Phase Diagrams and Thermodynamic Properties of Binary and Ternary Systems Based on Nitroaromatic Compounds

Sangster, James

doi:10.1063/1.556009

Cited by 8 publications

(5 citation statements)

References 12 publications

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“…The onset of the endotherm at low heating rate is 62 °C, which coincides with a reported peak temperature for a 1:1 cocrystal, 18 while again we have no reasons to claim a cocrystal detection here. This example is important, as according to the phase diagram given by Sangster, 49 the TNT/TNB system shows the peritectic for a 1:1 compound at 61.5 °C, and it apparently is the only example of peritectic in a set of compounds considered experimentally in the present study. Type C, when a cocrystal poses a greater melting point as compared to coformers, is the fourth frequent group among published ECC covering 9% of all cases.…”

Section: ■ Results and Discussionsupporting

confidence: 54%

Rational Screening of Cocrystals using Thermal Analysis: Benchmarking on Energetic Materials

Muravyev

Ферштат

Далингер

et al. 2022

Crystal Growth & Design

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Cocrystal design is an important and well-developed approach in the pharmaceutical industry. Energetic materials can be thought of as unique and challenging objects for cocrystal engineering since abundant explosophoric functionalities prevent exploiting common supramolecular synthons. Screening of cocrystal formation using thermal analysis methods is investigated. A few approaches from the literature are combined in a single procedure that allows for automation, high-throughput screening, and the usage of milligrams of material. To estimate the accuracy of the screening procedure, we compiled available literature data on 213 cocrystals with energetic or very similar to energetic materials. The recommended procedure can detect cocrystal formation in 75% cases (with no false positives), according to a smaller sample data set of 28 cocrystal-forming systems. The procedure was then used to screen for novel cocrystals among several acidic energetic materials, ammonium and hydroxylammonium energetic salts, 3-nitro-1,2,4-triazole as a coformers, and 13 cocrystals were discovered. Then, using the traditional solution procedure, eight novel cocrystals were prepared, and their X-ray structures were reported. One of the cocrystals discovered, a complex of promising energetic material, dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (also known as TKX-50) with 18-crown-6, is the first cocrystal of TKX-50 with a reported X-ray structure so far. Overall, we present a unified procedure of thermal screening for cocrystals and salts; benchmarking on challenging objects for cocrystal design (energetic materials) shows its high performance.

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Section: ■ Results and Discussionsupporting

confidence: 54%

Rational Screening of Cocrystals using Thermal Analysis: Benchmarking on Energetic Materials

Muravyev

Ферштат

Далингер

et al. 2022

Crystal Growth & Design

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“…However, it is interesting to note that at a 1:1 molar ratio of 1 : 2 the liquidus temperature is above ambient temperature, implying that some unmelted solid 2 should be present. This is not observed in the bulk samples and may indicate the tendency of the system to supercool . In addition, this implies that some heat is released upon the grinding of the two components which leads to complete melting of the mixture.…”

Section: Resultsmentioning

confidence: 93%

“…Binary phase diagrams were constructed from data obtained using the thaw−melt method of Rastogi and measurement of the liquidus temperatures using the visual-polythermal method …”

Section: Methodsmentioning

confidence: 99%

Understanding Solid/Solid Organic Reactions

et al. 2001

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The concept of an organic reaction between two macroscopic solid particles is investigated. Thus, we study several reactions that have been recently reported to proceed "in the solid phase" and clearly show that, in most cases, grinding the two solid reactants together results in the formation of a liquid phase. This is true both for catalytic transformations (e.g., aldol condensations and oligomerization of benzylic compounds) and for noncatalytic reactions (Baeyer-Villiger oxidations, oxidative coupling of naphthols using iron chloride, condensation of amines and aldehydes to form azomethines, homo-etherification of benzylic alcohols using p-toluenesulfonic acid, and nuclear aromatic bromination with NBS). This liquefaction implies the existence of a eutectic mixture with T(fusion) below ambient temperature (although both reagents have higher than ambient melting points). In cases where heating is required, it is again clear that a phase change (from solid to liquid) occurs, explaining the observed reaction kinetics. On the basis of 19 experimental examples, we discuss the possibility of solid-phase organic reactions and the implications of these findings to the reaction between two solid reagents. A general description of such reactive systems is proposed, based on a consideration of the potential for eutectic (or peritectic) formation between the constituents of the liquid phases that arise during the process of mechanical mixing of the solid reagents and products.

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“…According to our literature survey, among all mixtures, 58 systems are immiscible in the solid state. This subclass comprises simple eutectics of all considered types of phenolic acids including their precursors, namely, benzoic acid ,− and cinnamic acid ,, and their hydroxylated analogues. ,− ,− Although in simple eutectics the nonsubstituted benzoic acids are dominant, there are, however, some interesting exclusions. Indeed, examples of solid state associates formed by these coformers include many pharmaceutically relevant complexes, such as a carbamazepine-cinnamic acid molecular complex and benzoic acid cocrystals with many various APIs and drug-like compounds such as aromatic amides (isonicotinamide, 4-(1 H -pyrazol-1-ylmethyl)benzamide), amines (1,2-diaminobenzene, 1,2-diaminobenzene), diazepams (nevirapine), methylxanthines (caffeine, etofylline), and other heterocycles (trimethroprim, flucytosine).…”

Section: Resultsmentioning

confidence: 99%

Distinguishing Cocrystals from Simple Eutectic Mixtures: Phenolic Acids as Potential Pharmaceutical Coformers

Przybyłek

Cysewski

2018

Crystal Growth & Design

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The multiparameter model comprising 1D and 2D QSPR/QSAR descriptors was proposed and validated for phenolic acid binary systems. This approach is based on the optimization of regression coefficients for maximization of the percentage of true positives in the pool of systems comprising either simple binary eutectics or cocrystals. The training set consisted of 58 eutectics and 168 cocrystals. The solid dispersions collection used for model generation comprised literature data enriched with our new experimental results. From all 1445 descriptors computable in PaDEL, only 13 orthogonal descriptors with the highest predicting power were taken into account. The analysis revealed the importance of the parameters characterizing atom types (naaN, SHsOH, SsssN, nHeteroRing, maxHBint6, C1SP2), autocorrelation functions (ATSC1i, AATSC1v, MATS8m, GATS1i), and also other molecule structure measures (WTPT-5, MLFER_A, MDEN-22). The proposed approach is very simple and requires only information about the structure encoded in canonical SMILES string. The inversion of the problem of cocrystal screening and focusing on the homogeneous group of coformers for cocrystallization with a variety of drugs rather than seeking coformers for a particular active pharmaceutical ingredient proved to be very efficient. This led to very valuable clues for selection of pairs for cocrystallization with a probability of about 80%.

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Phase Diagrams and Thermodynamic Properties of Binary and Ternary Systems Based on Nitroaromatic Compounds

Cited by 8 publications

References 12 publications

Rational Screening of Cocrystals using Thermal Analysis: Benchmarking on Energetic Materials

Rational Screening of Cocrystals using Thermal Analysis: Benchmarking on Energetic Materials

Understanding Solid/Solid Organic Reactions

Distinguishing Cocrystals from Simple Eutectic Mixtures: Phenolic Acids as Potential Pharmaceutical Coformers

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