Medium effect on the reaction of N-butyl-2,4,6-trinitroaniline with NaOH

MARIA L. SALUM, RITA HOYOS DE ROSSI Y ELBA I. BUJÁN

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY

Lugar: ; Año: 2007 p. 2164 - 2174

1434-193X

The kinetics of the reaction of N-butyl-2,4,6-trinitroaniline (3) with NaOH have been studied in 10 and 60% 1,4-dioxane/ H2O at 25 °C. In both cases, several processes were observed. In 10% 1,4-dioxane/H2O the only product formed was 2,4,6-trinitrophenol (4), whereas in 60% 1,4-dioxane/ H2O a mixture of 4 and 5,7-dinitro-2-propyl-1H-benzimidazole 3-oxide (5) was observed in ratios that depend on the HO– concentration. A mechanism involving the formation ofN-butyl-2,4,6-trinitroaniline (3) with NaOH have been studied in 10 and 60% 1,4-dioxane/ H2O at 25 °C. In both cases, several processes were observed. In 10% 1,4-dioxane/H2O the only product formed was 2,4,6-trinitrophenol (4), whereas in 60% 1,4-dioxane/ H2O a mixture of 4 and 5,7-dinitro-2-propyl-1H-benzimidazole 3-oxide (5) was observed in ratios that depend on the HO– concentration. A mechanism involving the formation of3) with NaOH have been studied in 10 and 60% 1,4-dioxane/ H2O at 25 °C. In both cases, several processes were observed. In 10% 1,4-dioxane/H2O the only product formed was 2,4,6-trinitrophenol (4), whereas in 60% 1,4-dioxane/ H2O a mixture of 4 and 5,7-dinitro-2-propyl-1H-benzimidazole 3-oxide (5) was observed in ratios that depend on the HO– concentration. A mechanism involving the formation of2O at 25 °C. In both cases, several processes were observed. In 10% 1,4-dioxane/H2O the only product formed was 2,4,6-trinitrophenol (4), whereas in 60% 1,4-dioxane/ H2O a mixture of 4 and 5,7-dinitro-2-propyl-1H-benzimidazole 3-oxide (5) was observed in ratios that depend on the HO– concentration. A mechanism involving the formation of2O the only product formed was 2,4,6-trinitrophenol (4), whereas in 60% 1,4-dioxane/ H2O a mixture of 4 and 5,7-dinitro-2-propyl-1H-benzimidazole 3-oxide (5) was observed in ratios that depend on the HO– concentration. A mechanism involving the formation of4), whereas in 60% 1,4-dioxane/ H2O a mixture of 4 and 5,7-dinitro-2-propyl-1H-benzimidazole 3-oxide (5) was observed in ratios that depend on the HO– concentration. A mechanism involving the formation of2O a mixture of 4 and 5,7-dinitro-2-propyl-1H-benzimidazole 3-oxide (5) was observed in ratios that depend on the HO– concentration. A mechanism involving the formation of5) was observed in ratios that depend on the HO– concentration. A mechanism involving the formation of– concentration. A mechanism involving the formation of ó complexes through the addition of one or two HO– anions to unsubstituted ring positions is proposed for 2,4,6-trinitro- phenol formation. The presence of these complexes was confirmed by NMR studies in 60% [D8]1,4-dioxane/D2O. The mechanism suggested for the formation of the N-oxide includes the cyclization of an N-alkylidene-2-nitrosoanilinetype intermediate as the rate-determining step. The decrease in solvent polarity produces a decrease in the observed rate constant for the formation of 4 of about one order of magnitude making the cyclization reaction a competitive pathway. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)complexes through the addition of one or two HO– anions to unsubstituted ring positions is proposed for 2,4,6-trinitro- phenol formation. The presence of these complexes was confirmed by NMR studies in 60% [D8]1,4-dioxane/D2O. The mechanism suggested for the formation of the N-oxide includes the cyclization of an N-alkylidene-2-nitrosoanilinetype intermediate as the rate-determining step. The decrease in solvent polarity produces a decrease in the observed rate constant for the formation of 4 of about one order of magnitude making the cyclization reaction a competitive pathway. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)8]1,4-dioxane/D2O. The mechanism suggested for the formation of the N-oxide includes the cyclization of an N-alkylidene-2-nitrosoanilinetype intermediate as the rate-determining step. The decrease in solvent polarity produces a decrease in the observed rate constant for the formation of 4 of about one order of magnitude making the cyclization reaction a competitive pathway. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)N-oxide includes the cyclization of an N-alkylidene-2-nitrosoanilinetype intermediate as the rate-determining step. The decrease in solvent polarity produces a decrease in the observed rate constant for the formation of 4 of about one order of magnitude making the cyclization reaction a competitive pathway. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)N-alkylidene-2-nitrosoanilinetype intermediate as the rate-determining step. The decrease in solvent polarity produces a decrease in the observed rate constant for the formation of 4 of about one order of magnitude making the cyclization reaction a competitive pathway. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)4 of about one order of magnitude making the cyclization reaction a competitive pathway. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)