Abstract
Heats of formation and geometries of benzocyclopropene, cyclopropa[ b]naphthalene, bicyclo[4.1.0]hepta-2,4,7-triene, and benzannelated derivatives have been calculated with a combined force field-SCF program. The bicycloheptatrienes are stabilized relative to the isomeric arylcarbenes by benzannelation, and destabilized by loss of aromaticity and/or increased strain. 1-Naphthylcarbene, 2-naphthylcarbene, 9-phenanthrylcarbene and 9-anthrylcarbene were generated by gas-phase pyrolysis of the corresponding arene aldehyde tosylhydrazone sodium salts, diazomethanes, or 5-aryltetrazoles, and rearranged to cyclobuta[ de]naphthalene ( 21), cyclobuta[ jk]phenanthrene ( 33), and cyclobuta[ de] anthracene ( 38), respectively. 10,11-Dihydrodibenzo[ ad]cyclohepten-5-ylidene ( 15), similarly generated from 5-diazo-10,11-dihydro-5H-dibenzo [ ad]cycloheptene( 39), rearranged to 5a,9b-dihydro-5 H-benzo[3,4]cyclobut[1,2-a] indene( 40), 5 H-dibenzo[ ad]cycloheptene( 41), and 8,9-dihydro-4 H-cyclopenta[ def]phenanthrene( 44). 40 rearranged thermally to 41. The mechanisms of the rearrangements are discussed.
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