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1979 (1)
1Author    Bernhard Ciommer, Helmut SchwarzRequires cookie*
 Title    [1.3] -Hydroxylwanderung bei Radikalkationen von Allen-und Acetylenalkoholen [1] [l,3]-Hydroxyl Migration in Cation Radicals of Allene and Acetylene Alcohols  
 Abstract    Contrary to previous conclusions it is shown that the molecular ions of 1, 2, and 3 do not interconvert prior to dissociation. Investigation of labelled compounds establishes a new typ of intramolecular [1,3]-hydroxyl migration to allenic and acetylenic carbons. It is shown that both 1 and 2 undergo irreversible rearrangement to an a,^-unsaturated ketone 4. Methyl loss from the intermediate 4, which accounts for 90% of the total methyl elimination, is preceded by partial hydrogen exchange processes between the three methyl groups of 4. The actual dissociation can be described as an a-cleavage to the carbonyl function. The unusual formation of CH3CO 4 " is shown to occur exclusively from 1. However, 
  Reference    Z. Naturforsch. 34b, 1307—1319 (1979); eingegangen am 15. Mai 1979 
  Published    1979 
  Keywords    Rearrangement of Allenes, Hydroxyl Migration, Exchange Processes, Ion Structures, Gas Phase Chemistry 
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 TEI-XML for    default:Reihe_B/34/ZNB-1979-34b-1307.pdf 
 Identifier    ZNB-1979-34b-1307 
 Volume    34