REACTION OF LITHIUM DERIVATIVE OF DIETHYL PHENYLMETHANE-PHOSPHONATE WITH KETONES

Abstract

The reaction of the lithium derivative of diethyl ester of phenylmethanephosphonic acid (1-Li) with alkanones, cycloalkanones, alkylaryl and diarylketones 2s-b is studied at -70°C in THF. The corresponding adducts-diethyl esters of l-phenyl-2,2-dialkyl(phenyl)-2-hydroxyethanephosphonic acids 3s-h are isolated, their yields being usually higher at short reaction time. The olefination of 3-Li as well as of 3 (both by thermolysis or in acidic media) proceeds in low degree, while in the case of 3-Na the yields of alkenes 4 are good. The relative configurations of 3b. 31 and 3g are determined by IR and NMR-spectra, as well as by their stereospecific olefination. “Threo”-stereoselectivity of the addition stage of the reaction of 1-Li with 2b, 21 and 2g is observed, the “threo”/“erythro” ratio remaining independent on the reaction time.     

High-order numerical simulation and modelling of the interaction of energetic and inert materials

We present an integrated algorithm on a Eulerian grid, for multimaterial simulations of energetic and inert materials modelled by non-ideal equations of state. We employ high-resolution shock capturing numerical algorithms for each material inside its domain and use an overlap domain method across the interface, maintained by a recently developed, hybrid, level-set algorithm. For applications to condensed explosives we implement a non-ideal, wide-ranging equation of state and reaction rate law. For inert materials, like plastic, metal, water, etc., we implement a (linear in the pressure) Mie–Grüneisen, (U _p ?U _s ), equation of state. We present a series of verifications of the integrated multimaterial code and show validations against experiment. We show examples of simulations of various experiments associated with real or planned experiments, some of which contain energetic materials (specifically the condensed explosives PBX-9502 and PBX-9501).     

1H, 13C and 15N NMR spectral analysis of substituted 1,2,3,4‐tetrahydro‐pyrido[1,2‐a]pyrimidines

The NMR spectroscopic data of a series of thirty‐four 3‐acylpyrido[1,2‐a]pyrimidinium salts are analyzed, which were prepared as either perchlorates or chlorides. Methyl group substituted 3‐aroyltetrahydropyrido[1,2‐a]pyrimidines with the methyl substituent in positions 6, 8 and 9 as well as both in positions 6 and 8 were investigated bearing various aroyl substituents. Unequivocal assignment of all resonances was achieved via two‐dimensional ¹H,¹H‐COSY measurements, ¹H,¹³C and ¹H,¹⁵N HSQC as well as HMBC experiments, and important diagnostic CH and NH couplings in the heteroaromatic ring system are evaluated. The influence of the methyl substituents was analyzed on the proton, carbon and nitrogen shifts. A significant effect of the counter ion on some chemical shifts of the nuclei under discussion of the pyridopyrimidines is found, allowing the indirect detection of the anion, which is confirmed by direct measurement of the ³⁵Cl nucleus of the perchlorates. Copyright © 2013 John Wiley & Sons, Ltd.     

Responsive core–shell microgels: Synthesis,characterization, and possible applications

Core–shell microgels are of increasing interest as smart carriers of catalysts, as sensors, or as building blocks for colloidal superstructures. In the context of colloidal assemblies, photonic applications are probably the most promising ones. This progress report presents and discusses the most recent results in this area focusing on the last 2–3 years, and also gives some background information. In addition, potential perspectives of this area will be outlined. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1073–1083     

Open Chain Chiral Macrolide Building Blocks by Opening of Deoxygenated 1,6-Anhydrosugars with 1,3-Propanedithiol

Chiral building blocks for macrolides and related natural products are obtained from 1,6-anhydrosugars by conversion of the bicyclic acetals 2 or 12 into the open chain chiral 1,3-dithianes 6 and 13. Branched precursors can be obtained by opening of the ?erný epoxide 1 with the 1,3-dithiane anion to yield 7, followed by ring opening with 1,3-propanedithiol to the bis-1,3-dithiane 8.     

Rapid Synergistic Extraction And Atomic Absorption Spectrometric Determination Of Iron In Environmental Samples Using Tributyl Phosphate And N-Phenyl-2-Furylacrylohydoroxamic Acid

Abstract

Iron (III) was rapidly extracted as its ternary complex with tributyl phosphate and N-phenly1-2-furylacrylohydroxamic acid (PFHA) from weakly acidic (pH 1.0-1.5) solutions into isobutyl methyl ketone and was determined atomic absorption spectrometrically. The method tolerated the presences of a large number of anions and cations commonly associated with iron, and was successfully tested with certified samples of coal fly ash, alloys, and plant tissues. It was also applied to the analysis of animal tissues, natural waters, and wastewaters; validating it by standard addition technique. PFHA was selected from nine new hydroxamic acids.     

Transformation of macromonomers into ring‐opening polymerization macroinitiators: A detailed initiation efficiency study

In the present study, n‐butyl acrylate macromonomer (BAMM) (M_n = 1900 g mol^?1; PDI = 1.96) has been synthesized via a high‐temperature polymerization process. Subsequently, the olefinic termini of the BAMM have been transformed into a diol via a dihydroxylation process using KMnO₄ as an oxidizing agent. The OH‐terminated macroinitiator pBA(OH)₂ has subsequently been employed for the ring‐opening polymerization (ROP) of ε‐caprolactone via various catalytic systems, that is, organo‐(1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene), metal (tin(II) 2‐ethylhexanoate), and enzymatic catalysis (Novozym® 435). The obtained pBA‐b‐pCL block copolymers and the initiation efficiency of the BAMM macroinitiator have been investigated via size exclusion chromatography (SEC), electrospray ionization–mass spectrometry (ESI‐MS) hyphenated with SEC and liquid chromatography at the critical conditions of both poly(ε‐caprolactone) (pCL) and pBA. The in vitro enzyme catalysis (eROP) approach proved to be the most efficient catalysis system due to minor transesterification side reactions during the polymerization process. However, side reactions such as transesterifications occur in each catalytic system and—while they cannot be suppressed—they can be minimized. The species generated during the eROP process include the desired block copolymer pBA‐b‐pCL as main species as well as pCL homopolymer and residual macroinitiator pBA(OH)₂. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

On the redox reactions of radicals with AlIII(phthalocyaninate) pendants covalently bonded to poly(ethyleneamide). Mechanistic alterations when radicals are formed inside pockets of micelle‐like polymer aggregates

The mechanisms of the redox reactions between a polymer containing Al(III) sulfonated phthalocyanine pendants, (Al^III(^?NHS(O₂)trspc)^2?)₂, and radicals have been investigated in this work. Pulse radiolysis and photochemical methods were used for these studies. Oxidizing radicals, OH^?, HCO₃^?, (CH₃)₂COHCH₂^?, and N₃^?, as well as reducing radicals, e_aq^?, CO₂^??, and (CH₃)₂C^?OH, respectively accept or donate one electron forming pendent phthalocyanine radicals, Al^III(^?NHS(O₂)trspc ^?)^{? or 3?}. The kinetics of the redox processes is consistent with a mechanism where the pendants react with radicals formed inside aggregates of five to six polymer strands. Electron donating radicals, that is, CO₂^?? and (CH₃)₂C^?OH, produce one‐electron reduced phthalocyanine pendants that, even though they were stable under anaerobic conditions, donated charge to a Pt catalyst. While the polymer was regenerated in the Pt catalyzed processes, 2‐propanol and CO₂ were respectively reduced to propane and CO. The reaction of SO₃^?? radicals with the polymer stood in contrast with the reactions of the radicals mentioned above. A first step of the mechanism, the coordination of the SO₃^?? radical to the Al(III), was subsequently followed by the formation of a SO₃^?? ‐ phthalocyanine ligand adduct. The decay of the SO₃^?? ‐ phthalocyanine ligand adduct in a ～10² ms time domain regenerates the polymer, and it was attributed to the dimerization/disproportionation of SO₃^?? radicals escaping from the aggregates of polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The use of high-frequency filters in the investigation of the coloured-random-noise properties of cosmic-ray data

Summary This paper investigates the influence of high-frequency filtering the background white noise on the determination of the coloured-random-noise properties of cosmic-ray experimental signals. We consider fractal methods (Grassberger-Procaccia method, scaling exponent method and fractal length method) and statistical methods (comparison with the Gaussian curve, and the multivariate scaling-analysis technique). The investigation is carried out using two experimental time series with differentcolour (spectral indices α=1.6 and α=1.2) and their computer simulations of pure noise-freecoloured-random-noise signals. The results of the investigation is that the use of high-frequency filtering allows the algorithms employed in the various analyses to see the physical characteristics of the particular data set; the procedure should be reserved, however, to researchers with a good experience in the methods of fractal analysis so that they can identify and discard the artifacts introduced by the truncation applied to the power spectrum.