The carbon with the The carbon with the C=O group in ketones CHO group in is always labelled from aldehydes is always the shortest end. labelled 1. Aldehydes Ketones have the have the suffix -al. suffix -one. The The longest straight longest straight chain chain is taken, to is taken, to determine determine the stem. the stem. Any side Any side chains are added at the beginning chains are added at the beginning with with their associated their associated positioning numbers. positioning numbers.
Reactions of Carbonyls Compounds
- Oxidation of Primary Alcohols Primary alcohols can be oxidised to aldehydes and then to carboxylic Potassium Dichromate acids. (K2Cr2O7) and concentrated sulfuric acid (H2SO4) are used as an oxidising agent. The aldehyde must be distilled immediately to prevent further oxidation. To make a carboxylic acid, the solution must be heated under reflux, before distilling the
Oxidising Aldehydes Aldehydes can be oxidised further to form carboxylic acids. Acidified Potassium Dichromate can be used as a suitable oxidising agent. Turning
Reactions of Carbonyls Compounds
- Oxidation of Secondary Alcohols Secondary alcohols can be oxidised to form ketones. Potassium Dichromate (K2Cr2O7) and concentrated sulfuric acid (H2SO4) are used as an oxidising agent. To make a ketone, the solution must be heated under reflux, before distilling the product off.
Reduction of aldehydes and ketones
For both reduction reactions, either Sodium Borohydride (NaBH4) or Lithium Aluminum Hydride (LiAlH4) can be used as a reducing agent.
Reduction is just the
opposite of oxidation so the reactions look very similar, just in reverse and with [H] used instead of [O].
Nucleophilic Addition of Aldehydes
and Ketones The nucleophile splits by heterolytic fission initially. As in alkenes, it then adds across the double bond, except in carbonyls it is across the C=O, rather than a C=C. This leaves an electron proficient oxygen which is attacked by an electrophile in solution, often a proton (H+). The reactions are the same for both aldehydes and ketones.
Carbonyl compound tests
Bradys Reagent 2,4-dinitrophenylhydrazine (2,4-DNPH) is mixed with methanol and sulfuric acid to form a solution. When added to an aldehyde or a ketone, a positive colour change to a yellow/orange precipitate is formed. This 2,4-DNPH derivative shows a C=O group is present. However it does not work for esters or carboxylic acids due to their extra resonance structures, in which the carbonyl carbon has a weaker positive charge, so is insufficiently electrophilic to split the 2,4-DNPH.
Carbonyl compound tests continued
Tollens Reagent (Ammoniacal Silver Nitrate) A weak oxidising agent made up of aqueous sodium hydroxide and silver nitrate to make a brown silver oxide precipitate. This is then added to dilute ammonia until the solid dissolves. It determines whether it is an aldehyde or a ketone. An aldehyde produces positive silver mirror precipitate, a ketone does not react. It works as an aldehyde can be oxidised whereas a ketone cannot, so the resulting carboxylic acid shows the change, whereas the ketone remains as it is.
Carbonyl compound tests continued
2 Once a compound has been identified as either a ketone or an aldehyde, it can be possible to then accurately determine the compound structure itself. The 2,4-DNPH derivative is impure, and when filtered and recrystallized, is made pure. Once dry, this solid can be melted, with its melting point recorded. This value can then be compared to a data value/book, to identify the original carbonyl compound.
Carbonyl compound tests continued
3 Alternatively, to determine an alcohol, react with ceric nitrate reagent (Ce (NO3)6) to produce a colour change (yellow to red). Carbonyl compounds do not react with ceric nitrate. Production of a magenta colour therefore indicates the presence of an alcohol group.
Carbonyl compound tests continued
4 Plus, aldehydes react with Schiff's reagent (bisulfite ion) to produce a colour change (magenta-coloured addition product). The sulfur in the bisulfite ion acts as a nucleophile and adds to the carbonyl carbon. Because this is such a large nucleophile, it will only add to a relatively simple carbonyl. This requires that the carbonyl be part of an aldehyde in which one of the R groups is the very small hydrogen, or a ketone having small R and R groups. A ketone with large groups attached to the carbonyl will not react with bisulfite.
Carbonyl compound tests continued
5 The iodoform test indicates the presence of an aldehyde or ketone in which one of the groups directly attached to the carbonyl carbon is a methyl group. In the iodoform test, the unknown is allowed to react with a mixture of iodine and base. This forms the carboxylic acid salt plus iodoform, a yellow precipitate. Formation of a yellow precipitate therefore indicates the presence of a methyl group directly attached to the carbonyl.