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Etude du réarrangement de Beckmann des sels d'OTDP des oximes de cétones aromatiques et applications en synthèse

✍ Scribed by Sylvie Thiebaut; Christine Gerardin-Charbonnier; Claude Selve

Book ID
104209055
Publisher
Elsevier Science
Year
1999
Tongue
French
Weight
606 KB
Volume
55
Category
Article
ISSN
0040-4020

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✦ Synopsis

Becknmnn rearrangement of OTDP salts of oximes of aromatic ketones and synthetic applications. Reaction between tris(dimethylamino)-phosphine, carbon tetracldoride and oximes of ketones leads to the corresponding Oximoxy-Tris-(Dimethyiomino)-Phosphonium salts (OTDP salts), which are isolated in the form of hexafluorophosphates. These salts are solid and stable except if they are completely dehydrated. Their solutions, in non polar solvents Hke CHCI3 , give Beckmann rearrangement at room temperature. The kinetics and mechanism have been studied by NMR. We have defined the conditions of trapping of the cationic intermediates formed in the rearrangement, leading to an effective synthesis of amidines and an access to a glycoside structure using the hemiacetalic hydroxyl group of sugar as nucleophile.

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