Proximity effects in the mass spectra of crowded bis(dimethylamino)arenes: Part II—Rearrangements of the molecular radical cations of ‘proton sponges’ by reciprocal methyl/hydrogen transfer
✍ Scribed by Marina Rentzea; Thomas Saupe; Wolfgang Brox; Heinz A. Staab
- Publisher
- John Wiley and Sons
- Year
- 1989
- Tongue
- English
- Weight
- 410 KB
- Volume
- 24
- Category
- Article
- ISSN
- 1076-5174
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✦ Synopsis
The EI induced fragmentation pathways of 4,5-bis(dimethylamino)fluorew, 4-(d6dimethylamino)-5-(dimethylamino)fluorene, 4,5-bis(d6-dimethylamino)fluorene, 4-(dimethylamioo)-5-methylaminofluorene, 4,Sbis-(methylamiw)fluoreoe, 4-amino-5-methylaminofluorene, l,&bis(dimethylamino)naphthalene, l,&bis(d,dimethylamino)-naphthalene and l,&bis(dimethylamino)-2,7dimethoxynaphthalene were investigated. A mechanism is proposed for the surprising elimination of CH,-NH, from the molecular ion, followed by loss of C2Hi, C2H, and CH,CN and for the accompanying cyclizations to stable heterocyclic ions: prior to fragmentation the molecular radical ion rearranges to new, distonic radical ions by reciprocal H and CH, transfers between the adjacent dimethylamino groups. Each of these new, isomeric molecular ions decomposes subsequently in a characteristic way.