95207-36-6Relevant academic research and scientific papers
O-alkyl-N-acyl-N-phenylhydroxylamines as photochemical alkoxy radical precursors
Chowdhury, Nilanjana,Anoop, Anakuthil,Singh, N.D. Pradeep
experimental part, p. 1745 - 1754 (2012/07/27)
A simple and efficient technique for the photolysis of alkoxy radical precursors is developed. Irradiation of O-alkyl-N-acyl-N-phenylhydroxylamines, as representative alkoxy radical precursors, with ultraviolet light (254 nm) results in homolytic N-O bond cleavage to generate singlet alkoxy and acylaminyl caged radical pairs. These radicals, depending on the solvent employed, either escape from the cage to form fragmentation products, or undergo in-cage reactions to produce photorearrangement products. The homolytic cleavage of the N-O bond is analyzed using time-dependent density functional theory calculations. The nature of the N-acyl substituent on the O-alkyl-N-acyl-N- phenylhydroxylamines is shown to influence their ability to generate radicals. Furthermore, identification and trapping of the alkoxy radicals is demonstrated. Georg Thieme Verlag Stuttgart · New York.
N-Alkoxy-N-acylnitrenium Ions as Possible Intermediates in Intramolecular Aromatic Substitution: Novel Formation of N-Acyl-3,4-dihydro-1H-2,1-benzoxazines and N-Acyl-4,5-dihydro-1H,3H-2,1-benzoxazepine
Glover, Stephen A.,Goosen, Andre,McCleland, Cedric W.,Schoonraad, Johan L.
, p. 2255 - 2260 (2007/10/02)
N-Halogeno-N-alkoxyamides undergo intramolecular aromatic substitution by thermal- or Lewis acid-catalysed heterolysis of the nitrogen-halogen bond.N-Acyl-N-alkoxynitrenium ions are likely intermediates.N-Chloro-N-methoxybiphenyl-2-carboxamide (4) yields N-methoxyphenanthridone (11) quantitatively with AgBF4, while O-2-phenylethyl-N-chlorobenzohydroxamate (19) is converted in good yield into N-benzoyl-3,4-dihydro-1H-2,1-benzoxazine (21) with AgBF4, AgClO4, HgO, and Hg(OAc)2.N-Acetyl-3,4-dihydro-1H-2,1-bezoxazine (22) is formed similarly.O-3-Phenylpropyl-N-chlorobenzohydroxamate (23) cyclises to N-benzoyl-4,5-dihydro-1H,3H-2,1-benzoxazepine (24) with AgBF4.
