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首页> 外文期刊>Journal of King Saud University >Hydrophobicity and kinetic inspection of hydroxide ion attack on some chromen-2-one laser dyes in binary aqueous–methanol and aqueous–acetone mixtures: Initial state-transition state analysis
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Hydrophobicity and kinetic inspection of hydroxide ion attack on some chromen-2-one laser dyes in binary aqueous–methanol and aqueous–acetone mixtures: Initial state-transition state analysis

机译：疏水性和氢氧根离子对二甲基水-甲醇和水-丙酮混合物中某些铬-2-二酮激光染料侵蚀的动力学检查：初始状态-过渡态分析

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摘要

In the present study, reactivity base-catalyzed hydrolysis of 7-dimethylamino-4-methyl-2H-chromen-2-one (DMAC) and 7-diethylamino-4-methyl-2H-chromen-2-one (DEAC) in binary aqueous–methanol and aqueous–acetone mixtures was examined at 298 K. Kinetic results, rate laws and reaction mechanisms were established. Moreover, the change in the activation energy barrier of the investigated compounds from water to water–methanol and water–acetone mixtures was estimated from the kinetic data. Base-catalyzed hydrolysis of (DMAC) and (DEAC) in aqueous–methanol and aqueous–acetone mixtures follows a rate law with k obs = k 2 [OH]. The decrease in the rate constants of (DMAC) and (DEAC) as the proportion of methanol and acetone is due to the destabilization of OH ? ion. The solubilities of the studied compounds, DMAC and DEAC in water–methanol and water–acetone mixtures were established and their transfer chemical potentials were calculated. Solvent effect on reactivity trends of the investigated compounds has been analyzed into initial and transition state components by using the transfer chemical potentials of the reactants and the kinetic data of the studied compounds. The decrease in the observed rate constant values ( k obs ) of the base hydrolysis of DMAC and DEAC with increasing of methanol% or acetone% is dominated by the initial state (IS).
机译：在本研究中，反应性碱催化的二甲基7-二甲基氨基-4-甲基-2H-铬-2-酮（DMAC）和7-二乙基氨基-4-甲基-2H-铬-2-酮（DEAC）的水解在298 K下检查了甲醇水溶液和丙酮水溶液的混合物。建立了动力学结果，速率规律和反应机理。此外，根据动力学数据估算了所研究化合物从水到水-甲醇和水-丙酮混合物的活化能垒的变化。在水-甲醇和水-丙酮混合物中，碱催化的（DMAC）和（DEAC）水解遵循k obs = k 2 [OH]的速率规律。作为甲醇和丙酮的比例，（DMAC）和（DEAC）的速率常数的降低是由于OH-的不稳定。离子。建立了所研究化合物DMAC和DEAC在水-甲醇和水-丙酮混合物中的溶解度，并计算了它们的转移化学势。通过使用反应物的转移化学势和所研究化合物的动力学数据，已将溶剂对所研究化合物的反应趋势的影响分析为初始和过渡态组分。 DMAC和DEAC的碱水解的观察到的速率常数值（k obs）随甲醇％或丙酮％的增加而降低，主要由初始状态（IS）决定。

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