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Kinetic and Theoretical Condiderations in the Hydrolysis of Iminocarbonates

DOI: 10.1039/P29880001653

Source and publish data:

Journal of the Chemical Society. Perkin transactions II p. 1653 - 1660 (1988)

Update date:2022-08-05

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Authors:

Katzhendler, JehoshuaKatzhendler, Jehoshua

Goldblum, AmiramGoldblum, Amiram

Ringel, IsraelRingel, Israel

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Article abstract of DOI:10.1039/P29880001653

Analysis of the pH-rate profiles for the hydrolysis of 4-methyl-2-(N-phenylimino)-1,3-dioxolane (1) and 2--4-phenyl-1,3-dioxolane (2) together with product distribution of compounds (1)-(5) and pK values estimated for the various ionic forms T0, T+, T+/-, and T- of the tetrahedral intermediates, enables the determination of the reactivity of the tetrahedral intermediates along their reaction pathways.At pH <6, the only products formed are the amine and the carbonate (C-N fission) and at pH >6 C-O bond fission increases to form carbamates.The transition point corresponds to pK values of 9.2 and 8.5 for compounds (1) and (2), respectively.It is proposed that in acidic solution C-N bond fission proceeds via T+ <*> T+/- -> P while at a moderate pH this bond fission proceeds via a proton-switch mechanism T0 -> T+/-.At pH > 11 the only product produced is the hydroxycarbamate (C-O fission) via its anionic intermediate T-.Mono- and gem-dimethyl substituted iminocarbonates T- undergo two modes of ring-opening.Employing MNDO/H calculations the relative stability (ΔHF) of the intermediates and their formed products was predicted and correlated with actual experimental product distribution.

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Product name:4-chlorophenoxymethyl-2-(N-phenylimino)-1,3-dioxolane

Cas No:120235-64-5

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