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Die Allen‐Racemisierung, eine zweistufige Reaktion
Author(s) -
Roth Wolfgang R.,
Bastigkeit Thorsten
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.199619961231
Subject(s) - diradical , racemization , chemistry , allene , singlet state , enthalpy , photochemistry , radical , carbene , stereochemistry , catalysis , organic chemistry , thermodynamics , physics , nuclear physics , excited state
The Racemization of Allene, a Two‐Step Reaction For four vinyl‐ and phenyl‐substituted allenes racemization enthalpies have been determined, which are 2–6 kcal · mol ‐1 below the estimate derived from the parent system by correction for the additional radical stabilization of the intermediate allyldiradical 2 (I), indicating the growing importance of the carbene type structure 2 (II) for the intermediate. — The racemization of 1,3‐dimethylallene 1b at temperatures >300°C in the presence of NO allows the trapping of an intermediate, which is considered to be the orthogonal allyl diradical 2b . From the trapping kinetics (307–388°C), the reversible bimolecular addition of NO at low temperatures (225–285°C) and the strength of the CNO bond an enthalpy well for the singlet diradical of 2.7 kcal · mol ‐1 and a singlet‐triplet splitting of 5.6 kcal · mol ‐1 is derived with the triplet being the groundstate. — The postulated intermediate diradical 2 can be stabilized electronically by phenyl and vinyl groups or by strain when incorporated in an eight‐membered ring. Thermolyses of the optically active 1,2,5‐cyclooctatriene 18 in the presence of oxygen allows to determine the enthalpy well of the corresponding diradical 25 to be 13.1 kcal · mol ‐1 .