N‐[α‐Trimethylsiloxy‐alkyl]‐ und N‐[α‐tert.‐Butyloxy‐alkyl]‐carbonsäureamide

Abstract

N‐Trimethylsilyl‐N‐alkyl‐carbonsäureamide reagieren bereits ohne Zusatz eines Katalysators, N‐Trimethylsilyl‐succinimide erst in Gegenwart katalytischer Mengen Natrium‐trimethylsilanolat, hinreichend schnell mit Aldehyden zu N‐[α‐Trimethylsiloxy‐alkyl]‐Verbindungen. Vergleichenden IR‐ und NMR‐spektroskopischen Untersuchungen unter Verwendung von tert.‐Butyl‐Analogen zufolge sind am Grundzustand der Trimethylsiloxy‐Verbindungen mesomere Grenzstrukturen mit dπ‐pπ‐Bindung zwischen Silicium und Sauerstoff wesentlich beteiligt.

The Cathodic Cleavage of Ethanetetracarboxylate Esters

“…5.4 ppm which was broad and exchanged with D20. Hydroxymethyl(methyl)formamide contaminated with a little methylformamide was also obtained by reaction of methylformamide with paraformaldehyde (12) and its NMR spectrum is identical to that of the anodically formed material.…”

“…Oxidation of dimethylformamide.--A current of 0.25A was passed through a solution of tetraethylammonium perchlorate (2.30g; 0.010 mol) in a mixture of DMF (150 ml) and water (5 ml) at 60~176 in the cell used for the ester reductions. As soon as the current flow was initiated, the formation of a black solid, assumed to be tetraethylammonium amalgam (12), was noted o.n the surface of the mercury cathode. It dissolved within a few seconds after a temporary discontinuation of current flow.…”