Multicomponent one-pot synthesis of (dihydro-1H-benzo[d]imidazole) phosphonate

Abstract

We present a multicomponent reaction strategy to synthesize a (dihydro-1H-benzo[d]imidazole)phosphonate family of compounds, using benzimidazoles, diethyl chlorophosphate and aliphatic amines as starting reactants. Giving its simplicity, our procedure involves reaction times of only few hours and avoid the usage of any catalyst agent. All the newly synthesized compounds were characterized by Nuclear Magnetic Resonance spectroscopy (¹H, ¹³C and ³¹P) and mass spectrometry by the DART method.     

Controlling the propagation of broadband light pulses by Electromagnetically Induced Transparency

We present an experimental and theoretical investigation, performed on hot sodium atoms in a ladder scheme, showing the control of the absorption and of the propagation velocity of a probe light pulse with a spectral bandwidth as large as 1.8 GHz. The predictions of the theoretical model compare favorably with the experimental results.     

Hypercontractivity properties of nonsymmetric ornstein-uhlenbeck semigroups in hilbert spaces

We prove hypercontractivity of nonsymmetric Ornstein-Uhlenbeck semigroups in Hilbert spaces, using direct probabilistic arguments. Our results imply exponential convergence at infinity for the semigroup. We show by examples that in our setting logarithmic Sobolev inequalities do not hold in general     

Controlling 6-endo-selectivity in oxidation/bromocyclization cascades for synthesis of aplysiapyranoids and other 2,2,6,6-substituted tetrahydropyrans

A cascade, composed of (i) oxovanadium(V)-catalyzed oxidation of bromide by tert-butyl hydroperoxide and (ii) stereoselective 6-endo-bromocyclization, affords 3-bromo-2-aryl-2,6,6-trimethyltetrahydropyrans from styrene-type tertiary alkenols in synthetically useful yields. (E)-Alkenols add the bromo- and the alkoxy substituent anti-selectively across the double bond, indicating a bromonium ion-mechanism for the ring closure. 6-endo-control of the alkenol cyclization thereby arises from the polar effect of the aryl substituent. Two methyl substituents bound to the alkene terminus are not similarly able to favor 6-endo-cyclization, because strain arising from methyl group repulsion, as the bromonium-activated π-bond and the hydroxyl oxygen approach, directs bromocyclization of tertiary prenyl-type substrates toward tetrahydrofuran formation. A hexasubstituted bromotetrahydropyran prepared from the oxidation/bromocyclization cascade served as starting material for synthesis of racemic aplysiapyranoid A, in a sequence of free radical and polar functional group interconversion.     

Numerical differentiation on scattered data through multivariate polynomial interpolation

BIT Numerical Mathematics - We discuss a pointwise numerical differentiation formula on multivariate scattered data, based on the coefficients of local polynomial interpolation at Discrete Leja...     

Modelling and design of a novel air-spring for a suspension seat

Air-springs used in conjunction with auxiliary volumes provide both spring stiffness and damping. The damping is introduced through the flow restriction connecting the two air volumes. This article presents a simplified model of an air-spring with an auxiliary volume derived from first principles for simulation and design of an air-spring coupled to an auxiliary volume for a suspension seat. Tests were performed on an experimental apparatus to validate the model. The simulation model of the air-spring and auxiliary volume followed the trend predicted by the literature but showed approximately 27% lower transmissibility amplitude and 21% lower system natural frequency than that obtained by tests when using large diameter flow restrictions. This inaccuracy is assumed to be introduced by the simplified mass transfer equations defining the flow restriction between air-spring and auxiliary volume. The model showed closer correlation to the experimental results when the auxiliary volume size was decreased by two-thirds of the volume actually used for the experiment. A procedure, using the developed simulation model, for the design of a prototype air-spring and auxiliary volume, is presented for application in a typical articulated or rigid frame dump truck. The goal of the study was to design a suspension seat for this application and to obtain a SEAT value below 1.1. The design was optimised by varying auxiliary volume size and flow restriction diameters for different loads. A SEAT value of less than 0.9 was achieved, clearly indicating the effectiveness of using an auxiliary volume with an air-spring as seat suspension.