Thermolysis of Biphenylene toward Cyclo-ortho-phenylenes

The solvent and catalyst free thermolysis of biphenylenes at 350 degrees C furnishes [n]cyclo-ortho-phenylenes ([n]COPs, n=4-10) in one step and in high yields. At 400 degrees C biphenylene dimerizes into tetraphenylene, but lower reaction temperatures produce cyclooligomers. If suitably substituted, the oligomers are soluble and can be isolated and characterized. The products are exclusively cyclic. In the crystalline state, [6]COP displays an alternating crown-shaped conformation.