Статья посвящена поиску рационального селективного способа получения аммониевой соли 3,5-диаминопикриновой кислоты (АДАПК). Соединение представляет интерес как взрывчатое вещество, превосходящее по скорости детонации пикрат аммония, но, в то же время, менее чувствительное. Известно два основных способа получения АДАПК: викариозное нуклеофильное замещение водорода ароматического кольца пикриновой кислоты и селективное дезалкилирование 1,3,5-триметокси-2,4,6-тринитробензола в присутствии гидроксида натрия с образованием натриевой соли 3,5-диметоксипикриновой кислоты и ее амммонолиз. Каждый из методов имеет свои недостатки и может применяться лишь в лаборатории. В данной работе проведено исследование двух противоположных процессов: алкилирования тринитрофлороглюцина триэтилортоформиатом и гидролитического дезалкилирования 1,3,5-тринитро-2,4,6-триэтоксибензола с целью селективного получения 3,5-диэтоксипикриновой кислоты без применения щелочных агентов. Установлено, что реакция аликилирования тринитрофлороглюцина не избирательна, в зависимости от соотношения реагентов образуется смесь трех этоксипроизводных. Изучен процесс гидролиза 1,3,5-тринитро-2,4,6-триэтоксибензола в присутствии стехиометрического количества воды в среде различных растворителей. Установлено, что только в среде ДМФА при повышенной температуре происходит образование 3,5-диэтоксипикриновой кислоты с селективностью 97 %. Проведен успешный аммонолиз раствора 3,5-диэтоксипикриновой кислоты в ДМФА газообразным аммиаком. Результатом предложенного способа является технологичный, экономичный и селективный процесс получения АДАПК с суммарным выходом 93 %, высокой температурой разложения и содержанием основного вещества более 98 %. The paper is focused on finding a rational selective method for the synthesis of ammonium 3,5-diaminopicrate (ADAP). This compound is attractive as an explosive that is superior in detonation rate to ammonium picrate and yet is less sensitive. Two key synthetic methods for ADAP are known, these are the vicarious nucleophilic substitution of the aromatic hydrogen of picric acid and the selective dealkylation of 1,3,5-trimethoxy-2,4,6-trinitrobenzene over sodium hydroxide to furnish sodium 5-dimethoxypicrate followed by its ammonolysis. Each of the methods has its drawbacks and can only be employed in the laboratory setting. The present study explored two opposite processes: alkylation of trinitrophloroglucinol with triethyl orthoformate and hydrolytic dealkylation of 1,3,5-trinitro-2,4,6-triethoxybenzene for the selective synthesis of 3,5-diethoxypicric acid without using alkali agents. The alkylation reaction of trinitrophloroglucinol was found to be non-selective, resulting in three mixed ethoxy derivatives depending on the reactant ratio. The hydrolysis process of 1,3,5-trinitro-2,4,6-triethoxybenzene in the presence of a stoichiometric quantity of water in different solvents was examined. 3,5-Diethoxypicric acid was discovered to form only in DMF at elevated temperature, with a selectivity of 97 %. Successful ammonolysis of aqueous 3,5-diethoxypicric acid with ammonia gas was carried out in DMF. The approach suggested herein resulted in a technologically simple, economical and selective process for the synthesis of ADAP with a total yield of 93 %, high decomposition temperature, and an assay of over 98 %

Статья посвящена способу получения 1,3-диамино-2,4,6-тринитробензола – термически стабильного взрывчатого вещества – из 1,3-дигидрокси-2,4,6-тринитробензола в две стадии с суммарным выходом до 80 %. Изучена реакция алкилирования 1,3-дигидрокси-2,4,6-тринитробензола триэтилортоформиатом с образованием 1,3,5-тринитро-2,4-диэтоксибензола, определены оптимальные условия процесса. Показано, что аммонолиз алкокси-производного в среде ДМФА происходит с высокой скоростью, выходом и качеством 1,3-диамино-2,4,6-тринитробензола. The present study reports a two-stage synthetic method for 1,3-diamino-2,4,6-trinitrobenzene, a thermally stable explosive material, from 1,3-dihydroxy-2,4,6-trinitrobenzene, with a total yield of up to 80%. The alkylation reaction of 1,3-dihydroxy-2,4,6-trinitrobenzene with triethylorthoformate to give 1,3,5-trinitro-2,4-diethoxybenzene was examined, and the optimal conditions for the process were determined. The ammonolysis of the alkoxyl derivative in DMF was found to proceed with a high rate, yield and quality of 1,3-diamino-2,4,6-trinitrobenzene.

A study on the Pd-catalyzed hydrodebromination of 2,3,4,5-tetrabromothiophene (1) to 3,4-dibromothiophene (2) is reported. The effect of the solvent nature, main agent, temperature and concentration of 1 on the yield of 2 was studied. Optimal conditions of the process were found: a 5 % Pd/Sibunit catalyst constituting 10 % of the substrate weight, a temperature of 80 °С, a pressure of 0.7 MPa, dimethyl formamide with the addition of triethylamine as the main agent in the amount of 2.2 equiv per 1 equiv of the initial substance 1, and the yield of 2 constituting up to 97.5 %. It was shown that the catalyst could be reused with the preservation of the high yield of 2. In comparison with the conventional method of chemical reduction of 1 under the action of zinc in acetic acid, the novel method ensures high output and low wastes.

The catalytic properties of a copper-aluminum oxide catalyst obtained from double layered hydroxide have been studied in hydrogenation of 1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT) in a flow reactor. The reaction was carried out at temperature of 120°C, total pressure of 30 bar and substrate concentration of 0.10–0.15 M, using methanol as a solvent. 1,3,5-Triaminobenzene (TAB) and 2,4,6-triaminotoluene (TAT) were isolated from the reaction mixture in the form of double salts with sulfuric acid TAB⋅2H2SO4 and TAT⋅2H2SO4, the yield of which was 92 and 98%, respectively. At an initial trinitroarene concentration of 0.10 M, the hydrolysis of triaminobenzene salts made it possible to synthesize phloroglucinol and methylphloroglucinol in 78 and 91% yields. Increasing the concentration to 0.15 M reduces the yield to 71 and 88%, respectively. According to thermal analysis data, the observed differences in the yields of triaminobenzene salts and polyphenols are explained by the formation of different amounts of resinous by-products on the catalyst surface during hydrogenation of trinitroarene. Hydrogenation of TNT produces less resin, resulting in higher yields of TAT⋅2H2SO4 and methyl phloroglucinol. This is probably due to the presence of an electron-donating methyl substituent, which slows down polycondensation of TAT molecules.

The catalytic hydrogenation of dinitroaromatic compounds is an important reaction for the production of phenylenediamine derivatives, which are widely used in industry. In this work, the catalytic properties of a Cu–Al mixed oxide obtained from double layered hydroxide have been investigated in liquid-phase hydrogenation of 1,3-dinitrobenzenes under continuous-flow conditions. The reaction was carried out at temperature of 120 °C, total pressure of 30 bar, using methanol or methanol/isopropanol mixture as a solvent. It was found that hydrogenation of 1,3-dinitrobenzene, 2,4-dinitrotoluene, 2,4-dinitroanisole and 2,4-dinitromesitylene provides the selective formation of the corresponding diamines, which were isolated in the form of salts with sulfuric acid stable in storage. The effect of the reaction temperature, pressure, H2 flow rate, and solvent nature on the catalyst performance was studied.

Scholars from around the world have been attempting to simplify and cheapen the synthetic method for the promising high-energy compound CL-20 for decades. The lack of understanding of the formation mechanisms of hexaazaisowurtzitane derivatives―CL-20 precursors―is a barrier to solving the said problems. Here, we report the results from an in-depth study into the acid-catalyzed condensation between benzamide and glyoxal in a molar ratio of 2:1 in polar protic and aprotic solvents. Sixteen compounds were isolated and identified, of which eight were synthesized for the first time. A geminal diol, N,N’-(2,2-dihydroxyethane-1,1-diyl)dibenzamide, was synthesized. Two isomers of 1,2-bis(benzoylamino)-1,2-ethanediol were isolated and identified. N,N’-(1-oxoethane-1,2-diyl)dibenzamide and 2-oxo-2-[(phenylcarbonyl)amino]ethyl benzoate were produced that were likely formed due to the 1,2-hydride shift. N-polysubstituted 1,4-dioxane-2,3,5,6-tetramine was synthesized for the first time, whose structure may be of interest as a scaffold for new explosives. DMSO, THF and HCOOH were found to be able to engage in a reaction with benzamide, or condensation products thereof, and glyoxal under acid-catalyzed conditions.

Статья посвящена способу получения 2,4,6-тригидрокси-3-метилбензойной кислоты, выполняющей роль интермедиата в синтезе бензофуран-3(2Н)-онов и карбокси-2H-1-бензопиран-2-онов – важных прекурсоров сложных биологически активных молекул, проявляющих фунгицидную, антибактериальную противоопухолевую и др. виды активности. Предложен способ получения 2,4,6-тригидрокси-3-метилбензойной кислоты карбоксилированием натриевой соли 2,4,6-тригидрокситолуола диоксидом углерода. Изучено влияние мольного соотношения реагентов на конверсию 2,4,6-тригидрокситолуола, проведены кинетические исследования реакции методом ВЭЖХ. Предложенный способ более технологичен за счет повышения производительности и существенного снижения газообразования, а также характеризуется высоким выходом до 87 %. The article is devoted to the method of obtaining 2,4,6-trihydroxy-3-methylbenzoic acid, which plays the role of an intermediate in the synthesis of benzofuran-3(2H)-ones and carboxy-2H-1-benzopyran-2-ones – important precursors of complex biologically active molecules exhibiting fungicidal, antibacterial antitumor, etc. types of activity. A method for obtaining 2,4,6-trihydroxy-3-methylbenzoic acid by carboxylation of the sodium salt of 2,4,6-trihydroxytoluene with carbon dioxide is proposed. The effect of the molar ratio of reagents on the conversion of 2,4,6-trihydroxytoluene was studied, kinetic studies of the reaction by HPLC were carried out. The proposed method is more technologically advanced due to increased productivity and a significant reduction in gas formation, and is also characterized by a high yield of up to 87%.

Here, we investigated the synthetic processes for the methyl derivatives of sym-triaminobenzene and phloroglucinol, the essential chemical reactants coming into use in the production of dyes and pigments, and medicinal drugs for different purposes. The most eco-benign process for the synthesis of triamino derivatives involves the catalytic hydrogenation of corresponding nitroarenes. The present study investigated the hydrogenation of 2,4,6-trinitrotoluene, 2,4,6-trinitroxylene, and 2,4,6-trinitromesitylene over a Pd catalyst. A 1% Pd/Sibunit catalyst was found to be preferable to the 5% analogue with a preserved palladium loading because it shortens the reaction time and provides a higher yield of the target product. The hydrogenation in methanol (or mixed methanol/toluene) at 50–55 °C and 0.5 MPa pressure produced 2,4,6-triaminotoluene, 2,4,6-triaminoxylene, and 2,4,6-triaminomesitylene, which were isolated as sulfuric acid salts in 98, 91, and 97% yields, respectively. The hydrolysis process of the resultant salts was examined, and conditions leading to mono-, di-, and trimethyl derivatives of phloroglucinol (90, 77, and 82%, respectively,) were identified. The hydrogenation of the trinitrobenzene homologues in mixed 7:1 (v/v) acetone/water, followed by hydrolysis to the respective polyphenols, was explored. A successful result was achieved only for 2,4,6-trinitrotoluene. The catalyst activity was shown to decline negligibly throughout 10 cycles of reuse. 2-Methylphloroglucinol was synthesized in a high yield ranging from 85 to 91% calculated as 2,4,6-trinitrotoluene.

Статья рассматривает вопрос получения метил-, диметил- и триметилпроизводных флороглюцина – ценных полифенолов, применяемых в качестве реагентов в синтезе перспективных красителей и пигментов, биологически активных веществ и полимеров. Наиболее экологичным способом получения флороглюцина и его гомологов является каталитическое гидрирование соответствующих нитроаренов до триаминобензолов и их гидролиз. В качестве катализатора гидрирования использован 1 % Pd/Sibunit. В среде метанола (либо его смеси с толуолом) при температуре 50-55 °С и давлении 0,5 МПа синтезированы и выделены в виде серно-кислых солей 2,4,6-триаминотолуол, 2,4,6-триаминоксилол и 2,4,6-триаминомезитилен с выходами 98, 91 и 97 % соответственно. Показано, что метильные производные гидрируются с большей селективностью, чем незамещенный 1,3,5-тринитробензол. Исследован процесс гидролиза полученных солей, определены условия, в которых с высокими выходами образуются моно-, ди- и триметильные производные флороглюцина (90, 77 и 82 % соответственно). This paper looks into the issue of preparing methyl-, dimethyl- and trimethyl derivatives of phloroglucinol, which are valuable polyphenols used as reactants in the synthesis of promising colorants and pigments, bioactive substances, and polymers. The greenest method for the preparation of phloroglucinol and its homologues is the catalytic hydrogenation of the corresponding nitroarenes to triaminobenzenes with the subsequent hydrolysis of the latter. The catalyst used was 1 % Pd/Sibunit. 2,4,6-Triaminotoluene, 2,4,6-triaminoxylene and 2,4,6- trinitromesitylene were synthesized and isolated as sulfuric-acid salts at 50-55 °С and 0.5 MPa in methanol (or mixed methanol/toluene), in 98, 91 and 97 % yields, respectively. The methyl derivatives were shown to be hydrolyzed more selectively than unsubstituted 1,3,5-trinitrobenzene. The hydrolysis of the resultant salts was also examined and the conditions leading to mono-, di- and trimethyl derivatives of phloroglucinol in 90, 77 and 82 % yields, respectively, were identified

An environmentally friendly and safe synthesis of phloroglucinol and its derivatives through the flow hydrogenation of 1,3,5-trinitrobenzenes on heterogeneous copper catalysts is reported. It was found that hydrogenation of 1,3,5-trinitrobenzene, 2,4,6-trinitrotoluene, 2,4,6-trinitroxylene, and 2,4,6-trinitromesitylene in methanol over Cu-Al mixed oxides derived from layered double hydroxides led to selective formation of the corresponding triaminobenzenes, which were isolated from the reaction mixture in the form of double salts with sulfuric acid and were stable in storage. Subsequent hydrolysis in aqueous solution gave the phloroglucinol derivatives in good yields (75-82%).

The synthesis of substituted aza- and oxaazaisowurtzitanes via direct condensation is challenging. The selection of starting ammonia derivatives is very limited. The important step in developing alternative synthetic routes to these compounds is a detailed study on their formation process. Here, we explored an acid-catalyzed condensation between 4-tert-butyl-2,6-dimethylbenzenesulfonamide and glyoxal in aqueous H2SO4, aqueous acetonitrile and acetone, and established some new processes hindering the condensation. In particular, an irreversible rearrangement of the condensation intermediate was found to proceed and be accompanied by the 1,2-hydride shift and by the formation of symmetric disulfanes and sulfanes. It has been shown for the first time that aldehydes may act as a reducing agent when disulfanes are generated from aromatic sulfonamides, as is experimentally proved. The condensation between 4-tert-butyl-2,6-dimethylbenzenesulfonamide and formaldehyde resulted in 1,3,5-tris((4-(tert-butyl)-2,6-dimethylphenyl)sulfonyl)-1,3,5-triazinane. It was examined if diimine could be synthesized from 4-tert-butyl-2,6-dimethylbenzenesulfonamide and glyoxal by the most common synthetic procedures for structurally similar imines. It has been discovered for the first time that the Friedel–Crafts reaction takes place between sulfonamide and the aromatic compound. A new synthetic strategy has been suggested herein that can reduce the stages in the synthesis of in-demand organic compounds of symmetric and asymmetric aromatic sulfones via the Brønsted acid-catalyzed Friedel–Crafts reaction, starting from aromatic sulfonamides and arenes activated towards an electrophilic attack.

Статья посвящена способу получения 2,4,6-тригидрокситолуола – ценного реагента, который находит применение в синтезе перспективных азокрасителей и пигментов, лекарственных препаратов, обладающих различными видами активности, топливных присадок и полимеров. В работе обсуждается двухстадийный метод синтеза на основе 2,4,6-тринитротолуола. Первая стадия заключается в гидрировании тринитроарена в присутствии 1 % Pd/Cибунит в смеси ацетон/вода 7:1 (об./об.). Данный состав растворителя обладает хорошей растворяющей способностью по отношению ко всем компонентам смеси и способствует сохранению активности катализатора на протяжении 10 последовательных циклов. Предлагаемый способ не предусматривает выделения 2,4,6-триаминотолуола, и после подкисления серной кислотой и разбавления водой гидрогенизат подвергается гидролизу до 2,4,6-тригидрокситолуола. Исследовано влияние мольного соотношения H2SO4/тринитроарен на выход и качество 2,4,6-тригидрокситолуола. Определено, чтооптимальнымзначением является соотношение 1,8 моль H2SO4/ 1 моль нитропроизводного. В результате исследования получен ТГТ с высоким выходом, который снижается незначительно от первого к десятому циклу с 91 до 85 %. This paper describes a process for 2,4,6-trihydroxytoluene, a valuable reactant that comes into use for the synthesis of promising azo dyes and pigments, medicinal drugs exhibiting various activities, propellant additives, and polymers. The paper discusses a two-stage synthetic method starting from 2,4,6-trinitrotoluene. The first stage involves hydrogenation of trinitro arene over a 1 % Pd/Sibunit in mixed 7/1 (v/v) acetone/water. This solvent system has a good solubilizing ability towards all the ingredients of the reaction mixture and aids in preserving the catalyst activity throughout 10 successive cycles of reuse. The method proposed herein does not provide for the isolation of 2,4,6-triaminotoluene, and once H2SO4-acidified and water-diluted, the hydrogenation product is hydrolyzed to 2,4,6-trihydroxytoluene. The effect of the molar ratio of H2SO4/trinitroarene on the yield and quality of 2,4,6-trihydroxytoluene is examined. The ratio of 1.8 mol H2SO4/1 mol nitro derivative has been found to be optimum. This study has consequently resulted in THT in a high yield that lowers negligibly from 91 to 85 % between the first and tenth cycle.

Here, we investigated the reaction of 1,3-dipolar cycloaddition of 1,3-diazido-2-nitro-2- azapropane (DANP) to propargyl alcohol over a copper-based catalyst and identified the optimum reaction conditions that enable the synthesis of 2-nitro-1,3-bis(4,4′-dihydroxymethyl)-1,2,3-triazolyl-2-azapropane (1) in more than 84% yield. The reaction between DANP, 1,5-diazido-3-nitrazapentane, and phenylacetylene produced the respective 1,2,3-triazole derivatives in 83% and 71% yields, respectively. The structures of the resultant compounds were validated by infrared and NMR spectroscopies and elemental analysis. The structure of 1 was proved by single-crystal X-ray diffraction. This study demonstrated that 1 exhibits a dose-dependent antiarrhythmic activity towards calcium-chloride-induced arrhythmia and refers to Class III: moderately hazardous substances.

Статья посвящена способу получения флороглюцина, представляющего интерес в качестве основы для конструирования лекарственных средств, полимеров различного назначения и малочувствительного взрывчатого вещества 1,3,5-триамино-2,4,6-тринитробензола. Современным и наиболее экологичным методом получения флороглюцина является каталитическое гидрирование 1,3,5-тринитробензола на палладиевом катализаторе до 1,3,5-триаминобензола и его последующий гидролиз. Использование палладиевых катализаторов позволяет проводить восстановление в мягких условиях, но их высокая стоимость обуславливает потребность в поиске путей снижения расхода палладия и, соответственно, себестоимости процесса. В данном исследовании показано, что использование 1 %-го Pd/сибунит (50 % к массе субстрата) в сочетании с водно-ацетоновым раствором в качестве среды при проведении гидрирования способствует более длительному сохранению активности катализатора. Установлено, что оптимальное соотношение ацетона и воды находится в диапазоне от 4:1 до 7:1. В этом случае может быть проведено до 20 циклов гидрирования без добавления свежего катализатора, за счет чего удается снизить расход палладия в три раза по сравнению с другими известными методиками. Кроме того, подход позволяет исключить из схемы синтеза токсичный растворитель метанол. Триаминобензол, полученный в ходе гидрирования, без выделения подвергается гидролизу в присутствии серной кислоты с образованием флороглюцина. Изучена зависимость выхода флороглюцина от мольного соотношения серной кислоты и тринитробензола. Установлено, что оптимальное соотношение серная кислота : тринитробензол составляет 2,0-2,4 моль/моль. Суммарный выход флороглюцина составляет 76 % в пересчете на тринитробензол. The study is concerned with a synthetic method for phloroglucinol that is of great concern as a scaffold for designing medicinal drugs, different-purpose polymers and the insensitive explosive 1,3,5-triamino-2,4,6-trinitrobenzene. The current and most eco-benign method for the synthesis of phloroglucinol is through catalytic hydrogenation of 1,3,5-trinitrobenzene over the Pd catalyst to 1,3,5-triaminobenzene followed by its hydrolysis. The use of Pd catalysts allows the reduction under mild conditions, but their high cost necessitates the need to find ways how to spare the Pd usage and, consequently, the process cost. Here we demonstrated that the use of 1% Pd/Sibunite (50% to substrate weight) combined with a water-acetone solution as the medium in hydrogenation allows the catalyst to keep active longer. The optimum acetone-to-water ratio was found to be between 4:1 and 7:1. In this case, as many as 20 hydrogenation runs can be done without a fresh catalyst added whereby the Pd usage can be lowered threefold when compared to the other common methods in use. Besides, this approach allows the toxic solvent methanol to be expelled from the synthetic protocol. Triaminobenzene resulting from the hydrogenation without isolation undergoes hydrolysis in the presence of sulfuric acid to furnish phloroglucinol. The relationship between the phloroglucinol yield and the molar ratio of sulfuric acid and trinitrobenzene was also explored. The optimum sulfuric acid-to-trinitrobenzene ratio was found to be 2.0-2.4 mol/mol. The overall yield of phloroglucinol was 76% on a trinitrobenzene basis.

Статья посвящена усовершенствованию способа получения 2,4,6-тригидрокситолуола, востребованного химического реагента в синтезе азокрасителей и пигментов, а также химико-фармацевтических препаратов и различных полимеров. Основным сырьем для его получения является 2,4,6-тринитротолуол, который подвергают каталитическому гидрированию с последующим гидролизом образовавшегося 2,4,6-триаминотолуола. В данной работе предложены условия многоциклового использования палладиевого катализатора гидрирования 2,4,6-тринитротолуола, позволяющие сохранять активность катализатора и повысить выход 2,4,6-триаминотолуола выше 98 %. Аминопроизводное выделяется в виде дисульфата действием концентрированной серной кислоты. Кроме того, изучено влияние соотношения вода/дисульфат 2,4,6-триаминотолуола на выход 2,4,6-тригидрокситолуола; найдены условия, в которых выход на стадии гидролиза увеличен до 83-84 %. Проведен сравнительный анализ различных способов выделения 2,4,6-тригидрокситолуола из реакционной массы. The paper is concerned with upgrading the synthetic method for 2,4,6-trihydroxytoluene, an in-demand chemical reactant in the synthesis of azo-dyes and pigments, as well as chemical pharmaceuticals and various polymers. The basic feedstock for the synthesis thereof is 2,4,6-trinitrotoluene, which is subjected to catalytic hydrogenation followed by hydrolysis of the resulting 2,4,6-triaminotoluene. Here we suggest conditions for the multicycle use of Pd catalyst employed for the hydrogenation of 2,4,6-trinitrotoluene, which allow the catalyst activity to be retained and the yield of 2,4,6-triaminotoluene to be enhanced above 98%. The amino derivative is liberated as the disulfate by concentrated sulfuric acid. Moreover, we examined how the ratio of water / 2,4,6-triaminotoluene disulfate influences the yield of 2,4,6-trihydroxytoluene. Conditions were found in which the yield from hydrolysis is 83-84 %. Different methods for the isolation of 2,4,6-trihydroxytoluene from the reaction mixture were comparatively analyzed.

Results of the works on the development of the technology of phloroglucinol production are presented. Phloroglucinol is a known multipurpose organic reactant that has gained wide and diverse applications, in particular as the starting compound for the synthesis of 1,3,5-triamino-2,4,6-trinitrobenzene. A review of the known methods of phloroglucinol synthesis is presented. The method which is most promising from the standpoint of commercialization is studied. The method is based on the reduction of nitroaromatic precursors - 2,4,6-trinitrobenzoic acid and 1,3,5-trinitrobenzene - to 1,3,5-triaminobenzene, followed by its hydrolysis. Alternate approaches to the synthesis of 2,4,6-trinitrobenzoic acid from 2,4,6-trinitrotoluene are proposed. The catalytic hydrogenation of 2,4,6-trinitrobenzoic acid and 1,3,5-trinitrobenzene over palladium-containing catalysts was studied in detail, and the effect of various process parameters on the yield of the reaction product 1,3,5-triaminobenzene was determined. Hydrolysis of triaminobenzene to form phloroglucinol is considered.

This study was focused on investigating the formation of N-polysulfonylsubstituted aza- and oxaazaisowurtzitanes via condensation of 4-dimethylaminobenzenesulfonamide with glyoxal and discovering new polyheterocyclic caged systems. More specifically, we explored how a donor substituent incorporated into the para position of the phenylsulfonamide molecule would influence the formation of cage products. Four new oxaazaisowurtzitane derivatives bearing one to three aza groups in the cage were consequently synthesized. A side reaction was found to take place, leading to a product having a non-isowurtzitane structure and four 4-dimethylaminobenzenesulfonyl moieties. The side product was analyzed by X-ray diffraction.

В статье представлен материал, посвященный перспективному направлению прикладной химии переработке 2,4,6-тринитротолуола в продукцию гражданского применения. Проведена работа по усовершенствованию способа получения 2,4,6-тригидрокситолуола путем каталитического гидрирования 2,4,6-тринитротолуола на палладиевом катализаторе до 2,4,6-триаминотолуола с последующим гидролизом его сернокислой соли. Предложены условия получения и очистки 2,4,6-тригидрокситолуола с высоким выходом и качеством. The article presents the material devoted to the perspective direction of applied chemistry-processing of 2,4,6-trinitrotoluene into products of civil application. Work has been carried out to improve the method of obtaining 2,4,6-trihydroxytoluene by catalytic hydrogenation of TNT on a palladium catalyst to 2,4,6-triaminotoluene followed by hydrolysis of its sulfate salt. Conditions for the production and purification of 2,4,6-trihydroxytoluene with high yield and quality are proposed.

Рассмотрен трехстадийный способ получения флороглюцина на основе 2,4,6-тринитротоуола путем его переработки в 2,4,6-тринитробензойную кислоту, ее каталитического гидрирования до 1,3,5-триаминобензола с последующим гидролизом. Предложен новый метод окисления 2,4,6-тринитротолуола действием перманганата калия в кислой, нейтральной и щелочной средах. Показано, что только в кислой среде образуется 2,4,6-тринитробензойная кислота, в остальных случаях происходит ее декарбоксилирование до 1,3,5-тринитробензола. Изучен процесс гидрирования 2,4,6-тринитробензойной кислоты до 1,3,5-триаминобензола в кислой среде на палладиевом катализаторе. Исследовано влияние природы минеральной кислоты, а также давления и температуры процесса на выход солей триаминобензола. Гидролизом дисульфататриаминобензола получен флороглюцин с суммарным выходом до 44 в пересчете на исходный 2,4,6-тринитротолуол. Here we report a three-stage method for the synthesis of phloroglucinol starting from 2,4,6-trinitrotoluene (TNT) by conversion of TNT into 2,4,6-trinitrobenzoic acid and catalytic hydrogenation of the latter to 1,3,5-triaminobenzene followed by hydrolysis. A new method is suggested for oxidation of TNT with potassium permanganate in acidic, neutral and alkaline media. 2,4,6-Trinitrobenzoic acid was found to be formed only in acidic medium in other cases, it underwent decarboxylation to 1,3,5-trinitrobenzene. Hydrogenation of 2,4,6-trinitrobenzoic acid to 1,3,5-triaminobenzene in acidic medium over Pd catalyst was studied. The effects of mineral acid, reaction pressure and temperature on the yield of triaminobenzene salts were examined. Phloroglucinol was synthesized by hydrolysis of triaminobenzene disulfate in a total yield of up to 44 calculated as initial 2,4,6-trinitrotoluene.