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Effect of Alkyl Group Size on the Mechanism of Acid Hydrolyses of Benzaldehyde Acetals
journal contribution
posted on 2003-01-07, 00:00 authored by Alexanders T. N. Belarmino, Sandro Froehner, Dino Zanette, João P. S. Farah, Clifford A. Bunton, Laurence S. RomstedHydrolyses of benzaldehyde acetals, PhCH(OR)2, are specific hydrogen-ion catalyzed when R =
methyl, n-butyl, but with secondary and tertiary alkyl derivatives, R = i-propyl, s-butyl, t-butyl,
t-amyl, hydrolyses are general-acid catalyzed. The Brønsted α values for both secondary and tertiary
alkyl groups are in the range: α = 0.57−0.61. A simple iterative procedure was developed to estimate
the individual rate constants for general-acid catalysis by the diacid and monoacid forms of succinic
acid buffer. Plots of log kobs (at [buffer] = 0 M) against pH are linear for the secondary and tertiary
acetals, and plots of log kH for the H3O+-catalyzed reaction, 13C and 1H chemical shifts, and 1JCH
coupling constants against the Charton steric parameter, ν, for alkoxy groups are linear. The second-order rate constant, kH, increases about 100-fold on going from R = Me to R = t-amyl, indicating
the significant role of steric effects on reactivity. Steric effects upon 13C NMR chemical shifts and
coupling constants indicate that increasing the bulk of the alkoxy moiety increases the electron
density at the carbon reaction center, which accelerates hydrolysis. Analysis of the Jencks−More−O'Ferrall free energy diagram for the reaction provides support for concerted proton transfer and
C−O bond breaking in the transition state for hydrolyses of benzaldehyde acetals with secondary
and tertiary alkyl groups in contrast to specific hydrogen catalysis with R = Me and n-Bu. All our
results are consistent with rate-determining acid hydrolysis of benzaldehyde dialkyl acetals to
hemiacetal intermediates that breakdown rapidly to benzaldehyde.
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13 C NMR chemical shifts1 H chemical shiftsAlkyl Group SizeCharton steric parameterbenzaldehyde acetalscarbon reaction centerlog k obs1 J CHhydrolysealkoxy moiety increasesH 3 Obenzaldehyde dialkyl acetalssuccinic acid bufferlog k HBenzaldehyde Acetals HydrolysescatalysiBr ønsted α valueshydrolysisconstantalkyl groupsamylbutyl