85194-22-5Relevant academic research and scientific papers
Photoadditions of Anthracenes to 2,4-Hexadiene and 1,3,5-Cycloheptatriene
Kaupp, Gerd,Grueter, Heinz-Willi,Teufel, Eberhard
, p. 630 - 644 (2007/10/02)
Electronically excited 9-anthracenecarbonitrile (1*), in contrast to theoretical predictions, is trapped by 2,4-hexadiene to give the -adduct 3 with a trans-double bond, which forms the -adduct 4 above 0 deg C via suprafacial 1,3-shift.Also 1,3,5-cycloheptatriene (6) quenches 1* with the result of a thermolabile -adduct 7 (-> 8).In addition to 8, further adducts (9, 10, 11, 12) are formed via isomeric diradicals.Anthracene (19*) and 6 generate the -, -, -, substitutive, and peripheral adducts 20, 21, 22, 23, and 24. 9-Phenylanthracene (25*) and 6 form the corresponding, partly isomeric, adducts (26; 29; 27, 28; 30, 31; 32).The reactions are interpreted in terms of diradical mechanism.Numerous literature reports, which havealready been classified theoretically, are amended or corrected, the reasons for erroneous theoretical predictions are discussed.The diversity of products can be understood in detail by empirical extrapolations on the basis of the experimentally secured cyclovinylogy principle.
