Etude de la Fragmentation en Spectrographie de Masse de Spiropyrannes Benzodithioliques. Influence de la Position et de la Nature des Substituants

The mass spectra of 12 benzodithiolic spiropyrans are reported. Their fragmentation pathways have been determined by exact mass and metastable transition measurements. The nature of the fragmentation is strongly dependent upon the position and nature of the substituents. A comparison is made with their photo and thermochemical decompositions.     

Hétérocycles contenant du phosphore. XXXII. Etude de l'action des phosphorhydrazides sur les orthoesters,l'anhydride acétique et l'acide formique

The reaction of phosphodi- or trihydrazides with orthoesters affords mainly 2,3,4,5-tetrahydro-1,2,4,5,3-tetrazaphosphorines and sometimes 4-amino-1,2,4,3-triazaphospholidines. These 1,2,4,5,3-tetrazaphosphorines present a prototropy which explains different pathways of the reaction of these derivatives with formaldehyde or acetone, The structure of all heterocycles which were obtained was established by nmr spectra.     

Études calorimétriques en milieu solvant organique: II Enthalpies de dissolution et de dilution du boranate de lithium (LiBH4) et de l'alanate de lithium (LiAlH4) dans le tétrahydrofuranne

The enthalpies of dissolution and dilution of LiBH₄ and LiAlH₄ in THF have been determined.Dissolutions are exothermic. The endothermic dilution of LiAlH₄ suggests for this compound, either a dissociation or an association equilibrium.     

Sodium-23 Nuclear Magnetic Resonance Spectroscopy

With the availability of Fourier transform spectrometers, ²³Na-NMR spectroscopy has become an important tool. It affords direct insight into solvation and ion pairing phenomena, both in organic and in bio-inorganic systems. Monitoring the chemical shifts and linewidths of ²³Na signals gives access to binding constants, reorientational correlation times and the microdynamics of the sodium coordination shell. The binding of other cations can also be studied by ²³Na-NMR spectroscopy, in competition experiments.     

Synthesen von Moniliformin,einem Mycotoxin mit Cyclobutendion-Struktur

Syntheses of Moniliformin, a Mycotoxine with a Cyclobutenedione Structure Six different routes to 3-hydroxy-3-cyclobutene-1, 2-dione ( 4 ), the free acid of the mycotoxine Moniliformin (=alkali salt of 4 ) are described. A common feature of all pathways is the synthesis of cyclobutanes having the oxidation level 6. Moniliformin precursors which are easily transformed to 4 by acid catalysed hydrolysis include [2+2]-cycloadducts of ketene with tetraalkoxy-olefins, 3,4,4-trialkoxycyclobutenes, derivatives of polyfluorinated cyclobutenes, the brominated [2+2]-cycloadduct of ethyl vinyl ether and dichloroketene, tetrabromocyclobutanone, [2+2]-photocycloadducts of dichlorovinylenecarbonate with dichloroethylenes, and the dimer of chloroketene. The most convenient synthesis via the [2+2]-cycloadduct of tetraethoxyethylene and ketene ( 14b ) is reported in detail and produces 4 in four simple steps in 57% overall yield. In addition, two new syntheses of squaric acid ( 56 ) are described.     

Radical Cation States of 2,3,5,6,7,8-Hexamethylidenebicyclo [2.2.2]octane

The photoelectron spectrum of the title compound is reported and assigned by correlation with the photoelectron spectra of related molecules.