Aldehydes, Ketones and Carboxylic Acids: Step-by-Step Worked Examples (4)

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Question

Predict the product when acetaldehyde (CH3_3CHO) reacts with HCN. Show the mechanism and identify the type of reaction.

Solution — Step by Step

HCN adds across the C=O of an aldehyde. This is a nucleophilic addition — the cyanide ion (CN^-) is the nucleophile attacking the electrophilic carbonyl carbon.

HCN partially dissociates: HCN \rightleftharpoons H+^+ + CN^-. The CN^- ion attacks the carbonyl C of CH3_3CHO, breaking the π\pi-bond and pushing the electrons onto O.

Intermediate: CH3_3-C(CN)(H)-O^- (alkoxide).

The alkoxide picks up a proton from the medium (or HCN), giving the final product:

CH3_3-CH(OH)(CN) — known as 2-hydroxypropanenitrile (lactonitrile).

The C=O bond is polarized δ+\delta+C and δ\delta-O. CN^- attacks the δ+\delta+ carbon. After protonation, the OH and CN end up on the same carbon — the original carbonyl carbon.

Final answer: product is CH3_3-CH(OH)(CN), a cyanohydrin. Reaction: nucleophilic addition.

Why This Works

Carbonyl compounds are perfect substrates for nucleophiles because the C=O carbon is electron-poor. Aldehydes are more reactive than ketones because (a) less steric hindrance and (b) only one alkyl group donating electron density to the C.

The cyanohydrin product has a hydroxyl group and a nitrile, both useful for further synthesis — hydrolysing the nitrile to COOH gives an α\alpha-hydroxy acid (lactic acid in this case).

Alternative Method

Direct memorisation: aldehyde + HCN → cyanohydrin (general formula RCH(OH)CN). Pattern recognition saves you from drawing the mechanism on every question.

Remember the reactivity order for nucleophilic addition: HCHO > RCHO > R2_2CO. Formaldehyde reacts fastest; ketones slowest.

Common Mistake

Drawing the OH and CN on different carbons. Both end up on the original carbonyl carbon (which was the C of C=O). The mechanism doesn’t move the carbon backbone.

Confusing this with the haloform reaction (CH3_3CHO + halogen + base → carboxylic acid). HCN addition gives cyanohydrin; haloform gives a 1-1 carbon acid. Different reagents → different products.

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