ISSN:
0021-8383
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Electrochemical Oxidation of Organic Compounds in Fluorsulfuric Acid. X. Effect of the Increase in Acidity on the Anodic Behavior of Some Aromatic Compounds in the HSO3F—SbF5-SystemThe effect of the acidity on the anodic behavior of some aromatic nitrils, nitro compounds, amines, sulfonyl fluorides, carbonyl compounds, hydrocarbons, benzylic acetates and methoxy compounds is investigated by cyclic voltammetry in HSO3F and HSO3F—SbF5 (molecular ratio 15:1 and 3:1) at -76°C and in some cases in HSO3F—SbF5 (1:1) at -40°C. With increasing content of SbF5 in most cases a positive shift of the anodic half-peak potentials Δ Ep/2 is found, which depends on the type and on the strength of the interaction with the superacidic solvent. Δ Ep/2 increases from the protonated functional groups in the series —NH3⊕ (0.00 V), —CN (0.05-0.10 V), —SO2F (0.10-0.20 V), —COR (0.20-0.40 V), —NO2 (0.30-0.60 V), —OCH3 (〉0.8 V) to benzoylium ions (0.45-0.60 V), benzyl cations (0.60-0.80 V) and arenium ions (1.10-1.30 V). Besides, the anodic behavior depends to a large extent on the deprotonation rate of the substrate, which occurs precedingly to, simultaneously with or subsequent to the electron transfer.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19853270204
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