The photochemical reaction of 1,1-dicyano-3-phenylbut-1-ene. Simultaneous occurrence of pi-methane and di-pi-methane rearrangements

• Autor(a) principal: Silva,Francisco A. da
• Data de Publicação: 1999
• Outros Autores: Ferreira,Aurelio B.B., Neumann,Miguel G.
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Journal of the Brazilian Chemical Society (Online)
• Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50531999000500007
• topic: organic photochemistry; di-pi-methane rearrangement; pi-methane rearrangement; 1,2-hydrogen-photomigration

The direct photolysis of 1,1-dicyano-3-phenylbut-1-ene (3-MDCN) was investigated at room temperature in solvents of different polarities (hexane, dichloromethane and acetonitrile). Cyclopropanes arising from both the di-pi-methane and pi-methane (1,2-H migration) processes were obtained as photoproducts. The structures of the products were elucidated by ¹H-NMR, GC/MS, IR and chromatography. Relative quantum yield determination and GC analysis of sequential irradiations gave evidence that: i) no secondary reactions occur, even at high conversions; ii) the di-pi-methane rearrangement is significantly more affected by the solvent variation than the pi-methane reaction. Photosensitization with acetophenone or acetone did not yield any observable products. The existence of the simultaneous mechanisms and the observed effects were considered as evidence of a possible differentiation between localized and delocalized excitation on the excited state surface.