Octamethoxy-o -quaterphenyl (8a) was prepared in three steps from 4-bromo-1,2-dimethoxybenzene (5a) employing two base-mediated biaryl couplings. Demethylation of 8a followed by alkylation with decyl bromide gave the tetradecyloxy-o -quaterphenyl (8c) .Interest in o -quaterphenyls 1 has been stimulated by different research areas (Scheme 1). Všgtle for example used bridged, helical o -quaterphenyls (quaterphenylophanes) to study the dependence of the UV absorption from the twisting of the aryl rings. 1 o -Quaterphenyls were also employed in host-guest chemistry. The binding properties of EDTA analogues bearing an o -quaterphenyl central unit towards metal ions were determined by Všgtle. 2 Cram studied transacylase mimics based upon the quaterphenyl system. 3 It was also found that o -quaterphenyl derivatives are involved in carbonÐcarbon bond activation processes catalyzed by Ni, Pd and Pt complexes. 4,5 The synthesis of these quaterphenyls relies mainly on the classical Ullmann reaction. 1,6 In addition Pd-catalyzed Suzuki coupling of aryl boronates, 7 Ni-catalyzed Kumada coupling of aryl Grignard reagents, 8 Cu(II)-catalyzed rearrangements of bora-aromatics, 5a oxidative coupling of metal phenolates, 9 and oxidative addition of Ni(0) complexes to biphenylene were used as well. 4b We have recently found that 3,3',4,4'-tetramethoxybiphenyl 6a (R = Me) could be prepared in 79% yield by treatment of 4-bromo-1,2-dimethoxybenzene 5a with 0.5 equivalents of butyllithium in THF at Ð78¡C (Scheme 2). 10,11 The formation of 6a had been observed previously during bromine-lithium exchange in 5a with butyllithum. 12d We anticipated that this clean biaryl formation, which does not require the use of expensive or toxic coupling agents 12 might be useful for the synthesis of o -quaterphenyl derivatives 1 as outlined in Scheme 1. We were particularly interested in o -quaterphenyls 1 with long alkyl or alkoxy chains as potential new liquid crystals. The results towards this end are reported below. A preliminary study revealed the scope and limitations of the base-induced biaryl coupling. Whereas most aryl bromides, like 4-bromobenzene, 1-bromonaphthaline, 4-bromo-N,N' -dimethylaniline, 1-bromo-4-nitrobenzene, 4-bromoanisole, and 1-bromo-2,4-dimethoxybenzene either did not react in the presence of 0.5 equivalents of butyllithium in THF or gave the butylated products, 13 only 4-bromo-1,2-didecyloxybenzene 5b and 2-bromoanisole (5c) gave the corresponding biphenyls 6b in 37% and 6c in 19% yield, respectively (Scheme 2). Although compounds 6b , c were obtained in lower yields as compared to 6a , the tetradecyloxy derivative 6b in particular is worth mentioning, because it is an important precursor for the synthesis of discotic liquid crystals bearing the triphenylene moiety. 14,15