63017-05-0Relevant articles and documents
Synthesis of α,α-dialkoxy imines and α-keto acetals
De Kimpe,Stanoeva,Boeykens
, p. 427 - 431 (2007/10/02)
A convenient synthesis of monoacetals of α-diones, i.e. α-keto acetals, was developed by silver ion induced alcoholysis of regiospecifically formed α-bromo-α-chloro ketones. Similarly, the corresponding α,α-dialkoxy ketimines were synthesized from silver ion induced alcoholysis of α-bromo-α-chloro ketimines. Both methods provide an easy access to protected forms of α-diones, useful as building blocks in organic chemistry.
Rearrangement of 1-Aryl-2,2-dihalo-1-alkanones
Kimpe, Norbert De,Verhe, Roland,Buyck, Laurent De,Schamp, Niceas
, p. 2803 - 2813 (2007/10/02)
Reaction of 1-aryl-2,2-dichloro-1-alkanones with alkoxides in the corresponding alcohol afforded a mixture of 1-aryl-2,2-dialkoxy-1-alkanones and 1-aryl-1,1-dialkoxy-2-alkanones.The mechanism was shown to proceed via α-chloro-α'-alkoxy epoxides, which rearranged into 1-alkoxy-1-aryl-1-chloro-2-alkanones, the latter giving the final compounds via either another epoxide intermediate or a solvolysis mechanism. α,α-Dibromo- and α-bromo-α-chloroalkyl aryl ketones behaved analogously, but α-bromo-α-fluoro- and α-chloro-α-fluoroalkyl aryl ketones gave exclusively solvolysis of initially formed 1-alkoxy-1-aryl-1-fluoro-2-alkanones, resulting in rearranged 1-aryl-1,1-dialkoxy-2-alkanones. α,α-Difluoroalkyl aryl ketones did not rearrange but underwent reduction of the carbonyl function on treatment with sodium methoxide in methanol.The influence of varying factors, such as the steric requirements of the alkoxide and the substrate, the concentration of the alkoxide, the aromatic substituent, the temperature, and the halogens, was investigated and correlated to the mechanism involved.
