Carbonyl Group
Aldehydes and Ketones
Aldehydes and ketones are formed by the oxidation of alcohols; as summarized in the diagram below. The further oxidation of an aldehyde to a carboxylic acid is the basis of the Fehling's and Tollen's tests, since an aldehyde can be oxidised and a ketone can not.
It is also possible for us to go backwards, by reduction. The C=O bond is polar so the carbon becomes δ+ which means it can be attacked by a hydride ion (H-) that is supplied by reagents such as Sodium tetrahydridoborate (NaBH4). The mechanism for reducing an aldehyde to a primary alcohol is shown below.
Also, the same mechanism of nucleophillic addition applies to the addition of cyanide. Instead of an H, there would be NC:-. This reaction can form a racemate because attack by the cyanide nucleophille could occur on either side of the planar C=O bond.
Testing
There are two simple tests that you could use to distinguish between an aldehyde and ketone. You can use either Tollen's reagent or Fehling's solution; the two tests are outlined below.
| Testing Solution | Procedure | Result |
|---|---|---|
| Tollen's Reagent | An excess of aqueous ammonia is added to silver nitrate solution. This is gently warmed with the product being tested. | If an aldehyde is present it will reduce the complex ion: [Ag(NH3)2]+ to produce a silver mirror on the surface of the test tube. |
| Fehling's Solution | The Fehling's is added to the solution which turns it blue, and is then heated. | If an aldehyde is present the solution will turn red but a ketone will have no affect. |
Brief Note: Primary and secondary alcohols can be dehydrated so that the OH group is eliminated and the molecule becomes an alkene.
Carboxylic Acids and Esters
A carboxyic acid has the same functional groups as a carbonyl (C=O) and an alcohol (C-OH), however, they are both on the same carbon, which means they have different properties from either. So therefore it is a distinct homologous series with the functional group COOH.
As acids, carboxylic acids are weak. You can test for a carboxylic acid however by adding sodium hydrogencarbonate, and the gas CO2 is evolved.
CH3COOH + NaHCO3 ® CH3COONa + H2O + CO2
If a carboxylic acid is reacted an alcohol, in the presence of a strong acid catalyst, then an ester is formed. The esters are another homologous series that have the general structure as shown below.
Many people have trouble naming esters. But if you know the basic rules of organic nomenclature then it should be easy. The part highlighted in red comes from the carboxylic acid and is suffixed with -oate; for example, ethanoic acid becomes ethanoate. This is the part that has a carbonyl group. The alcohol contributes the other part. This bit is named in the same way all side chains are. So ethanol becomes ethyl ... Altogether, the molecule will the called ethyl ethanoate.
Esters often have pleasant smells. For example, ethyl pentanoate is said to smell of apple. Therefore, one of the uses of esters is in food flavouring. Other uses include as sovents, for example ethyl ethanoate is used as a solvent in glue. And esters can also be used as plasticisers, these are chemicals that are added to polymers (plastics) to make them less brittle.
Hydrolysis of Esters
Esters can be hydrolysed in the following reaction.
Ester + Alkali ® Alcohol + Carboxylate Salt
For example, the following is the reaction of ethyl ethanoate with sodium hydroxide.
CH3COOC2H5 + NaOH ® C2H5OH + CH3COONa
It is by this hydrolysis reaction that soaps are made. Since fats are esters, fats are boiled with an alkali which produces a 'fatty acid' and a carboxylate salt which is what we call the soap.
Acylation
Acyl chlorides and acyl anhydrides (see nomenclature) are commonly used in chemistry as intermediates. Below is the mechanism scheme for the reactions of acyl chlorides with a nucleophile which is a substitution-elimination reaction. In order to make it easier to understand it has been generalised. However, have a look at the individual mechanisms for the general form to be useful for you.
However, in industrial chemistry. ethanoic anhydride is more commonly used than ethanoyl chloride; for example, in the manufacture of aspirin. This is because it is cheaper, less reactive and so the reaction is easier to control; and HCl is not produced.