- Chelate ring sequence effects on thermodynamic, kinetic and electron-transfer properties of copper(II/I) systems involving macrocyclic lisands with S4 and NS3 donor sets
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The kinetic behavior of electron-transfer reactions involving several copper(II/I) complexes has previously been attributed to a dual-pathway "square scheme" mechanism in which changes in the coordination geometry occur sequentially, rather than concertedly, with the electron-transfer step. In the case of 14-membered macrocyclic quadridentate ligand complexes studied to date, the major geometric change appears to be the inversion of two coordinated donor atoms during the overall electron-transfer process. However, the relative importance of these two inversions has been a matter of speculation. In the current investigation, a comparison is made of Cu(II/I) systems involving two pairs of ligands with S4 and NS3 donor sets: 1,4,8,11-tetrathiacyclotctradecane ([14]aneS4-a); 1,4,7,11-tetrathiacyclotetradecane ([14]aneS4-b); 1,4,8-trithia-11-azacyclotetradecane ([14]aneNS3-fl); and 1,7,11-trithia-4-azacyclotetradecane ([14]aneNS3-b). In each pair of ligands, isomer a has the common chelate ring size sequence 5,6,5,6 while isomer b has the sequence 5,5,6,6. A crystal structure for [CuII([14] aneNS3-&)(H2O)](ClO4)2 demonstrates that, when coordinated to Cu(II), the b isomers stabilize the relatively rare ligand conformation designated as conformer II in which one donor atom is oriented opposite to the other three relative to the plane of the macrocycle. This eliminates one of the donor atom inversion steps which normally occurs during Cu(II/I) electron transfer. The copper complexes formed with these a and b isomers are examined in terms of (i) their CuIIL and CuIL stability constants, (ii) their CuIIL formation and dissociation rate constants, (iii) their CuII/IL redox potentials and (iv) their apparent electron self-exchange rate constants. Of the two donor atom inversions which occur in the case of the a-isomer complexes, the specific donor atom inversion which is common to the b-isomer complexes is judged to exhibit the larger energy barrier. Thus, it is presumed to represent the rate-limiting process responsible for the onset of "gated" electron transfer in previous studies on a-isomer complexes. The Royal Society of Chemistry 2003.
- Galijasevic, Semira,Krylova, Ksenia,Koenigbauer, Michael J.,Jaeger, Gregory S.,Bushendorf, Jeffery D.,Heeg, Mary Jane,Ochrymowycz, Leo A.,Taschner, Michael J.,Rorabacher, David B.
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- Face-to-face stacking in sulfonamide based bis-ethylene bridged heteroaromatic dimers
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Four sulfonamide based bis-ethylene bridged heteroaromatic dimers were synthesized for analysis of their structural and conformational properties. Interestingly, all models showed intramolecular offset face-to-face stacking between the tosyl group and heteroaromatic system in their solid state conformations. 1H NMR of the solutions revealed that the conformations were not far off from the solid state stacked geometry. However, gaseous state optimizations of different conformers divulged that the crystal structures were the lowest energy conformers.
- Kumar, Ranjeet,Rai, Sunil K.,Singh, Praveen,Gaurav, Archana,Yadav, Pratima,Khanna, Ranjana S.,Gupta, Hariom,Tewari, Ashish K.
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p. 97205 - 97211
(2015/12/01)
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- POLYMORPHIC FORM OF 5-(4-[4-(5-CYANO-1H-INDOL-3-YL) BUTYL] PIPERAZIN-1-YL) BENZOFURAN-2-CARBOXAMIDE AND PROCESS FOR PREPARING THEREOF
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The present invention provides a solid state Form-Z of 5-(4-[4-(5-cyano-1H-indol-3-yl)butyl]piperazin-1-yl)benzofuran-2-carboxamide. The present invention also provides a process for preparing Form-Z of 5-(4-[4-(5-cyano-1H-indol-3-yl)butyl]piperazin-1-yl)benzofuran-2-carboxamide comprising the steps of i) reacting solid state form of 5-(1-piperazinyl)benzofuran-2-carboxamide or its salts with 3-(4-chlorobutyl)-1H-indole-5-carbonitrile an organic solvent in presence of a base to obtain crude vilazodone free base; ii) purifying the crude vilazodone free base of step (i) in an organic solvent; iii) treating the purified vilazodone free base of step (ii) with an organic solvent to obtain solid state form-Z of vilazodone. The present invention further provides a pharmaceutical composition comprising a therapeutically effective amount of an amorphous form of vilazodone hydrochloride and use of solid state Form-Z of vilazodone for the treatment of major depressive disorders.
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Paragraph 0085
(2014/07/08)
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- POLYMORPHIC FORM OF 5-(4-[4-(5-CYANO-1H-INDOL-3- YL)BUTYL]PIPERAZIN-1-YL) BENZOFURAN-2-CARBOXAMIDE
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The present invention relates to a process for the preparation of 5-(4-[4-(5- cyano- 1 H-indol-3 -yl)butyl] piperazin- 1 -yl)benzofuran-2-carboxamide of Formula (1) or its pharmaceutically acceptable salt, solvates or hydrates thereof. In particular, the present invention provides a novel intermediate compound, 5-(4-substitutedpiperazin- 1-yl)benzofuran-2-carboxamide of Formula (X). The present invention further provides solid state form of 5-(4-[4-(5-cyano-1H-indol-3- yl) butyl]piperazin-1-yl)benzofuran-2-carboxamide of Formula (1) and process for its preparation.
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Page/Page column 23
(2014/01/07)
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- Structural analysis of bis-amidines and bis-nitriles in solid-state by combining NMR spectroscopy and molecular modeling
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The paper presents the analysis of the structures of four novel sulfonamide-based bis-amidines, and four novel interesting intermediates leading to them, named bis-nitriles, in solid-state based on 13C CP/MAS NMR spectroscopy and theoretical calculations of shielding constants at DFT level of theory. We have observed double 13C resonances in solid-state spectra as compared with solution spectra. The considerations of experimental chemical shifts followed by shielding computations allowed us to define essential geometric details regarding the most probable conformations in solid-state. All compounds have one independent molecule in the asymmetric unit, and a main reason of splittings of NMR signals in solid-state is different orientation of alkoxy fragments (methyl groups and linker) with reference to benzene rings.
- Zabiński, Jerzy,Maciejewska, Dorota,Ka?mierczak, Pawe?
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experimental part
p. 132 - 140
(2009/10/01)
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- New substituted spiro[cycloalkyl-1,3'-indo]-2'(1'H)-one derivatives and their use as p38 mitogen-activated kinase inhibitors
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This invention is directed to new inhibitors of the p38 mitogen-activated protein kinase having the general formula (I) to processes for their preparation; to pharmaceutical compositions comprising them; and to their use in therapy.
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Page/Page column 36
(2009/10/21)
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- INDAZOLE COMPOUND AND PHARMACEUTICAL USE THEREOF
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The present invention can provide a cancer treatment drug containing, as an active ingredient, a substance selected from the group consisting of an indazole compound of the following formula (I), a pharmaceutically acceptable salt, a hydrate, a water adduct and a solvate:
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(2010/11/24)
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- Enantiomers of 1-[(4-chlorophenyl)phenylmethyl]-4-[(4-methylphenyl) sulfonyl]piperazine
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Levorotatory and dextrorotatory enantiomers of 1-[(4-chlorophenyl)phenylmethyl]-4-[(4-methylphenyl)sulfonyl]piperazine of the formula STR1 their preparation and use for the preparation of substantially optically pure enantiomers of 1-[(4-chlorophenyl)phenylmethyl]piperazine, which are themselves valuable intermediate products for the preparation of optically active therapeutic compounds having a very high degree of optical purity.
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- Synthesis and antinociceptive activity of ring substituted N-[(2-phenyl-2-hydroxy)ethyl]-4-phenyl-4-carboethoxypiperidines
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A series of phenyl substituted N-[(2-phenyl-2-hydroxy)ethyl]-4-phenyl-4-carboethoxylpiperidine were synthesized and their antinociceptive activity tested in mice and compared with morphine sulphate. All compounds demonstrated antinociceptive activity in both the hot plate and the writhing tests. The studies showed that the antinociceptive activity is dependable on both the nature and the position of the substituent on the phenyl ring. Antagonism study with naloxone, suggests possible interaction of the new compounds with the opioid receptors.
- Al-Rashood,Madani,Ginawi,Ashraf,El-Obeid
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p. 1242 - 1245
(2007/10/02)
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- 1-Triarylalkyl-4-phenyl-4-piperidine carboxylic acids and derivatives
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The present invention encompasses compounds of the formula STR1 wherein the Alk is straight or branched chain alkylene containing 2-4 carbon atoms; Ar and Ar' are phenyl, Alkyl substituted phenyl wherein the alkyl contains from 1-4 carbon atoms or halo substituted phenyl; Ar" is phenyl, alkyl substituted phenyl wherein the alkyl contains 1-4 carbon atoms, halo substituted phenyl or pyridyl; X is hydrogen, halogen, trifluoromethyl or alkyl having from 1-4 carbon atoms; R is hydrogen, alkyl having from 1-7 carbon atoms, alkenyl having 3-7 carbon atoms, Ar" as herein before defined, or a cation selected from the group consisting of sodium, potassium, ammonium or calcium/2. Compounds of the present invention are potent antidiarrheal agents with little, if any, central nervous system activity.
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- 1-(3,3,3-Triarylalkyl)-4-phenyl-piperidinealkanols
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The present invention encompasses compounds of the formula STR1 and pharmaceutically acceptable acid addition salts thereof wherein the Alk is straight or branched chain alkylene containing 2-4 carbon atoms; M is alkylene having 1-4 carbon atoms; Ar and Ar' are phenyl, alkyl substituted phenyl wherein the alkyl contains from 1-4 carbon atoms or halo substituted phenyl; Ar" is phenyl, alkyl substituted phenyl wherein the alkyl contains 1-4 carbon atoms, halo substituted phenyl or pyridyl; X is hydrogen, halogen, trifluoromethyl or alkyl having from 1-4 carbon atoms; R is hydrogen alkyl having from 1-7 carbon atoms or an alkanoyl having from 2-5 carbon atoms. These compounds are potent antidiarrheal agents characterized by little, if any, central nervous system activity.
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