CHOLESTERYL PHOSPHITE AND RELATED COMPOUNDS

Abstract

The preparation of cholesteryl phosphorodichloridite (2) is described; this compound with aniline (2 mol. equiv.) gave the N-phenylphosphoramidochloridite (5) and the latter by condensation with water afforded the N-phenyl-amidophosphite (6).

Similarly the N-phenylphosphoramidochloridite (5) with morpholine gave the morpholidite (7); phenylhydrazine gave the hydrazinophosphite (8) and ethanol the amidoethyl phosphite (9). Cholesteryl phosphorodichloridite (2) by reaction with aniline (4 mol. equiv.) gave the N,N ¹?diphenylphosphorodiamidite (10).

The reaction of cholesteryl phosphorodichloridite (2) with methanol and ethanol are discussed in relation to the analogous reactions with cholesteryl phosphorodichloridate. Boiling ethanol gave cholesterol as the only isolatable product but at room temperature a low yield of the diethylphosphite (11; R=Et) was obtained. The yield of the phosphite was greatly increased in the presence of base. Similarly the dichloridite 2 with boiling water gave cholesterol (1), but at room temperature cholesteryl phosphite 3 was isolated: the mechanistic basis for these different results is briefly discussed.

trans-4-t-Butylcyclohexanol with phosphorus trichloride gave the phosphorodichloridite, which was characterised by conversion to the corresponding N,N ¹?diphenylphosphorodiamidite.     

Radon concentration in drinking water sources of the region adjacent to a tectonically active Karak Thrust,southern Kohat Plateau,Khyber Pakhtunkhwa,Pakistan

A total of 84 drinking water samples from tube wells, natural springs, hand pumps and open wells in the region adjacent to a tectonically active Karak Thrust, Pakistan, were analyzed for radon content determination. These samples have a mean, maximum and minimum radon values of 9.4 ± 0.4, 25.1 ± 0.9, and 1.1 ± 0.2 Bq l^?1, respectively. This study indicates that 24 % of samples from tube wells, 44 % from springs, and 50 % from hand pumps have radon levels in excess of the EPA recommended maximum contaminant level of 11.1 Bq l^?1. The mean annual effective doses of all the samples are lower than the reference level of 0.1 mSv a^?1. Drinking water from majority of the sources within the region is generally safe as far as radon related health hazards are concerned with exception of few isolated cases.     

Decay of cystalline order and equilibration during the solid-to-plasma transition induced by 20-fs microfocused 92-eV free-electron-laser pulses

We have studied a solid-to-plasma transition by irradiating Al foils with the FLASH free electron laser at intensities up to 10(16) W/cm(2). Intense XUV self-emission shows spectral features that are consistent with emission from regions of high density, which go beyond single inner-shell photoionization of solids. Characteristic features of intrashell transitions allowed us to identify Auger heating of the electrons in the conduction band occurring immediately after the absorption of the XUV laser energy as the dominant mechanism. A simple model of a multicharge state inverse Auger effect is proposed to explain the target emission when the conduction band at solid density becomes more atomiclike as energy is transferred from the electrons to the ions. This allows one to determine, independent of plasma simulations, the electron temperature and density just after the decay of crystalline order and to characterize the early time evolution.     

The crystal structure and low temperature magnetic susceptibility of square-planar bis(1,5-diazacyclooctane)nickel(II) perchlorate dihydrate

Summary We have carried out low temperature magnetic susceptibility measurements and a redetermination of the crystal and molecular structure of bis(1,5-diazacyclooctane)nickel(II) perchlorate dihydrate from three-dimensional intensity data collected on a CAD4 diffractometer. The structure was refined by full-matrix least-squares to the R value of 6.3% for 1501 observed reflections. The positions of the hydrogen atoms were obtained from the diffraction data. Contrary to our earlier conclusions drawn by inspection of molecular models of bis(diazacyclooctane) complexes, the axial sites in the actual crystal structure are open for ligation. The Ni-N bonds are, however, sterically protected by the coplanar N-H bonds, allowing maximum ligand-field stabilization for the squareplanar geometry around the nickel atom. The observed magnetic transition from a diamagnetic state at room temperature to a paramagnetic state at 78 K is explained on the basis of long-range exchange interactions along sterically unshieldedz axis. The crystal structure is compared with other similar structures.     

An improved method of synthesis of N-protected L-amino acids as their benzoxymethyl esters

An improved method for the synthesis of L-amino acids as their benzoxymethyl esters has been reported. All the synthesized compounds were characterized by (1)H NMR, EI-MS and IR spectroscopic methods.     

Aluminium Lyman-beta satellite emission in non-Maxwellian dense laser produced plasmas

High-energy decay channels of the Al Lyman-β satellite have been observed in X-ray emission from highly ionized plasma jets created by intense laser irradiation of aluminium foil targets. Atomic structure calculations show that the Lyman β satellite emission consists from six emission groups close to the He-like Al 1s²-1s4p (He_γ) and 1s²-1s5p (He_δ) resonance lines. This provides new possibilities for space resolved analysis of high density plasmas. Non-Maxwellian simulations of the plasma emission carried out with the MARIA code demonstrate that the intensity ratios of the Lyman-β satellites and the He_γ and He_δ resonance lines are very sensitive to the bulk electron temperature. In contrast to standard diagnostic methods, parameter studies show that this bulk electron diagnostics is practically unaffected by suprathermal electrons having less than 10% of the bulk electron density.     

The magnetic structure of Ba2MnWO6

Powder neutron diffraction and magnetic measurements have shown that the ordered perovskite Ba₂MnWO₆ is antiferromagnetic with a Néel temperature of 7.5 ± 1°K. Below this temperature, ordering of the second kind occurs, with the Mn moments directed perpendicular to the [111] axis.