(a) Oxidation

 Aldehydes are easily oxidised to carboxylic acids by common oxidising agents such as
acidified potassium manganate(VII) or acidified potassium dichromate(VI) and even
by molecular oxygen.
RCHO + [O]  RCOOH
 For example:
CH3CHO + [O]  CH3COOH
CH3—CH—CH2CHO + [O]  CH3—CH—CH2COOH
I I
CH3 CH3
(3-methylbutanol) (3-methylbutanoic acid)

+ [O] 

(benzaldehyde) (benzoic acid, white solid)

CH3(CH2)4—C—H + [O]  CH3(CH2)4—C—OH

II II
O O
(hexanal) (hexanoic acid)

 Ketones in contrast to aldehydes are difficult to oxidise and requires prolong boiling
with the oxidising agents. This is because there is no oxidise hydrogen atom bonded
to the carbonyl group.
 Vigorous oxidation of a ketone involves the breaking of strong carbon-carbon bonds
for example. For example:

CH3—C—CH3 + 4[O]  CH3COOH + CO2 +H2O

II
O

CH3CH2CH2—C—CH2CH3 + 7[O]  CH3CH2CH2COOH + 2CO2 + 2H2O

II
O
CH3CH2CH2—C—CH2CH3 + 10[O]  CH3CH2COOH + 3CO2 +3H2O
II
O
 An important industrial application of this reaction is the oxidation of cyclohexanone
by concentrated nitric acid (a very powerful oxidising agent) to hexanedioic acid
(also known as adipic acid), one of the monomers of nylon 6,6.
 + 3[O]  HOOC—CH2CH2CH2CH2—COOH

 One disadvantage of oxidation by either acidified KMnO4 or K2CR2O7 is that other

oxidizable groups present will also be affected. One such group is the C=C double
bond.
 For example, when 2-butenal is treated with warm acidified KMnO4, not only is the
aldehyde group oxidised to an acid, the carbon-carbon double bond is also oxidised
to a diol.

CH3—CH=CH—C—H + 2[O] + H2O  CH3—CH—CH—COOH

II I I
O OH OH
(2-butenal) (2,3-dihydroxybutanoic acid)

(b) Reduction
 Aldehydes and ketones are reduced to primary alcohols and secondary alcohols
respectively.
R—C—H + 2[H]  RCH2OH
II
O

R—C—R + 2[H]  R—CH—R

II I
O OH
 For example:
CH3CHO + 2[H]  CH3CH2OH

(benzaldehyde) + 2[H]  phenylmethanol

CH3CH2CH2—C—CH3 + 2[H]  CH3CH2CH2—CH—CH3

II I
O OH
 The normal reducing agents used are:
(a) Lithium aluminium hydride, LiAlH4, in dry ether at rom temperature followed by
H+ (aq)
(b) Hydrogen gas in the presence of nickel with heat.

 However, catalytic reduction with hydrogen has a disadvantage in

that some other functional groups are also reduced under these
conditions. An example is the carbon-carbon double bonds or triple
bonds. For example:
 + 2H2

(c) Nucleophilic Addition

 Due to polarisation of the carbon-oxygen bond, the oxygen-carrying carbon acquires

a partial positive charge.
 As a result, the carbonyl carbon is subjected to attack by nucleophiles. And since the
carbonyl group is unsaturated, it undergoes addition reaction
 One of the most important nucleophilic addition of carbonyl compounds is the
addition of aqueous hydrogen cyanide (in the presence of sodium cyanide as
catalyst) to produce a cyanohydrin or hydroxynitrile.
 For example,
H
I
CH3—C—CH3 + HCN  CH3—C—CN
II I
O OH
(propanone) (propanone cyanohydrin)
 Hydroxynitriles can be hydrolysed by boiling with dilute sulphuric acid to produce 2-
hydroxyacids or α-hydroxyacids(AHA), an important ingredient in most moisturising
lotions or creams. For example,
CH3 CH3
I I
CH3—C—CN + 2H2O + H+  CH3—C—COOH
I I
CH3 CH3
2-methyl-2-hydroxypropanenitrile 2-methyl-2-hydroxypropanoic acid

 The addition of HCN to an aldehyde or a ketone is a convenient method to add an

extra carbon atom to the molecule

(d) Haloform reaction

 i) ethanal from other aldehydes because ethanal is the only aldehydes that gives a
positive iodoform test
 ii) ethanol and secondary alcohols that contains the CH3CH(OH)- group give a
positive iodoform test.
 iii) methyl ketones (ketones that contain CH3CO- group) give positive iodoform test.
 For example:
Propanone and phenylethanone give a yellow
precipitate but 3-pentanone and
diphenylmethanone give negative iodoform test.