The goal of this and two succeeding papers was to investigate the effects of rigid tetrahedral cores (such as adamantane) on the properties of aramid and poly(phenylene) dendrimers as well as dendrimers that form single molecule micelles. This paper deals with model compound studies dealing with generating tetrasubstituted derivatives of adamantane. A previously reported procedure (for making tetraphenyladamantane) using tert-butyl bromide-AlCl3 catalyzed arylation of 1-bromoadamantane was found not to be a general synthetic method for the preparation of other substituted adamantane derivatives. Adamantane derivatives with multiple phenyl substituents were isolated only when benzene and bromobenzene were used in the Friedel-Crafts reaction. Tetraphenyl-substituted adamantane derivatives were formed, however, by the traditional Friedel-Crafts arylation of 1,3,5,7-tetrabromoadamantane with bromobenzene and 1,3-dibromobenzene. A lack of regioselectivity for these reactions (isolated mixtures of the meta/para isomers or ortho/meta isomers) was observed. Large quantities (50-100 g) of 1,3,5,7-tetraphenyladamantane (1) were prepared from 1-bromoadamantane using a slightly modified literature procedure. This organic insoluble compound was iodinated with [bis(trifluoroacetoxy)iodo]benzene to give the all-para-substituted compound, 5. Compound 5 was further reacted to give numerous derivatives and used as a core in the synthesis of first generation dendrimers.