Dimensiosolvatic Effects. VI. Rates of Ionization of 2-Fluoro-4,4,5,5-tetramethyl-1,3-dioxolane: Dimensiosolvatic vs. Hydrogen-Bond Effects

doi:10.1246/BCSJ.72.1343

Paper

Dimensiosolvatic Effects. VI. Rates of Ionization of 2-Fluoro-4,4,5,5-tetramethyl-1,3-dioxolane: Dimensiosolvatic vs. Hydrogen-Bond Effects

Published Jun 1, 1999 · M. Ōki, H. Ikeda, S. Toyota

Bulletin of the Chemical Society of Japan

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Abstract

The title compound was prepared by treating 4,4,5,5-tetramethyl-1,3-dioxolan-2-yl acetate with cesium fluoride. Rates of ionization of this compound were determined in various solvents by the dynamic NMR technique. While effects due to polarity as well as solvent molecular size were observed in many solvents examined, the rates in solutions of which the solvent is capable of being an acceptor in hydrogen-bond formation with the substrate were unusually small, and this effect is diminished in bulky solvents. Such results are attributed to stabilization of the original state due to hydrogen-bond formation with the acidic C(2) – H group of the substrate in those solvents. The hydrogen-bond formation is hindered by the steric effects in bulkier solvents than in smaller solvents. The rates of contact ion pair and solvent-separated ion pair formations should be independently determined in 2-fluoro-4,4,5,5-tetramethyl-1,3-dioxolane, but so far no clear example which shows that the rate-limiting step is the solve...

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Rates of ionization of 2-fluoro-4,4,5,5-tetramethyl-1,3-dioxolane in various solvents show small hydrogen-bond formation effects, with steric effects hindering hydrogen-bond formation in bulkier solvents.

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

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Paper

Dimensiosolvatic Effects. VI. Rates of Ionization of 2-Fluoro-4,4,5,5-tetramethyl-1,3-dioxolane: Dimensiosolvatic vs. Hydrogen-Bond Effects

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References

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Photooxygenation of chromone-2-carboxylic acid in aerated ethanol solution produces 4-hydroxycoumarine, with chemiluminescence measuring successfully detecting the intermediate ketohydroperoxide.

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2-Fluoro-4,4,5,5-tetramethyl-1,3-dioxolane effectively determines the rate constants of contact and solvent-separated ion pair formations, with identical results for toluene-d 8 and chloroform-d solutions.

Acidity, Basicity, and the Stability of Hydrogen Bonds: Complexes of RO- + HCF3

The structure of RO-HCF3 complexes can be understood through electrostatic arguments rather than differences in acidity between ion and neutral states.

Dimensiosolvatic Effects. IV. Topomerization in Alkyl α-Chlorobenzyl Ethers and Insights into Mechanisms of Their Thermolyses

Topomerization in alkyl -chlorobenzyl ethers is ionic, enhanced in polar solvents and by electron-donating substituents, with smaller rates in bulky solvents and no effect on substrate concentration below 0.2 mol L1.

DIMENSIOSOLVATIC EFFECTS. III. QUANTIFICATION OF DIMENSIOSOLVATIC EFFECTS BY SOLVOLYSES OF 2-BROMOADAMANTANE IN WATER-ALCOHOL MIXTURES

Selectivity of 2-bromoadamantane in water-alcohol mixtures is almost constant at 1.0:0.8, independent of temperature, and can be used to measure dimensiosolvatic effects.

Citations

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This study developed a new and efficient strategy for the synthesis of coumarin-linked nicotinonitrile derivatives using a cooperative vinylogous anomeric-based oxidation mechanism, resulting in good to high yields under solvent-free conditions.

Ionically Tagged Magnetic Nanoparticles with Urea Linkers: Application for Preparation of 2-Aryl-quinoline-4-carboxylic Acids via an Anomeric-Based Oxidation Mechanism

Ionically tagged magnetic nanoparticles with urea linkers can efficiently prepare 2-aryl-quinoline-4-carboxylic acid derivatives under solvent-free conditions.