Reactions of Aldehydes and Ketones

TOPIC
CARBOXYLIC ACIDS AND ESTERS

175
CARBOXYLIC ACIDS AND
ESTERS
• Carboxylic Acids
• Nomenclature of Carboxylic Acids
• Reactions of Carboxylic Acids
• Esters
• Nomenclature of Esters
• Hydrolysis and Reduction of Esters
Carboxylic Acids
• CnH2n + 1COOH (n ≥ 0)
• RCOOH
• Sour tasting
• Weak acids
• Citric acid
 found in citrus fruit
• Ethanoic acid = acetic acid, CH3COOH
 vinegar
• Methanoic acid = formic acid, HCOOH
 insect bites and stings
Carboxylic Acids
Preparation of Carboxylic Acids
• Made by the oxidation of aldehydes and primary alcohols

CH2OH C OH
[O]

Benzyl alcohol Benzoic acid

O O

C C
H [O] OH

Benzaldehyde Benzoic acid

1.8 Carboxylic Acids and Esters
Nomenclature of Carboxylic Acids
• Carboxylic acid group always on end of main chain
– has highest naming precedence of functional
groups
• C of group always C1
– position not indicated in name
• Change ending to oic acid
O
CH3CH2CH2CH2CH2C OH
6 5 4 3 2 1

Hexanoic acid or caproic acid

which causes foot odor
1.8 Carboxylic Acids and Esters
Nomenclature of Carboxylic Acids

CH2CH3 O CH3 O
3 3
CH3CH2CHCHCH2C OH CH3CH2CH2CCH2C OH
6 5 4 2 1 6 5 4 2 1
Cl OH
3-chloro-4-ethylhexanoic acid 3-hydroxy-3-methylhexanoic acid

4 O
COOH
C OH
3 1
2

3-cyclohexylbutanoic acid cyclopentanecarboxylic acid

1.8 Carboxylic Acids and Esters
Exercise 46 : Give the IUPAC name for the following
compound

COOH
COOH COOH

A B C
1.8 Carboxylic Acids and Esters
Reactions of Carboxylic Acids
1. Reactions with Thionyl Chloride:
Conversion of carboxylic acids into acid chlorides
O O
SOCl2
H3C C OH H3C C Cl
Acid chloride

2. Reactions with Ammonia:

Conversion of carboxylic acids into amide

O O
NH3
H3C C OH H3C C NH2
Heat
Amide
1.8 Carboxylic Acids and Esters
Reactions of Carboxylic Acids
3. Reactions with Alcohol
Conversion of carboxylic acids into esters
O CH3CH2OH O

H3C C OH Conc. H2SO4 H3C C OCH2CH3

Ethyl acetate

4. Reactions with Reducing Agent

Conversion of carboxylic acids into alcohols

O
1. LiAlH4
H3C C OH H3C CH2OH + H2O
2. H2O
Ethanol
Esters
• R–COO–R′
• Sweet odor
• Made by reacting carboxylic acid with an alcohol in the
presence of conc. sulphuric acid as catalyst
RCOOH + R′OH conc. H2SO4 RCOOR′ + H2O
1.8 Carboxylic Acids and Esters
Nomenclature of Esters
• Carboxylic acid group always on end of main chain
– unless carboxylic acid group present
• C of ester group on C1
– position not indicated in name
• Begin name with alkyl group attached to O
• Name main chain with oate ending
1.8 Carboxylic Acids and Esters
Nomenclature of Esters
3-methylbutyl acetate Isopropyl pentanoate

CH3 O O CH3
H2 1 H2
CH 2 C C 1 H2C 2 C C CH
3 1 2 4
H3C C O CH3 C 3 C 5 O 2 CH3
4 H2 H2 H2 1

O O
H2 H2 H2 H2
H3C 2 C C 2 C C C
1 1 3 H3C 2 C 2
C 3 O C CH3 1 3
CH 3 O C CH3
H2 H2 4 H2 4
CH3
Butyl propanoate 1 Butyl isobutyrate

Group in pink circle is carboxylate

Group in blue square is alkyl
Exercise 47 : Give the IUPAC name for the following
compound
O
O
C
C O
O

A B

C
O

C
1.8 Carboxylic Acids and Esters
Hydrolysis of Esters
• Hydrolysis of esters is the reverse of esterification
• Acid Hydrolysis of an ester in the presence of dilute
HCl or dilute sulphuric acid produces an alcohol and a
carboxylic acid
• If an alkali is used instead of an acid, the carboxylic
acid formed will be converted to the salt

CH3CH2COOCH3 + H2SO4 reflux CH3CH2COOH + CH3OH

methylpropanoate propanoic acid methanol

CH3CH2COOCH3 + NaOH reflux CH3CH2COONa + CH3OH

methylpropanoate sodium propanoate methanol
1.8 Carboxylic Acids and Esters
Reduction of Esters
• Esters can be reduced to produce two alcohols by
strong reducing agent such as lithium aluminium
hydride (LiAlH4)

CH3CH2COOCH3 1. LiAlH4 CH3CH2CH2OH + CH3OH

methylpropanoate 2. H2O propanol methanol
1.8 Carboxylic Acids and Esters
Exercise 48 : Draw the products formed when A, B and C
undergo hydrolysis
O
O
C
C O
O

A B

C
O

C
TOPIC and Ketones
Reactions of Aldehydes
1.9 AMINES

175
1.9 Amines
•Amines are organic derivatives of ammonia with one or
more alkyl or aryl groups bonded to nitrogen atom
•Many are biological active
O O

O O

N
N

Nicotine Cocaine

HO NH

H2N N
HO NH2
Dopamine Histamine
1.9 Amines

Biological Activity
• Neurotransmitters: dopamine
• Bioregulators: epinephrine
• Vitamins: niacin, B6
• Alkaloids: nicotine, morphine, cocaine
• Amino acids
1.9 Amines
Classes of Amines
• Primary (1): one C-N bond, 2
N-H bonds (RNH2). CH3
H3CH2C C NH2
H
Butan-2-amine

• Secondary (2): two C-N

bonds, 1 N-H bond (R2NH). H
H3C C CH2CH3
H N CH2CH3
N-ethylbutan-2-amine
1.9 Amines

Classes of Amines

• Tertiary (3): three C-N CH3CH2CH2CHCH2CH3

bonds, no N-H bond
H3C N CH2CH3
(R3N).
N-ethyl-N-methylhexan-3-amine

• Quaternary (4): four C-N CH2CH2CH3

bonds, nitrogen has a +
H3C N+ CH2CH3
formal charge.
CH2CH3
1.9 Amines
Nomenclature of Amines
• Primary amines are named in IUPAC system. Name
the alkyl or aryl groups bonded to nitrogen, then add
suffix -amine.
• Name is based on longest carbon chain.
• -e of alkane is replaced with -amine.
CH3
H2N
CH3 C NH2
CH3
1,1-Dimethylethylamine Cyclohexylamine
or
tert-Butylamine
H2N

4,4-Dimethylcyclohexanamine
1.9 Amines
Nomenclature of Amines
Symmetrical secondary and tertiary amines are named
by adding the prefix di- or tri- to alky group

CH3 CH2CH3
H3C N H3CH2C N
CH3 CH2CH3 N
H
Trimethylamine Triethylamine Diphenylamine
1.9 Amines
Nomenclature of Amines
•Unsymmetrical substituted secondary and tertiary
amines are named as N-substituted primary amines
•Largest alkyl group is chosen as the parent name, and
the other alkyl groups are N-substitutents on the parent
1 CH3
CH3
H H N
H3C N CH2CH2CH3 H3C N CH CH2CH3
1 2 3 2

N-methylpropan-1-amine CH2CH2CH2CH3
3 4 5 6
N-methylhexan-2-amine N-ethyl-N-methylcyclohexylamine
CH2CH3 CH3
H3C N CH3CH2 N
H3C
CH2CH2CH2CH3 CH3
1 2 3 4 N
H
N-ethyl-N-methylbutan-1-amine N,N-Dimethylpropylamine N-methylcyclopentanamine
1.9 Amines
Nomenclature of Amines
Amine as Substituent
• On a molecule with a higher priority functional group
the amine is named as a substituent. –NH2 as an
amino
NH2
NH2
CH3CH2CH2CHCH2CH2COOH OH
4-Aminoheptanoic acid
2-aminocyclopentanol

NH2
H3C CH3
N
CH3
CH3CH2CH2CHCH2COOCH3
OHC
4-amino-4-methylcyclohexanecarbaldehyde methyl 3-(dimethylamino)hexanoate
1.9 Amines
Nomenclature of Amines
Aromatic Amines
• Amino group is bonded to a benzene ring. Parent
compound is called aniline.
NH2
NH2 H3C N CH3

CH3
Aniline N,N-dimethylbenzenamine 4-Methylanaline
p-toluidine
1.9 Amines
Exercise 49 :Give the IUPAC name for the following
compound

N H
N
A

H
N
H C
1.9 Amines
Hinsberg Test
This test is used to distinguish between 1o, 2o and 3o amines

This test is carried out by shaking a mixture of

benzenesulphonyl chloride and an amine in the presence of
excess NaOH solution, followed by addition of HCl solution.

1o amine- a clear solution is formed on shaking and a white

precipitate is formed upon addition of acid

2o amine- a white precipitate is formed on shaking and no

changes upon addition of acid

3o amine – no reaction
1.9 Amines
Exercise 50 : Compound A, B and C are isomeric with
molecular formula C3H9N. Three compounds are carried
out in Hinsberg’s Test. The results as followed
Test A B C
Observations
Shaking a compound No A clear White
with benzenesulphonyl reaction solution precipitate
chloride in presence of formed formed
excess NaOH solution
Addition of HCl No White No change
reaction precipitate
formed

Deduce the structural formula of compound A, B and C