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In the following reaction:
carbonyl compound + MeOH $$\overset{\mathrm{HCl}}{\rightleftharpoons}$$ acetal
Rate of the reaction is the highest for:
We are dealing with the acid-catalysed conversion of a carbonyl compound to an acetal in methanol. The simplified mechanism proceeds through these key elementary steps:
$$\text{(1) Protonation of the carbonyl: }R_{2}C=O + H^+ \longrightarrow R_{2}C=OH^+$$
$$\text{(2) Nucleophilic attack by methanol: }R_{2}C=OH^+ + MeOH \longrightarrow R_{2}C(OMe)OH + H^+$$
The overall rate, to a very good approximation in the initial stages, is proportional to the concentrations of the species actually colliding in the slow step. After the fast proton-transfer of step (1), the slow or rate-determining step is generally step (2). Therefore we can write
$$\text{Rate} \propto [\text{protonated carbonyl}]\,[\text{MeOH}].$$
Now we compare the options on the basis of two independent factors that control this rate expression:
Factor 1: Nature of the carbonyl electrophile.
An aldehyde is more electrophilic than a ketone because:
(i) it has only one electron-donating alkyl group instead of two, so the carbonyl carbon bears a larger partial positive charge, and
(ii) it suffers less steric hindrance to nucleophilic attack.
Hence $$\text{Rate}_{\text{aldehyde}} > \text{Rate}_{\text{ketone}}.$$
Between the substrates listed, propanal (an aldehyde) is thus inherently faster than acetone (a ketone).
Factor 2: Concentration of the nucleophile MeOH.
The rate expression contains $$[\text{MeOH}],$$ so increasing the concentration of methanol directly raises the rate. Using methanol in excess means a higher $$[\text{MeOH}]$$ than in a stoichiometric amount.
Therefore $$\text{Rate}_{\text{excess MeOH}} > \text{Rate}_{\text{stoichiometric MeOH}}.$$
Let us rank the four options by systematically combining these two factors.
Step 1 - Substrate effect:
Propanal options (B and C) > Acetone options (A and D).
Step 2 - Methanol concentration effect (within each substrate type):
Excess MeOH (B and D) > Stoichiometric MeOH (A and C).
Combining both steps:
The single option that has the more reactive aldehyde and methanol in excess is Option B.
Mathematically, if we denote the proportionality constant as $$k$$ and use subscripts to distinguish situations, we can write
$$\text{Rate}_{\text{B}} = k[\text{propanal}\!-\!\text{H}^+][\text{MeOH}]_{\text{excess}},$$
$$\text{Rate}_{\text{C}} = k[\text{propanal}\!-\!\text{H}^+][\text{MeOH}]_{\text{stoich}},$$
and clearly $$[\text{MeOH}]_{\text{excess}} > [\text{MeOH}]_{\text{stoich}},$$ so $$\text{Rate}_{\text{B}} > \text{Rate}_{\text{C}}.$$
Any rate involving acetone will already be slower due to the less electrophilic carbonyl, cementing the conclusion that
$$\text{Rate}_{\text{B}} > \text{Rate}_{\text{D}} \gt \text{Rate}_{\text{C}} \gt \text{Rate}_{\text{A}}.$$
Hence, the correct answer is Option B.
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