Mechanism acetal hydrolysis

Basing your answers on the general mechanism for the first stage of acid catalyzed acetal hydrolysis... 

Fig. 8.1. Representation of transition states for the first stage of acetal hydrolysis, (a) Initial C—O bond breaking (b) concerted mechanism with C—O bond breaking leading O—H bond formation (c) concerted mechanism with proton transfer leading C—O bond breaking (d) initial proton transfer.

Fig. 8.2. Contour plot showing a favOTed concerted mechanism for the first step in acetal hydrolysis, in which proton transfer is more complete in the transition state than C—O bond breaking.

This results in a pH-rate profile as shown in Fig. 8.P21, with the acetate catalysis being signifieant in the pH range 3-6. Discuss how this catalysis by acetate ion might oeeur. What are the most likely mechanisms for hydrolysis at pH < 2 and pH > 7, where the rates are linear in [H+] and [ OH], respectively ... 

The mechanisms for hydrolysis of 0,5-acetals have been reviewed. The following acid-catalyzed cleavage rates show that the 0,5-acetals have a stability that lies between thioacetals and acetals ... 

Naturally occurring compounds called cyanogenic glycosides, such as lotau-stralin, release hydrogen cyanide, HCN, when treated with aqueous acid. The reaction occurs by hydrolysis of the acetal linkage to form a cyanohydrin, which then expels HCN and gives a carbonyl compound-fa) Show the mechanism of the acetal hydrolysis and the structure of the cyanohydrin that results. 

The mechanism, which involves initial formation of a hemiacetalj is the reverse of that given for acetal hydrolysis (10-6) ... 

The carbonyl group can be deprotected by acid-catalyzed hydrolysis by the general mechanism for acetal hydrolysis (see Part A, Section 7.1). A number of Lewis acids have also been used to remove acetal protective groups. Hydrolysis is promoted by LiBF4 in acetonitrile.249 Bismuth triflate promotes hydrolysis of dimethoxy, diethoxy, and dioxolane acetals.250 The dimethyl and diethyl acetals are cleaved by 0.1-1.0 mol % of catalyst in aqueous THF at room temperature, whereas dioxolanes require reflux. Bismuth nitrate also catalyzes acetal hydrolysis.251... 

This is known as specific add catalysis, specific in that H30 is the only acidic species that catalyses the reaction the reaction rate is found to be unaffected by the addition of other potential proton donors (acids) such as NH4 , provided that [H3Offi], i.e. pH, is not changed, indirectly, by their addition. The mechanism of the above acetal hydrolysis is believed to be,... 

It is clear that the high efficiency is a property of the salicylate system and is not limited to acetal hydrolysis. Similar highly efficient catalysis is observed also in the hydrolysis of salicyl phosphate [12], and a similar mechanism appears to be involved (Bromilow and Kirby, 1972). The essential structural... 

As one might expect the rate of p-nitrophenyl heptanoate hydrolysis increased at low ethanol concentrations as a result of apolar binding. The rate of p-nitrophenyl acetate hydrolysis also increased markedly at low ethanol concentration. This finding was explained by a conformational effect on the polymer, that is, lower ethanol concentration brings about a shrinkage of the polymer, which increases concerted interactions of the imidazole residues. The hydrolysis of 3-nitro-4-dodecanoyloxybenzoate was found to be 1700 times faster in the presence of poly[4(5)-vinylimidazole] compared to free imidazole (77). A double-displacement mechanism was demonstrated for this system (75). 

Prior to 1967 acetal hydrolysis had been found to be a specific-acid catalysed reaction with the accepted mechanism [equation (46)] involving fast pre-equilibrium protonation of the acetal by hydronium ion, followed by unimolecular rate-determining decomposition of the protonated intermediate to an alcohol and a resonance stabilized carbonium ion (Cordes, 1967). An A-1 mechanism was supported by an extremely large body of evidence, but it appeared unlikely that such a mechanism could expledn the... 

FIG. 4. An overall reaction mechanism for 4-nitrophenyl acetate hydrolysis catalyzed... 

Although, so far in this section, we have discussed the kinetic evidence in terms of the A-l and A-2 mechanisms favoured by Bunton et al. (p. 224), the same points which give rise to differences in detailed interpretation of mechanism for hydrolysis of acyl halides apply with equal weight to the hydrolysis of anhydrides. Butler and Gold67,68,298,299 have studied the spontaneous hydrolysis of acetic anhydride and presented the following scheme. 

The formation or the hydrolysis of an acetal function proceeds by the mechanism described in Fig. 16 in which oxonium ions and hemiacetals occur as intermediates. It has also been established (76) that the rate determining step in acetal hydrolysis is generally the cleavage of the C—bond of the protonated acetal 100 to form the oxonium ion 111, This ion is then rapidly hydrated to yield the protonated hemiacetal 112 which can give the aldehyde product after appropriate proton transfers. It is pertinent therefore to find out if stereoelectronic effects influence the rate determining step (110 111) of this hydrolysis reaction. 

Formulating credible mechanisms, i.e. accounting for all the electron movements and bonding changes in an acid- or base-catalysed reaction, is a difficult task although the framework on which the final mechanism is based is relatively easy to write. For this reason, and in the absence of evidence suggesting otherwise, a mechanism is conventionally illustrated as a series of steps as this enables the electron accounting to be most easily determined. This is illustrated by the mechanism for acid-catalysed acetal hydrolysis (Scheme 11.1a) shown... 

The mechanism of acetal hydrolysis is the reverse of acetal formation. The first four steps convert the acetal to the hemiacetal. 

D-Altrosan is a glycoside. The anomeric carbon—the one with two oxygen substituents—has an alkoxy group attached to it. Hydrolysis of D-altrosan follows the general mechanism for acetal hydrolysis. 

Under basic conditions, the hydroxide ion acts as the nucleophile. For example, the mechanism of hydrolysis of ethyl acetate is shown (in fig.K). However, the mechanism does not stop here. The carboxylic acid which is formed reacts with sodium... 

One can also acetalize carbonyl compounds completely without using the alcohol in excess. This is the case when one prepares dimethyl or diethyl acetals from carbonyl compounds with the help of the ortho formic acid esters trimethyl ortho formate HC(OCH3)3 or triethyl ortho formate HC(OC2H5)3, respectively. In order to understand these reactions, one must first clearly understand the mechanism for the hydrolysis of an orthoester to a normal ester (Figure 9.13). ft corresponds nearly step by step to the mechanism of hydrolysis of 0,0-acetals, which was detailed in Figure 9.12. The fact that the individual steps are analogous becomes very clear (see Figure 9.13) when one takes successive looks at... 

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