Synthetic utilization of polynitroaromatic compounds. 1. S-derivatization of 1-substituted 2,4,6-trinitrobenzenes with thiols.
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.
Zlotin
S G
SG
Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6197, USA.
Kislitsin
P G
PG
Samet
A V
AV
Serebryakov
E A
EA
Konyushkin
L D
LD
Semenov
V V
VV
Buchanan
A C
AC
Gakh
A A
AA