Spontaneous Resolution of Chiral 3-(2,3-Dimethylphenoxy)propane-1,2-diol under the Circumstances of an Unusual Diversity of Racemic Crystalline Modifications

Бредихин, А. А.; Zakharychev, Dmitry V.; Бредихина, З. А.; Kurenkov, A. V.; Krivolapov, Dmitry B.; Gubaidullin, А. Т.

doi:10.1021/acs.cgd.7b00510

Cited by 8 publications

(6 citation statements)

References 33 publications

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“…From the thermochemical data in combination with the values of the heat capacities for all the observed phases in the temperature range from standard conditions up to the melt, it is possible to compare the Gibbs free energies of these phases in the indicated temperature range on the basis of the relationships linking the changes in the thermodynamic functions with the thermochemical characteristics of the samples obtained by the DSC method: Details of such calculations are given in our previous papers. , …”

Section: Resultsmentioning

confidence: 99%

Solid Phase Behavior, Polymorphism, and Crystal Structure Features of Chiral Drug Metaxalone

Бредихин

Zakharychev

Gubaidullin

et al. 2018

Crystal Growth & Design

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In addition to the previously known A-rac and Brac polymorphs of the chiral drug metaxalone 1, an enantiopure A-(S)-form was obtained and studied. According to X-ray analysis, the crystalline organization of this form is close to the A-rac-1 polymorph. Crystallization of metaxalone melts is accompanied by the formation of a previously unknown metastable C-phase, which in the case of both racemic and enantiomeric samples are transformed into A-rac-1 or A-(S)-1. Analysis of the PXRD and IR spectra of crystalline samples revealed a similarity of the internal structure for the A-(S)-1, Arac-1, C-(S)-1, and C-rac-1 crystalline forms and the essential difference of all of these phases from the B-rac-1 phase. According to the thermochemical data, the dependences of the change in the Gibbs free energy for all the phases studied are plotted in the interval from the melting point to 20 °C. Under standard conditions, the crystalline modifications of metaxalone, relative to ΔG 0 , form such a series: B-rac-1 < A-(S)-1 ≈ A-rac-1 < C-rac-1 < C-(S)-1. A model that describes all the experimentally revealed features of metaxalone crystallization is proposed.

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Section: Resultsmentioning

confidence: 99%

Solid Phase Behavior, Polymorphism, and Crystal Structure Features of Chiral Drug Metaxalone

Бредихин

Zakharychev

Gubaidullin

et al. 2018

Crystal Growth & Design

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“…In our practice, we widely used an approach based on the obtained thermochemical parameters of the identified forms, as well as DSC measurements of the dependence of the heat capacity of these forms on temperature, to rank the crystalline modifications of the studied chiral substance by free energies. The main features of this approach and the assumptions made at the same time are described in detail in previous works. ,, The diagrams obtained in this way (SI, Figures S1–S3), displaying the temperature dependences of the ratios between the free energies of the phases constituting the system, make it possible to visualize the regions of stability of these phases and demonstrate the transitions between stable and metastable phases realized in such a system.…”

Section: Resultsmentioning

confidence: 97%

“…The main features of this approach and the assumptions made at the same time are described in detail in previous works. 36,6,26 The diagrams obtained in this way (SI, Figures S1−S3), displaying the temperature dependences of the ratios between the free energies of the phases constituting the system, make it possible to visualize the regions of stability of these phases and demonstrate the transitions between stable and metastable phases realized in such a system.…”

Section: ■ Resultsmentioning

confidence: 99%

Crystal Landscape of Chiral Drug Chlorphenesin and Its Structural Analogues: Polymorphism of Racemic and Enantiopure Samples, Metastable and Stable Racemic Conglomerates, Diverse in Unity Crystal Motifs

Бредихин

Zakharychev

Губайдуллин

et al. 2021

Crystal Growth & Design

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The phase behavior of chiral API Chlorphenesin 1 and its structural analogues 2 and 3 was investigated by DSC and PXRD methods. For the entire family of compounds 1–3, many crystalline modifications have been found for the first time. It has been shown that both racemic and enantiopure samples 1 form stable and metastable phases; racemic meta-derivative 2, along with stable and metastable racemic compounds, is capable of forming a metastable racemic conglomerate. In the case of the ortho-derivative 3, metastable crystalline racemic compounds were not detected, while both stable and metastable homochiral forms are capable of forming racemic conglomerates. For compounds 1–3, the free energies of metastable forms were estimated experimentally relative to the thermodynamically most stable racemic compounds. All racemic compounds of chloro- and methyl-substituted chlorphenesin analogues, studied by X-ray diffraction analysis, form a common supramolecular motif, while three different crystal organizations have been identified for enantiopure forms. In 7 cases out of the 9 studied, the crystal packing is formed with the participation of two symmetry independent molecules. Apparently, both the unusual diversity of the crystalline landscape and the increased frequency of Z′ > 1 cases in the series under study have a common reason and reflect the variety of ways for intermolecular hydrogen bond formation in the crystals of aryl glycerol ethers.

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“…Instead, for high-energy compounds strong H-bonded interactions are disadvantageous as these can prevent molecules from dense packing [57][58][59]. The appearance of particular H-bonded motifs (spiral chains, bilayers, and others) is characteristic for spontaneous resolution of racemic and nonracemic mixtures of some chiral compounds [60][61][62] at crystallizations. Other applications of the analysis of H-bonded associates include salt formation via evaluating synthon competition [63,64], assessing putative structures from crystal structure prediction [65], and analysis of H-bonding in drugs and vitamins [66].…”

Section: Search On Hydrogen-bond Motifsmentioning

confidence: 99%

Intermolecular Interactions in Functional Crystalline Materials: From Data to Knowledge

Вологжанина

2019

Crystals

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Intermolecular interactions of organic, inorganic, and organometallic compounds are the key to many composition-structure and structure-property networks. In this review, some of these relations and the tools developed by the Cambridge Crystallographic Data Center (CCDC) to analyze them and design solid forms with desired properties are described. The potential of studies supported by the Cambridge Structural Database (CSD)-Materials tools for investigation of dynamic processes in crystals, for analysis of biologically active, high energy, optical, (electro)conductive, and other functional crystalline materials, and for the prediction of novel solid forms (polymorphs, co-crystals, solvates) are discussed. Besides, some unusual applications, the potential for further development and limitations of the CCDC software are reported. Crystals 2019, 9, 478 2 of 40 these fields, the manuscript cites only (i) recent works devoted to the analysis of correlations between intermolecular interactions and properties of a small molecule (for example its inclination to form polymorphs, solvates, and co-crystals), or a corresponding solid (from a well-known requirement for non-linear optical materials to crystallize in acentric space groups, to recent studies devoted to the effect of solvent presence on mechanical properties), and (ii) the corresponding software developed to investigate these correlations and to design novel solid forms with desired physicochemical properties. As the description of structure-property networks describes mainly the papers published in the last 10 years in the field of organic, organometallic, and coordination crystals, then the software under discussion will be limited with those developed by the Cambridge Crystallographic Data Centre (CCDC) for material chemistry and crystallography. Various examples of applications of the CCDC software to functional materials including their combination with other software, and restrictions found, will be given.First, the Cambridge Structural Database (CSD) and components of the CSD-Enterprise will be described in Section 2. Then, some properties related to the appearance of a given supramolecular associate, and the tools to search for an associate in the CSD will be reported in Section 3. The properties of solids dependent on the crystal morphology, the Bravais, Friedel, Donnay, and Harker (BFDH) tool for crystal morphology prediction and its' application to affect crystal morphology, polymorphism, and solvatomorphism will be reported in Section 4. Knowledge-based predictions of H-bonded polymorphism, co-crystal formation, mapping of likely intermolecular interactions, and conformer generation for the synthesis of novel functional materials will be discussed in Section 5, and the analysis of local connectivity and whole architectures of solvent molecules in Section 6. Finally, Section 7 contains information about Python API algorithms compatible with the CSD-Enterprise and about some examples of the successful combination of the CSD-Enterprise tools with exte...

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Spontaneous Resolution of Chiral 3-(2,3-Dimethylphenoxy)propane-1,2-diol under the Circumstances of an Unusual Diversity of Racemic Crystalline Modifications

Cited by 8 publications

References 33 publications

Solid Phase Behavior, Polymorphism, and Crystal Structure Features of Chiral Drug Metaxalone

Solid Phase Behavior, Polymorphism, and Crystal Structure Features of Chiral Drug Metaxalone

Crystal Landscape of Chiral Drug Chlorphenesin and Its Structural Analogues: Polymorphism of Racemic and Enantiopure Samples, Metastable and Stable Racemic Conglomerates, Diverse in Unity Crystal Motifs

Intermolecular Interactions in Functional Crystalline Materials: From Data to Knowledge

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