title: Formation of allenyl ketones, 3-ethynylcoumarins, and arylfurans, furylfurans, and furylthiophenes by flash vacuum thermolysis of 3-methylidenefuran-2(3H)-ones.
abstract: Flash vacuum thermolysis (FVT) of 3-methylidenefuran-2(3H)-ones 3 causes cheletropic extrusion of CO with formation of allenyl ketones 4. o-Chloro- and o-bromophenylmethylidenefuranones also afford allenyl ketones upon flash vacuum thermolysis, but in addition, 3-ethynylcoumarins 6 are formed via E/Z isomerization of the methylidenefuranones, cyclization, halogen atom migration, and HCl (HBr) elimination. The presence of strongly electron-withdrawing groups (nitroaryl or acetyl) on the acylallene moiety causes rearrangement to give 2-arylfurans 10 and 13 as well as 2-furylfurans and 2-furylthiophenes 16 by cyclization of the allenyl ketones. The reaction mechanisms are supported by calculations at the M06-2X/6-311+G(d,p) level of theory.
authors: Institut für Chemie and Center of Interface Science, Carl von Ossietzky Universität Oldenburg , P.O. Box 2503, 26111 Oldenburg, Germany.
authors: Rainer
authors: R
authors: Koch
authors: Hans Michael
authors: HM
authors: Berstermann
authors: Curt
authors: C
authors: Wentrup