Aldehydeandketone
Aldehydeandketone
Aldehydeandketone
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
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
C O C CH3
CH3
CHCl3
PhCOOOH
Perbenzoic acid
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.
Ph3P CH R
Thank You