Collect. Czech. Chem. Commun.
1983, 48, 1608-1617
https://doi.org/10.1135/cccc19831608
Kinetics of reaction of 1-chloro-2,4,6-trinitrobenzene with enolate ions of 2,4-pentanedione and methyl 3-oxobutanoate
Vladimír Macháček, Jaroslav Andrle and Vojeslav Štěrba
Department of Organic Chemistry, Institute of Chemical Technology, 532 10 Pardubice
Abstract
Reaction of 1-chloro-2,4,6-trinitrobenzene (I) with anions of 2,4-pentanedione (II) and methyl 3-oxobutanoate (III) produces 3-(2,4,6-trinitrophenyl)-2,4-pentanedione (IV) and methyl 2-(2,4,6-trinitrophenyl)-3-oxobutanoate (V), respectively, besides 2,4,6-trinitrophenol (VI). Amount of 2,4,6-trinitrophenol decreases with increasing amount of dimethyl sulphoxide and 2,4-pentanedione in methanol. A mechanism of formation of 2,4,6-trinitrophenol is suggested. Rate constant of formation of 3-(2,4,6-trinitrophenyl)-2,4-pentanedione in methanol-dimethyl sulphoxide mixtures increases with increasing content of dimethyl sulphoxide and decreases with increasing LiCl concentration. In methanol, 1-chloro-2,4,6-trinitrobenzene reacts with anion of 2,4-pentanedione about 20x slower than with anion of methyl 3-oxobutanoate.
