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ChemistryClass 123 marksmedium
Aldehydes, Ketones and Carboxylic Acids
Why do aldehydes and ketones undergo nucleophilic addition reactions? Give one example.
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The carbonyl group (C=O) is polar because oxygen is more electronegative than carbon, so the carbon carries a partial positive charge and the oxygen a partial negative charge. This makes the carbonyl carbon electrophilic, so it is readily attacked by nucleophiles, leading to nucleophilic addition. For example, with hydrogen cyanide (HCN), the addition gives a cyanohydrin: R-CHO + HCN -> R-CH(OH)-CN. Aldehydes are more reactive than ketones towards nucleophilic addition due to less steric hindrance and a greater positive charge on the carbonyl carbon.
R-CHO + HCN -> R-CH(OH)-CN
Marking-scheme points
- ✓C=O is polar; carbonyl carbon is electrophilic (partial positive)
- ✓Nucleophile attacks the carbonyl carbon (nucleophilic addition)
- ✓Example: R-CHO + HCN -> R-CH(OH)-CN (cyanohydrin)
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Aldehydes, Ketones and Carboxylic Acids
Why are carboxylic acids more acidic than phenols? How do electron-withdrawing groups affect their acidity?
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Carboxylic acids are more acidic than phenols because the carboxylate ion formed after the loss of the proton is stabilised by resonance in which the negative charge is spread equally over two electronegative oxygen atoms, making it very stable. In the phenoxide ion the negative charge is mainly on one oxygen and partly on less electronegative ring carbons, so it is less stabilised. Electron-withdrawing groups (like -Cl or -NO2) increase acidity because they further disperse and stabilise the negative charge of the carboxylate ion (for example, chloroacetic acid is stronger than acetic acid), while electron-releasing groups decrease acidity.
Marking-scheme points
- ✓Carboxylate ion: charge spread equally over two oxygen atoms (very stable)
- ✓Phenoxide ion is less stabilised
- ✓Electron-withdrawing groups increase acidity; electron-releasing groups decrease it
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Amines
How are primary amines prepared by the reduction of nitro compounds and by Hofmann's bromamide reaction?
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(1) Reduction of nitro compounds: a nitro compound is reduced (with H2/Ni, or Sn/HCl, or Fe/HCl) to a primary amine; for example, nitrobenzene is reduced to aniline, C6H5NO2 + 6[H] -> C6H5NH2 + 2H2O. (2) Hofmann's bromamide degradation: an amide is treated with bromine and a strong alkali (Br2 + NaOH/KOH) to give a primary amine with one carbon atom less than the amide, R-CONH2 + Br2 + 4NaOH -> R-NH2 + Na2CO3 + 2NaBr + 2H2O.
R-CONH2 + Br2 + 4NaOH -> R-NH2 + Na2CO3 + 2NaBr + 2H2O
Marking-scheme points
- ✓Reduction of nitro compound -> primary amine (nitrobenzene -> aniline)
- ✓Hofmann bromamide: amide + Br2 + NaOH -> amine with one carbon less
- ✓R-CONH2 + Br2 + 4NaOH -> R-NH2 + Na2CO3 + 2NaBr + 2H2O
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Amines
Why are amines basic in nature? Compare the basic strength of amines in the gaseous phase.
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Amines
How is benzenediazonium chloride prepared? Write one of its reactions (Sandmeyer reaction).
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Biomolecules
What are proteins? What is meant by denaturation of a protein?
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