Ultrafast time-resolved infrared spectroscopy study of the photochemistry of N,N-diethyldiazoacetamide: rearrangement in the excited state.
Ultrafast infrared spectroscopy shows that in chloroform, beta-lactam is formed immediately after the laser pulse but gamma-lactam is formed from both slow and fast processes. It is concluded that beta-lactam is formed from the diazoamide excited state via the rearrangement in the excited state (RIES) mechanism and that gamma-lactam is formed from both RIES and carbene. In methanol, both carbene decay and the rise of amide ether product are observed directly. Predictions from density functional theory calculations are consistent with these observations.
Zhang
Yunlong
Y
Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA.
Burdziński
Gotard
G
Kubicki
Jacek
J
Platz
Matthew S
MS
D000081:Acetamides / Q000737:chemistry*; D003979:Diazonium Compounds / Q000737:chemistry*; D007769:Lactams / Q000737:chemistry; D010782:Photolysis; D017550:Spectroscopy, Fourier Transform Infrared; D013997:Time Factors
D000081:Acetamides; D003979:Diazonium Compounds; D007769:Lactams; C543685:N,N-diethyldiazoacetamide