Studies in the chemistry of halogenated benzynes

Chapter 1 deals with the principal methods for the generation of arynes and reviews briefly some of the properties of these reactive intermediates. Chapter 2 deals with the reactions of tetrafluorobenzyne generated from pentafluorophenyl magnesium chloride or pentafluorophenyl lithium with anisole, phenetole, p-cresol methyl ether, the 3 isomeric dimethoxybenzenes, symmetrical trimethoxybenzene 2,6-dimethoxytoluene, 1-methoxy-5,6,7,8-tetrafluoronaphthalene and N,N-dimethyl-p-toluidine. The pyrolysis and photolysis of some of the adducts are discussed. Ketonic adducts have been shown to eliminate ketenes. Chapter 3 investigates the reactions of tetrafluorobenzyne with 2-methyl, 2,5-dimethyl and 2-methyl-5-tert-butylfurans. Attempts to prepare anthracenes by elaboration of the adducts with butadiene are discussed. Chapter 4 studies the reactions of benzynes with various polycyclic hydrocarbons (namely fulvenes, phenanthrene, methanocyclodecapentaene, acenaphthene and acenaphthylene). The reaction of tetrafluorobenzyne with dimethyl fulvene yields interesting 2-to-1 adducts. Chapter 5 deals with the PMR spectral data of most of the adducts reported in Chapters 2, 3 and 4. Several ABX spectra have been calculated and compared with the observed spectra.