CATALYSE INTRAMOLECULAIRE DE L'AMINOLYSE DES HETEROCYCLES PHOSPHORES DERIVES DES α AMINOAMIDES. II: ETUDE DE LA CYCLISATION DES PHOSPHORDIAMIDES INCORPORANT UN RESIDU DE β AMINOACIDE,REACTIVITE VIS A VIS DE NUCLEOPHILES DES HETEROCYCLES FORMES

Abstract

Derivatives of β aminoacids in form of esters 1 or nitrile 4 (table I) undergo in an alcohol-ate/alcohol medium a rearrangement (Fig. 2), with formation of a β peptide link, resulting in the formation of esters 6 (table II). According to the experimental conditions the six membered ring heterocycles 5 are detected or isolated. They are also synthetized by cyclisation of acids 2 or hydrazide 3 (Fig. 5). While phosphorus easily reacts with alcohols and water, leading respectively to esters 6 and acids 9 (Fig. 7), it remains unaffected by amines. These results are discussed in term of mechanisms of the phosphorylation. The applications for β peptide synthesis and the participation of the p amide group in phosphorylation are limited.     

High Speed Video Camera and Electrical Signal Analyses of Arcs Behavior in a 3-Phase AC Arc Plasma Torch

A 3-phase AC plasma torch has been developed and aims at overcoming some limits of the classical DC torches in terms of efficiency, cost and reliability. However, the arc behavior in 3-phase plasma torch remains poorly explored. This paper is dedicated to the high speed video camera at 100,000 frames per second and electrical signal analyses of arcs behavior in a 3-phase AC arc plasma torch. First, a reference case at 150 A, in nitrogen as working gas, has been deeply analyzed. Afterwards, a parametric study based on current and inter-electrode gap has been carried out. Results show that only one arc can exist at a given time and arcs rotate by switching from a pair of electrodes to another one, following the maximal electrical gap potential. However, a particular “abnormal” arc behavior was sometimes observed. Indeed, the arc motion within the inter-electrode gap increases the heat exchange and stabilizes the 3-phase discharge whereas the system is unbalanced when the arc is in the periphery. The analysis highlights that the arc motion is strongly influenced by the electrode jet velocity and repulsive Lorentz forces. The parametric study shows that the current increases both jet velocity and arc discharge stability. Elsewhere, the increase of the inter-electrode gap can also stabilizes the electrical 3-phase arc discharge. Furthermore, the correlation between arc motion and current waveform is highlighted. This work is likely to open the way toward a better understanding of 3-phase discharges in the perspective of their further optimization.     

Electrochemical Dehydrogenative C−H Aminomethylation of Imidazopyridines and Related Heterocycles

A facile and environmentally friendly electrochemical protocol is herein reported for the C(sp²)−C(sp³) cross dehydrogenative coupling between imidazopyridines and N,N-dimethylanilines. The broad functional group compatibility includes halogens, ester, alcohol, sulfone as well as thiophene. This methodology is also suitable for benzo[d]imidazo[2,1-b]thiazole, thiazoimidazole and tetrahydroisoquinoline, and can be scaled up to 5 mmol. Mechanistic insights are discussed.     

Simulations of ferrite-dielectric-wire composite negative index materials

We perform extensive finite difference time domain simulations of ferrite based negative index of refraction composites. A wire grid is employed to provide negative permittivity. The ferrite and wire grid interact to provide both negative and positive index of refraction transmission peaks in the vicinity of the ferrite resonance. Notwithstanding the extreme anisotropy in the index of refraction of the composite, negative refraction is seen at the composite air interface allowing the construction of a focusing concave lens with a magnetically tunable focal length.     

Network Bending: Expressive Manipulation of Generative Models in Multiple Domains

This paper presents the network bending framework, a new approach for manipulating and interacting with deep generative models. We present a comprehensive set of deterministic transformations that can be inserted as distinct layers into the computational graph of a trained generative neural network and applied during inference. In addition, we present a novel algorithm for analysing the deep generative model and clustering features based on their spatial activation maps. This allows features to be grouped together based on spatial similarity in an unsupervised fashion. This results in the meaningful manipulation of sets of features that correspond to the generation of a broad array of semantically significant features of the generated results. We outline this framework, demonstrating our results on deep generative models for both image and audio domains. We show how it allows for the direct manipulation of semantically meaningful aspects of the generative process as well as allowing for a broad range of expressive outcomes.     

Rh(I)-catalyzed carbonylative ring opening of diazabicycles with acyl anion equivalents

A catalytic desymmetrization of strained alkenes by ring-opening of meso-diazabicycles with acyl anion nucleophiles is reported. Densely functionalized trans-1,2-hydrazinoacyl cyclopentene building blocks are obtained stereoselectively. The acyl anion equivalent is generated in situ under very mild conditions from readily available organoboron precursors.     

Electrical Conductivity in TCNQ Salts of Bis(4-dimethylaminophenylimino) sulfur and its Structural Analogues

Four compounds, N,N,N',N'-tetramethyl-p-phenylene diamine, N,N,N',N'-tetramethyl-benzidine, 4,4'-bis(dimethylamino)azobenzene and bis(4-dimethylaminophenylimino)sulfur (BAPIS) were examined electrochemically and spectroscopically. Each was shown to be a fairly good donor forming in its first oxidation state a radical-cation. The latter two materials surprisingly exhibited only single one-electron oxidations. Conformational flexibility about the -NSN- unit was studied by NMR spectroscopy and ab initio molecular orbital theory. The experimental ΔG* for a cis-trans to trans-cis interconversion in BAPIS was found to be 11.9 kcal/mole.

The four donors all form 1:1 adducts with TCNQ. The compaction resistances of the complexes have been measured as a function of temperature. Of the four, (BAPIS)(TCNQ) appears to be a one-dimensional material. The other three complexes behave as typical mixed stack organic semiconductors.     

A discrete spectrum of solutions of the wave equation with strong cubic nonlinearity

The nonlinear wave equation, _tt –+³=0, has many solutions that are periodic in time and localized in space, all with infinte energies. The search for spherically symmetric solutions that are well represented by the simple approximation, (r, t)A(r) sin t, leads to a discrete spectrum of solutions{ _N (r, t; )}. The solutions are nonlinear wavepackets, and they can be regarded as particles. The asymptotic theory () of the motion of the guiding center of theNth wavepacket, in the presence of a specified potential, is characterized by an infinite mechanical mass and an infinte interaction mass, and they are compatible. The rest mass in the classical relativistic mechanics of guiding centers ism ₀ c ²= _N ; i.e. the spectrum { _N } determines a spectrum of Planck's constants.On leave (1972–73) Université de Paris VI, Département de Mécanique, 75 Paris 5^e, France.