20376-70-9Relevant academic research and scientific papers
Efficient demethylation of N,N-dimethylanilines with phenyl chloroformate in ionic liquids
Imori, Satomi,Togo, Hideo
, p. 2629 - 2632 (2008/09/16)
Demethylation of N,N-dimethylanilines was carried out in various ionic liquids and acetonitrile as well as under solvent-free conditions. We have demonstrated that their reactivity dramatically depends on the ionic liquid employed; [bmim]Cl showed the bes
Basic Hydrolysis of Some Alkyl and Phenyl N-Aryl-N-methylcarbamates.
Broxton, Trevor J.
, p. 2203 - 2209 (2007/10/02)
Rate constants for the basic hydrolysis of methyl, ethyl and phenyl N-aryl-N-methylcarbamates in the presence and absence of micelles of cetyltrimethylammonium bromide are reported.Hammett plots for the methyl aand ethyl carbamates were curved, and this is explained by consideration of the competition between C-N and C-OR bond breaking for decomposition of the tetrahedral intermediate.In one case (p-nitro-substituted), rate-determining formation of the tetrahedral intermediate is suggested, whereas for other compounds rate-determining C-N bond breaking or C-OR bond bre aking is proposed.Micellar catalysis for each of the reactions is reported, and large catalysis (x 50) was observed for compounds where C-N bond breaking was kinetically significant.This is compared with results in the literature for amide and ester hydrolysis.Whereas, for ester hydrolysis, loss of alkoxide ion from the tetrahedral intermediate is favoured over loss of hydroxide ion, in carbamate hydrolysis, loss of hydroxide ions is favoured.A possible reason for this reversal of nucleofugicity of OH- and OR- is proposed.
