Amines as Leaving Groups in Nucleophilic Aromatic Substitution Reactions. Part 4. -Adducts Formation in the Hydrolysis of 1-Amine-2,4,6-trinitrobenzenes

ELBA I. BUJÁN; M. VIRGINIA REMEDI; RITA H. DE ROSSI

Royal Society of Chemistry

Año: 2000 p. 969 - 969

he kinetic study of the reaction of 2,4,6-trinitro-1-pyrrolidinobenzene 3, 2,4,6-trinitro-1-piperidinobenzene 1 and 1-morpholino-2,4,6-trinitrobenzene 2 was made in 1,4-dioxane?water mixtures at 25 C. In all cases, several processes were observed, the slowest of them leading to the formation of picrate ion. The fastest processes involved the formation of σ complexes by addition of one or two HO to unsubstituted ring positions and the ionisation of the 1 : 1 complex. Besides, for compounds 1 and 3, cis?trans isomerisation of 1 : 2 complexes was kinetically detected. Substitution occurred by displacement of the amino group on the substrate and the 1 : 1 complex. The reaction pathway for the formation of phenol which involves the formation of these complexes has lower energy than that which results from addition to the 1 position of the substrate.