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Authors = Lamia Yaakoubd

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19 pages, 358 KiB  
Article
Correlation of the Rates of Solvolysis of Two Arenesulfonyl Chlorides and of trans-β-Styrenesulfonyl Chloride — Precursors in the Development of New Pharmaceuticals
by Zoon Ha Ryu, Sang Wok Lee, Malcolm J. D’Souza, Lamia Yaakoubd, Samantha E. Feld and Dennis N. Kevill
Int. J. Mol. Sci. 2008, 9(12), 2639-2657; https://doi.org/10.3390/ijms9122639 - 17 Dec 2008
Cited by 12 | Viewed by 13243
Abstract
Additional specific rates of solvolysis have been determined, mainly in fluoroalcohol containing solvents, for benzenesulfonyl chloride (1) and p-nitrobenzenesulfonyl chloride (2). For trans-β-styrenesulfonyl chloride (3), a study has been carried out in 43 pure and binary solvents, covering a wide range of [...] Read more.
Additional specific rates of solvolysis have been determined, mainly in fluoroalcohol containing solvents, for benzenesulfonyl chloride (1) and p-nitrobenzenesulfonyl chloride (2). For trans-β-styrenesulfonyl chloride (3), a study has been carried out in 43 pure and binary solvents, covering a wide range of hyroxylic solvent systems. For the specific rates of solvolyses of each of the three substrates, a good correlation was obtained over the full range of solvents when the extended Grunwald-Winstein equation was applied. The sensitivities to changes in solvent nucleophilicity and solvent ionizing power are similar to values determined earlier and an SN2 process is proposed. For 3, kinetic solvent isotope effects of 1.46 for kH2O/kD2O and 1.76 for kMeOH/kMeOD were determined. These are also compared to literature values for other sulfonyl chlorides. Full article
(This article belongs to the Special Issue Grunwald-Winstein Equations – 60 Years & Counting)
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12 pages, 283 KiB  
Article
Concerted Solvent Processes for Common Sulfonyl Chloride Precursors used in the Synthesis of Sulfonamide-based Drugs
by Malcolm J. D’Souza, Lamia Yaakoubd, Stacey L. Mlynarski and Dennis N. Kevill
Int. J. Mol. Sci. 2008, 9(5), 914-925; https://doi.org/10.3390/ijms9050914 - 24 May 2008
Cited by 16 | Viewed by 10616
Abstract
Specific rates of solvolysis in hydroxylic solvents available for the solvolysis of 2-thiophenesulfonyl chloride and phenylmethanesulfonyl chloride are supplemented by determining the values in fluoroalcohol-containing solvents. The data sets are then correlated using the extended Grunwald-Winstein equation. For both substrates, it is found [...] Read more.
Specific rates of solvolysis in hydroxylic solvents available for the solvolysis of 2-thiophenesulfonyl chloride and phenylmethanesulfonyl chloride are supplemented by determining the values in fluoroalcohol-containing solvents. The data sets are then correlated using the extended Grunwald-Winstein equation. For both substrates, it is found that a single correlation controls the influence of solvent over the full range of solvent composition. The sensitivities to solvent nucleophilicity and solvent ionizing power are compared to values available for other substrates. Three of these previous studies are upgraded by the incorporation of additional specific rate values from the recent literature. With a methyl, isopropyl, benzyl, aromatic or heteroaromatic group as the R group of RSO2Cl, a concerted SN2 mechanism is proposed for the solvolysis. Full article
(This article belongs to the Special Issue Grunwald-Winstein Equations – 60 Years & Counting)
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