Untersuchungen an Diazomethanen, XXVI¹⁾ Isodiazomethan  Knallsäureamid  N‐Isocyan‐amin

Abstract

Aus den NMR-und IR-Spektren von Isodiazomethan in Perdeuterodiathylather wird fur dieses Isomere des Diazomethans die N-Isocyan-amin-Struktur H2N-N=CI abgeleitet. Die Reaktion von Isodiazomethan und Chloral zu Trichlormilchsaure-[(2.2.2-trichlor-athyliden)hydrazid] (3) spricht ebenfalls fur diese Struktur. Mit Benzoylchlorid liefert Isodiazomethan 2-Phenyl-5-benzoyl-l.3.4-oxadiazol (5).

Free and Metal‐Coordinated (N‐Isocyanimino)triphenylphosphorane: X‐ray Structures and Selected Reactions

“…[3] Later, for more than 30 years, alternative constitutions were favoured, and it was not until 1968 that Müller et al returned to Staudinger's formula. [2,4] In the mid-1970s, the first metal complexes of 1 were synthesised in our laboratory both from Müller's isodiazomethane solutions and, much more elegantly, from a stable, storable derivative, Wiberg's CϵN-N(SiMe 3 ) 2 (2), by hydrolysis at the protecting metal. [5,6] The only disadvantage of 2 was its problematic accessibility, requiring many steps and costly low-temperature techniques.…”

Isodiazomethane revisited. N-aminoisonitriles

“…(6). 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).…”

“…The apparently anomalous reaction of (IV) with saccharin and thiosaccharin (13) may be explained by the mechanism shown in eqn. (6). 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).…”

“…group followed by an internal acylation of the free amino group. The lack of reaction of (IV) with benzaldehyde, benzoic anhydride, and tosyl chloride (12) clearly suggests^a large contribution of mesomeric structure H2N-N= C which would deplete the NH2 group of any nucleophilic character; in this sense, N-aminoisonitriles are properly considered as amides of fulminic acid [H-O-N=C:J (6), thus rendering unlikely the suggestion (6) that the reaction of chloral hydrate with (IV) to give (VI) (eqn. ( 3)) proceeds via initial condensation between the -NH2 and the -CHO to give a hydrazone.…”

Rearrangement of an exchangeable hydrogen during the reduction of maleimide with lithium aluminum hydride

“…A1 23-Pyrrolin-2-one (2) thus formed could then undergo 1.4-reduction to yield the intermediate 3. The enamine 3 rearranges to the more stable imine9 4 with the migration of a hydrogen atom from N to C-3.…”