Phosphorylthioacetamides in the synthesis of annulated quinoxalines

Diethoxyphosphorylthioacetamide in the reaction with 2,3-dichloroquinoxaline acted as a thionating reagent, giving diethoxyphosphorylacetonitrile and 2-chloro-3-[(3-chloro-2-quinoxalinyl)thio]quinoxaline. Reactions of phosphorylthioacetamides with N-methylquinoxalinium iodide in alcohol media in the presence of a base proceeded stereoselectively to afford cis-3-phosphoryl-1,3,3a,4,9,9a-hexahydro-2H-pyrrolo[2,3-b]quinoxaline-2-thiones. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1010–1013, May, 2007.     

Synthesis of stable azomethine ylides by the rearrangement of 1,3-dipolar cycloadducts of 3,4-dihydroisoquinoline-2-oxides with DMAD

1-Aryl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolines were prepared according to a one-pot procedure involving the reaction of 2-(3,4-dimethoxyphenyl)-ethylamine with aromatic aldehydes in TFA at reflux. The tetrahydroisoquinolines were treated with H₂O₂-WO₄²⁻ in methanol at room temperature to give the corresponding 3,4-dihydroisoquinoline-2-oxides. Treatment of these cyclic nitrones with DMAD in toluene at room temperature gave the corresponding isoxazolo[3,2-a]isoquinolines. These compounds were heated in toluene at reflux to give the corresponding ylides in high yields (Method A). The effect of the substituents on the rate of the rearrangement of such compounds prompted us to discuss a new mechanism involving consecutive C-C bond heterolysis and 1,3-sigmatropic shift. A one-pot reaction involving the treatment of the nitrones with equimolar amounts of DMAD in refluxing toluene also gave the ylides (Method B). The structures of the prepared compounds were elucidated by spectral means and elemental analyses.     

Concentrated electrolyte solutions at high temperatures and pressures

A survey is given of recent experimental results obtained from high-temperature, high-pressure investigations with water, aqueous solutions, and ionic fluids. Data on the static dielectric constant of water to 550°C and 5 kbar are given and discussed with respect to their relation to water structure. Infrared and Raman spectra of HDO in pure water have been obtained to 400°C and 4 kbar, which give information on hydrogen bonding. Xe–H₂O and CO₂–H₂O mixtures were investigated in the infrared. Ni(II) and Cu(II) complexes were investigated by absorption spectroscopy in aqueous solutions of high chloride content to 350°C and 2–6 kbar. The gas-liquid critical point of ammonium chloride was found at 880°C and 1635 bars. This fluid appears to be predominantly ionic even in the critical region. The possibility of converting pure polar fluids such as ammonia and water into concentrated ionic solutions by self-ionization at very high pressures is mentioned.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.     

Complexation of Ni (II) and Zn(II) ions by 3-(1-naphthyI)-2-mercaptopropenoic acid

The complexation equilibria between Ni(II) and Zn(II) metal ions with 3-(1-naphthyl)-2-mercaptopropenoic acid (H₂NMP) were studied by glass electrode potentiometry, at 25 °C and 1.0 mol·dm^–3 in NaClO₄ as constant ionic medium in 50% (v/v) water-ethanol solutions. Formation constants for the complexes Ni(NMP), Ni(NMP) ₂ ^2– , Zn(NMP) and Zn(NMP) ₂ ^2– , refined by the MINIGLASS program, are reported.     

Reflected Brownian motion in a cone: Semimartingale property

Summary In this paper, the object of study is reflected Brownian motion in a cone ind-dimensions (d3) with nonconstant oblique reflection on each radial line emanating from the vertex of the cone. The basic question considered here is When is this process a semimartingale?. Conditions for the existence and uniqueness of the process for which the vertex is an instantaneous state were given by Kwon, which is resolved in terms of a real parameter depending on the cone and the direction of reflection. It is shown that starting from any point of the cone, the process is a semimartingale if < 1, + 0 and not a semimartingale if < < 2.This research is supported by KOSEF grant 941-0100-011-1     

Anomalous hydroalumination of methyl nopol ether with a LiAlH4-3AlBr3 system

Hydroalumination of methyl nopol ether with a LiAlH₄-3AlBr₃ system is accompanied by a skeleton rearrangement and gives 6-dibromoalumo-7-methoxymethyl-2-menthene. Further hydroalumination affords a mixture of 2,6- and 2,5-bis(dibromoalumo)-7-(methoxymethyl)menthanes in 8020 ratio. Hydrolysis and oxidation of these organoaluminum compounds were carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 506–510, March, 1994.     

Shock fluctuations in the asymmetric simple exclusion process

Summary We consider the one dimensional nearest neighbors asymmetric simple exclusion process with ratesq andp for left and right jumps respectively;q<p. Ferrari et al. (1991) have shown that if the initial measure isv _, , a product measure with densities and to the left and right of the origin respectively, <, then there exists a (microscopic) shock for the system. A shock is a random positionX _t such that the system as seen from this position at timet has asymptotic product distributions with densities and to the left and right of the origin respectively, uniformly int. We compute the diffusion coefficient of the shockD=lim _t t ^–1(E(X _t )²–(EX _t )²) and findD=(p–q)(–)^–1((1–)+(1–)) as conjectured by Spohn (1991). We show that in the scale the position ofX _t is determined by the initial distribution of particles in a region of length proportional tot. We prove that the distribution of the process at the average position of the shock converges to a fair mixture of the product measures with densities and . This is the so called dynamical phase transition. Under shock initial conditions we show how the density fluctuation fields depend on the initial configuration.     

Brownian confinement and pinning in a Poissonian potential. II

Summary We continue our study ofd-dimensional Brownian motion in a soft repulsive Poissonian potential over a long time interval [0,t]. We prove here a pinning effect: for typical configuratons, with probability tending to 1 ast tends to , the particle gets trapped close to locations of near minima of certain variational problems. These locations lie at distances growing almost linearly witht from the origin, and the particle gets pinned within distance smaller than any positive power oft of one such location. In dimension 1, we can push further our estimates and show that in a suitable sense, the particle gets trapped with high probability, within time t and within distance (logt)²⁺ from a suitable location at distance of ordert/(logt)³ from the origin.This article was processed by the author using the LATEX style filepljour1m from Springer-Verlag     

Essential spectrum and -solutions of one-dimensional Schrödinger operators

In 1949, Hartman and Wintner showed that if the eigenvalue equations of a one-dimensional Schrödinger operator possess square integrable solutions, then the essential spectrum is nowhere dense. Furthermore, they conjectured that this statement could be improved and that under this condition the essential spectrum might always be void. This is shown to be false. It is proved that, on the contrary, every closed, nowhere dense set does occur as the essential spectrum of Schrödinger operators which satisfy the condition of existence of -solutions. The proof of this theorem is based on inverse spectral theory.

     

Perturbation analysis of the orthogonal procrustes problem

Given two arbitrary real matricesA andB of the same size, the orthogonal Procrustes problem is to find an orthogonal matrixM such that the Frobenius norm MA – B is minimized. This paper treats the common case when the orthogonal matrixM is required to have a positive determinant. The stability of the problem is studied and supremum results for the perturbation bounds are derived.