M. D. Dutov

Synthesis, antifungal activity and QSAR study of 2-arylhydroxynitroindoles

A series of 2-arylhydroxynitroindoles were prepared and tested for antifungal activity in vitro. The preliminary bioassays indicated that some compounds are comparable to the commercial fungicide (triadimefon). To further explore the structure-activity relationships, the data set of the seventeen structures and their quantitative values of antifungal activities were used for QSAR modeling. Based on the obtained QSAR models four new chemical compounds were designed, synthesized and tested in fungicidal assays. Reasonable correspondence between the experimental and predicted values of antifungal activity was observed.

Combustion of nitro derivatives of azidobenzenes and benzofuroxans

Abstract Combustion of o -, m -, and p -nitroazidobenzene; 2,4-, 2,6-, 3,5-dinitroazidobenzene; 4,6-dinitro-2-azidophenol; 2,4,6-trinitroazidobenzene; 4,6-dinitro-1,3-diazidobenzene; 2,4,6-trinitro-1,3,5-triazidobenzene, and some furoxans formed on decomposition of azides was studied in the 0.1–36-MPa pressure range. The temperature profile in the combustion wave of benzofuroxan and isomers of mononitroazidobenzene was measured using 5-μm-thick Π-shaped tungsten-rhenium tape thermocouples. The effect of the initial temperature on the burning rate of p -nitroazidobenzene was studied. It is shown that the structure of aromatic nitroazides exerts a decisive influence on the burning rate, which is seen most clearly from the burning rates of isomers. Heat release in the condensed phase is shown to play a dominant role in the combustion of mononitroazidobenzenes. The oxygen in the nitro group of the nitroazidobenzene molecule does not take part in the reactions determining the burning rate of the compound. The measured temperatures of the products of combustion of mononitroazidobenzenes and benzofuroxan are 300–450 K lower than the calculated values. A suggestion is made that this is due to the fact that one of the nitrogen atoms of the azide group or of the furoxan ring remains in the combustion products in the form of the energetic nitrile group. On the basis of the results of thermocouple-aided measurements, a scheme of transformation of mononitroazidobenzene and benzofuroxan in the combustion wave is proposed.

New aryloxy-substituted condensation polymers

Abstract Large family of new aromatic diamines containing aryloxy side groups was developed. All the diamines were obtained on the basis of 2,4,6-trinitrotoluene (TNT) — very cheap and available explosive material. TNT was converted into 1,3,5-trinitrobenzene (TNB); subsequent aromatic nucleophilic nitro-displacement reactions led to mono- and diaryloxy-substituted mono- and dinitrobenzenes which were converted into the final aryloxy-substituted diamines. Interaction of the diamines obtained with aromatic dicarboxylic acids chlorides and aromatic tetracarboxylic acids dianhydrides led to the formation of new aryloxy-substituted polyimides and polyimides combining high thermal properties with solubility in organic solvents.

Combustion of Derivatives of 1,5-Diaminotetrazole

Combustion behavior of 1,5-diaminotetrazole (DAT), its salt with perchloric acid DAT·HClO4, and coordination compounds (CCs) with Ni(II), Co(II), Cu(II), Cd, and Zn perchlorates in the interval of pressures from 0.1 to 36 MPa are studied. Despite the high energy content, DAT starts to burn only at extremely high pressures (above 24 MPa). Diaminotetrazole perchlorate possesses the maximum burning rate among all known organic perchlorates, and its combustion is described by a gas-phase model. The CC burning rates are also very high: the burning rate of [Cu(DAT)6](ClO4)2 reaches the record-beating value (for laminar combustion) of 1670 mm/sec at a pressure of 34 MPa. CC combustion is also assumed to follow a gas-phase model. The influence of the metal nature on the combustion behavior of explosive coordination compounds is discussed.

New condensation aromatic polymers containing phenoxy, thiophenoxy, and phenylsulphone side groups

Abstract New condensation monomers—primarily diamines containing phenoxy, thiophenoxy and phenylsulphone substituents were obtained from 2,4,6-trinitrotoluene (TNT). Interaction of some dinitro compounds containing strong electron-withdrawing groups in meta -positions with bis-phenols under conditions of aromatic nucleophilic polynitro substitution reactions led to the formation of aromatic oligoethers. Based on aromatic diamines containing phenoxy and thiophenoxy substituents under conditions of traditional polycondensation and polycyclo condensation reactions, aromatic polyamides and polyimides demonstrating improved processability combined with high thermal stability were obtained.

Studies on substitution of nitro groups in 1,3,5-trinitrobenzene with NH-azoles

Conditions were found under which NH-azoles (benzotriazole and its derivatives, 1,2,3- and 1,2,4-triazoles, pyrazole and its derivatives) replace one nitro group in 1,3,5-trinitrobenzene (TNB) to form the corresponding N-(3,5-dinitrophenyl)azoles in the presence of inorganic bases in aprotic dipolar solvents. The reaction pathway was found to depend on the structure of the starting azole. The benzotriazolyl and 1,2,4-triazolyl fragments activate the replacement of the meta-nitro group to virtually the same extent as the nitro group in TNB, which made it possible to successively replace all three nitro groups in TNB.

Nitro group substitution in 2,4,6-trinitrotoluene under the action of arenethiols and transformations of the reaction products

The reactions of 2,4,6-trinitrotoluene with arenethiols in the presence of inorganic bases in dipolar aprotic solvents led to the replacement exclusively of the ortho-nitro group to form 2-arylthio-4,6-dinitrotoluenes. Substitution, oxidation, and reduction of the latter and their transformation products provided the basis for the preparation of mono- and di-ortho-S-substituted nitrotoluenes and aminotoluenes. Factors favoring the regiospecificity of ortho-substitution in 2,4,6-trinitrotoluene are discussed.

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.

Synthesis of 1-(N-nitropyrazolyl)-1Н-tetrazoles – a new type of heteronuclear N-nitropyrazole derivatives

A general method has been developed for the synthesis of 1-pyrazolyl-1Н-tetrazoles, and N-nitration of these compounds was studied. The structural features affecting the direction of nitration were identified. A series of 1-(N-nitropyrazolyl)-1Н-tetrazoles was obtained, representing a new type of heteronuclear N-nitropyrazole derivatives.

Intramolecular cyclization of O-(3,5-dinitrophenyl) and O-(3-amino-5-nitrophenyl) ketoximes, products of transformations of 1,3,5-trinitrobenzene. The synthesis of nitrobenzo[b]furans and 4-hydroxynitroindoles

O-(3,5-Dinitrophenyl) ketoximes obtained in the reactions of ketoximes with 1,3,5-trinitrobenzene undergo acid-catalyzed cyclization into 2-substituted or 2,3-disubstituted 4,6-dinitrobenzo[b]furans. In analogous cyclization, products of selective reduction of a nitro group in O-(3,5-dinitrophenyl) ketoximes unexpectedly yield, along with 6-amino-4-nitrobenzofurans, 4-hydroxy-6-nitroindoles. The 4-NO2 group is displaced from 4,6-dinitrobenzo[b]furans in reactions with thiols in the presence of K2CO3. Conditions for nitration and sulfochlorination of 4,6-dinitrobenzo[b]furans in position 3 were found. Condensation of a 2-methyl derivative with dimethylformamide acetal was accomplished.