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Organic Reactions at High Pressure: Cycloaddition Reactions of 11‐Methylene‐1,6‐methano[10]annulene
Author(s) -
Klärner FrankGerrit,
Dogan Barbara M. J.,
Weider Richard,
Ginsburg David,
Vogel Emanuel
Publication year - 1986
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198603461
Subject(s) - annulene , cycloaddition , methylene , adduct , tautomer , chemistry , valence (chemistry) , high pressure , medicinal chemistry , computational chemistry , photochemistry , organic chemistry , thermodynamics , catalysis , physics
A remarkable pressure dependence is exhibited by the reaction of 11‐methylene‐1,6‐methano[10]annulene with dicyanoacetylene. At normal pressure, one obtains the 1:1 adduct 1a/1b , a fluxional system that is the first example of its kind of a methylenenorcaradiene/heptafulvene valence tautomerism. At 7000 bar, the main product formed is the 2:1 adduct 2 . Despite the less favorable geometry, 2 must have been formed by [8+2] cycloaddition of dicyanoacetylene to 1b.