02050nas a2200193 4500008004100000022001400041245012900055210006900184260007100253300001400324490000600338520126600344100002501610700002101635700002401656700002301680700002501703856012801728 2005 eng d a1528-748300aIdentical molecular strings woven differently by intermolecular interactions in dimorphs of myo-inositol 1,3,5-orthobenzoate0 aIdentical molecular strings woven differently by intermolecular  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcSEP a1977-19820 v53 a

myo-Inositol 1,3,5-orthobenzoate exhibits polymorphic behavior depending upon the solvent and time allowed for crystallization. Long plates (form I, monoclinic P2(1)/n) are produced on crystallization from methanol, while crystallization from ethyl acetate mostly yielded squarish plates (form II, monoclinic P2(1)/c). The latter could also be obtained by achieving rapid nucleation from a supersaturated solution of methanol. Remarkably, the overall conformation of the individual molecules is very similar in both polymorphs, although free rotations were possible for the phenyl ring and for the three O-H groups. O-H center dot center dot center dot O linked one-dimensional isostructural molecular strings in the two forms weave differently by weak intermolecular interactions to produce the dimorphs. Striking difference is seen in the ``zipping'' of molecular layers via phenyl center dot center dot center dot phenyl contacts; thermodynamic crystals of form I utilize a well-recognized ``edge-to-face'' herringbone pattern, making C-H center dot center dot center dot pi interactions, whereas the kinetic crystals of form II show rather uncommon ``edge-to-edge'' organization, which makes short Ph-H center dot center dot center dot H-Ph contacts.

1 aBhosekar, Gaurav, V.1 aMurali, Chebrolu1 aGonnade, Rajesh, G.1 aShashidhar, M., S.1 aBhadbhade, Mohan, M. uhttps://library.ncl.res.in/content/identical-molecular-strings-woven-differently-intermolecular-interactions-dimorphs-myo-102132nas a2200253 4500008004100000022001400041245017900055210006900234260007300303300001400376490000800390520117100398653000801569653001301577653001501590653001801605653002201623653000801645100002101653700002701674700002401701700002501725856012801750 2007 eng d a0927-775700aInvestigating organization of molecules that facilitates intermolecular acyl transfer in crystals: reactivity and x-ray structures of O-benzoyl-myo-inositol 1,3,5-orthoesters0 aInvestigating organization of molecules that facilitates intermo aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcFEB a1153-11590 v2933 a

{Crystal structure analysis of racemic 2,6-di-O-benzoyl-myo-inositol 1,3,5-orthobenzoate reveals helical organization of the molecules, remarkably similar to that observed earlier in crystals of racemic 2,6-di-O-benzoyl-myo-inositol 1,3,5-orthoformate. Both these dibenzoates are isostructural despite the bulkier phenyl substituent in place of hydrogen. The latter compound shows highly facile intermolecular benzoyl transfer reactivity in its crystals and as anticipated from the crystal structure, the orthobenzoate indeed exhibits facile benzoyl transfer reactivity in its crystals. 2-O-Benzoyl-myo-inositol 1,3,5-orthoformate and the corresponding orthobenzoate also undergo transesterification in their crystals, but the specificity of acyl transfer is very low, and the reaction yields a mixture of products. The parameters of helical molecular assembly that facilitates acyl transfer in crystals have been investigated. A comparison of the molecular assemblies and lattice interactions in crystals of all the four compounds with the observed reactivity patterns show that facile acyl transfer reaction is brought about by a modular ``reaction tunnel''

10aAOT10aCdS-Ag2S10acore-shell10aNanoparticles10aw/o microemulsion10aXPS1 aMurali, Chebrolu1 aShashidhar, Mysore, S.1 aGonnade, Rajesh, G.1 aBhadbhade, Mohan, M. uhttps://library.ncl.res.in/content/investigating-organization-molecules-facilitates-intermolecular-acyl-transfer-crystals-002641nas 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

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.

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-001739nas a2200241 4500008004100000022001400041245011700055210006900172260007700241300001200318520085800330653001401188653001801202653001401220653001301234653002201247653001301269653001301282100002101295700002301316700002701339856013101366 2010 eng d a1434-193X00aIntramolecular hydrogen abstraction in radicals derived from inositol 1,3-acetals: efficient access to cyclitols0 aIntramolecular hydrogen abstraction in radicals derived from ino aPO BOX 10 11 61, D-69451 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcFEB a755-7643 a

The benzylidene acetals obtained by cleavage of the orthobenzoate moiety in myo-mositol 1,3,5-orthobenzoate were used to prepare mono- as well as di-deoxy inositol derivatives via their xanthates. The dideoxygenation is a result of intramolecular abstraction of the benzylidene acetal hydrogen and subsequent cleavage of the acetal ring. Such a cleavage does not take place in analogous acetals derived from other orthoesters. The 1,3-acetals derived from myoinositol 1,3,5-orthoesters were also used to prepare neo-inositol and isomeric deoxy-amino inositols, Most of the reactions in these synthetic sequences starting from myo-inositol give one product in each step. The results presented here show that myo-inositol 1,3,5-orthobenzoate offers many advantages over other orthoesters for the synthesis of cyclitol derivatives from myo-inositol.

10acyclitols10aDeoxygenation10aInosamine10aInositol10aRadical reactions10aRadicals10aXanthate1 aMurali, Chebrolu1 aGurale, Bharat, P.1 aShashidhar, Mysore, S. uhttps://library.ncl.res.in/content/intramolecular-hydrogen-abstraction-radicals-derived-inositol-13-acetals-efficient-access-0