95826-77-0Relevant academic research and scientific papers
Transanular Interaction in Phanes, 27: Models for Excimers and Exciplexes: Phanes of Fluorene, 9-Fluorenone, and 9-Fluorenyl Anion
Haenel, Matthias W.,Irngartinger, Hermann,Krieger, Claus
, p. 144 - 162 (2007/10/02)
anti- and syn-(2,7)-fluorenophane (1, 2) as well as their 5,16-dioxo and 5-oxo derivatives 3, 5, and 6 containing two or one 9-fluorenone units were synthesized: Cyclisation of the bis(bromomethyl) compounds 7 and 10 with the bis(mercaptomethyl) compounds 9 and 12 gave the dithiaphanes 14, 16, and 18 containing fluorene and 9-fluorenone units bridged at the 2,7-positions.Oxidation to the disulfones 15, 17, and 18 and vapour phase pyrolysis (500 degC, 0.1 Torr) led to 1/2, 3, and 5/6, respectively.The molecular geometry of 1 was determined by X-ray structure analysis.On treatment of suspensions of 1 and 2 in hexamethylphosphoric triamide with n-butyllithium in n-hexane red solutions of the dianions 21 and 22 were generated, which were characterized by 1H NMR spectroscopy.With deuterium oxide the dianion 22 yielded 2>-anti-(2,7)fluorenophane (24), with methyl iodide exo-5,exo-16-dimethyl-anti-(2,7)fluorenophane (26).Multiple metalation with n-butyllithium and reaction with methyl iodide led to 5,5,16,16-tetramethyl-anti-(2,7)flourenophane (27).
