Zlotin S G, Kislitsin P G, Samet A V, Serebryakov E A, Konyushkin L D, Semenov V V, Buchanan A C, Gakh A A
Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6197, USA.
J Org Chem. 2000 Dec 15;65(25):8430-8. doi: 10.1021/jo000479d.
Reactions of 1-R-2,4,6-trinitrobenenes (R = alkyl, protected aldehyde, aminocarbonyl, cyano groups, or isoxazole ring) with thiol salts were investigated. In most cases, these reactions gave a mixture of minor para and major ortho substitution products. Reactions of N,N-disubstituted 2,4,6-trinitrobenzamides with S-,O-, and N-nucleophiles afforded products of substitution of the p-nitro group exclusively. 1-Cyano-2,4,6-trinitrobenzene was found to be the most reactive and the least selective: all three nitro groups can be substituted using an excess of thiol salts. 2-R-4, 6-dinitrobenzamides showed no regioselectivity under similar conditions to yield 1:1 mixtures of para and ortho isomers.
