Methyleneketenes and methylenecarbenes. III. Pyrolytic synthesis of arylacetylenes and their thermal rearrangements involving arylrnethylenecarbenes

Abstract
Flash vacuum pyrolysis (550-600�) of 5-benzylidene derivatives of 2,2- dimethyl-1,3-dioxan-4,6-dione(isopropylidene malonate) gives phenylacetylenes bearing m- or p-substituents (H, Me, MeO, Cl, CN)in 64-98% yield. o-Methoxy- and o-phenyl-benzylidene derivatives give the arylacetylenes even at 420�. Arylacetylenes equilibrate with arylmethylenecarbenes, ArCH=C:, at 550-720�, as shown by labelling experiments using 13C and by the formation of products of interaction with o-substituents. Methylenebenzocyclobutene and o-tolylacetylene each form indene at 700-720�.

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