THE FIRST SYNTHESIS OF A 2H-1,4-BENZOTHIAZINE-BASED PHOSPHINE OXIDE AND SULFIDE

Abstract

The synthesis of a cyclic α-amino phosphine oxide and sulfide with an incorporated benzo-thiazine moiety is described. The products can be regarded as analogues of the biologically active thiazolidinylphosphonates, in which several characteristic functional groups have been modified.     

Some Unusual Reactions in Organophosphorus Chemistry

Methylenephosphinophosphorane 1 reacts with azides without evolution of nitrogen to give zwitterionic phosphorazide 3 and iminophosphorazide 4 , which are in equilibrium to each other; 1 reacts with hexafluoroacetone (HFA) in a different way to give zwitterionic product 5 , which may have the ylidic structure 5' . HFA and thio-HFA react analogously with methylenediphosphines 6 to give corbodiphosphoranes 7 . Reaction of 6 with activated alkenes 9 gives monoylide 10 , which is a useful synthone for the synthesis of fluorosubstituted conjugated triene 12 and diylides 13 and 14 . Reaction of 10 with TOB gives unusually stable betaine 15 . Reaction of the other activated alkene 16 with 6 unexpectedly gave the unusual zwitterionic compound 17 .     

The Effect of Oxygen on Conversion in the Organic Peroxide-initiated High-Pressure Polymerization of Ethylene

To initiate the high-pressure polymerization of ethylene, oxygen is used together with organic peroxides in a number of tubular reactor processes. Since molecular oxygen is capable of promoting or inhibiting radical polymerization, depending on the reaction conditions chosen, controlled experiments were carried out to clarify these aspects of high pressure ethylene polymerization. In continuous polymerization tests carried out at 1700 bar and temperatures between 110 and 320°C, conversions were determined with tert-amyl perneodecanoate and di-tert-butyl peroxide initiation in the presence of various quantities of oxygen. Batch tests using a photo-initiator together with oxygen were also carried out. A comparison with polymerizations under conditions of careful elimination of oxygen shows no effect on the peroxide-initiated polymerization up to temperatures of 160 to 170°C. Although oxygen is an initiator at higher temperatures, the conversions obtained from the simultaneous addition of controlled quantities of oxygen and organic peroxides is lower than that obtained by adding together the conversions from the separate polymerizations.     

Heterobimetallic Cuprates Consisting of a Redox‐Switchable,Silicon‐Based Metalloligand: Synthesis,Structures, and Electronic Properties

A series of bimetallic silyl halido cuprates consisting of the new tripodal silicon‐based metalloligand [κ³N‐Si(3,5‐Me₂pz)₃Mo(CO)₃]^? is presented (pz=pyrazolyl). This metalloligand is straightforwardly accessible by reacting the ambidentate ligand tris(3,5‐dimethylpyrazolyl)silanide ({Si(3,5‐Me₂pz)₃}^?) with [Mo(CO)₃(η⁶‐toluene)]. The compound features a fac‐coordinated tripodal chelating ligand and an outward pointing, “free” pyramidal silyl donor, which is easily accessible for a secondary coordination to other metal centers. Several bimetallic silyl halido cuprates of the general formula [CuX{μ‐κ¹Si:κ³N‐Si(3,5‐Me₂pz)₃Mo(CO)₃}]^? (X=Cl, Br, I) have been synthesized. The electronic and structural properties of these complexes were probed in detail by X‐ray diffraction analysis, electrospray mass spectrometry, infrared‐induced multiphoton dissociation studies, cyclic voltammetry, spectroelectrochemistry, gas‐phase photoelectron spectroscopy, as well as UV/Vis and fluorescence spectroscopy. The heterobimetallic complexes contain linear two‐coordinate copper(I) entities with the shortest silicon–copper distances reported so far. Oxidation of the anionic complexes in methylene chloride and acetonitrile solutions at ${E{{0\hfill \atop 1/2\hfill}}}$ =?0.60 and ?0.44 V (vs. ferrocene/ferrocenium (Fc/Fc⁺)), respectively, shows substantial reversibility. Based on various results obtained from different characterization methods, as well as density functional theory calculations, these oxidation events were attributed to the Mo⁰/Mo^I redox couple.     

Reaction kinetics and solubility in water‐organic binary solutions are governed by similar solvation equilibria

The solvation effects observed in water‐organic solutions were studied by combining data for reaction kinetics and dissolution equilibria by means of a linear free‐energy (similarity) analysis. Kinetic data for the pH‐independent hydrolysis of (4‐methoxyphenyl)‐2,2‐dichloroacetate measured in this work and solubility data for naphthalene, and other substrates of low polarity, in aqueous binary mixtures of methanol, ethanol, acetonitrile, dimethyl sulfoxide (DMSO), and 1,4‐dioxane were used. Linear similarity relationships were discovered for these data over the full range of solvent compositions studied. To gain insight into the similarities observed between these different phenomena, molecular dynamics simulations were carried out for naphthalene and an ester in water–acetonitrile solutions. The results revealed considerable preferential solvation of these substrates by the co‐solvent. Linear relationships between the experimental data and the mole fractions of acetonitrile in the solvation shells of substrates were found. Surprisingly, a linear relationship was found between the mole fractions of acetonitrile in the solvation shells of the ester and naphthalene. This linearity indicated that a similar solvation mechanism governs even such different phenomena as dissolution and reaction kinetics. The relationships between the experimental data and the results of the molecular dynamics calculations found in this work explained the solvent effect observed in water‐organic solutions on the molecular level. Copyright © 2015 John Wiley & Sons, Ltd.     

Effective fields in laser-driven electron recollision and charge localization

We propose a model to describe correlated two-electron dynamics in strong laser fields during laser-induced recollision between an electron and its parent ion. We derive an effective interaction potential which describes the effect of the laser-driven electron collision with an ion while retaining the correlation between the colliding and the bound electron. Using dissociative ionization of molecular hydrogen as an example, we analyze the dynamics of correlation-driven electron localization in a dissociating hydrogen molecular ion.