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- W2017138919 abstract "The rates of the acid-catalyzed hydrolysis of methyl dimethyl-, diethyl-, diisopropyl-, and di-tert-butylphosphinate in D 2 SO 4 –D 2 O and of p-methoxybenzyl, p-chlaorobenzyl, p-nitrobenzyl, and benzyl diethylphosphinate in H 2 SO 4 – 70% w/w DMSO-H 2 O have been studied. The bell-shaped pH-rate profiles, the Bunnett–Olsen Φ (0.91 to 1.28), Bunnett w (2.28 to 3.52) and w* (−0.94 to +0.17), and Yates-McClelland r (0.61 to 2.6) values, and the entropies of activation (−18 to −24 eu) all support an A2 mechanism for the methyl esters. The suggested mechanism for the benzyl esters is a unimolecular hydrolysis (A a1 1). This conclusion is supported by the pH-rate profiles, the Φ r values (−0.12 to −0.29) and the entropies of activation (−4 to −7 eu). The pK a 's of the esters are also reported and they range between −2.4 to −3.3." @default.
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- W2017138919 date "1977-11-01" @default.
- W2017138919 modified "2023-09-26" @default.
- W2017138919 title "The acid-catalyzed hydrolysis of phosphinates. III. The mechanism of hydrolysis of methyl and benzyl dialkylphosphinates" @default.
- W2017138919 doi "https://doi.org/10.1139/v77-527" @default.
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