Collect. Czech. Chem. Commun. 1979, 44, 1453-1459

Reactions of 1-substituted 2,4,6-trinitrobenzenes with nucleophiles

Jaromír Kaválek, Ahmad Ashfaq and Vojeslav Štěrba

Department of Organic Chemistry, Institute of Chemical Technology, 532 10 Pardubice


Rate constants have been determined of nucleophilic aromatic substitution of 2,4,6-trinitrophenyl methyl ether (Ia), 2,4,6-trinitrophenyl ethanoate (Ic), 2,4,6-trinitrochlorobenzene (Ib), 2,4,6-trinitrodiphenyl ether (Id), 2,4,6-trinitro-4'-bromodiphenyl ether (Ie), 2,3',4,6-tetranitrodiphenyl ether (If) and 2,4,4',6-tetranitrodiphenyl ether (Ig) with methoxide, ethanoate and methyl cyanoethanoate (II) anions in methanol. For the compounds Ia,b rate and equilibrium constants of addition of the anion II(-) at positions 3 and 5 have been measured, too. In reactions of the compounds Ia to Ig with ethanoate anion the first (rate-limiting) step produces the phenyl ester Ic which reacts with a further ethanoate anion to give 2,4,6-trinitrophenol (Ih) and ethanoic anhydride. In reactions of the bromo derivative Ie and, to a still larger extent, compound Id the methyl derivative Ia is formed besides the compound Ih.