Carboxylic acids and derivatives

A carboxylic acid 羧酸 has the $\text{–COOH}$ (carboxyl) functional group. It is a weak acid.

Vinegar is a dilute solution of ethanoic acid, a carboxylic acid

Making carboxylic acids

• oxidation 氧化 of a primary alcohol 醇 or an aldehyde 醛 with acidified $\text{K}_2\text{Cr}_2\text{O}_7$ or $\text{KMnO}_4$, with reflux 回流 (so it is fully oxidised).
• hydrolysis 水解 of a nitrile 腈 with dilute acid or alkali, then acidifying.
• hydrolysis of an ester 酯 with dilute acid or alkali and heat, then acidifying.

Reactions of carboxylic acids

These reactions all show that carboxylic acids are acids:

• with a reactive metal (a redox 氧化还原 reaction): gives a salt 盐 and hydrogen.

• with an alkali (a neutralisation 中和): gives a salt and water.

• with a carbonate 碳酸盐: gives a salt, water and carbon dioxide. The fizzing of $\text{CO}_2$ is a test for a carboxylic acid.

Carboxylic acids behave as acids: a salt with a metal (+ H$_2$), with an alkali (+ water), or with a carbonate (+ water + CO$_2$ — the fizz is a test)

Two reactions change the functional group:

• esterification 酯化 with an alcohol (concentrated $\text{H}_2\text{SO}_4$ catalyst) gives an ester.
• reduction 还原 by $\text{LiAlH}_4$ gives a primary alcohol.

An ester has the $\text{–COO–}$ group. It often smells sweet or fruity.

Esters give many fruits and perfumes their sweet smell

Making esters

An ester forms in a condensation 缩合 reaction between an alcohol and a carboxylic acid, with concentrated $\text{H}_2\text{SO}_4$ as catalyst. A water molecule is lost, and the reaction is reversible:

Esterification is a condensation: the –OH from the acid and the –H from the alcohol leave as water, forming the C–O–C ester link

Hydrolysis of esters

Hydrolysis splits the ester back apart. The conditions change the products:

• dilute acid and heat: reversible. Gives back the carboxylic acid and the alcohol.
• dilute alkali and heat: not reversible. Gives the alcohol and the salt of the carboxylic acid (the carboxylate ion).

Hydrolysing an ester: dilute acid (reversible) gives the carboxylic acid and alcohol; dilute alkali (not reversible) gives the carboxylate salt and alcohol

Worked example. Name the ester made from ethanol and propanoic acid, and say which part comes from which. In an ester name the alcohol gives the first word (the alkyl part) and the acid gives the second (the -oate part). Ethanol supplies $\text{C}_2\text{H}_5-$ and propanoic acid supplies $\text{CH}_3\text{CH}_2\text{COO}-$, so the ester is ethyl propanoate, $\text{CH}_3\text{CH}_2\text{COOC}_2\text{H}_5$. It is made by refluxing the two with a concentrated $\text{H}_2\text{SO}_4$ catalyst, and the reaction is reversible, so the yield is never complete. The trap is naming it backwards: propyl ethanoate is a completely different ester (made from propan-1-ol and ethanoic acid). Alcohol first, acid second.

• Carboxylic acids react with carbonates to give $\text{CO}_2$ (fizzing) — this distinguishes them from phenols.
• Explain acid strength via the delocalised carboxylate ion; electron-withdrawing groups (e.g. Cl) increase strength.
• Esterification (with concentrated $\text{H}_2\text{SO}_4$) is reversible; name esters as alkyl alkanoate.
• Know the products of acid vs alkaline hydrolysis of an ester (they differ).