Kinetics and Mechanism of the Pyridinolyses of O‐Methyl and O‐Ethyl Phenyl Phosphonochloridothioates in Acetonitrile
作者： Md. Ehtesham Ul Hoque , Hai Whang Lee
DOI: 10.1002/KIN.20773
关键词: Kinetic energy 、 Medicinal chemistry 、 Chemistry 、 Substituent 、 Organic chemistry 、 Break point 、 Leaving group 、 Free-energy relationship 、 Nucleophile 、 Acetonitrile 、 Kinetics
摘要: Kinetic studies on the reactions of O-methyl (2) and O-ethyl (3) phenyl phosphonochloridothioates with X-pyridines have been carried out in acetonitrile at 35.0°C. The pyridinolysis rates 2 are slightly faster than those 3. substituent effects X 3 similar. Hammett Bronsted plots nucleophiles biphasic concave upward a break point = 3-Ph for both substrates. stepwise mechanism rate-limiting leaving group departure from intermediate is proposed based βX values free energy relationship relationships rationalized by frontside nucleophilic attack TSf more basic pyridines backside TSb less
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