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Photoinduced Acylotropic Rearrangement of Crown-Containing 2-[N-Acetyl-N-(4-aminobenzo-15-crown-5)methylene]-2,3-dihydrobenzo[b]thiophen-3-one
Authors:V P Rybalkin  A D Dubonosov  E N Shepelenko  L L Popova  V A Bren' and V I Minkin
Institution:(1) Research Institute of Physical and Organic Chemistry, Rostov State University, pr. Stachki 194/2, Rostov-on-Don, 344090, Russia
Abstract:2-N-(4-Aminobenzo-15-crown-5)methylene-2,3-dihydrobenzob]thiophen-3-one and its acetyl derivative were synthesized. Their treatment with lithium, sodium, or potassium iodide in acetonitrile solution leads to formation of the corresponding crown-metal complexes. Irradiation of the acylated compounds at lambda 436 nm induces NO migration of the acetyl group to give O-acyl isomer which is characterized by a considerable blue shift of the long-wave absorption band (Deltalambda = 70 nm). The quantum yields of the photo- induced acylotropic reaction for the free ligand and its complexes with alkali metal cations change in the series: phivL > phivK+ > phivNa+ > phivLi+.
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