Syntheses and configurations of some heterocyclic amidoximes. X-Ray crystal structure of 3-phenyl-5,6-dihydro-2(1H)-pyrazinone-O-methyloxime

O-Methyl-α-ketophenylacetohydroximoyl chloride ( 1 ) was prepared by the reaction of O-methyl-α-methoxyphenylacetohydroximoyl chloride ( 5 ) with N-bromosuccinimide and concentrated hydrobromic acid. Reaction of 1 with ethylenediamine gave 3-phenyl-5,6-dihydro-2(1H)-pyrazinone-O-methyloxime ( 6 ). 3-Phenyl-5,6-cyclohexano-5,6-dihydro-2(1H)-pyrazininone-O-methyloxime ( 7 ) was prepared by reaction of 1 with trans-1,2-diaminocyclohexane. The X-ray structure of 6 has been determined. The crystals are orthorhombic, space group Pbca with a = 10.264(3), b = 18.262(4), c = 23.530(4)Å, V = 4411(2)ų, and Z = 16. The structure, which was refined to R = 0.038 using 1652 observed reflections, shows the amidoxime moiety to be the Z configuration. Reaction of benzohydroximoyl chloride with aziridine gave (Z)-aziridinylbenzaldoxime ( 16a ). Ultraviolet irradiation of a benzene solution of 16a gave a mixture of the Z and E isomers 16a and 16b . The E isomer 16b underwent thermal isomerization to 16a at 100°. Reaction of 16a with dimethyl sulfate in sodium hydroxide solution gave (Z)-O-methylaziridinylbenzaldoxime ( 17a ). Photoisomerization of a hexane solution of 17a gave a mixture of the Z and E isomers 17a and 17b which were separated by preparative glc. The isomers 17a and 17b are resistant to thermal Z = E isomerization. The mechanisms of thermal isomerization of benzamidoximes are discussed.     

Determination de la structure de perfluoroalcenes a chaines longues par R.M.N. du19F : lère Partie : pefluoroalcenes-1

After a review of 1-perfluoroalkene R_FCFCF₂ synthesis, with R_FC₄F₉, C₅F₁₁, C₆F₁₃, we have studied their fine structures by ¹⁹F N.M.R. This study has led us to first generalize the rules set for the chemical shifts and coupling constants of olefinic fluorine atoms of fluoropropene and their derivatives. Then, we have been able to determinate unambiguously the chemical shifts of the difluoromethylene groups of the perfluorinated chains. We have thus shown, by irradiation, that inversions may take place in the chemical shifts of the CF₂ groups at the β and γ position of the double bond.     

Remarques sur un article de Israel Aharoni sur les prolongements lipschitziens dansc 0

We give a purely metric proof of the following result: let (X,d) be a separable metric space; for all ?>0 there is an injectionf ofX inC ₀ ⁺ such that: $$\forall x,y \in X,d(x, y) \leqq \parallel f(x) - f(y)\parallel _\infty \leqq (3 + \varepsilon )d(x, y).$$ It is a more precise version of a result of I. Aharoni. We extend it to metric space of cardinal α⁺ (for infinite α).     

Synthese et reactivite d'organomagnesiens perfluores. V.[1] Synthese et identification de nouveaux composes perfluoroalkyles du mercure a chaine longue.

The reaction of mercuric salts HgY₂ or organic mercuric compounds R_HHgX with long chain perfluorinated Grignard reagents R_FMgBr leads to a series of new perfluoroalkyl mercury derivatives with the general formula R_FHgZ (R_F=C₄F₉, C₆F₁₃, C₈F₁₇ ; Z=R_F,R_H,Y with Y = I,Br,Cl, NO₃,OCOCH₃,OCOCF₃).The synthesis of these organomercuric compounds is described, and their spectroscopic properties are reported.     

Decarboxylation catalytique et quantitative d'acides arylacetiques en presence'de cuivre I

Copper(I) salts of arylacetic acids $\text{1}$ RCO₂H readily undergo a catalytic and quantitative decarboxylation in acetonitrile leading to hydrocarbons $\text{2}$ RH when the corresponding carbanions R are stabilized by resonance and/or electronwithdrawing substituents.     

无零级衍射干扰的彩色数字全息研究

彩色数字全息研究中,用球面波为重建波及角谱衍射公式进行波前重建是一种有效的方法.然而,重建图像上通常伴有强烈的零级衍射干扰.本文通过理论分析,对波前重建过程作了重要改进.用改进后的方法进行彩色数字全息的实验研究表明,重建彩色图像的质量获得显著改善. 关键词： 彩色数字全息 波前重建 零级衍射干扰     

Closed-System Solution of the 1D Atom from Collision Model

Obtaining the total wavefunction evolution of interacting quantum systems provides access to important properties, such as entanglement, shedding light on fundamental aspects, e.g., quantum energetics and thermodynamics, and guiding towards possible application in the fields of quantum computation and communication. We consider a two-level atom (qubit) coupled to the continuum of travelling modes of a field confined in a one-dimensional chiral waveguide. Originally, we treated the light-matter ensemble as a closed, isolated system. We solve its dynamics using a collision model where individual temporal modes of the field locally interact with the qubit in a sequential fashion. This approach allows us to obtain the total wavefunction of the qubit-field system, at any time, when the field starts in a coherent or a single-photon state. Our method is general and can be applied to other initial field states.     

A reliable algorithm to solve 3D frictional multi-contact problems: Application to granular media

We present in this paper an improved non-smooth Discrete Element Method (DEM) in 3D based on the Non-Smooth Contact Dynamics (NSCD) method. We consider a three-dimensional collection of rigid particles (spheres) during the motion of which contacts can occur or break. The dry friction is modeled by Coulomb’s law which is typically non-associated. The non-associativity of the constitutive law poses numerical challenges. By adopting the use of the bi-potential concept in the framework of the NSCD DEM, a faster and more robust time stepping algorithm with only one predictor-corrector step where the contact and the friction are coupled can be devised. This contrasts with the classical method where contact and friction are treated separately leading to a time stepping algorithm that involves two predictor-corrector steps. The algorithm has been introduced in a 3D version of the NSCD DEM software MULTICOR. Numerical applications will show the robustness of the algorithm and the possibilities of the MULTICOR software for solving three-dimensional problems.     

Telecom-grade fiber laser-based difference-frequency generation and ppb-level detection of benzene vapor in air around 3 μm

We report on the development of a field deployable compact laser instrument tunable over ∼232 cm⁻¹ from 3.16 to 3.41 μm (2932.5–3164.5 cm⁻¹) for chemical species monitoring at the ppb-level. The laser instrument is based on widely tunable continuous-wave difference-frequency generation (DFG), pumped by two telecom-grade fiber lasers. DFG power of ∼0.3 mW near 3.3 μm with a spectral purity of ∼3.3 MHz was achieved by using moderate pumping powers: 408 mW at 1062 nm and 636 mW at 1570 nm. Spectroscopic performance of the developed DFG-based instrument was evaluated with direct absorption spectra of ethylene at 3.23 μm (∼3094.31 cm⁻¹). Absorption spectra of vapor-phase benzene near 3.28 μm (∼3043.82 cm⁻¹) were recorded with Doppler-limited resolution. Line intensities of the most intense absorption lines of the ν ₁₂ band near 3043.8 cm⁻¹ were determined to support development of sensitive mid-infrared trace gas detection of benzene vapor in the atmosphere. Detection of benzene vapor in air at different concentration levels has been performed for the first time using multi-pass cell enhanced direct absorption spectroscopy at ∼3.28 μm with a minimum detectable concentration of 50 ppb (1σ).