Short contact time reactions of large organic free radicals

New Reactions of N‐tert‐Butylimines; Formation of N‐Heterocycles by Methyl Radical Elimination on Flash Vacuum Thermolysis of N‐Benzylidene‐ and N‐(2‐Pyridylmethylidene)‐tert‐butylamines

“…Because the spectral data for 14 described in ref. [15] are incomplete, additional data are reported here: 1…”

“…Some typical reactive intermediates generated under FVT conditions are ketenes, radicals, carbenes, and nitrenes. [1,2] For compounds containing a tertbutyl group attached to an sp 2 or sp 3 nitrogen atom, a typical and facile reaction is the intramolecular elimination of isobutene and formation of the N-unsubstituted imine. [3] However, the details of these reactions are not well understood.…”

Pyrolysis of hydrazine derivatives and related compounds with N N single bonds

“…These reactions 68 have been reviewed extensively [4,5,6] and will not be repeated here. A review on short-69 contact time, radical-forming gas-phase pyrolyses, which includes some hydrazine 70 derivatives, has been published [7]. We will deal primarily with pyrolysis reactions of 71 hydrazine derivatives understood in the widest sense.…”

Flash vacuum pyrolysis of N-phenylbenzamide oxime and related compounds

“…In view of the complexity of these processes, it was hoped that a study of the thermolysis of a series of Narylbenzamide oximes in the gas-phase under flash vacuum pyrolysis (FVP) conditions would greatly favour intermolecular reactions and lead to a simplification of the reaction profile. Indeed, N-O bond cleavage of oximes and oxime ethers by FVP is a well known method of generating iminyl radicals [2,3]. In the event, under FVP conditions, the major thermolysis mechanisms were non-radical in nature and, surprisingly, the product profile proved to be very different from that obtained in the condensed phase.…”