02641nas a2200241   4500008004100000022001400041245014300055210006900198260007700267300001200344490000700356520171700363653001402080653001802094653001902112653001402131653002602145100002102171700002702192700002402219700002502243856013102268       2009                        eng d  a0947-653900aEnhancing intermolecular benzoyl-transfer reactivity in crystals by growing a ``reactive'' metastable polymorph by using a chiral additive0 aEnhancing intermolecular benzoyltransfer reactivity in crystals   aPO BOX 10 11 61, D-69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcNOV  a261-2690 v153 a<p>Racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoacetate, which normally crystallizes in a monoclinic form (form I, space group P2(1)/n) could be persuaded to crystallize out as a metastable polymorph (form II, space group C2/c) by using a small amount of either D- or L- 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoformate as an additive in the crystallization medium. The structurally similar enantiomeric additive was chosen by the scrutiny of previous experimental results on the crystallization of racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoacetate. Form II crystals call be thermally transformed to form I crystals at about 145 degrees C. The relative organization of the molecules in these dimorphs vary slightly in terms of the helical assembly of molecules, that is, electrophile (El)center dot center dot center dot nucleophile (Nu) and C-H center dot center dot center dot pi interactions, but these minor variations have a profound effect on the facility and specificity of benzoyl-group-transfer reactivity in the two crystal forms. While form II crystals undergo a clean intermolecular benzoyl-group-transfer reaction, form I crystals are less reactive and undergo non-specific benzoyl-group transfer leading to a Mixture of products. The role played by the additive in fine-tuning small changes that are required in the molecular packing opens up the possibility of creating new polymorphs that show varied physical and chemical properties. Crystals of D-2.6-di-O-benzoyl-myo-inositol-1,3,5-orthoformate (additive) did not show facile benzoyl-group-transfer reactivity (in contrast to the corresponding racemic compound) due to the lack of proper juxtaposition and assembly of molecules.</p>10aAcylation10acarbohydrates10aCrystal growth10acyclitols10asolid-state reactions1 aMurali, Chebrolu1 aShashidhar, Mysore, S.1 aGonnade, Rajesh, G.1 aBhadbhade, Mohan, M.  uhttps://library.ncl.res.in/content/enhancing-intermolecular-benzoyl-transfer-reactivity-crystals-growing-reactive-metastable-001563nas a2200217   4500008004100000022001400041245018000055210006900235260010600304300001400410490000700424520066300431653001301094653001901107653001301126653001401139653002101153100001601174700002701190856012801217       2012                        eng d  a0040-402000aElaboration of the ether cleaving ability and selectivity of the classical pearlman's catalyst [Pd(OH)(2)/C]: concise synthesis of a precursor for a myo-inositol pyrophosphate0 aElaboration of the ether cleaving ability and selectivity of the  aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcNOV  a9769-97760 v683 a<p>The cleavage of propargyl, allyl, benzyl, and PMB ethers by Pd(OH)(2)/C can be tuned in that order, by varying the reaction conditions. Other moieties such as C-C double bonds, esters, trityl ether, p-bromo and p-nitrobenzyl ethers are stable to these reaction conditions. Cleavage of allyl ethers can be made catalytic by using 1:1 mixture of Pd(OH)(2)/C and Pd/C. The synthetic potential of the selective ether cleaving ability of Pd(OH)(2)/C, essentially under neutral conditions, has been demonstrated by an efficient synthesis of a precursor for the preparation of an inositol pyrophosphate derivative. (C) 2012 Elsevier Ltd. All rights reserved.</p>10aCyclitol10aEther cleavage10aInositol10aPalladium10aProtecting group1 aMart, Alson1 aShashidhar, Mysore, S.  uhttps://library.ncl.res.in/content/elaboration-ether-cleaving-ability-and-selectivity-classical-pearlmans-catalyst-pdoh2c-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-structures01598nas 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-bis4