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The highly strained, new xylene isomers (1) and (2) are of interest for mechanistic studies. (1) undergoes thermal isomerization to (3) and (4). In n-heptane solution, (2) forms (1) [which in turn gives a little (3) and (4)], whereas (3) and (4) are formed directly from (2) in the gaseous phase. Formation of (5) is surprising.