ALDEHYDE AND KETONE

P.M. Jadhav
Assistant Professor
Dept. of Chemistry
M.S.P. Mandals, Shri Muktanand college,
Gangapur, Dist. Aurangabad.
 Aldehydes and ketones
Aldehydes and ketones are the carbonyl compounds with general formula
CnH2nO. Aldehydes have at least one hydrogen atom bonded to the carbonyl
group and other group is either hydrogen or an alkyl or aryl group.
Aldehyde has one alkyl or aryl group and one of the hydrogen bonded to the
carbonyl carbon with characteristics functional group -CHO.
O

C
R H
Aldehyde

In ketones, the carbonyl group is bonded to a two alkyl or aryl groups with –
CO- functional group. The two groups bonded to a ketone may be similar or
different resulting in a symmetrical or an unsymmetrical ketone.
O

C
R R'
Ketone
Nomenclature of Aldehydes and Ketones
Systematic names for aldehydes are obtained by replacing suffix -e of the
corresponding alkane by prefix –al i.e. aldehydes are named as alkanal. The
carbonyl carbon of the aldehydes is assigned 1 position.
Formula Compound Common name IUPAC name
CH2O HCHO Formaldehyde Methanal
C2H4O CH3CHO Acetaldehyde Ethanal
C3H6O CH3CH2CHO Propionaldehyde Propanal
C4H8O CH3CH2CH2CHO Butaraldehyde Butanal
Systematic names for ketone are obtained by replacing suffix -e of the
corresponding alkane by prefix –one. I.e. ketones are named as alkanone. The
position of carbonyl group in the ketone is assigned by the number.
Formula Compound Common name IUPAC name
C3H6O CH3-CO-CH3 Acetone Propanone
C4H8O CH3CH2-CO-CH3 Ethyl methyl ketone Butanone
C5H10O CH3CH2-CO-CH2CH3 Diethyl ketone 3-pentanone
C5H10O CH3CH2CH2-CO-CH3 Methyl propyl ketone 2-pentanone
 Preparation Methods
1. Rosenmunds reaction(Reduction of acid chloride):The reduction of acid chloride
in presence of palladium supported catalyst like palladium on BaSO4 or Charcoal to
give product aldehyde.
O O
Pd / BaSO4
R C Cl H2 R C H HCl
Acid chloride Aldehyde
2. Gatterman Synthesis: Preparation of aromatic aldehyde by the reaction of phenol
ether and HCN in presence of Lewis acid catalyst AlCl3 or ZnCl2 to give product
substituted aromatic aldehyde.
OCH3 OH

HCl
HCN NH4Cl
AlCl3

Methoxy benzene CHO

p-methoxy benzaldehyde
3. Gatterman- Koch Reaction: The reaction involves formation of aromatic
aldehyde by the reaction of carbon monoxide and hydrochloric acid in presence of
Lewis acid (AlCl3) as catalyst. CHO

CO AlCl3
HCl

Benzene
Benzaldehyde
4. Ketone from Nitrile or cyanide: Ketone prepared from Grignard reagent and
nitrile. The Grignard reagent attack on electrophilic carbon of nitrile to give a imine
salt which on hydrolysis to gives ketone. O
R'-Mgx
R C N R C R'
H2O
Nitrile Ketone
5. Ketone from Carboxylic acid: The calcium salt of carboxylic acid on heating to
O
gives ketone.
R C O O
Heat
Ca R C R CaCO3
R C O

O
6. Oxidation of alcohols: Oxidation of Alcohols with oxidizing agents such as
potassium permangnate (KMnO4), K2Cr2O7/H2SO4, chromic acid or MnO2 to give a
carbonyl compounds aldehyde and ketone.
O
K2Cr2O7
H3C CH2 OH H3C C H
H2SO4
Ethanol Acetaldehyde
O

CH3
K2Cr2O7
H3C CH H3C C CH3
H2SO4
OH Acetone
2-Propanol
7. Ozonolysis of alkenes: Ozone reacts with alkene to form ozonide intermediate
which on treatment with reducing agent to gives aldehydes this reaction is called
ozonolysis.
Zn dust
R HC CH R O3 2. R CHO
H2O
Alkene Aldehyde
 Chemical Reactions
1. Formation of acetals: Aldehydes and ketones react with two molecules of
alcohols to give geminal diether is known as acetal. The ketone derivatives are
known as ketal.
O OH OC2H5
C2H5OH C2H5OH
H3C C H H3C CH OC2H5 H3C CH OC2H5
Aldehyde Hemi-acetal Acetal
O OH OC2H5
C2H5OH C2H5OH
H3C C CH3 H3C C OC2H5 H3C C OC2H5
Ketone CH3 CH3
Hemi-ketal Ketal
2. Oxidation of Aldehyde and ketone: The presence of hydrogen atoms in
aldehydes make easily to oxidized to carboxylic acids containing the same numbers
of carbon atoms with a oxidizing agents like chromic acid, chromium trioxide. The
silver oxide (Ag2O) in aqueous ammonia solution (Tollen’s reagent) is mild reagent
give good yield at room temperature.
O O

H3C C H CrO3 H3C C OH

Acetaldehyde Acetic acid
3. Reduction of aldehyde and ketone: The reduction of aldehydes to primary
alcohol and ketones to secondary alcohol in presence of reducing agents likes
LiAlH4, NaBH4 etc.
O
LiAlH4
H3C C H H3C CH2 OH
Dry ether / H2O
Acetaldehyde Ethanol
O OH
NaBH4
H3C C CH3 H3C CH CH3
CH3OH
Acetone 2-propanol

4. Knoevenagel Reaction: The condensation of aldehyde or ketone having no α-

hydrogen with active methylene compound in presence of weak base to give
unsaturated compound is known as Knoevenagel reaction.
O
OH
Base -H2O
H3C C H CH2(COOH)2 H3C CH CH COOH H3C CH CH COOH
Acetaldehyde Malonic acid -CO2
COOH
Crotonic acid
5. Aldol Condensation: Aldehydes having α-hydrogen atoms which undergo
reaction in presence of base alkali to give codensation product β-hydroxy aldehyde is
known as aldol and the reaction is called aldol condensation. The ketones also
undergo condensation reaction to give product aldol of ketone.
O OH
NaOH H3C CH CH2 CHO
2. H3C C H
Acetaldehyde Aldol
O OH O

NaOH H3C C CH2 C CH3

2. H3C C CH3
Acetone
CH3
Self-aldol condensation: The aldol condensation when two same aldehydes or
ketones molecule having α-hydrogen atom condensed is known as self-aldol
condensation. O O OH
NaOH
H3C C H H3C C H H3C CH CH2 CHO
Acetaldehyde Acetaldehyde Aldol
Cross-aldol condensation: The aldol condensation when two different aldehydes
or ketones molecule having α-hydrogen atom condensed is known as cross-aldol
condensation. O O OH OH
NaOH
H3C C H H3C CH2 C H H3C CH CH CHO H3C CH2 CH CH2 CHO
Acetaldehyde Propionaldehyde CH3
6. Perkins Reaction: The aromatic aldehyde when react with aliphatic acid
anhydride in presence of sodium salt of acetic acid to give a product α,β-
unsaturated acid is known as Perkins reaction.
CHO CH CH COOH
CH3COONa
(CH3CO)2O
Heat
Acid anhydride
Benzaldehyde Cinnamic acid

7. Mannich Reaction: The compound containing at least one active methylene

hydrogen atom condensed with formaldehyde and ammonia, primary or
secondary amine in the form of hydrochloride to give a product Mannich base (β-
amino carbonyl compound) is known as Mannich reaction.
O O O
C2H5OH
H3C C CH3 H C H (CH3)2NH2Cl H3C C CH2 CH2NH(CH3)2Cl
HCl
Acetone Formaldehyde Mannich base
8. Baeyer-Villiger oxidation: Oxidation of ketone to ester in presence of peracid
or hydrogen peroxide is known as Baeyer-Villiger oxidation. The hydrogen
peroxide is commonly used. Other peracids used are peracetic acid, perbenzoic
acid, performic acid or m-chloroperbenzoic acid, etc.
O O

C O C CH3
CH3
CHCl3
PhCOOOH
Perbenzoic acid

Acetophenone Phenyl acetate

9. Cannizzaro’s Reaction: Cannizzaro reaction is redox reaction in which two

molecules of an aldehyde with no α-hydrogen when reacted with base sodium
hydroxide undergo self-oxidation and reduction to produce an alcohol and the salt
of corresponding carboxylic acid.
O O O
NaOH / KOH
H C H H C H CH3OH H C ONa
Formaldehyde Formaldehyde Methyl alcohol Sodium formate
10. Benzoin Condensation: The benzoin condensation is a coupling reaction of
two molecules of aromatic aldehyde with no α-hydrogen in presence of potassium
cyanide in ethanol as catalyst to give product Benzoin (α-hydroxy ketone) is known
as benzoin condensation.
O O

C C O OH
H H
CN, Heat C C
EtOH, H2O
H
Benzaldehyde Benzaldehyde Benzoin
11. Reformatsky Reaction: The reaction of carbonyl compound like aldehyde and
ketone with α-haloester in presence of zinc in inert solvent ether to give β-
hydroxyester this reaction is known as Reformatsky Reaction.
O
OH
Zn, Ether
R C H Br CH2 COOR R C CH2 COOR
Aldehyde Haloester H3O H
B-Hydroxy ester
O
OH
Zn, Ether
R C R' Br CH2 COOR R C CH2 COOR
Ketone Haloester H3O R'
B-Hydroxy ester
12. Meerwin-pondorf-verly reduction (MPV): The reduction of carbonyl
compound like aldehyde or ketone in presence of aluminum alkoxide and isopropyl
alcohol to give product corresponding alcohol is known as Meerwin-pondorf-verly
reduction. The reduction of aldehyde gives primary alcohol whereas ketone gives
secondary alcohol. O Al(iso-OPr)3 /
iso-PrOH
H3C C H H3C CH2 OH
Acetaldehyde H3O Ethanol
O Al(iso-OPr)3 / OH
iso-PrOH
H3C C CH3 H3C CH CH3
Acetone H3O Propanol
13. Clemmensen Reduction: When aldehyde or ketone heated with zinc amalgam
and hydrochloric acid to gives corresponding alkane. The reaction in which the
reduction of carbonyl group into a methylene groups (-CH2-) this reaction is known
as Clemmensen reduction.
O
Zn-Hg
H3C C H H3C CH3 H2O
Acetaldehyde HCl
Ethane
 14. Wittig Reaction: The reaction of phosphorous ylides with carbonyl
compound aldehyde or ketone to give alkene is known as Wittig reaction.
Phosphorus ylide is from by the reaction of triphenylphosphine and alkyl halides
in the presence of strong base. The phosphorous ylides react with aldehyde or
ketone to give a betain as intermediate which further eliminates
triphenylphosphine oxide to give alkene.

R CH2 X Ph3P Base

Ph3P CH2 RX Ph3P CH R
Alkyl halide Triphenyl Phosphonium salt Phosphorous ylides
phosphine

Ph3P CH R
Thank You