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Open AccessArticle

Oxidations of Benzhydrazide and Phenylacetic Hydrazide by Hexachloroiridate(IV): Reaction Mechanism and Structure–Reactivity Relationship

College of Chemistry and Chemical Engineering, Shandong University, Jinan 250014, China
Molecules 2020, 25(2), 308; https://doi.org/10.3390/molecules25020308
Received: 27 September 2019 / Revised: 30 December 2019 / Accepted: 9 January 2020 / Published: 12 January 2020
Benz(o)hydrazide (BH) is the basic aryl hydrazide; aryl hydrazides have been pursued in the course of drug discovery. Oxidations of BH and phenylacetic hydrazide (PAH) by hexachloroiridate(IV) ([IrCl6]2−) were investigated by use of stopped-flow spectral, rapid spectral scan, RP-HPLC and NMR spectroscopic techniques. The oxidation reactions followed well-defined second-order kinetics and the observed second-order rate constant k′ versus pH profiles were established over a wide pH range. Product analysis revealed that BH and PAH were cleanly oxidized to benzoic acid and phenylacetic acid, respectively. A reaction mechanism was proposed, resembling those suggested previously for the oxidations of isoniazid (INH) and nicotinic hydrazide (NH) by [IrCl6]2−. Rate constants of the rate-determining steps were evaluated, confirming a huge reactivity span of the protolysis species observed previously. The enolate species of BH is extremely reactive towards reduction of [IrCl6]2−. The determined middle-ranged negative values of activation entropies together with rapid scan spectra manifest that an outer-sphere electron transfer is probably taking place in the rate-determining steps. The reactivity of neutral species of hydrazides is clearly not correlated to the corresponding pKa values of the hydrazides. On the other hand, a linear correlation, logkenolate = (0.16 ± 0.07)pKenol + (6.1 ± 0.8), is found for the aryl hydrazides studied so far. The big intercept and the small slope of this correlation may pave a way for a rational design of new antioxidants based on aryl hydrazides. The present work also provides the pKa values for BH and PAH at 25.0 °C and 1.0 M ionic strength which were not reported before. View Full-Text
Keywords: benzhydrazide; phenylacetic hydrazide; hexachloroirridate(IV); oxidation; reaction mechanism; structure–reactivity relationship benzhydrazide; phenylacetic hydrazide; hexachloroirridate(IV); oxidation; reaction mechanism; structure–reactivity relationship
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MDPI and ACS Style

Zhang, X. Oxidations of Benzhydrazide and Phenylacetic Hydrazide by Hexachloroiridate(IV): Reaction Mechanism and Structure–Reactivity Relationship. Molecules 2020, 25, 308.

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