32763-17-0Relevant academic research and scientific papers
REACTIONS OF 1-ARYL-2,2-DICHLORO-1-PROPANONES. II. REACTION OF 1-(4-R-PHENYL)-2,2-DICHLORO-1-PROPANONES WITH SOME NUCLEOPHILES
Bratchanskii, P. E.,Komissarova, G. G.,Esipov, G. V.
, p. 1961 - 1964 (2007/10/02)
The reactions of 1-(4-R-phenyl)-2,2-dichloro-1-propanones with alkali-metal alkoxides and certain amines (morpholine, piperidine) and also their conversion into α-diketones were studied.By IR and mass spectrometry it was shown that the methoxylation of these compounds with sodium methoxide leads to the formation of the products from direct substitution of the halogen atoms by methoxyl groups.The kinetics of methoxylation are described by a second-order equation, and a Hammett correlation with a positive reaction constant is observed in the rate constants.
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.
