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Reactivity differences of O ‐aryl O ‐(4‐nitrophenyl) thionocarbonates versus their homolog carbonates: Micellar catalysis in hydrolysis reactions
Author(s) -
Santos José G.,
Aliaga Margarita E.,
Márquez Mariana F.,
Oyarzún Mauricio
Publication year - 2019
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3845
Subject(s) - chemistry , cationic polymerization , catalysis , hydrolysis , reactivity (psychology) , micelle , aryl , aqueous solution , medicinal chemistry , inorganic chemistry , boron , pulmonary surfactant , nuclear chemistry , organic chemistry , alkyl , medicine , biochemistry , alternative medicine , pathology
The alkaline hydrolysis reaction of O ‐(4‐cyanophenyl), O ‐(4‐methylphenyl), and phenyl O ‐(4‐nitrophenyl) thionocarbonates ( 1 , 2 , and 3 , respectively) and O ‐(4‐cyanophenyl) and phenyl O ‐(4‐nitrophenyl) carbonates ( 4 and 5 , respectively) has been spectrophotometrically studied in aqueous borate buffer media, in the presence of the cationic surfactant CTAB. The pseudophase model successfully explained the results obtained, in the presence of this cationic micelle, and various kinetic parameters were determined. Results show that the catalytic efficiency increases in carbonates and thionocarbonates. In fact, a catalytic efficiency ( k obs max / k ′ w ) of 485‐fold was found in the hydrolysis reaction of thionocarbonate 1 , while in the carbonate homolog 4 , the effect was of 146‐fold. In addition, we found that at the same experimental conditions (Borate buffer pH = 9.0 and 25°C), an increase in the concentration of the buffer led to a decrease of the hydrolysis rate.