Chapter 18 Carbonyl compounds
基础知识：Carbonyl group： C = O
Compound Position of carbonyl group Naming Example
aldehydes the carbonyl group is positioned at the end of a carbon chain Suffix ‘-anal’ Methanal HCHO
ketones carbonyl group is attached to two other carbon atoms. Suffix ‘- anone’ Propanone CH3COCH3
Preparation of aldehydes and ketones:
1 oxidation of a primary alcohol
Oxidising agent: potassium dichromate (VI), acidified with dilute sulfuric acid
Condition: heat
General formula: primary alcohol + oxygen atom from oxidising agent → aldehyde + water
Appearance: reaction mixture turns green as the orange dichromate ions, CrO 2–(aq), are reduced to green Cr3+(aq) ions.
Note (备注)；further heating with acidified dichromate solution will oxidise the aldehyde produced to a carboxylic acid.
2 Oxidation of a secondary alcohol
Oxidising agent: potassium dichromate (VI), acidified with dilute sulfuric acid
Condition: reflux /heat
General formula: secondary alcohol + oxygen atom from oxidising agent → ketone + water
Appearance: reaction mixture turns green as the orange dichromate ions, CrO 2–(aq), are reduced to green Cr3+(aq) ions.
Reduction of aldehydes and ketones
Reduction of an aldehyde or ketone produces an alcohol.
Reducing agent:
Reducing agent Condition
aqueous alkaline solution of sodium tetrahydridoborate, NaBH4, Warming
lithium tetrahydridoaluminate, LiAlH4, in dry ether (such as diethyl ether) room temperature
dry (a powerful reducing agent and reacts vigorously in water)
General formula: using the symbol [H] to represent a hydrogen atom from the reducing agent.
aldehyde + reducing agent →primary alcohol
ketone + reducing agent →secondary alcohol
Nucleophilic addition with HCN
1 nucleophilic addition
Aldehydes and ketones both undergo addition reactions with hydrogen cyanide, HCN
-C≡N is a nucleophile
addition of HCN takes place across the C =O bond.
2 About the -C≡N group
The HCN is generated in situ (in the reaction vessel) by the reaction of sodium cyanide, NaCN, and dilute sulfuric acid.
addition of the nitrile group (-C≡N) increases the length of the hydrocarbon chain in the original aldehyde molecule by one carbon atom.
The nitrile group (-C≡N) can then be easily:
hydrolysed to a carboxylic acid: refluxing with dilute hydrochloric acid:
reduced to an amine: using sodium and ethanol
3 Mechanism of nucleophilic addition
First The carbonyl group, -C =O is polarised due to the high electronegativity
step of the oxygen atom
Gives a partial negative charge O atom and a partial positive charge C
atom.
δ +¿ C atom open to attack by a nucleophile, such as the cyanide ion,
CN–
Forms a negatively charged intermediate
Second negatively charged intermediate is highly reactive and quickly reacts
step with an H+ ion (from HCN, from dilute acid or from water present in the
reaction mixture)
Forms the 2-hydroxynitrile product
Testing for aldehydes and ketones:
Testing agent Testing for Observation Related reaction
2,4-DNPH (2,4- Aldehyde and A deep orange precipitates condensation reaction
dinitrophenylhydrazine ) ketone (Identity of the precipitation can
be found by referring to melting
point data)
Tollens’ reagent aldehyde form a ‘mirror’ silver ions, Ag+, in the solution act as a mild oxidising
Warm, aqueous solution of agent.
silver nitrate in excess When warmed, the Ag+ ions will oxidise an aldehyde to
ammonia solution form a carboxylate ion.
(ammoniacal silver nitrate The Ag+ ions are reduced to Ag metal.
solution)
Fehling’s solution aldehyde clear blue Fehling’s solution the Cu2+ ions act as an oxidising agent.
alkaline solution containing turns an opaque red/orange When warmed, the Cu2+ ion oxidise an aldehyde to a
copper(II) ions colour precipitate of carboxylate ion
copper(I) oxide The Cu2+ ions are reduced to Cu+ ions.
Reactions to form tri-iodomethane
1 Testing for CH3CO- group
Alkaline solution of iodine reacts with compounds containing the CH3CO- group, such as methyl ketone, will forms as a yellow precipitate (tri-
iodomethane CHI3 with melting point of 119 °C)
Reagent: I2, NaOH(aq) / alkaline solution of iodine
Condition: warmed
First step an alkaline solution of iodine,warmed
halogenation of the methyl group
Second step the intermediate is hydrolysed to form the yellow
precipitate of tri-iodomethane, CHI3
2 Testing for the CH3CH(OH)- group
The tri-iodomethane test can also be used to identify the presence of CH3CH(OH)- , a secondary alcohol group on the carbon atom adjacent
to a methyl group.
This group is firstly oxidised by the alkaline iodine solution forms a methyl ketone, RCOCH 3,
RCOCH3 reacts with alkaline solution of iodine to give the yellow tri-iodomethane precipitate, CHI 3.