Phosphoranes par fermeture trans-annulaire: III—Conformation—configuration—labilité

The analysis of the n.m.r. spectra of the two isomers of 1,6,6-trimethyl-3-phenyl-2,8-dioxa-5-aza-1-phospha ^vbicyclo[3.3.0]octane allows us to propose a conformation for each 5-membered ring and for the configuration of the phosphorus atom. The lability of the H? P proton, revealed by high temperature experiments and by P? H ? P? D exchange, is significantly different in the two isomers.     

The influence of aliphatic diols on the temperature of maximum density of water

The influence of various aliphatic diols on the temperature of maximum density (TMD) of water has been investigated. 1,2-Propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 2,5-hexanediol were found to yield positive structural contributions to the solute-induced shift in the TMD, i.e., they are structure makers. Contrariwise, data from the literature indicate that 1,2-ethanediol is a structure breaker. Relationships between the structure making/breaking tendencies of the solutes and the relative positions of the two hydroxyl groups are discussed.     

Long time behaviour of the solution to non-linear Kraichnan equations

We consider the solution of a nonlinear Kraichnan equation with a covariance kernel k and boundary condition H(t, t)=1. We study the long time behaviour of H as the time parameters t, s go to infinity, according to the asymptotic behaviour of k. This question appears in various subjects since it is related with the analysis of the asymptotic behaviour of the trace of non-commutative processes satisfying a linear differential equation, but also naturally shows up in the study of the so-called response function and aging properties of the dynamics of some disordered spin systems.     

Heterocycles contenant du phosphore-XXI. Etude par RMP de déeriveés de l'oxazaphospholane-l,3,2: I-Analyse des spectres des composksés non substitués en 4 et 5.

The PMR spectra of the title 1,3,2-oxazaphospholane derivatives present an ABKLX pattern. The subspectral analysis of such a system shows that there are eight solutions. INDOR experiments permit the establishment of the energy diagram and the selection of the correct solution.