2876-33-7Relevant academic research and scientific papers
THE PHOTOCYCLIZATION OF N-ACYL-2-NITRODIPHENYLAMINES TO PHENAZINE N-OXIDES: SCOPE AND MECHANISM
Fasani, Elisa,Pietra, Silvio,Albini, Angelo
, p. 573 - 584 (2007/10/02)
The photocyclization of N-acyl-2-nitridiphenylamines to phenazine N-oxides is extended to several dinitro derivatives and a pyridine analogue obtaining N-oxides of otherwise difficult access.In the presence of some additives, the reaction takes a different course.Thus, with acids deacylation occurs, with triphenylphosphine a N-phosphoranylidene amine is formed and with 2,6-di-tert-butylphenol the corresponding nitrosodiphenylammine is obtained.A mechanism starting from the nitroamide triplet and involving several discrete intermediates is proposed in order to account for such observations.
Photochemical Reaction of 2,4-Dinitrodiphenylacetamide and Related Compounds: Spectroscopic and Chemical Identification of Intermediates
Fasani, Elisa,Mella, Mariella,Albini, Angelo
, p. 2689 - 2692 (2007/10/02)
2,4'-Dinitrodiphenylacetamide 1b reacts via the triplet state to give 3-nitrophenazine 5-oxide 2b.The initial step is addition of the nitro group to the C=O bond.This intermediate 7 rearranges in the ms time scale to yield an O-acylnitro derivative 8.This, in turn, undergoes heterocyclic cleavage (rate dependent upon solvent polarity) and the aminium cation thus formed cyclizes to 2b.Intermediate 7 is sensitive to acid-catalysed hydrolysis, and the cleavage of 8 and subsequent cyclization are influenced by various additives.Thus, with triphenylphosphine a phosphoranylidenamino derivative is obtained, and 2,6-di-tert-butylphenol gives 4-nitro-2-nitrosodiphenylamine.Two other amides are compared.
