Synthesis of Thiochroman 1,1-Dioxide Derivatives on the Basis of 2,4,6-Trinitrotoluene

Treatment of 2,4,6-trinitrotoluene with -mercaptocarboxylic acid esters and subsequent oxidation gave 2-(alkoxycarbonyl-R-methylsulfonyl)-4-X-6-nitrotoluenes which were brought into Knoevenagel condensation with aromatic aldehydes (heating in benzene in the presence of secondary amine acetates). As a result of intramolecular cyclization, 2-alkoxycarbonyl-3-aryl-2-R-5-X-7-nitrothiochroman 1,1-dioxides (R = H, Me; X = NO₂, R'SO₂) were obtained. The developed procedure opens the way to hitherto unknown thiochroman 1,1-dioxide derivatives.     

A new method for the synthesis of sulfonated polynaphthylimides

A new method for the synthesis of sulfonated polynaphthylimides has been developed on the basis of the postsulfonation of high-molecular-mass polynaphthylimides with a sulfuric acid-oleum mixture. Sulfonated polymers of this type have been obtained from the polycondensation products of 5-phenylthiophenylene-1,3-diamine with dianhydrides of 1,4,5,8-naphthalenetetracarboxylic acid and 4,4′-(1,4-phenylenedicarbonyl)-bis-naphthalene-1,8-dicarboxylic acid. It has been shown that hydrogen peroxide oxidation of sulfide bridge groups of these polymers in an acidic medium yields high-molecular-mass compounds that contain sulfonic bridge fragments and, therefore, have increased thermal stabilities and enhanced proton conductivities.     

Regioselective replacement of nitro groups in 2,4,6-trinitrotoluene under the action of alkanethiols. Synthesis of ortho-(alkylthio)-substituted nitrotoluenes and their oxidation to sulfoxides and sulfones

The reactions of 2,4,6-trinitrotoluene with alkanethiols in the presence of K₂CO₃ (the molar ratio of the reactants is 1 : 1 : 1) in dipolar aprotic solvents result in selective replacement of the ortho-nitro group to form 2-alkylthio-4,6-dinitrotoluenes, which can be oxidized to the corresponding sulfoxides or sulfones. The second ortho-nitro group can be replaced under the action of one more equivalent of alkanethiol on sulfides as exemplified in PhCH₂SH.     

TNT-Based condensation monomers and polymers

New aromatic diamines were obtained on the basis of available and inexpensive 2, 4, 6-trinitrotoluene (trotyl, TNT). Monomers obtained were used for the preparation of the new organo-soluble polyimides containing thiophenoxy and phenoxy side groups.     

Arylation of Substituted Anilines Catalyzed by Palladium

Arylation catalyzed by palladium complexes of substituted anilines obtained by modification of 2,4,6-trinitrotoluene makes possible preparation of various diaryl- and arylheterylamines in high yields.     

Aromatic polyethers based on 3,5-dinitrodiphenylsulfone

Aromatic polyethers with phenylsulfone side groups were obtained via the reaction of aromatic nucleophile substitution using 3,5-dinitrodiphenylsulfone as an electrophilic monomer activated by meta-substituents. The polymers are characterized by solubility in a variety of organic solvents and by large intervals between the softening and thermal degradation temperatures, properties that determine their improved processability into articles.