Continuous chemoselective methylation of functionalized amines and diols with supercritical methanol over solid acid and acid-base bifunctional catalysts

The selective N-methylation of bifunctionalized amines with supercritical methanol (scCH(3)OH) promoted by the conventional solid acids (H-mordenite, beta-zeolite, amorphous silica-alumina) and acid-base bifunctional catalysts (Cs-P-Si mixed oxide and gamma-alumina) was investigated in a continuous-flow, fixed-bed reactor. The use of scCH(3)OH in the reaction of 2-aminoethanol with methanol (amine/CH(3)OH = 1/10.8) over the solid catalysts led to a significant improvement in the chemoselectivity of the N-methylation. Among the catalysts examined, the Cs-P-Si mixed oxide provided the most efficient catalyst performance in terms of selectivity and reactivity at 300 degrees C and 8.2 MPa; the N-methylation selectivity in the products reaching up to 94% at 86% conversion. The present selective methylation was successfully applied to the synthesis of N-methylated amino alcohols and diamines as well as O-methylated ethylene glycol. Noticeably, ethoxyethylamine was less reactive, suggesting that the hydroxy group of the amino alcohols is a crucial structural factor in determining high reactivity and selectivity, possibly because of the tethering effect of another terminus, a hydroxo group, to the catalyst surface. The magic-angle-spinning NMR spectroscopy and X-ray diffraction analysis of the Cs-P-Si mixed oxide catalyst revealed that the acidic and basic sites originate from P(2)O(5)/SiO(2) and Cs/SiO(2), respectively, and the weak acid-base paired sites are attributed to three kinds of cesium phosphates on SiO(2). The weak acid-base sites on the catalyst surface might be responsible for the selective dehydrative methylation.     

A density-functional study for the liquid-vapor coexistence curve of nitrogen fluid

We have used a density-functional theory based on the interaction site model to predict the liquid-vapor coexistence curve of nitrogen fluid. The pressure and chemical potential were calculated from thermodynamic integrations. The different paths of thermodynamic integration provide slightly different predictions for the liquid-vapor coexistence curve. However, these critical points and coexistence curves evaluated by the theory are in qualitative agreement with the experimental data. The theoretical coexistence curves scaled to critical constants agree with the experimental data quantitatively.     

Complete memory of chirality upon photodecarboxylation of mesityl alkanoate to mesitylalkane: theoretical and experimental evidence for cheletropic decarboxylation via a spiro-lactonic transition state

The photodecarboxylation of chiral mesityl alkanoate to mesitylalkane has been studied experimentally/theoretically, and it has been found that the photodecarboxylation proceeds to give the product in > 99% enantiomeric excesses under a variety of conditions, indicating no involvement of any radical intermediates, but that the reaction proceeds through the concerted cheletropic extrusion of CO2 from the energetically less-favored s-cis conformation.     

Glochidionionosides A-D: megastigmane glucosides from leaves of Glochidion zeylanicum (Gaertn.) A. Juss

Five megastigmane glucosides were isolated from the leaves of Glochidion zeylanicum. One of them was a known compound, blumenol C O-beta-D-glucopyranoside (1), and the structures of the four new compounds, glochidionionosides A-D (2-5), were mainly elucidated by spectroscopic methods, including a modified Mosher's method. The absolute configurations of the six-membered ring of glochidionionoside D (5) were deduced by beta-D-glucopyranosylation-induced shift trends in the (13)C-NMR spectra and confirmed by X-ray analysis as its p-bromobenzoate (5b), and the axis chirality of C-7 was determined to be R.     

Dynamic Entanglement and Separability Criteria for Quantum Computing Bit States

A theoretical framework is demonstrated to evaluate the degree of entanglement of bit states in quantum computing. Separability of general superposition of Hilbert space unit vectors is discussed, and criteria in amplitude as well as in phase are derived. By these criteria the possibility of different quantum gates such as controlled not (CN), controlled controlled not (CCN), controlled rotation (CR), and controlled phase shift (CPS), to create the entanglement is examined. Furthermore, the selection of measurement mode external to the quantum system is incorporated in the formula using Kronecker delta (δ _kx ), introducing the concept of dynamic entanglement. With this the process of wavefunction collapse upon measurement is understood as the result of the activation of the dynamic entanglement. A firefly in a box model is used to show a pure state of ontological uncertainty, which is in a dynamically entangled state in Hilbert space.     

Extended Hydrodynamics from Enskog’s Equation for a Two-Dimensional System General Formalism

Balance equations are derived from Enskog’s kinetic equation for a two-dimensional system of hard disks using Grad’s moment expansion method. This set of equations constitute an extended hydrodynamics for moderately dense bi-dimensional fluids. The set of independent hydrodynamic fields in the present formulations are: density, velocity, temperature and also—following Grad’s original idea—the symmetric and traceless pressure tensor p _ij and the heat flux vector q ^k . An approximation scheme similar in spirit to one made by Grad in his original work is made. Once the hydrodynamics is derived it is used to discuss the nature of a simple one-dimensional heat conduction problem. It is shown that, not too far from equilibrium, the nonequilibrium pressure in this case only depends on the density, temperature and heat flux vector. PACS: 51.10.+y, 05.20.Jj, 44.10.+i, 05.70.Ln     

A new minor butenolide from <Emphasis Type="Italic">Machilus odoratissima</Emphasis>

A new butenolide, designated odoratinolide (1), was isolated from the bark of the Vietnamese medicinal plant Machilus odoratissima. Its structure was determined by spectroscopic analyses.