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Thermal stability of spiro[adamantane‐[1,2]dioxetanes]
Author(s) -
Adam Waldemar,
Arias Encarnación Luis A.,
Zinner Klaus
Publication year - 1983
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19831160302
Subject(s) - diradical , chemistry , alkane stereochemistry , isomerization , stereochemistry , singlet state , crystallography , crystal structure , organic chemistry , excited state , physics , nuclear physics , catalysis
The thermal stability of several spiroadamantane‐substituted 1,2‐dioxetanes was determined by means of chemiluminescence (Table 1). The evident stabilization of dioxetanes by such substitution cannot be interpreted in terms of “inertial mass” or “torsional” arguments in the case of concerted decomposition nor by “compressional” arguments in the case of diradical decomposition. It is suggested that a transoid diradical 19t , in which the engaged orbitals are antiperiplanar arranged, promotes CC cleavage. The bulky adamantane substituent encumbers such conformational isomerization of the initially formed cisoid diradical 19c into the preferred 19t .