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Intramolecular Carbene Addition to a Triple Bond – Matrix Photochemistry of α‐Diazo‐2‐ethynylacetophenone
Author(s) -
Komnick Peter,
Sander Wolfram
Publication year - 1996
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.199619960103
Subject(s) - chemistry , ketene , intramolecular force , carbene , diazo , wolff rearrangement , photochemistry , double bond , irradiation , photodissociation , medicinal chemistry , stereochemistry , polymer chemistry , organic chemistry , catalysis , physics , nuclear physics
The irradiation (λ =403 nm) of α‐diazo‐2‐ethynylacetophenone ( 1 a ) in solid argon at 10 K leads to (2‐ethynylphenyl)ketene ( 11 ) as the major product. A minor product is benzo‐4‐oxo‐2,5‐cyclohexadienylidene ( 6 ) which on 475‐nm irradiation reversibly rearranges to cycloprop[ a ]inden‐6(6a H )‐one ( 5a ). This demonstrates that the intramolecular addition of the carbene center to the double bond can compete with the Wolff rearrangement.