02007nas a2200241   4500008004100000022001400041245014900055210006900204260007700273300001600350490000700366520105300373653001401426653002101440653003201461653002601493653002201519100002301541700002701564700002401591700002701615856012301642       2013                        eng d  a0947-653900aIdentification of molecular crystals capable of undergoing an acyl-transfer reaction based on intermolecular interactions in the crystal lattice0 aIdentification of molecular crystals capable of undergoing an ac  aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcSEP  a12867-128740 v193 a<p>Investigation of the intermolecular acyl-transfer reactivity in molecular crystals of myo-inositol orthoester derivatives and its correlation with crystal structures enabled us to identify the essential parameters to support efficient acyl-transfer reactions in crystals: 1)the favorable geometry of the nucleophile (OH) and the electrophile (CO) and 2)the molecular assembly, reinforced by CH interactions, which supports a domino-type reaction in crystals. These parameters were used to identify another reactive crystal through a data-mining study of the Cambridge Structural Database. A 2:1 co-crystal of 2,3-naphthalene diol and its di-p-methylbenzoate was selected as a potentially reactive crystal and its reactivity was tested by heating the co-crystals in the presence of solid sodium carbonate. A facile intermolecular p-toluoyl group transfer was observed as predicted. The successful identification of reactive crystals opens up a new method for the detection of molecular crystals capable of exhibiting acyl-transfer reactivity.</p>10aAcylation10adomino reactions10aintermolecular interactions10asolid-state reactions10aX-ray diffraction1 aTamboli, Majid, I.1 aKrishnaswamy, Shobhana1 aGonnade, Rajesh, G.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/identification-molecular-crystals-capable-undergoing-acyl-transfer-reaction-based-002437nas a2200277   4500008004100000022001400041245017600055210006900231260006700300300001000367490000700377520139300384653001801777653001401795653002201809653003201831653002101863653002101884653001701905653002601922100002301948700001701971700002401988700002702012856012002039       2014                        eng d  a0108-270100aCorrelation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4 `-bipyridine cocrystal with their crystal structures0 aCorrelation of the solidstate reactivities of racemic 246diObenz  a111 RIVER ST, HOBOKEN 07030-5774, NJ USAbWILEY-BLACKWELLcNOV  a1040+0 v703 a<p>Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8, (1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4 `-bipyridine molecules in its cocrystal, C21H18O8 center dot C10H8N2, (1)center dot BP, inhibits the intermolecular benzoyl-group transfer reaction. In (1), molecules are assembled around the crystallographic twofold screw axis (b axis) to form a helical self-assembly through conventional O-H center dot center dot center dot O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El center dot center dot center dot Nu geometry favourable for the acyl transfer reaction. In the cocrystal (1)center dot BP, the dibenzoate and bipyridine molecules are arranged alternately through OH center dot center dot center dot N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.</p>10aacyl transfer10acocrystal10acrystal structure10adesign of functional solids10ahelical assembly10ahydrogen bonding10amyo-inositol10asolid-state reactions1 aTamboli, Majid, I.1 aBahadur, Vir1 aGonnade, Rajesh, G.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/correlation-solid-state-reactivities-racemic-246-di-o-benzoyl-myo-inositol-135-002688nas a2200181   4500008004100000022001400041245018200055210006900237260007100306300001400377490000700391520188100398100002302279700002702302700002402329700002702353856012602380       2014                        eng d  a1528-748300aCrystal-to-crystal thermal phase transformation of polymorphs of isomeric 2,3-naphthalene diol ditoluates: mechanism and implications for molecular crystal formation and melting0 aCrystaltocrystal thermal phase transformation of polymorphs of i  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcOCT  a4985-49960 v143 a<p>Isomeric para- (1) and meta- (2) ditoluate derivatives of naphthalene 2,3-diol exhibited polymorphism producing three (Forms 1I, 1II, 1III) and two (Forms 2I, 2II) polymorphs each, respectively, depending on the solvent and conditions of crystallization. Crystal forms 1I, 1II, and 2I could be obtained repeatedly, whereas crystal forms 1III and 2II were obtained (separately) in one of the crystallization experiments, each. All the crystal forms were stable at ambient conditions, except for Form 2II, which disintegrated to a powder over 45 days. In contrast, the ortho-ditoluate (3) of naphthalene 2,3-diol did not exhibit polymorphism; it yielded fibrous chiral crystals from different solvents/conditions. Crystal structure analysis of all these polymorphs revealed dominance of energetically similar weak intermolecular interactions such as CH center dot center dot center dot O, CH center dot center dot center dot pi, pi center dot center dot center dot pi, and their interplay in molecular aggregation resulting in polymorphic modifications. Differential scanning calorimetry (DSC), hot stage microscopy, single crystal and powder X-ray diffraction measurements revealed crystal-to-crystal thermal transformation of Forms 1I and 1II crystals to Form 1III crystals and Form 2II crystals to Form 2I crystals. The transformation of Form 1I and Form 1II crystals to Form 1III crystals can be viewed as progressive destabilization of the crystal lattice during heating and converting to metastable phase, whereas the conversion of Form 2II to Form 2I crystals can be considered as reorganization of an unstable crystalline phase to a stable crystalline phase. Hence comparative studies of the structure of stable, metastable, or transient crystals and crystal-to-crystal transformations involving these forms could aid in unraveling the process of crystallization.</p>1 aTamboli, Majid, I.1 aKrishnaswamy, Shobhana1 aGonnade, Rajesh, G.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/crystal-crystal-thermal-phase-transformation-polymorphs-isomeric-23-naphthalene-diol-002400nas a2200181   4500008004100000022001400041245024500055210006900300260007100369300001400440490000700454520154000461100002302001700001702024700002402041700002702065856012602092       2015                        eng d  a1528-748300aCocrystallization of 2,3-dihydroxynaphthalene with its para-, meta-, and ortho-ditoluates: insight into cocrystal formation and clues for the construction of supramolecular assemblies capable of intermolecular acyl group transfer reactivity0 aCocrystallization of 23dihydroxynaphthalene with its para meta a  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAR  a1226-12320 v153 a<p>2,3-Dihydroxynaphthalene forms 2:1 cocrystals with its p-ditoluate and 1:1 cocrystals with its m-ditoluate but not with the o-ditoluate. In 2:1 cocrystals of the p-ditoluate, naphthalene diol molecules form a dimeric motif through OH...O hydrogen bonding interactions. The adjacent dimers sandwich the molecules of p-ditoluate through C-H...pi interactions. In 1:1 cocrystals of the m-ditoluate, naphthalene diol molecules generate a zigzag pattern through O-H...O hydrogen bonding interaction involving -OH of the diol and the C=O of the m-ditoluate. Intermolecular toluoyl group transfer reaction was more facile in cocrystals of the p-ditoluate as compared to cocrystals of the m-ditoluate. This difference in reactivity is consistent with the relative geometry of the electrophile (El, C-O) and the nucleophile (Nu, OH) in these cocrystals. A comparison of the cocrystallization behavior and structure of the two cocrystals with their constituents suggests that the position of the methyl group is crucial for cocrystal formation. A survey of the CSD revealed that the incidence of polymorphism and cocrystals formation decreases (number of hits) in the order para- &gt; ortho- &gt; meta- for disubstituted benzene derivatives. This suggests that compounds prone to exhibit polymorphism have more propensities to form cocrystals as compared to those that resist polymorphism. This information could be useful while selecting cocrystal formers and construction of supramolecular functional assemblies with desired properties.</p>1 aTamboli, Majid, I.1 aBahadur, Vir1 aGonnade, Rajesh, G.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/cocrystallization-23-dihydroxynaphthalene-its-para-meta-and-ortho-ditoluates-insight-001936nas a2200241   4500008004100000022001400041245017900055210006900234260007500303300001600378490000700394520095700401653002401358653001401382653001401396653003001410653002601440100002301466700002701489700002401516700002701540856012701567       2015                        eng d  a0947-653900aIntramolecular cyclization of carbonate and thiocarbonate derivatives of myo-inositol in the solid state: implications for acyl group transfer reactions in molecular crystals0 aIntramolecular cyclization of carbonate and thiocarbonate deriva  aPOSTFACH 101161, 69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcSEP  a13676-136820 v213 a<p>Racemic 4-O-phenoxycarbonyl and 4-O-phenoxythiocarbonyl derivatives of myo-inositol orthoformate undergo thermal intramolecular cyclization in the solid state to yield the corresponding 4,6-bridged carbonates and thiocarbonates, respectively. The thermal cyclization also occurs in the solution and molten states, but less efficiently, suggesting that these cyclization reactions are aided by molecular pre-organization, although not strictly topochemically controlled. Crystal structures of two carbonates and a thiocarbonate clearly revealed that the relative orientation of the electrophile and the nucleophile in the crystal lattice facilitates the intramolecular cyclization reaction and forbids the intermolecular reaction. The correlation observed between the chemical reactivity and the non-covalent interactions in the crystal of the reactants provides a way to estimate the chemical stability of analogous molecules in the solid state.</p>10acrystal engineering10acyclitols10ainositols10anucleophilic substitution10asolid-phase synthesis1 aTamboli, Majid, I.1 aShashidhar, Mysore, S.1 aGonnade, Rajesh, G.1 aKrishnaswamy, Shobhana  uhttps://library.ncl.res.in/content/intramolecular-cyclization-carbonate-and-thiocarbonate-derivatives-myo-inositol-solid-002567nas a2200169   4500008004100000245018900041210006900230260000800299300001000307490000700317520183900324100002302163700002802186700002402214700002702238856013202265       2016                        eng d00aEngineering crystals that facilitate the acyl-transfer reaction: insight from a comparison of the crystal structures of myo-inositol-1,3,5-orthoformate-derived benzoates and carbonates0 aEngineering crystals that facilitate the acyltransfer reaction i  cNOV  a875-+0 v723 aMinor variations in the molecular structure of constituent molecules of reactive crystals often yield crystals with significantly different properties due to altered modes of molecular association in the solid state. Hence, these studies could provide a better understanding of the complex chemical processes occurring in the crystalline state. However, reactions that proceed efficiently in molecular crystals are only a small fraction of the reactions that are known to proceed (with comparable efficiency) in the solution state. Hence, for consistent progress in this area of research, investigation of newer reactive molecular crystals which support different kinds of reactions and their related systems is essential. The crystal structures and acyl-transfer reactivity of a myo-inositol-1,3,5-orthoformate-derived dibenzoate and its carbonate (4-O-benzoyl-2-O-phenoxycarbonyl-myo-inositol 1,3,5-orthoformate, C21H18O9) and thiocarbonate (4-O-benzoyl-2-O-phenoxythiocarbonyl-myo-inositol 1,3,5-orthoformate, C21H18O8S) analogs are compared with the aim of understanding the relationship between crystal structure and acyl-transfer reactivity. Insertion of an O atom in the acyl (or thioacyl) group of an ester gives the corresponding carbonate (or thiocarbonate). This seemingly minor change in molecular structure results in a considerable change in the packing of the molecules in the crystals of myoinositol-1,3,5-orthoformate-derived benzoates and the corresponding carbonates. These differences result in a lack of intermolecular acyl-transfer reactivity in crystals of myo-inositol-1,3,5-orthoformate-derived carbonates. Hence, this study illustrates the sensitivity of the relative orientation of molecules, their packing and ensuing changes in the reactivity of resulting crystals to minor changes in molecular structure.1 aTamboli, Majid, I.1 aKrishanaswamy, Shobhana1 aGonnade, Rajesh, G.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/engineering-crystals-facilitate-acyl-transfer-reaction-insight-comparison-crystal-structures01744nas a2200181   4500008004100000022001400041245021900055210006900274260000800343300001400351490000700365520096500372100002401337700002701361700002301388700002401411856012701435       2017                        eng d  a1528-748300aClues from crystal structures pave the way to access chiral myo-inositol derived versatile synthons: resolution of racemic 4-o-allyl-myo-inositol-1,3,5-orthoesters via corresponding dicamphanates by crystallization0 aClues from crystal structures pave the way to access chiral myoi  cOCT  a5432-54400 v173 aRacemic 4-O-allyl-myo-inositol-1,3,5-orthoesters were resolved as the corresponding diastereomeric dicamphanates by crystallization from alcoholic solvents. Crystals of the two diastereomers of myo-inositol orthoacetate and one diastereomer each of myo-inositol orthoformate and myo-inositol orthobenzoate were obtained in &gt;99% purity, on gram scale. The configuration of all these diastereomers was established by conversion to known chiral myo-inositol derivatives as well as by single crystal structure analysis. It is interesting to note that the procedures for the separation of diastereomeric myo-inositol orthoesters could be evolved due to the knowledge of crystal growth and crystal structures of inositol derivatives of comparable molecular structures. Due to the synthetic versatility of myo-inositol orthoesters, the methods described provide rapid and convenient access to a variety of chiral inositol derivatives with high synthetic potential.1 aPatil, Nivedita, T.1 aShashidhar, Mysore, S.1 aTamboli, Majid, I.1 aGonnade, Rajesh, G.  uhttps://library.ncl.res.in/content/clues-crystal-structures-pave-way-access-chiral-myo-inositol-derived-versatile-synthons01598nas a2200181   4500008004100000245016400041210006900205260000800274300001400282490000700296520086600303100002301169700002701192700002701219700002401246700001801270856012801288       2018                        eng d00aEffect of crystal packing on the thermosalient effect of the pincer-type diester naphthalene-2,3-diyl-bis(4-fluorobenzoate): a new class II thermosalient solid0 aEffect of crystal packing on the thermosalient effect of the pin  cMAR  a4133-41390 v243 aThe pincer-like double ester naphthalene-2,3-diyl-bis(4-fluorobenzoate) (2) is pentamorphic. Upon heating crystals of form I to below their melting point (441-443 K), they undergo a phase transition accompanied by a thermosalient effect, that is, rare and visually striking motility whereby the crystals jump or disintegrate. The phase transition and the thermosalient effect are reversible. Analysis of the crystal structure revealed that form I is a class II thermosalient solid. Crystals of form III also underwent a reversible phase transition in the temperature range of 160 to 170 K; however, they were not thermosalient. Comparison of the structures and the mechanical responses of the two polymorphs revealed that the thermosalient effect of form I was due to reversible closing and opening of the arms of the diester molecules in a tweezer-like action.1 aTamboli, Majid, I.1 aKarothu, Durga, Prasad1 aShashidhar, Mysore, S.1 aGonnade, Rajesh, G.1 aNaumov, Pance  uhttps://library.ncl.res.in/content/effect-crystal-packing-thermosalient-effect-pincer-type-diester-naphthalene-23-diyl-bis401468nas a2200181   4500008004100000245015200041210006900193260000800262300001000270490000800280520075300288100001801041700002501059700002701084700002301111700002401134856012801158       2018                        eng d00a Lithium hydride as an efficient reagent for the preparation of 1,2-anhydro inositols: does the reaction proceed through 'axial rich' conformation?0 aLithium hydride as an efficient reagent for the preparation of 1  cJUL  a32-360 v4633 ascyllo-Inositol derived 1,2-trans-diequatorial halohydrins can be efficiently converted to the corresponding epoxides in the presence of lithium hydride. The structure of one of the epoxides was determined by single crystal X-ray diffraction analysis. This provides a potential route for the preparation of ring modified inositol derivatives. DFT calculations suggest that this epoxide formation could be proceeding through the intermediacy of the cyclohexane ring-inverted axial-rich conformer (1,2-trans-diaxial halohydrin). This is supported by the results of DFT calculations on the formation of inositol orthoformate, where the product is locked in the axial-rich conformation, while the starting inositol has the equatorial-rich conformation.1 aSarkar, Nitai1 aSardessai, Richa, S.1 aShashidhar, Mysore, S.1 aTamboli, Majid, I.1 aGonnade, Rajesh, G.  uhttps://library.ncl.res.in/content/lithium-hydride-efficient-reagent-preparation-12-anhydro-inositols-does-reaction-proceed00795nas a2200169   4500008004100000022001400041245026000055210006900315260000800384300000900392490000700401100002300408700001700431700002400448700002700472856012600499       2019                        eng d  a1528-748300aCocrystallization of 2,3-dihydroxynaphthalene with its para-, meta-, and ortho-ditoluates: insight into cocrystal formation and clues for the construction of supramolecular assemblies capable of intermolecular acyl group transfer reactivity (vol 15, pg 120 aCocrystallization of 23dihydroxynaphthalene with its para meta a  cOCT  a59980 v191 aTamboli, Majid, I.1 aBahadur, Vir1 aGonnade, Rajesh, G.1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/cocrystallization-23-dihydroxynaphthalene-its-para-meta-and-ortho-ditoluates-insight-1