Abstract

GALLO, Ignacio Martín, CARESANA, Ana María, CAPPETTA, Jorge et al. Reactivity of bis-(2,4-dinitrophenyl)-ether and analog thioether from carboxylic and thiocarboxylic anions. Rev. Soc. Quím. Perú, Apr./Jun. 2012, vol.78, no.2, p.91-104. ISSN 1810-634X.

It is pretended to establish the relative order of reactivity of bis-(2,4-dinitrophenyl) ether and bis-(2,4-dinitrophenyl) thioether, towards acetate, thioacetate, benzoate and thiobenzoate anions in methanol - acetone (1:1), by following the development of said reactions by HPLC. Acetate, thioacetate, benzoate and thiobenzoate anions act as nucleophilic reagents towards both substrates, attacking them by means of a bimolecular nucleophilic aromatic substitution mechanism or, indirectly, activating the nucleophilicity of methanol, solvent mixture component. For the interpretation of data obtained from chromatograms, concentration vs. time graphs are built for the substrates and the main products of the reactions, after interpolating the corresponding peak areas in calibration curves built with standard solutions. Research results indicate a higher reactivity of the thioether with respect to ether, confirming results already published; also there are differences in the acetate and thioacetate vs. benzoate and thiobenzoate reactions group due to differences of steric impediments between these groups. There are also very significant reactivity differences when the carboxylic oxygen anion acts or thiocarboxylic sulfur anion as nucleophile.

Keywords: nucleophilic aromatic substitution; reactivity of diaryl ethers nitrated; reactivity of diaryl thioether nitrated; reactivity of carboxylic anions and thiocarboxylic; acylation reactions.