CARBONYL COMPOUNDS

CARBONYL COMPOUNDS
• Aldehydes and Ketones
• Nomeclature of Carbonyl Compounds
• Nucleophilic Addition Reactions of
Carbonyl Compounds
• Reduction of Carbonyl Compounds
• Oxidation of Carbonyl Compounds
 1.7 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
 1.7 Aldehydes And Ketones
Aldehyde Odors and Flavors
• butanal = butter

• vanillin = vanilla

• benzaldehyde = almonds

• cinnamaldehyde = cinnamon
 1.7 Aldehydes And Ketones
Ketone Odors and Flavors

• acetophenone =
pistachio

• carvone = spearmint

• ionone = raspberries

• muscone = musk
 1.7 Aldehydes And Ketones
Aldehydes Nomenclature

• 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
 1.7 Aldehydes And Ketones
Aldehydes Nomenclature

3 1
2 5 4 2
O 3
3 O
2 4
1 1
2-methylpropanal 2,2-dimethylbutanal O
2-isobutylpentanal

4 2 1
5 3
4 6 6
2
O 3 5 7
1
2-methyl-2-isopropylheptanal 2-secbutylhexanal
 1.7 Aldehydes And Ketones
Ketones Nomenclature
1
O
2 5

5 7 6
1 3 7
4 2
3 4 8
6 8 9
O
3-ethyl-2-methyloctan-4-one 4-ethylnonan-3-one
or 3-isopropyloctan-4-one

7 6 O
1
5 2
5 3
O
4
6 4
3 2
1
4-ethyl-5-methylheptan-2-one 3-isobutylhexan-2-one
Exercise 41 : Name the following compounds using the
IUPAC system of nomenclature

H
O

O
O
 1.7 Aldehydes And Ketones
Nucleophilic Addition Reactions of Carbonyl
Compounds

The carbonyl group in aldehydes and ketones has a

constant polarity.
The nucleophiles attack the The electrophiles attack
δ+ δ−
electron-deficient C atom the electron rich O atom
C O
 1.7 Aldehydes And Ketones

Addition of HCN to C=O

Polar molecule HCN adds across the C=O, with the
positive part (H) attaching to O; the nucleophile CN-
attaching to C atom
H H
NaCN
C O + HC N N C C OH

H H
Formaldehyde 2-Hydroxyacetonitrile

H3C CH3
NaCN
C O + HC N N C C OH

H3C CH3
2-Propanone 2-Hydroxy-2-methylpropanenitrile

Compounds produced are called cyanohydrins

 1.7 Aldehydes And Ketones
Mechanism Addition of HCN to C=O

STEP 1: Cyanide adds to the carbonyl

H H
..N .
C.
..O ..N ..O ..
-
C .. C C .. -

H H
STEP 2: Protonation gives the cyanohydrin
H H

..N ..O . .
N. ..N ..OH
C C ...
- H C C C ..
H H
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)
 1.7 Aldehydes And Ketones
Hydrolysis and Reduction of Cyanohydrin
Compounds
Hydrolysis: Conversion of cyanohydrin into -
hydroxycarboxylic acids
H H O
+
H3O
HO C C N HO C C OH
heat
H H
2-hydroxyacetonitrile 2-hydroxyacetic acid

Reduction: Conversion of cyanohydrin into amines

H H H
1. LiAlH4,ether
HO C C N HO C C NH2
2. H2O
H H H
2-hydroxyacetonitrile 2-aminoethanol
Exercise 42 : Draw structural formula for the product
formed by treating each of the following compounds
with KCN in aqueous HCN
O

H
O

O
O
 1.7 Aldehydes And Ketones
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

 1.7 Aldehydes And Ketones
Addition of Grignard Reagents to C=O

H H
1. Ether
C O + CH3CH2 MgBr H3CH2C C OH
+
2. H3O
H H
Formaldehyde Ethyl magnesiumbromide 1-Propanol

H H
1. Ether
C O + CH3CH2CH2 MgCl H3CH2CH2C C OH
+
2. H3O
H3CH2C CH2CH3
Propanal Propyl magnesiumchloride 3-Hexanol

H3 C CH3
1. Ether
C O + CH3CH MgI H3CHC C OH
+
2. H3O
H3 C CH3
CH3 CH3
2-Propanone Isopropyl magnesiumciodide 2,3-Dimethyl-2-butanol
 1.7 Aldehydes And Ketones
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
H3CH2CH2C C O-Mg+Cl
H3CH2C
1. Ether CH2CH3
Propanal
STEP 2: The Grignard reagent attacks a carbonyl carbon to
form alkoxide salt
H H H

H3CH2CH2C C O-Mg+Cl O+ H3CH2CH2C C OH

2. H
H
CH2CH3 CH2CH3
3-Hexanol
Exercise 43 :Predict the product of the reaction of 4,4-
dimethyl-2-pentanone and 2-isopropyl-3-methylbutanal
with isobutylmagnesium bromide in dry ether, followed
by hydrolysis in aqueous acid.
 1.7 Aldehydes And Ketones

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
 1.7 Aldehydes And Ketones
Reduction of Carbonyl Compounds
H
H
Reduction reactions: Ni/H2 or LiAlH4 H C OH
•Formaldehyde will C O
H
form methyl alcohol H
Methanol
Formaldehyde
H
H
Ni/H2 or LiAlH4
•Aldehyde will form C O H C OH
primary alcohol H3CH2C CH2CH3
Propanal 1-Propanol

CH3
•Ketone will form H3C
Ni/H2 or LiAlH4
secondary alcohol C O H C OH

H3C CH3
2-Propanone 2-Propanol
 1.7 Aldehydes And Ketones
Oxidation of Carbonyl Compounds

Aldehydes are easily oxidised using mild oxidising agents

 Ketones would not oxidise even using strong oxidising agents

A. Tollen’s reagent (Silver mirror test)

Tollen’s 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

 1.7 Aldehydes And Ketones
Oxidation of Carbonyl Compounds
B. Fehling’s reagent test for aldehydes
Fehling’s reagent consists of a basic solution of
Cu(II) complex with a deep blue colour.
It oxidises aldehyde, and is itself reduced to a brick-
red deposit of Cu(I) oxide. Ketones give no reaction.
RCHO + 2Cu2+(complex) + 5OH‒  RCOO‒ + Cu2O + 3H2O

*Aldehydes also decolourise acidified solution of KMnO4

 1.7 Aldehydes And Ketones
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.
Exercise 44 : Draw the structural formula for compound
A, B, C and D

LiAlH4 Na2Cr2O7
A O B

LiAlH4 Na2Cr2O7
C O D
Exercise 45 : Both compound A and B are isomeric with
a molecular formula C5H10O. When A is boiled with
acidified potassium manganate (IV), a carboxylic acid
formed and the product is optically active, but B does
not react with acidified potassium manganate (IV).
When compound A and B are warmed with alkaline
iodine, only B gives a yellow solid.

i) Deduce the structure A and B

ii) Give the IUPAC name for the compound A and B
iii) Draw the optical isomer of carboxylic acid