William Rand Kenan

Activated Metals : VI*. Preparation and Reactions of Higly Reactive Indium Metal☆

Abstract Highly reactive indium powder, prepared by alkali metal reduction of indium salts in hydrocarbon solvents, reacts at moderate temperatures in hydrocarbon solvents with alkyl iodides to give dialkylindium iodides, and with iodine to give indium monoiodide.

The regioselective and stereospecific substitution of unsymmetrical 1,2-diols using the 1,3,2λ5-dioxaphospholane methodology.

Abstract Stercospecific tosylate (−OTs) or azide (N3−) substitution at the C-4 stereocenter of a monosubstituted 1,3,2λ5-dioxaphospholane (the equivalent of the C-2 stereocenter in an unsymmetrical 1,2-diol) is readily achieved by treatment with either p -toluenesulfonic acid ( p -TsOH) in tetrahydrofuran solvent or p -TsOH/sodium azide in acetonitrile solvent, respectively.

Lanthanide induced 17O NMR shifts of diastereotopic oxygen atoms in 1-thiadecalin 1,1-dioxide and related compounds.

Abstract Lanthanide-induced 17 O NMR shifts of diastereotopic sulfonyl oxygens provide a basis for determining equilibrium constants between diastereomeric Ln·sulfone complexes.

Conformational analysis of 3-aminothiacyclohexane and derivatives by low-temperature 13C NMR

Abstract Several gauche interactions between sulfur and nitrogen functions are determined from measurement of conformational equilibria of 3-(X)-thiacyclohexanes (X = NH2, NMe2, NHPh and NHCO2But), their epimeric sulfoxides, and the corresponding sulfones, by low-temperature carbon-13 and proton NHR spectroscopy. The (RNH/S) gauche interaction is 0.18 (R=H), -0.04 (R=Ph) and -0.31 (R=CO2But) kcal/mol. The (Me2N/S) gauche interaction is 0.70 kcal/mol, of which 0.26 kcal/mol is estimated to arise from the gauche repulsive effect between the electron lone pairs. The (RNH/SOx) gauche interactions in the trans-sulfoxides (x=1) are approximately as destabilizing as expected on simple steric grounds, whereas in their cis epimeres and in the sulfones they are 0.65 (R=H, x=1), 0.28 (R=H, x=2), -0.78 (R=Ph, x=1), -0.22 (R=Ph, x=2),

Whitehead Memorial Lecture: Interface effects in the electrical response of non-metallic conducting solids and liquids

Two of the recent J. B. Whitehead Memorial Lecturers, J. G. Trump and Bernhard Gross, have discussed Whitehead the man, and Gross has touched on Whiteheads work on the anomalous properties of dielectrics, emphasizing and reiterating Whiteheads feeling about the great divergence between the points of view of experimentalists and theorists in the field.