A practical synthesis of (+/-)-alpha-isosparteine from a tetraoxobispidine core

[reaction: see text] The title alkaloid was synthesized in racemic form from 3,7-diallyl-2,4,6,8-tetraoxo-3,7-diazabicyclo[3.3.1]nonane (7) by a regioselective diallylation reaction followed by double ring-closing olefin metathesis and exhaustive reduction. Tetraoxobispidine 7 was itself prepared in three simple operations from dimethyl malonate. The entire sequence to alpha-isosparteine was conducted on a multigram scale and proceeded without recourse to chromatography.     

ESI‐MS/MS of expanded porphyrins: a look into their structure and aromaticity

Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.     

A combination of high-resolution X-ray diffractometry and diffraction imaging techniques applied to the study of MOVPE-grown CdxHg1−xTe/CdTe on GaAs

We have applied a range of high-resolution X-ray diffractometry and diffraction imaging techniques to study the structural properties of Cd_xHg_1-xTe (CMT) grown epitaxially on GaAs by MOVPE. In this paper we specifically describe three such techniques and evaluate and compare the results from each.

Automated double crystal diffractometry with a mapping facility provides information on the quality and uniformity of the layers. 004 rocking curve widths vary from < 70 arc seconds on the best samples to substantially higher values on poorer material. Study of non-uniform layers shows that lattice tilts are a dominant influence on rocking curve widths and large (up to 2°) misorientations between epilayer and substrate (100) planes are found on some samples. These characteristics are further investigated using triple crystal diffractometry. X-ray topography of the layers shows orientation-contrast features which correlate directly with the GaAs substrate dislocation distribution.

A number of layers with varying degrees of structural quality have been examined using a combination of the above techniques. Recent results are reported illustrating the value of each technique and we demonstrate how the application of a combination of X-ray diffraction techniques can be a powerful tool for investigating the nature of structural defects in this highly mismatched heteroepitaxial system.     

Study of DyFe12−xMx compounds by57Fe and161Dy Mössbauer spectroscopy

DyFe_12?xM_x (M=Si,Ti,Cr) were studied with⁵⁷Fe and¹⁶¹Dy Mössbauer spectroscopy. The deduced coupling constants J_RFe of these compounds are about equal. It is found that Si is substituting one particular Fe-site, while Cr is substituting Fe randomly. In DyFe₁₀Si₂ two Fe-sites favour a c-axis anisotropy, while the third one favours the basal plane.