The mechanism of photoinduced acylation of amines by N-acyl-5,7-dinitroindoline as determined by time-resolved infrared spectroscopy.
[reaction: see text] The photochemistry of N-acyl-5,7-dinitroindoline (1) was studied in acetonitrile using nanosecond time-resolved infrared (TRIR) spectroscopy. Upon photolysis, two nearly but not completely overlapping sets of transient IR bands are observed that are assigned to two non-interconvertible conformers of mixed acetic nitronic anhydride 7. While syn-7 reverts rapidly to 1, anti-7 is long-lived and is able to acylate amines. Results of density functional theory calculations support conclusions based on experimental TRIR data.
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Andrew D
AD
Cohen
Céline
C
Helgen
Christian G
CG
Bochet
John P
JP
Toscano