CYCLOPHANES .9. DIBENZO[DEF,PQR]TETRAPHENYLENE - BENZOANNULATED CYCLOOCTATETRAENE COMPOSED OF ORTHOGONAL AROMATIC SYSTEMS

2,17-Dithia[3.3](3,3′)biphenylophane (10) was prepared from the coupling of 3,3′-bis(bromomethyl)biphenyl and 3,3′-bis(mercaptomethyl)biphenyl. Bridge contraction to generate the bis(methylthio) ether 14 and subsequent oxidation gave the disulfoxide 15 which undergoes thermal elimination of methylsulfenic acid to yield [2.2](3,3′)-biphenylophane-l,15-diene (9). Oxidative photocyclization of the diene 9 gave dibenzo[def,pqr]tetraphenylene (13), an analogue of [8]circulene. Raney nickel desulfurization of the disulfoxide 15 or thermal elimination of sulfur dioxide from the disulfone 12 produced the [2.2](3,3′)biphenylophane (16), which has a preferred anti geometry which is in contrast to the syn geometry of the corresponding diene 9. © 1978, American Chemical Society. All rights reserved.