CHAPTER 9

CARBONYL
COMPOUNDS
 LEARNING OUTCOMES

At the end this topic, student should be able to:

9.1 Introduction
a) State the general formula of aldehydes and ketones.
b) Give the name for aldehyde and ketones according to the IUPAC
nomenclature
c) Give the structure for aldehyde and ketones in 9.1(b) (parent chain <
C10)

9.2 Preparation of Carbonyl Compounds

a) Explain the preparation of carbonyl compounds through:
(i) ozonolysis of alkenes
(ii) Friedel–Crafts acylation to produce aromatic ketone
(iii) oxidation of alcohols
 LEARNING OUTCOMES
9.3 Chemical Properties of Carbonyl Compounds:
a) Explain the chemical properties with
reference to: b) Explain the identification tests for
aldehyde and ketone using:
i) nucleophilic addition with KCN/H+ or
NaCN/H+ , water, alcohol, sodium bisulphite, i) 2,4-dinitrophenylhydrazine
NaHSO3 and Grignard reagent. (2,4-DNPH),
ii) reduction to alcohol using LiAlH4 ii) Tollens’, Fehlings’,
followed by H3O+ or NaBH4 in Methanol or H2/
catalyst. and Benedict’s
iii) condensation with ammonia derivatives b) Differentiate between:
such as hydroxylamine, hydrazine, i) carbonyl and other compounds
phenylhydrazine and
ii) aldehydes and ketone
2,4- Dinitrophenylhydrazine (2,4-DNPH) as
(Experiment 6 : Aldehyde and ketone)
identification test for carbonyl
compounds. d) Outline the synthesis of compounds
involving carbonyl compounds.
iv) oxidation with KMnO4/H+ or Cr2O72-/H+
v) iodoform test to identify methyl carbonyl
group.
 9.1 INTRODUCTION TO CARBONYL COMPOUNDS
❖ Functional group: carbonyl, C=O
❖ General formula: CnH2nO
❖ Aldehyde & Ketone are isomeric
❖ Carbonyl compounds are polar
❖ In general, an aldehyde > reactive than
ketone towards nucleophilic addition reaction
❖ The simplest carbonyl compounds KETONE ALDEHYDE
❖ Aldehyde contains at least one
O – O –
H atom bonded to the c=o,
C + C +
whereas ketone has wo alkyl or
R R' R H
aryl group bonded to it
RCOR RCHO
R & R : alkyl,aryl R : alkyl, aryl @ H
 9.2 NOMENCLATURE OF CARBONYL COMPOUNDS
Aldehyde
• Aldehyde is named by
substituting the letter –e of the
corresponding alkane with –al
• Parent name depends on the
longest chain with –CHO group
• The chain must be numbered
by starting with –CHO group as
C-1
9.2 NOMENCLATURE OF CARBONYL COMPOUNDS
Aldehyde • When the -CHO group is attached to a ring, suffix -
carbaldehyde is used

Cyclohexanecarbaldehyde 2-hydroxycyclopentanecarbaldehyde
 9.2 NOMENCLATURE OF CARBONYL COMPOUNDS
ketone

• Ketone is named by
substituting the letter –e of
corresponding alkane with –
one
• The longest chain with carbonyl
group is numbered so that C in
carbonyl group gets the
smallest number.
 IDENTIFICATION TEST FOR
ALDEHYDE & KETONE

01 2,4-dinitrophenylhydrazine

R' H R'
C O NNH NO2 C NNH NO2 + H2O
R H R
NO2 NO2
2,4-dinitrophenylhydrazine @ 2,4-DNPH

Brady's reagent Yellow @ orange precipitate

Observation: Orange or yellow precipitate formed

 IDENTIFICATION TEST FOR
ALDEHYDE & KETONE
• Tollens’ reagent : Silver (I) oxide in aqueous ammonia,
02 Tollens' test ( Ag(NH3)2+) @ [Ag(NH3)2]+/OH-
• In this reaction aldehyde is oxidised to carboxylate ion and argentum
is deposited on the wall of the test tube as a silver mirror.

O O
CH3CH2C H + [Ag(NH3)2]+ + OH - CH3CH2C O - + Ag
silver mirror
Observation: Silver mirror precipitate formed

O O
C H + [Ag(NH3)2]+ + OH - C O- + Ag
silver mirror
Observation: Silver mirror precipitate formed
 IDENTIFICATION TEST FOR
ALDEHYDE & KETONE

02 Tollens' test

Observation: No silver mirror precipitate formed

 IDENTIFICATION TEST FOR
ALDEHYDE & KETONE
• Prepared by mixing copper(II) sulphate solution with sodium potassium tartrate
Fehling’s test in NaOH (aq)
03
• Function: used to identify aliphatic aldehydes.
• Fehling's reagent will oxidise aliphatic aldehydes only.
• In this reaction copper(II) is reduced to copper(I)

Before After

Observation: Brick red precipitate formed

 IDENTIFICATION TEST FOR
ALDEHYDE & KETONE
• Prepare by mixing CuSO4 solution, citrate ions and NaOH(aq).
04 Benedict’s test • Benedict’s reagent contains blue copper sulfate(CuSO4.5H2O)
• Function : used to identify aliphatic aldehydes.
• Products : Produce carboxylate ion and copper (I) oxide.

Before After
Observation: Brick red precipitate formed
C HCarboxylic
A P TAcids
ER& its1 0
derivatives
Prepared with ♥️by : Mdm Lizawati Binti Mohamad Ham
Learning Outcomes
At the end of the lesson the students should be able to:

10.1 Introduction.
a) State the general formula of carboxylic acids:
RCOOH and ArCOOH
b) Give the name of carboxyl compounds according to the IUPAC
nomenclature.
c) State the common names of carboxylic acids with parent chain ≤ C5
d) Give the structural formulae of carboxyl compounds (parent chain ≤
C10)
10.2 Physical Properties
a) Explain the physical properties:
i. boiling point
ii. solubility in water
 Learning Outcomes
At the end of the lesson the students should be able to:

10.2 Physical Properties

b) Explain the acidity of:
i. carboxylic acid in comparison with alcohol and phenol
ii. halogenated carboxylic acids based on the:
- number of halogens
- position of halogens
*include inductive effect or function of halogen as Electron
Withdrawing Group

10.3 Preparation
a) Explain the preparation (synthesis) of carboxylic acid through:
i. oxidation of alkylbenzene, alcohol and aldehyde
ii. hydrolysis of nitrile compound
iii. carbonation of Grignard reagent
Learning Outcomes
At the end of the lesson the students should be able to:
10.4 Chemical Properties
a) Explain the chemical properties with reference to :
i. neutralisation with a base
ii. reaction with electropositive metals such as Na, K, Mg or Ca.
iii. reduction with LiAlH4 followed by H3O+
iv. acyl chloride formation
v. anhydride formation
vi. Esterification
vii. amide formation
b) Explain the reducing property of methanoic acid with:
i. KMnO4/H3O+
ii. Tollens’ reagent
c) Outline the synthesis of compounds involving carboxylic acids.
d) Explain the preparation of synthetic polymers through condensation
polymerization to produce polyamides (e.g. Kevlar. Nylon 6, nylon 6,6)
and polyester (e.g. dacron/terylene)
Learning Outcomes
At the end of the lesson the students should be able to:

10.1 Write the general formula of carboxylic acids. RCOOH and ArCOOH

10.2 Nomenclature of Carboxylic Acids

a) Draw the structures and name the carboxyl compounds
(parent chain ≤ C10) according to the IUPAC nomenclature.
b) Give common name with parent chain ≤ C5

10.3 Physical Properties of Carboxylic Acids

a) Explain the physical properties:
i. boiling point
ii. solubility in water
 Learning Outcomes
At the end of the lesson the students should be able to:

10.3 Physical Properties of Carboxylic Acids

b) Explain the acidity of:
i. carboxylic acid in comparison with alcohol and phenol
ii. halogenated carboxylic acids based on the:
- number of halogens
- position of halogens
c) Compare the acidity between carboxylic acids.

10.4 Synthesis Of Carboxylic Acids

a) Explain the preparation (synthesis) of carboxylic acid through:
i. oxidation of alkylbenzene, alcohol and aldehyde
ii. hydrolysis of nitrile compound
iii. carbonation of Grignard reagent
 Learning Outcomes
At the end of the lesson the students should be able to:
10.5 Chemical Properties of Carboxylic Acids
a) Explain the chemical properties with reference to :
i. neutralisation with a base
ii. reaction with electropositive metals such as Na, K, Mg or Ca.
iii. reduction with LiAlH4 followed by H3O+
iv. acyl chloride formation
v. anhydride formation
vi. Esterification
vii. amide formation
b) Predict the products of reactions of carboxylic acids with reagents in
(a).
c) Explain the reducing property of methanoic acid with:
i. KMnO4/H3O+
ii. Tollens’ reagent
d) Outline the synthesis of compounds related to reactions of
 10.1 Introduction
10.2 Nomenclature
of carboxylic acids
 10.1 Introduction to carboxylic acids
What is carboxylic acids?
Is an organic acid
Contain one or more carboxyl group as functional group

General formula?

R C OH
RCOOH or RCO2H

Where R ≡ alkyl, aryl or H

 10.2 Nomenclature of carboxylic acids
Naming aliphatic carboxylic acids

The longest chain must contain the carboxyl group.

The carboxyl group is at the terminal, therefore the carbon of the

carboxyl group is not numbered.
One COOH – carboxyl group is at one end
Two COOH – carboxyl groups are at both ends

Name the compound as alkane, drop ‘e’ in alkane and add ‘oic
acid’ (eg: methanoic acid)
 10.2 Nomenclature of carboxylic acids
IUPAC & Common Name For Some Carboxylic Acids
STRUCTURAL COMMON
IUPAC NAME
FORMULA NAME

HCOOH Methanoic acid Formic acid

CH3COOH Ethanoic acid Acetic acid

CH3CH2COOH Propanoic acid Propionic acid

CH3CH2CH2COOH Butanoic acid Butyric acid found in butter, ghee,

raw milk, animal fats
and plant oils
CH3CH2CH2CH2COO Pentanoic
Valeric acid
H acid Methyl pentanoate, with a fruity odour,
used in fragrances, beauty care, soap,
laundry detergents at levels of 0.1–1%
 10.2 Nomenclature of carboxylic acids
Naming aliphatic carboxylic acids

When a compound contains a carboxyl group and other functional

group (s), the priority is given to the carboxylic acid as the parent
name.
Example:

O 6 CH 3 O
Br CH3
CH3 CHCHCH2 C OH HO CH CH 2 CH 2 CH 2 C OH
5 4 3 2 1 5 4 3 2 1

4-bromo-3-methylpentanoic acid 5-hydroxyhexanoic acid

 10.2 Nomenclature of carboxylic acids
Naming aliphatic carboxylic
acids
Carboxylic acid with double bonding are named as
x – alkenoic acid [x = position of double bond]
Example:

1 4
O CH3 HOOC COOH
2 3
C C
HO C CH2 CH CH CH CH3
1 2 3 4 5 6
H H

5-methyl-3-hexenoic acid cis-2-butenedioic acid

 10.2 Nomenclature of carboxylic acids
Naming aliphatic dicarboxylic acids

Two COOH groups, the compound will be named as:

(i) alkanedioic acid
(ii) alkenedioic acid
Example:

O CH3 O
5 6
HO C CH2 CH CH2 CH2 C OH H CH2 COOH
1 2 3 4 5 6
3 4
3-methylhexanedioic acid C C
1 2
HOOC CH2 H

trans-3-hexenedioic acid
 10.2 Nomenclature of carboxylic acids
Naming aliphatic cyclic carboxylic acids

A cyclic carboxylic acid is named as:

(i) cycloalkanecarboxylic acid
(ii) cycloalkenecarboxylic acid
The C atom which is attached to –COOH is numbered as C1
Example:
COOH
2 1
3 6 2
1
COOH
3
5
4 CH3
5 4

cyclopentanecarboxylic acid 3-methyl-2-cyclohexenecarboxylic acid

 10.2 Nomenclature of carboxylic acids
Naming aliphatic cyclic dicarboxylic acids

A cyclic dicarboxylic acid is named as:

(i) 1,x – cycloalkanedicarboxylic acid
(ii) 1,x – cycloalkenedicarboxylic acid
Example: 6
1 COOH
5
6
COOH
5
1 Cl 4 2 COOH
3
4
2
COOH 4-chloro-1,2-cyclohex-1-enedicarboxylic acid
3
1,2-cyclohexanedicarboxylic acid
 10.2 Nomenclature of carboxylic acids
Naming aromatic carboxylic acids

When R is an aryl group, the parent name is benzoic acid

Example:
COOH CH3
3 2 1 2
3
6 2
Cl 4 1 COOH 4 1
COOH
3
5
5 6 4
NO2 5 6

4-chlorobenzoic acid 3-nitrobenzoic acid 2-methylbenzoic acid

@ @ @
p-chlorobenzoic acid m-nitrobenzoic acid o-methylbenzoic acid
 10.2 Nomenclature of carboxylic acids
Naming aromatic dicarboxylic acids

An aromatic dicarboxylic acid is named as

1,x-benzenedicarboxylic acid
Example:

HOOC
3 2
HOOC
4 3 4 1
CH3 COOH
2
5 CH CH3
5 6
6 1 1,3-benzenedicarboxylic acid
COOH
2-isopropyl-1,4-benzenedicarboxylic acid
 10.3 Physical
properties of
carboxylic acids
 Boiling Point of carboxylic acid
• Straight chain carboxylic acid has higher boiling
Isomeric carboxylic point than more branched carboxylic acid because it
acid has bigger contact surface area and stronger van
Butanoic acid der Waals forces between its molecules
(Mr = 89)
(B.P. = 163.5 ℃)
• Branched chain carboxylic acid has lower boiling
point than straight chain carboxylic acid because it
2-methylpropanoic acid has smaller contact surface area and weaker
(Mr = 89)
(B.P. = 155 ℃)
van der Waals forces between its molecules
Boiling Successive • As the number of carbon increases, the molecular
point carboxylic acid size/mass/weight also increases.
• The contact surface area become bigger
• The strength of van der Waals forces become
Propanoic acid Butanoic acid stronger.
(Mr = 74) (Mr = 89) • Therefore boiling point increases.
(B.P. = 141.2 ℃) (B.P. = 163.5 ℃)
Carboxylic acid vs • Dicarboxylic acid has higher boiling point than
Dicarboxylic acid carboxylic acid with similar molecular mass because
dicarboxylic acid has more carboxyl group and
can form more hydrogen bond between its
Butanoic acid Ethanedioic acid molecules than carboxylic acid.
(Mr = 89 ; B.P. = 163.5 ℃) (Mr = 90 ; B.P. = 365.1 ℃)
 Comparison boiling point between organic compounds
(with comparable relative molecular mass)
Can form stronger
More polar than aldehyde and Can form strong hydrogen bond
can form stronger dipole-dipole hydrogen bond between between its
forces between its molecules its molecules compared molecules in form of
compared to aldehyde to carboxylic acid stable dimer

Carboxylic
Alkanes < Haloalkanes < Aldehyde < Ketones < Alcohols < acid

Can form Can form weaker More polar than

weakest dipole-dipole haloalkanes and can
London between its form strong dipole-
dispersion molecules dipole forces
forces between compared to between its
its molecules aldehyde & ketones molecules compared
to haloalkanes
 Solubility of carboxylic acid in water
• Carboxylic acids are soluble in water due to the
Carboxylic formation of hydrogen bond between the water
acid molecules and carboxylic acid molecules.
• Simple carboxylic acids (C1 – C5) are completely
soluble in water.

Solubility
in water

Successive
Carboxylic • As the number of carbon increases, the molecular
acid size/mass/weight also increases.
• The hydrophobic area become bigger.
• More difficult to form hydrogen bond with water molecules
• Therefore, solubility decreases.
 Solubility of carboxylic acid in water
• Aromatic carboxylic acids are slightly soluble in
Aromatic
water due to the huge aromatic ring
Carboxylic
acid

Solubility
in water • Dicarboxylic acid is more soluble in water than
carboxylic acid because it has more carboxyl
group and can form more hydrogen bond with
water molecules than carboxylic acid
Dicarboxylic
acid vs
carboxylic
acid
 Solubility of carboxylic acid in water
• Carboxylic acid is more soluble in water than alkane
Carboxylic because it can form hydrogen bond with water molecules
acid vs whereas alkane cannot form hydrogen bond with water
Alkane molecules since it does not has any hydroxyl group

Solubility
in water Butanoic acid Butane

• Carboxylic acid is more soluble in water than alcohol

because it can form more hydrogen bond with water
molecules through both hydroxyl group and carbonyl
Carboxylic
group whereas alcohol can only form less hydrogen bond
acid vs between water molecules
Alcohol

Butanoic acid 1-butanol

 Solubility of carboxylic acid in organic solvent
Non-polar • Carboxylic acids are soluble in non polar solvent such
as benzene due to the formation of van der Waals
organic
forces between the benzene and alkyl group of
solvent
carboxylic acids.

Solubility
in organic
solvent

• Carboxylic acids are soluble in polar solvent such as

Polar ether through to the formation of van der Waals forces
organic between the ether and alkyl group of carboxylic
solvent acids.
• Carboxylic acids are also soluble in alcohol through the
formation of hydrogen bond between hydroxyl group of
alcohol and carboxyl group of carboxylic acids
Acidity of carboxylic acids (Resonance effect)
Phenol
❑ Phenol dissociate in water to form phenoxide
ion.
❑ The negative charge in phenoxide ion are
delocalised in the benzene ring.
❑ The resonance structure of carboxylate ion
is more stable than the phenoxide ion.
❑ Therefore carboxylic acid are more acidic
than phenol.

Alcohol
❑ Alcohol dissociate in water to form alkoxide ion
❑ Alcohol is the least acidic compare to carboxylic acid and phenol due to the electrons
are localized at oxygen atom in alkoxide ion.
Acidity of carboxylic acids (Resonance effect)
Carboxylic acids
❑ Carboxylic acids are more acidic than phenol and alcohol due to the :
❖ resonance stabilisation of the carboxylate ion (the stabilization by delocalisation of
pi electrons)
❖ The negative inductive effect of carbonyl group (the shift of electron density from
one atom to another to form polar bond)
❑ The electrons in carboxylate ion are delocalised between two oxygen atoms which
stabilises the carboxylate ion and promotes the release of H+
❑ The carboxylate ion is delocalised to a far extent than corresponding phenoxide ion.
Hence, carboxylic acids is a stronger acid than phenol.
❑ The C=O group in carboxylic acid is an electron-withdrawing group (EWG) which
reduce the electron density of O – H .
❑ Therefore the O – H bond becomes weaker and H+ is easily donated
❑ Thus, carboxylic acid is stronger acid than alcohol and phenol.
Acidity of carboxylic acids (Inductive effect)
❑ An electron withdrawing
group (EWG), that attached to
a carboxylate ion will
delocalise the negative
EWG
charge, thereby stabilises the
carboxylate ion and increases
acidity.
Inductive effect of EWG
❑ The EWG reduce the electron density
O
of O – H.
❑ Thus, the O – H bond becomes weaker
C
and H+ can be easily released/donated.
-
O ❑ The compound is more acidic.
❑ Therefore, EWG increases the acidity.

❑ More electronegative
EWG O–H Easier to More
Greater acidic @
❑ Distance EWG bond donate/
inductive acidity
closer to COOH become released
effect increase
❑ More number of weaker H+
EWG

Increasing
- I < - Br < - Cl < - F strength of
EWG
 Acidity of carboxylic acids (Inductive effect)
The presence of EWG
O O
OH OH
Cl
A B
❑ The inductive effect of Cl is an
electron-withdrawing groups,
reduce the electron density of O-H.
❑ Thus the O-H bond becomes weaker
and H+ can be easily
released/donated
❑ Thus, compound B is more acidic
than A
❑ Therefore, electron-withdrawing
groups increase the acidity.
Electronegativity of EWG
O O
OH OH
F Cl
C D
❑ Both F and Cl are electron withdrawing
group (EWG)
❑ F is more electronegative than Cl.
❑ Hence, the inductive effect of F is
stronger than Cl.
❑ The electron density of O-H bond in C is
less, thus the O-H bond is weaker than D.
Therefore, H+ can be easily
released/donated.
❑ Thus, compound C is more acidic than D
 Acidity of carboxylic acids (Inductive effect)
The position of EWG Number of EWG
O Cl O O O

OH OH OH OH
Cl Cl Cl Cl
E F G H

❑ The distance between Cl atom and ❑ Both compound contain Cl which is an

carboxyl group in E is nearer
compare to in F, which will gives a
greater inductive effect
❑ The O – H bond in E is weaker than
in F, so H+ is easily
released/donated.
❑ Thus, compound E is more acidic
than F
electron withdrawing group (EWG)
❑ G contains 2 Cl atoms which creates a
greater inductive effect and makes the
bond of O-H weaker than H with only
one Cl atom.
❑ Thus, H+ is easily released/donated.
❑ Thus, compound G is more acidic
than H
Acidity of carboxylic acids (Inductive effect)
Inductive effect of EDG
❑ An electron O ❑ The EDG increase the electron density
donating group
of O – H.
(EDG) will EDG C ❑ Thus the O – H bond becomes stronger
destabilise the
- and H+ can be difficult to be released.
carboxylate ion and O ❑ The compound is less acidic.
decreases acidity
❑ EDG decreases the acidity.

❑ Presence of EDG Less

❑ Bigger size of Greater O–H Difficult to
acidic @
EDG inductive bond donate/
acidity
❑ More number of effect become released
decrease
EDG stronger H+
 Acidity of carboxylic acids (Inductive effect)
The presence of EDG
O O
OH OH
Cl
P Q
❑ Cl is an electron-withdrawing group
(EWG), while CH3 is an electron-
donating group (EDG).
❑ EDG increase the electron density
of O – H.
❑ Thus the O-H bond in P becomes
stronger and H+ is difficult to be
released/donated than Q
❑ Thus, compound Q is more acidic
than P
Bigger size of EDG
O O
OH OH
R S
❑ R is an electron donating group (EDG).
❑ The size of –R group in S is larger than in
R, so CH3CH2- is a stronger EDG than
CH3-.
❑ The electron density of O-H in S increases
and H+ is difficult to be released/donated
than R
❑ Thus, compound R is more acidic than S
❑ EDG reduce the acidity of a carboxylic
acid.
Acidity of carboxylic acids
(Inductive effect)
More electronegative Greater
EWG/ Distance EWG
Number of EDG inductive effect
closer to COOH/ More
O O number of EWG

OH More acidic Easier to O – H bond

OH @ acidity donate/ become
increase released H+ weaker

T U

❑ T contains 2 R groups which creates a Bigger size of Greater

greater inductive effect and makes the EDG/ More inductive effect
bond of O-H bond stronger than U number of EDG
(with only one R group).
❑ Thus, H+ is difficult to be
Less acidic Difficult to O – H bond
released/donated. become
@ acidity donate/
❑ Thus, compound U is more acidic decrease released stronger
than T H+