Kinetics and mechanism of the chromic oxidation of 3-O-methyl-d-glucopyranose

The oxidation of 3-O-methyl-d-glucopyranose (Glc3Me) by Cr^VI in acid medium yields Cr^III, formic acid and 2-O-methyl-d-arabinose as final products when a 50-times or higher excess of Glc3Me over Cr^VI is used. The redox reaction takes place through the combination of Cr^VI → Cr^IV → Cr^II and Cr^VI → Cr^IV → Cr^III pathways. Intermediacy of free radicals and Cr^II in the reaction was demonstrated by the observation of induced polymerization of acrylamide and detection of CrO₂²⁺ formed by reaction of Cr^II with O₂. Intermediate oxo-Cr^V–Glc3Me species were detected by EPR spectroscopy. In 0.3–0.5 mol/L HClO₄, intermediate Cr^V rapidly decompose to the reaction products, while, at pH 5.5–7.5, where the redox processes are very slow, five-coordinate Cr^V bis-chelates of the pyranose and furanose forms of Glc3Me remain more than 15 h in solution. The C1–C2 bond cleavage of Glc3Me upon reaction with Cr^VI distinguishes this derivative from glucose, which is oxidized to gluconic acid.     

2-Hydroxy-2-oxo-1,4,2-oxa-aza-phospha(V) cyclohexane-4-methylene phosphonic acid (OAPhMPh): its structure and symmetry by vibrational spectroscopy

2-Hydroxy-2-oxo-1,4,2-oxa-aza-phospha(V) cyclohexane-4-methylene phosphonic acid (OAPhMPh) was obtained by a Mannich type reaction. From NMR spectroscopy a chair-conformed heterocyclic structure is suggested. Infrared and Raman data are in agreement with this symmetry and show no evidence of dimeric structure.     

A ‘waterproof’ catalyst for the oxidation of secondary amines to nitrones with alkyl hydroperoxides

Catalytic oxidation of secondary amines to nitrones using alkyl hydroperoxides as primary oxidant has been demonstrated for the first time. The titanium alkoxide catalyst is protected from co-product water by the combined use of a tightly binding trialkanolamine ligand and molecular sieves. Nitrones can be obtained in high yield (up to 98%) under homogeneous, anhydrous conditions and even in the absence of solvent. The reactions are fast (2-7 h) and good selectivity can be achieved with as little as 1% catalyst.     

Stochastic time-dependent current-density-functional theory

A time-dependent current-density-functional theory for many-particle systems in interaction with arbitrary external baths is developed. We prove that, given the initial quantum state |Psi0> and the particle-bath interaction operator, two external vector potentials A(r,t) and A'(r,t) that produce the same ensemble-averaged current density, j(r,t), must necessarily coincide up to a gauge transformation. This result greatly expands the applicability of time-dependent density-functional theory to open quantum systems, and allows for first-principles calculations of many-particle time evolution beyond Hamiltonian dynamics.     

Next-to-next-to-leading-order subtraction formalism in hadron collisions and its application to Higgs-boson production at the large hadron collider

We consider higher-order QCD corrections to the production of colorless high-mass systems (lepton pairs, vector bosons, Higgs bosons, etc.) in hadron collisions. We propose a new formulation of the subtraction method to numerically compute arbitrary infrared-safe observables for this class of processes. To cancel the infrared divergences, we exploit the universal behavior of the associated transverse-momentum (qT) distributions in the small-qT region. The method is illustrated in general terms up to the next-to-next-to-leading order in QCD perturbation theory. As a first explicit application, we study Higgs-boson production through gluon fusion. Our calculation is implemented in a parton level Monte Carlo program that includes the decay of the Higgs boson into two photons. We present selected numerical results at the CERN Large Hadron Collider.     

Equivalent dissipation postulates in classical plasticity

Summary In classical plasticity dissipation postulates on cycles, such as those proposed by Drucker, Martin e Il'yushin, rule the evolution of elastic-plastic deformation processes. In this paper, within the framework of the infinitesimal theory of isotropic materials with elastic range of [7], each one of those three postulates is given an equivalent local formulation; moreover, they are shown to be all equivalent.

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Sommario In plasticitá classica l'evoluzione dei processi elasto-plastici é regolata da postulati di dissipazione su cicli quali quelli proposti da Drucker, Martin e Il'yushin. In questo lavoro, nell'ambito della teoria infinitesima dei materiali isotropi con dominio elastico proposta in [7], si fornisce una formulazione locale equivalent per ciascuno di quei tre postulati e si mostra che essi sono tutti tra loro equivalenti.

     

Dividing a complex reaction involving a hypervalent iodine reagent into three limiting mechanisms by ab initio molecular dynamics

The electrophilic N‐trifluoromethylation of MeCN with a hypervalent iodine reagent to form a nitrilium ion, that is rapidly trapped by an azole nucleophile, is thought to occur via reductive elimination (RE). A recent study showed that, depending on the solvent representation, the S_N2 is favoured to a different extent over the RE. However, there is a discriminative solvent effect present, which calls for a statistical mechanics approach to fully account for the entropic contributions. In this study, we perform metadynamic simulations for two trifluoromethylation reactions (with N‐ and S‐nucleophiles), showing that the RE mechanism is always favoured in MeCN solution. These computations also indicate that a radical mechanism (single electron transfer) may play an important role. The computational protocol based on accelerated molecular dynamics for the exploration of the free energy surface is transferable and will be applied to similar reactions to investigate other electrophiles on the reagent. Based on the activation parameters determined, this approach also gives insight into the mechanistic details of the trifluoromethylation and shows that these commonly known mechanisms mark the limits within which the reaction proceeds. © 2015 Wiley Periodicals, Inc.