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Die heterolytische Fragmentierung von Benzoin-O-(carbamoyl)oximen

✍ Scribed by Karl-Heinz Pfoertner; Joseph Foricher; Walter Meister


Publisher
John Wiley and Sons
Year
1980
Tongue
German
Weight
430 KB
Volume
63
Category
Article
ISSN
0018-019X

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✦ Synopsis


The Heterolytic Fragmentation of Benzoin‐O‐(carbamoyl)oximes

While the known heterolytic fragmentation reactions give only three, thermal decomposition of benzoin‐O‐(carbamoyl)oximes results in at least four fragments: nitrile or isocyanide, carbonyl compound, CO~2~ and amine. This exception is due to the transformation of the nucleofugal group 3 into the unstable carbamic acid and its decomposition (s. Scheme 1). Since only the configuration of benzoin (E)‐O‐(carbamoyl)oximes is satisfactory for concerted reactions, we conclude that the nitrile producing fragmentation of these (E)‐compounds is concerted, whereas in the isocyanide producing fragmentation of the corresponding (Z)‐compounds several steps are involved. – In contrast to the benzoin‐O‐(carbamoyl)oximes the pyrolysis of benzil‐(E)‐O‐(methylcarbamoyl)oxime starts with the elimination of methyl isocyanate and the following fragmentation is that of the oxime.