Journal of Organic Chemistry p. 973 - 980 (1980)
Update date:2022-07-29
Topics:
Duerr, Heinz
Nickels, Helmut
Pacala, Luba A.
Jones, Maitland
EHT and CNDO/2 calculations on benzocyclobutenylidene (6) are described.Flash pyrolysis of the tosylhydrazone salt 7 affords benzocyclobutene and o-xylene in low yield, along with the formal syn and anti carbene dimers 13 and 14.Condensed-phase reactions were achieved by photolysis of the salt 15.Benzocyclobutenylidene (6) gave rise to the formal carbene dimers 17 and 18.Insertion of carbene 6 into the carbon-hydrogen bonds of 2,3-dimethylbutane produced the benzocyclobutenes 20 and 21 (insertion ratio tertiary:primary = 9:1).Cycloaddition of 6 to olefins gave only spiro<3.2>hexene derivatives 22.Multiplicity studies of 6 with cis or trans olefins indicated that 6 undergoes <1+2> cycloaddition in a stereospecific manner.Competition experiments using dienes and monoolefins implicate an equilibrium between singlet and triplet 6.Further competition experiments with styrene/para-substituted styrene pairs demonstrated that 6 reacts faster with electron-poor styrenes.Possible explanations for this apparent anomaly are discussed.
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