A. Barkow et Hf. Grutzmacher, FORMATION AND ELECTROCYCLIZATION OF GASEOUS ALPHA-PHENYL-ORTHOQUINODIMETHANE RADICAL CATIONS, International journal of mass spectrometry and ion processes, 142(3), 1995, pp. 195-208
Citations number
23
Categorie Soggetti
Spectroscopy,"Physics, Atomic, Molecular & Chemical
alpha-Aryl-ortho-quinodimethane radical cations are generated by the l
oss of water via a two-step process (''ortho-effect'') from metastable
molecular ions of 2-methylbenzhydrol derivatives. A competing fragmen
tation is the loss of the methyl substituent from metastable molecular
ions which, however, is also observed for the corresponding meta and
para isomers and which does not interfere with the formation of alpha-
phenyl-ortho-quinodimethane radical cations. The reaction of these lat
ter ions was studied with the aid of specifically labelled derivatives
. The results can be interpreted by an electrocyclization of the alpha
-phenyl-ortho-quinodimethane radical ions to form dihydroanthracene ra
dical cations which decompose by loss of a hydrogen atom or a substitu
ent from one of the phenyl rings in the case of substituted alpha-phen
yl-ortho-quinodimethane radical cations. However, in competition with
this cyclization process via a six-membered transition state the loss
of a methyl radical from the alpha-phenyl-ortho-quinodimethane radical
cations is observed which is the consequence of a cyclization via a f
ive-membered transition state. This latter process is best depicted as
an intramolecular aromatic substitution by a radical.