Untersuchungen an Diazomethanen, XXVIII¹⁾ Knallsäureamid: Das doppelt Tautomere des Diazomethans

Abstract

Durch geeignete Alkylierung kann man Knallsaureamid (1) in bekannte N-Isocyan-dialkylamine (2, 3) uberfiihren. Mit Stickstoffwasserstoffsaure entsteht 1 -Amino-tetrazol (6). Die massenspektrometrische Fragmentierung der Deirivate 7 von 6 mit Aldehyden ist durch eine ungewohnliche C=N-Bindungsspaltung gekennzeichnet. -Durch Umsetzung von 1 mit Kobalt(I1)-halogeniden und Trieisendodecacarbonyl entstehen Schwermetallkomplexe (10-12). Ihre 1R-Spektren beweisen die Fixierung ides Knallsaureamid-Molekiils. Die Doppeltautomerie Diazomethan d Knallsaureamid wird erortert.

Isodiazomethane revisited. N-aminoisonitriles

“…In the presence of a proton acceptor, benzoyl chloride gives a low yield (19%) of 2-benzoyl-5-phenyI-1,3,4-oxadiazole with (IV) (6). N-Aminoisonitrile reacts with hydrazoic acid to yield N-aminotetrazole (8,14) and can be ethylated in low yield (8) to the previously reported N-(diethylamino)isonitrile (7a); transition metal complexes have also been obtained (8).…”

“…possibility that even nitrilimine (I) could participate as a transient intermediate (8). The previously reported reactions (1) of (IV) can be interpreted via Passerini-type reactions of the isonitrile group (9)(10)(11).…”

“…Preparation Bredereck (15) and Hagedorn (16) and their groups were the first to report the isolation of derivatives of (IV) back in 1962 although Muller and Ludsteck (17) also considered the N-aminoisonitrile structure. Since the work of Hagedorn has appeared without experimental details (14,18), the two papers of Bredereck and his students (7) constitute the bulk of our current knowledge of N-(dialkylamino)isonitriles (8) which are best obtained by the dehydration of the appropriate formylhydrazines (7).…”

“…In 1968, Muller and his group (6) presented compelling evidence that isodiazomethane (nitrilimine (I)) was in reality N-aminoisonitrile (IV), the parent compound of a group of compounds described earlier by Bredereck (7) and Hagedorn (8) and their students.…”

General and theoretical aspects of the diazonium and diazo groups

“…Gcncral and thcorctical aspccts of the diazonitin? and diazo groups 43 and protonated diimide the inversional barrier is lower than the rotational barrier for isomerization, but the corresponding barriers for the protonated form are l o w r than those for thc unprotonated form. Rclative to the cncrgy of the t r m s isomer.…”