ChemInform Abstract: FUNCTIONAL MICELLAR CATALYSIS. PART 2. ESTER HYDROLYSIS PROMOTED BY MICELLES CONTAINING THE IMIDAZOLE RING AND THE HYDROXY-GROUP

1977 ◽  
Vol 8 (33) ◽  
pp. no-no
Author(s):  
U. TONELLATO
Keyword(s):  
Hydroxy Group ◽  
Imidazole Ring ◽  
Ester Hydrolysis ◽  
Micellar Catalysis

Hydroxy-group participation in ester hydrolysis

1973 ◽  
pp. 1118 ◽  
Author(s):  
Brian Capon ◽  
Samuel T. McDowell ◽  
William V. Raftery
Keyword(s):  
Hydroxy Group ◽  
Ester Hydrolysis ◽  
Group Participation

ChemInform Abstract: HYDROXY-GROUP PARTICIPATION IN ESTER HYDROLYSIS

1973 ◽  
Vol 4 (33) ◽  
pp. no-no
Author(s):  
BRIAN CAPON ◽  
SAMUEL T. MCDOWELL ◽  
WILLIAM V. RAFTERY
Keyword(s):  
Hydroxy Group ◽  
Ester Hydrolysis ◽  
Group Participation

Basic hydrolysis of some alkyl and phenyl N-Aryl-N-methylcarbamates

1983 ◽  
Vol 36 (11) ◽  
pp. 2203 ◽  
Author(s):  
TJ Broxton
Keyword(s):  
Rate Constants ◽  
Cetyltrimethylammonium Bromide ◽  
Ester Hydrolysis ◽  
Micellar Catalysis ◽  
Bond Breaking ◽  
Methyl Ethyl ◽  
Hydroxide Ion ◽  
Tetrahedral Intermediate ◽  
Basic Hydrolysis ◽  
Hydrolysis Of

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 and 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 breaking is proposed. Micellar catalysis for each of the reactions is reported, and large catalysis (× 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 ion is favoured. A possible reason for this reversal of nucleofugicity of OH- and OR- is proposed.

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