32461-97-5Relevant articles and documents
Effect of alkyl group size on the mechanism of acid hydrolyses of benzaldehyde acetals
Belarmino, Alexanders T. N.,Froehner, Sandro,Zanette, Dino,Farah, Joao P. S.,Bunton, Clifford A.,Romsted, Laurence S.
, p. 706 - 717 (2003)
Hydrolyses 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 Broonsted 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, v, 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.
A Ta/W mixed addenda heteropolyacid with excellent acid catalytic activity and proton-conducting property
Li, Shujun,Peng, Qingpo,Chen, Xuenian,Wang, Ruoya,Zhai, Jianxin,Hu, Weihua,Ma, Fengji,Zhang, Jie,Liu, Shuxia
, p. 1 - 7 (2016/08/12)
A new HPAs H20[P8W60Ta12(H2O)4(OH)8O236]·125H2O (H-1) which comprises a Ta/W mixed addenda heteropolyanion, 20 protons, and 125 crystalline water molecules has been prepared through ion-exchange method. The structure and properties of H-1 have been explored in detail. AC impedance measurements indicate that H-1 is a good solid state proton conducting material at room temperature with a conductivity value of 7.2×10?3?S?cm?1 (25?°C, 30% RH). Cyclic voltammograms of H-1 indicate the electrocatalytic activity towards the reduction of nitrite. Hammett acidity constant H0 of H-1 in CH3CN is ?2.91, which is the strongest among the present known HPAs. Relatively, H-1 exhibits excellent catalytic activities toward acetal reaction.
