Preferred Conformations of Stabilized Phosphorus Ylides

The stabilized phosphorus ylides, Ph₃P=C(CO.R′)CO.OR; 1, R=Et, R′=CH₂P⁺Ph₃; 2, R=R′=Me; 3, R=Et, R′=Me; 4, R=Prⁱ; R′=Me; 5, R=Bu^t; R′=Me, adopt a near planar conformation in the crystal which allows extensive electronic delocalization. The keto and alkoxylic oxygens are oriented and align favorably with the cationoid phosphorus. These conformations bring methyl hydrogens in the ester residue into proximity with the face of a phenyl group and lead to π-shielding and upfield shifts of the ¹HNMR signals of 3 over a wide temperature range (-50–95°C) in (CD₃)₂CO, CDCl₃ and DMSO_d-6. Geometries of 2 and 3, optimized by using the HF 3-21 (G^*) or 6-31 (G^*) basis sets, are very similar to those in the crystal, but semiempirical treatments generate structures in which either the ester or keto moiety is twisted out of plane.

     

A combination of flow and batch mode processes for the efficient preparation of mGlu2/3 receptor negative allosteric modulators (NAMs)

Benzodiazepinones are privileged scaffolds with activity against multiple therapeutically relevant biological targets. In support of our ongoing studies around allosteric modulators of metabotropic glutamate receptors (mGlus) we required the multigram synthesis of a β-ketoester key intermediate. We report the continuous flow synthesis of tert-butyl 3-(2-cyanopyridin-4-yl)-3-oxopropanoate and its transformation to potent mGlu_2/3 negative allosteric modulators (NAMs) in batch mode.     

THE KINETICS AND MECHANISM OF THE REACTION OF TRICOORDINATE PHOSPHORUS COMPOUNDS WITH SULFENATE ESTERS

Abstract

The kinetics and mechanism of the reaction of tricoordinate phosphorus compounds, Ar_nP(OCH₂CF₃)_3-n with arylsulfenate esters, ArSOCH₂CF₃, are reported. Product analysis, kinetic order, activation parameters, Hammett data and solvent effects are the criteria used to elucidate the two step mechanism involving arylthiophosphoranes as intermediates.     

Continuum limits for classical sequential growth models

A random graph order, also known as a transitive percolation process, is defined by taking a random graph on the vertex set {0,…,n ? 1} and putting i below j if there is a path i = i₁…i_k = j in the graph with i₁ < … < i_k. Rideout and Sorkin 14 provide computational evidence that suitably normalized sequences of random graph orders have a “continuum limit.” We confirm that this is the case and show that the continuum limit is always a semiorder. Transitive percolation processes are a special case of a more general class called classical sequential growth models. We give a number of results describing the large‐scale structure of a general classical sequential growth model. We show that for any sufficiently large n, and any classical sequential growth model, there is a semiorder S on {0,…,n ‐ 1} such that the random partial order on {0,…,n ‐ 1} generated according to the model differs from S on an arbitrarily small proportion of pairs. We also show that, if any sequence of classical sequential growth models has a continuum limit, then this limit is (essentially) a semiorder. We give some examples of continuum limits that can occur. Classical sequential growth models were introduced as the only models satisfying certain properties making them suitable as discrete models for spacetime. Our results indicate that this class of models does not contain any that are good approximations to Minkowski space in any dimension ≥ 2. © 2009 Wiley Periodicals, Inc. Random Struct. Alg., 2010     

Investigation of aging processes of graphite tubes modified with iridium and rhodium used for atomic spectrometry

UV spectrometry (187–380 nm) with charge coupled device (CCD) detection was used to study the evolution of absorption spectra during the vaporization of various species in the pyrocoated graphite furnace, with electrodeposited Ir and Rh as modifiers. In order to mimic a typical matrix composition, various salts of aluminum, manganese, copper, magnesium, sodium, and lead were used in microgram amounts. Changes in spectra and vapor release rate, along with aging of the tubes in the repetitive temperature cycles, were observed.     

Polyelectrolyte complexation between poly(methacrylic acid,sodium salt) and poly(diallyldimethylammonium chloride) or poly[2‐(methacryloyloxyethyl) trimethylammonium chloride]

Polyelectrolyte complexes between poly(methacrylic acid, sodium salt) and poly(diallyldimethylammonium chloride) (PDADMAC) or poly[2‐(methacryloyloxyethyl)trimethylammonium chloride] (PMOETAC) form gels, liquid phases, or soluble complexes depending on charge ratio, total polymer loading, polymer molecular weight, and ionic strength. Increasing the ionic strength of the medium led most polyelectrolyte pairs to transition from gel through liquid complexes (complex coacervate) to soluble complexes. These transitions shift to higher ionic strengths for higher molecular weight polymers, as well as for PMOETAC compared to PDADMAC. The complex phases swelled with increasing polymer loading, ultimately merging with the supernatant phase at a critical polymer loading. The isolated liquid complex phases below and above this critical loading were temperature‐sensitive, showing cloud points followed by macroscopic phase separation upon heating. Incorporating 5 mol % lauryl methacrylate into the polyanion led to increased complex yield with PDADMAC, and increased resistance to ionic strength. In contrast, incorporating 30 mol % of oligo(ethylene glycol) methacrylate into the polyanion led to decreased complex yield, and to lower resistance to ionic strength. Two polyelectrolyte systems that produced liquid complexes were used to encapsulate hydrophobic oils, and in one case were used to demonstrate the feasibility of crosslinking the resulting capsule walls. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4129–4143, 2007     

Magneto-photoluminescence of AlGaN/GaN quantum wells

The magneto-luminescence of GaN/AlGaN quantum wells in fields up to 52 T shows a field dependence that is strongly dependent on the well width. Strong redshifts are seen for the narrowest wells that are attributed to a Zeeman splitting. This is unexpected, since in bulk GaN epilayers the electron and hole g-factors of the lowest valence band cancel each other almost exactly. Therefore, we attribute this splitting to a reordering of the valence band due to the different band offsets caused by the strain and the aluminium component in the AlGaN barriers. The field dependence also gives information on the size of the exciton that has been converted into values for the exciton binding energy, and these values agree reasonably well with a theory that includes the presence of the electric field.     

On a universal best choice algorithm for partially ordered sets

For the only known universal best choice algorithm for partially ordered sets with known cardinality and unknown order (proposed by J. Preater) we improve the estimation of the lower bound of its chance of success from the hitherto known constant 1/8 to 1/4. We also show that this result is the best possible for this algorithm, i.e., the 1/4 bound cannot be further improved. © 2007 Wiley Periodicals, Inc. Random Struct. Alg., 2008     

Use of a scientific microwave apparatus for rapid optimization of reaction conditions in a monomode function and then substrate screening in a multimode function

Recently, a new apparatus has become available, which aims to bring together in one unit the advantages of a monomode and a multimode microwave device. We have assessed the applicability of the apparatus toward rapid optimization of reaction conditions in a monomode function and then substrate screening in a multimode function. We have also probed the effects of differences in microwave absorptivity of reaction mixtures on the product conversions in screening multiple substrates simultaneously in a multimode microwave apparatus. We find that when the microwave absorptivity of a reaction mixture is dictated by the solvent, there is little effect on the heating profile of varying the substrate in a screening run. However, this is not the case when reactions involving non-microwave absorbant solvents are used. In this case the characteristics of the substrate can affect significantly the outcome of the reaction.