Carbonyl Compounds

Introduction
Carbonyl compounds contain the C=O group The bond contains a and bond Oxygen is more electronegative than carbon and so the bonding electrons are pulled towards the oxygen, making the bond polar The polar nature of the bond makes the carbon atom susceptible to attack from nucleophiles. Nucleophile a species with a lone pair of electrons that is used to form a bond with a + atom Aldehydes Have a hydrogen bonded to the C=O group Formulae can be represented RCHO (where R is an alkyl group or benzene ring) Ketones Do not have a hydrogen bonded to the C=O group Formulae can be represented RCOR Geometry Around the C=O Group The carbon atom has 2 single bonds, 1 double bond and 0 lone pairs, so the electrons in the 3 bonds repel each other an take up the position of maximum separation and minimum repulsion. This is a planar shape with bond angles of 120O. The planar shape makes it easy for nucleophiles to attack from above or below the plane, and so a single optical isomer is never formed with addition to carbonyl compounds. The polarity of the C=O bond is not cancelled out by the rest of the molecule, and so therefore aldehydes and ketones are polar molecules.

Physical Properties
Boiling Point The molecules are polar, so dipole-dipole forces as well as london forces exist. Intermolecular hydrogen bonding is not possible because neither aldehydes nor ketones have a hydrogen atom that is sufficiently +. Therefore, they have lower boiling points that the equivalent alcohols, but higher boiling points than the equivalent alkanes and alkenes. Solubility The lower carbon chain members of both aldehydes and ketones are soluble in water. This is due to the hydrogen bonding between the lone pair of electrons in the - oxygen in the carbonyl compound and the + hydrogen in the water molecule. Smell Lower carbon chain members have pungent odours Ketones have much sweeter smells than aldehyde Complex aldehydes are often used as perfumes

Laboratory Preparation
Aldehydes Oxidation of a primary alcohol Oxidised by potassium/sodium dichromate (VI) in dilute sulphuric acid Temperature must be below boiling point of the alcohol and above that of the aldehyde. This means that the aldehyde is boiled off as it is formed, so it cannot be oxidised further If the mixture is heated under reflux, the aldehyde would be oxidised to a carboxylic acid Method: Heat alcohol in a flask using an electric heater Add a solution of K2Cr2O7 in dilute H2SO4 slowly from a tap funnel Collect the aldehyde in a flask surrounded by ice water

Reactions of Aldehydes and Ketones

Both aldehydes and ketones undergo nucleophilic addition because of the polar C=O bond Aldehydes and ketones both undergo addition/elimination reactions Aldehydes can be oxidised to carboxylic acids, and are therefore reducing agents Ethanal and methylketones react with iodine in alkali to form a precipitate of iodoform, CHI3.

Nucleophilic Addition Reaction with HCN This reaction takes place only at about pH 8. This pH provides a catalyst of CN ions. If the pH is too low, there are not enough CN ions for the first step to take place; if the pH is too high, there are not enough HCN molecules for the second step. Some base is added to produce the CN ions. HCN + OH CN + H2O The same reaction takes place with ketones, but at a slower rate. Stereochemistry of Addition When HCN adds onto an aldehyde or asymmetrical ketone, the product is a racemic mixture. This is because the carbonyl compound is planar around the C=O group, and therefore the cyanide ion can attack from above or below the plane. Reduction Aldehydes and ketones can be reduced by lithium tetrahydridoaluminate (III), LiAlH4. This is a source of H ions. There are 2 steps to the reaction: 1. Addition of H to the + C atom. In this step, the reagents must be kept dry (dissolve in dry diethyl ether) 2. Addition of an aqueous solution of acid, which protonates the O formed in the first step

Condensation (Addition followed by Elimination) Testing for a carbonyl compound: 1. React the carbonyl compound with a solution of Bradys reagent 2. Filter off the precipitate 3. Recrystallise the precipitate using the minimum amount of hot ethanol 4. Dry the purified product and measure its melting temperature 5. Refer to the data book to compare the melting temperature with the Bradys reagent derivatives