92492-99-4Relevant academic research and scientific papers
Selective Aromatic Hydroxylation with Dioxygen and Simple Copper Imine Complexes
Becker, Jonathan,Gupta, Puneet,Angersbach, Friedrich,Tuczek, Felix,N?ther, Christian,Holthausen, Max C.,Schindler, Siegfried
, p. 11735 - 11744 (2015)
The formation of a bis(μ-oxido)dicopper complex with the ligand 2-(diethylaminoethyl)-6-phenylpyridine (PPN) and its subsequent hydroxylation of the pendant phenyl group (studied earlier by Holland et al., Angew. Chem. Int. Ed. 1999, 38, 1139-1142) has been reinvestigated to gain a better understanding of such systems in view of the development of new synthetic applications. To this end, we prepared a simple copper imine complex system that also affords selective o-hydroxylation of aromatic aldehydes by using dioxygen as the oxidant: Applying the ligand N′-benzylidene-N,N-diethylethylenediamine (BDED), salicylaldehyde was prepared in good yields and we show that this reaction also occurs through an intermediate bis-μ-oxido copper complex. The underlying reaction mechanism for the PPN-supported complex was studied at the BLYP-D/TZVP level of density functional theory and the results for representative stationary points along reaction paths of the BDED-supported complex reveal a closely related mechanistic scenario. The results demonstrate a new facile synthetic way to introduce OH groups into aromatic aldehydes.
SYNTHESIS AND SOME TRANSFORMATIONS OF 1-ARYL-2-AZA-1,3-BUTADIENES
Nikogosyan, L. L.,Nersesyan, K. A.,Satina, T. Ya.,Panosyan, G. A.,Indzhikyan, M. G.
, p. 671 - 675 (2007/10/02)
The synthesis of 1-aryl-2-aza-1,3-butadienes was realized by the alkaline cleavage of diethylmethyl(4-aryl-3-aza-3-butenyl)ammonium iodides or by the dehydrochlorination of 1-chloro-4-phenyl-3-aza-3-butene.They react with alcohol at the terminal vinyl group.The direction of reaction with amines depends to a large degree on the nature of the nucleophile.
