium anion that is detected as the [M - H](-) ion in the mass spectrum. The preference for this mechanistic pathway could be rationalized by DFT calculations. In the case of alkynyl carbene complexes, experiments combining deuterated substrate, additive, and solvent demonstrate that the previously proposed allene-anion carbene complex is not formed. Instead, the H transfer from the ethoxy group in the anion radical, followed by extrusion of a hydrogen radical, leads to an allenyl anion that is detected in the ESI-MS as [M - H - CO](-). 相似文献
beta-Nitrogen-functionalized vinylic organolithium compounds derived from secondary aliphatic allylamines have been found to undergo upon heating (reflux of THF) either a dimerization or a regio- and stereoselective cyclodimerization reaction affording diamino 1,4-dienes or cis-2,3-disubstituted 4-methylenepyrrolidines, respectively, according to reaction time. In contrast, the corresponding dianions derived from aromatic allylamines underwent protonation by the solvent under analogous thermal treatment. A mechanism accounting for all these results has been proposed, which involves a spontaneous beta-elimination of lithium hydride and an intramolecular nucleophilic cyclization by addition of a lithium amide to an alkene group as critical steps. In addition, experimental evidence is provided about the formation of 3-lithio-1-aza 1,3-dienes as intermediates in these unusual thermal transformations. 相似文献
The preparation of indigo from Indigofera suffruticosa following the procedures attributed to ancient Mayas was electrochemically monitored using the voltammetry-of-microparticles
approach. The mechanism formation of indigotin and indirubin from its precursors, indican and isatan, is discussed. Comparison
of voltammetric profiles for differently prepared and commercial indigos and genuine Maya Blue samples suggests that the preparation
procedure of indigo changed during the Late Classical Maya period.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
[reaction: see text] Potassium peroxomonosulfate deposited onto silica SiO2 x KHSO5 efficiently reacts with ketones in dichloromethane at room temperature to give the corresponding esters or lactones in quantitative yields. This method avoids hydrolysis of the reaction products. The Baeyer-Villiger reaction is catalyzed by potassium hydrogensulfate present in the supported reagent. 相似文献
Biogenic amines, as dabsyl derivatives, were determined in beer samples, intermediate products, and raw materials (malt and maize) by HPLC. A procedure for the extraction of the amines from malt and maize with diluted hydrochloric acid was optimised by combining a Response Surface Methodology with a Simultaneous Decision Making Approach. The results of the analysis indicate that, in brewing, technology and hygiene are the decisive factors that determine the amine concentrations in the final product. 相似文献
Molecular-dynamics simulations for linear quadrupole liquids are presented. The study is carried out for two different molecular lengths at constant density and a number of temperatures and quadrupole moments. All the simulated thermodynamic states correspond to the condensed phases and some of them show typical features of a solid structure. Furthermore, a change on the preferred intermolecular orientation in the liquid phase is observed from a shifted parallel molecular arrangement to a perpendicular orientation as the quadrupole raises. This change depends on the quadrupole moment as well as on the molecular length and is put in relation with the solid structure of different "diatomic" molecules such as nitrogen, ethane, and acetylene. The appearance of a plastic solid phase at low quadrupole moment and density is also justified. A thoroughly discussion about the availability of classical perturbation theories for this kind of systems is presented. 相似文献
As a model of the chemical reactions that take place in the active site of gluthatione reductase, the nature of the molecular mechanism for the hydride transfer step has been characterized by means of accurate quantum chemical characterizations of transition structures. The calculations have been carried out with analytical gradients at AM1 and PM3 semiempirical procedures, ab initio at HF level with 3-21G, 4-31G, 6-31G, and 6-31G basis sets and BP86 and BLYP as density functional methods. The results of this study suggest that the endo relative orientation on the substrate imposed by the active site is optimal in polarizing the C4-Ht bond and situating the system in the neighborhood of the quadratic region of the transition structure associated to the hydride transfer step on potential energy surface. The endo arrangement of the transition structure results in optimal frontier HOMO orbital interaction between NADH and FAD partners. The geometries of the transition structures and the corresponding transition vectors, that contain the fundamental information relating reactive fluctuation patterns, are model independent and weakly dependent on the level of theory used to determine them. A comparison between simple and complex molecular models shows that there is a minimal set of coordinates describing the essentials of hydride transfer step. The analysis of transition vector components suggests that the primary and secondary kinetic isotope effects can be strongly coupled, and this prompted the calculation of deuterium and tritium primary, secondary, and primary and secondary kinetic isotope effects. The results obtained agree well with experimental data and demonstrate this coupling. 相似文献
In this article results given in a previous paper (part I), concerning the spectra of NH and ND species recorded with a polarization parallel to the c axis are analyzed, the necessary corrections on the raw data performed, vs bands and their first moments are then compared with corresponding quantities predicted from a simple theory which describes quantitatively the anharmonic interactions of a single H-bond with a low frequency vibration of the same H-bond and with binary combinations of modes (Fermi resonances). This allows us to determine the magnitudes of the various anharmonic interactions involved. It appears that the low frequency vibration which modulates vs is a bending mode of the H-bond (NH ↑ … N), a finding somewhat unexpected, as this low frequency vibration is usually thought to be the stretching vibration vσ of the H-bond 相似文献
A comprehensive laboratory experiment suitable for advanced undergraduate organic chemistry students has been designed. The experiment is based on the dienone-phenol rearrangement reaction of the sesquiterpene santonin to give -desmotroposantonin acetate. It challenges students to solve an earlier controversial stereochemical problem. The students carry out the reaction and analyze spectroscopic data to determine the stereochemistry of the starting material and the product. In addition, they perform simple molecular modeling calculations, which enable them to rationalize the stereochemical outcome of the transformation and discuss the mechanism of the dienone-phenol rearrangement and related rearrangements reported in the literature. 相似文献
Flash-induced absorbance spectroscopy was used to analyze the proton uptake and electron transfer properties of photosynthetic reaction centers (RC) of Rhodobacter capsulatus that have been genetically modified near the primary quinone electron acceptor (Q(A)). M246Ala and M247Ala, which are symmetry-related to the positions of two acidic groups, L212Glu and L213Asp, in the secondary quinone electron acceptor (QB) protein environment, have been mutated to Glu and Asp, respectively. The pH dependence of the stoichiometry of proton uptake upon formation of the P+Q(A)- (H+/P+Q(A)-) and PQ(A) (H+/Q(A)-) (P is the primary electron donor, a noncovalently linked bacteriochlorophyll dimer) states have been measured in the M246Ala --> Glu and the M247Ala --> Asp mutant RC, in the M246Ala-M247Ala --> Glu-Asp double mutant and in the wild type (WT). Our results show that the introduction of an acidic group (Glu or Asp) in the QA protein region induces notable additional proton uptake over a large pH region (approximately 6-9), which reflects a delocalized response of the protein to the formation of Q(A)-. This may indicate the existence of a widely spread proton reservoir in the cytoplasmic region of the protein. Interestingly, the pH titration curves of the proton release caused by the formation of P+ (H+/P+: difference between H+/P+Q(A)- and H+/PQ(A)- curves) are nearly superimposable in the WT and the M246Ala --> Glu mutant RC, but substantial additional proton release is detected between pH 7 and 9 in the M247Ala --> Asp mutant RC. This effect can be accounted for by an increased proton release by the P+ environment in the M247Ala --> Asp mutant. The M247Ala --> Asp mutation reveals the existence of an energetic and conformational coupling between donor and acceptor sides of the RC at a distance of nearly 30A. 相似文献