CARBONYL COMPOUNDS

PREPARED BY
SYED ABDUL ILLAH ALYAHYA
UNIVERSITI TEKNOLOGI MARA
PUNCAK ALAM CAMPUS

CARBONYL COMPOUNDS
Aldehydes and Ketones
Nomeclature of Carbonyl Compounds
Nucleophilic Addition Reactions of
Carbonyl Compounds
Reduction of Carbonyl Compounds
Oxidation of Carbonyl Compounds

Aldehydes and Ketones

Contain the carbonyl group
Aldehydes = at least 1 side H
Ketones = both sides R groups
Many aldehydes and ketones have
pleasant tastes and aromas
Formaldehyde : H2C=O
pungent gas
formalin = a preservative
wood smoke, carcinogenic
Acetone : CH3C(=O)CH3
nail-polish remover

Aldehydes and Ketones

Aldehyde Odors and Flavors

butanal = butter
vanillin = vanilla
benzaldehyde = almonds
cinnamaldehyde = cinnamon

Aldehydes and Ketones

Ketone Odors and Flavors

acetophenone =
pistachio

carvone = spearmint
ionone = raspberries
muscone = musk

Nomenclature of Carbonyl
Compounds
Main chain contains C=O group
Number the main chain from end closest to C=O
For aldehydes, give base name al ending
always on C1

For ketones, give base name one ending and according

to number of C on chain where C=O attached

Nomenclature of Carbonyl
Compounds
Aldehydes
1

3
2
O
2

5
O

1
2-methylpropanal

3
1

O
2-isobutylpentanal

2,2-dimethylbutanal

2
O

2-methyl-2-isopropylheptanal

7
2-secbutylhexanal

Nomenclature of Carbonyl
Compounds
Ketones

2
7

6
3
2

O
4-ethylnonan-3-one

3-ethyl-2-methyloctan-4-one
or 3-isopropyloctan-4-one
6

1
2

6
3

1
4-ethyl-5-methylheptan-2-one

3-isobutylhexan-2-one

Nucleophilic Addition Reactions of

Carbonyl Compounds
The carbonyl group in aldehydes and ketones has a
constant polarity.

The nucleophiles attack the

electron-deficient C atom

C O

The electrophiles attack

the electron rich O atom

Nucleophilic Addition Reactions of

Carbonyl Compounds
Addition of HCN to C=O
Polar molecule HCN adds across the C=O, with the
positive part (H) attaching to O; the nucleophile CNattaching to C atom
H

H
C

+ HC

NaCN
N

OH

H
2-Hydroxyacetonitrile

Formaldehyde

CH3

H3C
C

H3C
2-Propanone

+ HC

NaCN
N

OH

CH3
2-Hydroxy-2-methylpropanenitrile

Compounds produced are called cyanohydrins

Nucleophilic Addition Reactions of

Carbonyl Compounds
Mechanism Addition of HCN to C=O
STEP 1: Cyanide adds to the carbonyl
H

..N

.
C.
-

..O
..

..N

..O .
...
-

C
H

STEP 2: Protonation gives the cyanohydrin

H

..N

C
H

..O .
...
-

.
N.

..N

..OH
..

HCN is weak acid, not very nucleophilic because low ionize to form
CN-. Therefore, source CN- such as KCN and NaCN are used and
prepared in acid solution (H2SO4)

Nucleophilic Addition Reactions of

Carbonyl Compounds
Addition of Grignard Reagents to C=O
Grignard Reagents are powerful carbon nucleophiles.
They undergo addition reactions with aldehydes and
ketones:
Formaldehyde yield primary alcohol
Aldehyde yield secondary alcohol
Ketones yield tertiary alcohol
An excellent method for synthesis of alcohols

Nucleophilic Addition Reactions of

Carbonyl Compounds
Addition of Grignard Reagents to C=O
H

H
C

+ CH3CH2 MgBr

1. Ether
2. H3O

H3CH2C

OH

H
1-Propanol

Formaldehyde Ethyl magnesiumbromide

H
O + CH3CH2CH2 MgCl

1. Ether

H3CH2CH2C

2. H3O+

H3CH2C

CH2CH3
Propyl magnesiumchloride

Propanal

3-Hexanol
CH3

H3C
C

OH

O + CH3CH

H3C
2-Propanone

CH3

MgI

1. Ether
2. H3O

Isopropyl magnesiumciodide

H3CHC

OH

CH3 CH3
2,3-Dimethyl-2-butanol

Nucleophilic Addition Reactions of

Carbonyl Compounds
Mechanism Addition of Grignard Reagents to C=O
STEP 1: The Grignard reagent attacks a carbonyl carbon to
form alkoxide salt
H

H
C

O + CH3CH2CH2 MgCl

H3CH2C

H3CH2CH2C

1. Ether

O-Mg+Cl

CH2CH3

Propanal

STEP 2: The Grignard reagent attacks a carbonyl carbon to

form alkoxide salt
H

H
H3CH2CH2C

O-Mg+Cl

2. H

O+
H

H3CH2CH2C

CH2CH3

OH

CH2CH3
3-Hexanol

Reduction of Carbonyl
Compounds
Aldehydes and ketones are generally synthesized by
the oxidation of alcohols
Therefore, reduction of an aldehyde or ketone results
in an alcohol.
Common reducing agents are H2 with a Ni catalyst,
NaBH4, and LiAlH4

Reduction of Carbonyl
Compounds
H

Reduction reactions:
Formaldehyde will
form methyl alcohol

Ni/H2 or LiAlH4
C

OH

H
Formaldehyde

Methanol
H
Ni/H2 or LiAlH4

H3CH2C

OH

CH2CH3

Propanal

Ketone will form

secondary alcohol

Aldehyde will form

primary alcohol

1-Propanol
CH3

H3C

Ni/H2 or LiAlH4
C

H3C
2-Propanone

OH

CH3
2-Propanol

Oxidation of Carbonyl
Compounds
Aldehydes are easily oxidised using mild oxidising agents
Ketones would not oxidise even using strong oxidising agents

A. Tollens reagent (Silver mirror test)

Tollens reagent is a solution of silver nitrate in
ammonium hydroxide containing the silver complex
Ag(NH3)2 +,
An aldehyde is oxidised by Ag(NH3)2 + , which is
reduced to metallic Ag. Ketones give no reaction.
RCHO + 2Ag(NH3)2+ + OH RCOO + 2Ag + 2NH4+ + 2NH3

Oxidation of Carbonyl
Compounds
B. Fehlings reagent test for aldehydes
Fehlings reagent consists of a basic solution of
Cu(II) complex with a deep blue colour.
It oxidises aldehyde, and is itself reduced to a brickred deposit of Cu(I) oxide. Ketones give no reaction.
RCHO + 2Cu2+(complex) + 5OH RCOO + Cu2O + 3H2O
*Aldehydes also decolourise acidified solution of KMnO4

Oxidation of Carbonyl
Compounds
C. Iodoform test for ethanal, CH3CHO, and methyl Ketones
A methyl ketone has a CH3 group attached to the carbonyl
carbon.
O
R C CH3 R = H or any alkyl group
The reagent consists of an aqueous solution of I2 in NaOH or
KOH. On reacting with ethanal, a yellow precipitate of
triiodomethane (iodoform) appears.
CH3CHO + 3 I2 + NaOH CH3COONa + CH3I + 3HI

OH

Note: ethanol, CH3CH2OH or a sec. alcohol with the group CH3CH CH3
also give positive iodoform tests.