Preparation of 1,1,2,2,9,9,10,10‐Octafluoro[2.2]paracyclophane and Perfluoro[2.2]paracyclophane

The Unexpected Formation of 9,9,10,10-Tetrafluoro-1,2,4,12-tetraphenyl[2.2]paracyclophan-1-ene

“…The most famous of these compounds is undoubtedly [2.2]­paracyclophane, whose chemistry has been thoroughly studied and reviewed over the last six decades. − This field continues to thrive because of the increasingly successful application of these molecules in the areas of chiral catalysis and material science . Our own interest in this broad field has been in the realm of fluorinated paracyclophanes, and convenient synthetic routes generating 1,1,2,2,9,9,10,10-octafluoro[2.2]­paracyclophane (OFP, 1 ) − and, more recently, the perfluoroparacyclophane (PFP) have been reported . In addition to the commercial value and industrial potential of such molecules (e.g., for use as monomers for fluoroparylene polymers), such practical and convenient syntheses have permitted the exploration of the chemistry of these interesting fluorinated phanes. − …”

Parylene AF‐4 via the Trapping of a Phenoxy Leaving Group

“…Octafluoro[2.2]paracyclophane, the precursor for parylene AF‐4, is 75 times the cost of [2.2]paracyclophane, the precursor for parylene N, and its supply chain reliability is not certain. Although progress has been made, the difficulty with this synthesis is that it takes three steps and the last step is not very scalable and of low yield (40 − 60%) . Typically, this third step needs to be undertaken under more dilute conditions because there is competition between cyclophane formation and polymerization.…”