Keele Research Repository

Chapter One describes the search for a synthetic route to 2-azidodiphenylmethanes and 2-azidotriphenylmethanes carrying electron withdrawing substituents in the 4'- and 4W- positions. Extensive use is made of the new Grignard reagent, 4~(1,3-dioxan-2-yl)phenylmagnesium bromide to prepare many novel diphenyl- and triphenyl-methanols, and benzophenones. The reduction of these compounds to the required diphenyl- and triphenyl-methanes is difficult, however, and although 2-amino-4'-carboxymethyldiphenylmethane is obtained in one instance, the reaction is not reproducible.
Further uses for the 3- and 4-0,3-dioxan-2-yl)phenylmagnesium bromide synthons are investigated in Chapter Two. These Grignard reagents provide a useful synthetic route to many known compounds, and also to some previously unprepared compounds such as 3- and 4—0— hydroxyethyl)benzaldehyde, and 4-(l,3-dioxan-2-yl)benzyl bromide.
Chapter Three describes the preparation and decomposition of 2-azido-4*,4",bis(dimethylamino)triphenylmethane and 2-azidophenyl-2- thiazolylmethane. Extensive tar formation occurs during both decompositions. 2-Aminophenyl-2-thiazolylmethane is the only identified product from the thermolysis of 2-azidophenyl-2-thiazolylmethane. The thermolysis of 2-azido-4',4"-bis(dimethylamino)triphenylmethane, however, results in the formation of 3-dimethylamino-9-(4'-dimethylaminopheny1)acridine, and the "rearranged" 2-dime thylamino-9-(4'-dimethylaminophenyl)acridine.
"Rearranged" acridines have not previously been obtained from the decomposition of members of the 2-azidotriphenylmethanes.