ORGANIC CHEMISTRY

CHM 207

Chapter 8
Carboxyl Compounds
(Aliphatic and Aromatic)
Content
Carboxyl
Compound
s

Uses of
carboxylic
acid

Reactions of
- Acidity
-
carboxylic acids Formation of salt Nomen
and benzoic
acid
- Formation of ester clature
- Formation of acid chloride
- Formation of anhydrides
- Formation of amides
Physical
- Reduction of alcohols
properties
Functional group: carboxyl group, -COOH

O
C OH
 General formulae:

O
R C OH R = alkyl g ro u p

O
Ar C OH A r = aryl g ro u p
NOMENCLATURE OF CARBOXYLIC ACIDS
• The carbonyl group (-C=O) is always at the
beginning of a carbon chain.

• The carbonyl carbon atom is always

designated as C-1.

3 2 1
 Find the parent: The parent compound (or chain)
must have the carboxyl carbon in the chain.
Parent compound should have the longest
carbon atom.
 The parent name is formed by changing the –e
ending of the alkane to –oic acid.

methane methanoic acid

 Examples of carboxylic acids

O O
3 4 3 2
2 1
CH 3 CH C O H CH 3 C H CH C O H
1
Br C H 3 CH 3
2-brom opropanoic acid 2,3-dim ethylbutanoic acid
 Organic acids are usually known by common
names.

IUPAC name: IUPAC name:

ethanoic acid methanoic acid
Common name: Common name:
acetic acid formic acid
 CARBOXYLIC ACID DERIVATIVES
Group replacing Classes of General Example
the –OH group compound formula
of RCOOH
-X (halogen) Acyl
halide/acid
O O
H3C C CI
chlorides R C X ethanoyl chloride
-OR’ Ester
O O
H3C C OC2H5
R C OR' ethyl ethanoate
-NH2 Amide
O O
H 3C C NH 2

Acid R C NH2 e th a n a m id e

O anhydride O O
O O
H 3C C O C CH 3
O C R' R C O C R' ethanoic anhydride
 NOMENCLATURE OF AROMATIC
CARBOXYLIC ACIDS
General formula for the aromatic carboxylic acids:
Ar-COOH, where Ar is aryl group (aromatic group).
Examples:

O
C OH COOH COOH
1
OH 6 2
3
5
4 NO2
benzoic acid 2-hydroxybenzoic acid 3-nitrobenzoic acid
 NOMENCLATURE OF ALIPHATIC
DICARBOXYLIC ACIDS

Carboxylic acids containing two carboxyl groups are

called dicarboxyl acids.
Their systematic names have the suffix ‘dioic’.

COOH COOH
COOH CH2 (CH2)4
COOH COOH COOH
ethanedioic acid propanedioic acid hexanedioic acid
(oxalic acid) (malonic acid) (adipic acid)
PHYSICAL PROPERTIES OF CARBOXYLIC
ACIDS

 Methanoic acid has a pungent odour.

 Ethanoic acid and propanoic acids have strong
vinegar smell.
 The higher members of the homologous series
(acids with four to eight carbon atoms) have a very
strong unplesent odour of rancid butter.
 Butanoic acid is present in human sweat and in
butter.
Boiling point:
 Aliphatic acids with one to 10 carbon atoms are liquids.
 The boiling points increase with increasing relative molecular
mass.
 Carboxylic acids have higher melting and boiling points than
alkanes of similar relative molecular mass.
- reason: carboxylic acid can form hydrogen bonds with one
another in the solid and liquid states.
 Boiling points of carboxylic acid is higher than alcohols,
aldehyde or ketone with similar relative molecular mass.

O O
CH3 C OH CH3CH2CH2-OH CH3 C CH3
acetic acid 1-propanol propanone
(RMM 60) (RMM 60) (RMM 58)
o
bp 118 C bp 97oC bp 56oC
Reason:
i) Carboxylic acids form stronger hydrogen bonds than that
alcohols. The carbonyl, C=O group in a carboxylic acid is an
electron withdrawing group. This causes the –OH group in a
carboxylic acid to be more polarised than that the –OH group in an
alcohol.
O H
R C O H

δ- δ+
R C O H
H

F O R M A T I O N O F D I M E R S

h y d r o g e n b o n d

O H O

δ- δ+
R C C R
O H O

h y d r o g e n b o n d

ii) Formation of dimers between two molecules of carboxylic acids to

form a single molecule via
O hydrogen bonding.
H
R C O H
R C O H
H

F O R M A T IO N O F D IM E R S

h y d ro g e n b o n d

O H O
R C C R
O H O

h y d ro g e n b o n d
Solubility in water:
 Carboxylic acids are fairly soluble in water due to hydrogen
bonding with H2O molecule.
 The solubility of carboxylic acids in water decreases as the relative
molecular mass increases. For examples, propanoic acid is very
soluble in water, butanoic acid and pentanoic acid are soluble in
water, but hexanoic acid is only slightly soluble in water.
 The solubility of carboxylic acids in non-polar solvents such as
hexane increases as the carbon chain gets longer.

R H O
H C O
δ+
O H O δ-
δ- δ+
H δ-
H

O δ+H
hydrogen bonds
 PHYSICAL PROPERTIES OF BENZOIC
ACIDS

 Crystalline compound
 Melting points: 122 oC
 Slightly soluble in water at room temperature
but dissolve readily in hot water.
 Soluble in benzene and other organic
solvents.
 In organic solvent, it exists as a dimer
through hydrogen bonding.
 ACIDITY OF CARBOXYLIC ACIDS

1) The acidity of carboxylic acids compared with

alcohols and phenols.
 Carboxylic acids are acidic because they dissolve in
water to give hydronium ions (H3O+).
RCOOH + H2O RCOO- + H3O+
 Carboxylic acids are stronger acids than alcohols and
phenols.
 Reasons:
i) the negative inductive effect of the carbonyl group
ii) the resonance effect of the carbonyl group.
 Strong negative inductive effect of the carbonyl
oxygen
 Inductive effect: the shift in electron density from one atom to
another to form a polar bond.
 Indicated by an arrow showing the direction of the shift of the
electronic charge.

δ+ δ-
C Cl

The arrow in the representation of the inductive effect shows

that
a) the carbon atom repels electrons
b) the chlorine atom attracts electrons because of its higher
electronegativity
 The oxygen atom in –C=O group is
electronegative and acts as a powerful electron-
withdrawing atom.

 The withdrawal of electrons away from the

carboxyl hydrogen atom weakens the O-H bond.
The carbonyl group can lose a proton readily. This
means that a carboxylic acid is much stronger
acid than an alcohol.
δ-
O
δ+
CH3 C
O H
 Resonance effect of the carbonyl group
The carboxylate anion is a resonance hybrid of two resonance
structures.
O O
R C R C
O O

 In the carboxylate anion, the negative charge is delocalised over

two carbon-oxygen bonds.

 The delocalisation or resonance stabilises the carboxylate anion.

 The carboxylate anion has less tendency to accept H3O+ ions and
the equilibrium tends to the right.
RCOOH + H2O RCOO- + H3O+

 Delocalisation of electrons in the carboxylate anion promotes the

release of a proton and makes the carboxylic acid a stronger acid
than alcohols and phenol.
2) Effects of substituent groups on the acidity of
carboxylic acids.
i) electron-withdrawing groups increase acidity

- an electron withdrawing group attached to a carboxylate

ion will delocalize the negative charge, thereby stabilizes
carboxylate ion and increasing acidity.
- Example of an electron-withdrawing group: halogen
atom, –NO2

EWG C O
 EFFECT OF ELECTRON-WITHDRAWING GROUPS ON
ACID STRENGTH

Formula pKa
CH3COOH 4.74
I CH2COOH 3.12 ACID
Br CH2COOH 2.90 STRENGTH
INCREASES
Cl CH2COOH 2.86
F CH2COOH 2.66
O2N CH2COOH 1.67

• Fluorine is more electronegative than chlorine and therefore

has a stronger electron-withdrawing effect.
• Fluoroethanoic acid is a stronger acid than chloroethanoic
acid
ii) Number of halogen atoms and acid strength
- the acid strength will increases when the number of
halogen atoms increases.
- trichloroethanoic acid (Cl3C-COOH) is more acidic than
ethanoic acid and dichloroethanoic acid (Cl2CHCOOH).
Formula pKa
CH3COOH 4.74
Cl CH2COOH 2.86
ACID
Cl STRENGTH
CH2COOH 1.29
Cl INCREASES

Cl
Cl CH2COOH 0.65

Cl
iii) Effect of position of halogen atom on acid strength
- The magnitude of the inductive effect is dependent on its
distance from the carboxyl group.
- substituents on the α-carbon (the carbon atom next to the –
COOH group) are the most effective in increasing acid
strength.
- the effect of a chlorine substituent decreases rapidly as the
substituent moves further from the carboxyl group.
- the inductive effect is negligible after the second carbon.

Formula pKa
Cl
2.84 ACID
CH3CH2CH COOH STRENGTH
Cl DECREASES
4.06
CH3CH CH2 COOH
Cl
CH2CH2 CH2 COOH
4.52
- aromatic nucleus (benzene ring) and multiple bonds
are electron-withdrawing groups and possess negative
inductive effects, therefore increase acidity.
- benzoic acid is a stronger acid than ethanoic acid
and the unsaturated acid (CH2=CHCOOH) is a stronger
acid than the corresponding saturated acid,
CH3CH2COOH.
Formula pKa
C H 3 C O O H
4.74
C O O H

C H 3 C H 2 C O O H 4.19
C H 2 = C H C O O H

C H 3 C O O H

C O O H
4.87
C H C H C O O H
C H 2
3 2

= C H C O O H
4.26
iv) electron-donating groups decrease acidity
- an electron-donating group destabilizes the
carboxylate anion by increasing the charge density of
the oxygen atom in the C-O bond and decrease acidity.
CH3
CH3 C O-
CH3 Increase in charge density

- The increase in charge density strengthens the –OH bond.

- This makes proton loss more difficult.
- Thus, the presence of electron-donating groups decreases the
strength of an acid.
- Example of electron-donating groups: alkyl and ethoxy (-OR)
EFFECT OF ELECTRON-DONATING GROUPS ON
ACID STRENGTH

Formula pKa
H-COOH 3.77
CH3 COOH 4.74
CH3 CH2 COOH 4.88
ACID
CH3 STRENGTH
4.85 DECREASES
CH COOH
CH3

CH3
5.07
CH3 C O-
CH3
 Trends in acidity of substituted benzoic acids

COOH COOH
COOH

OCH3 NO2
4-methoxybenzoic acid benzoic acid 4-nitrobenzoic acid
pKa = 4.46 pKa = 4.19 pKa = 3.41

acid strength increases

* methoxy substituent (CH3O-) : electron-donating and decreases the acid strength

* -NO2 : electron-withdrawing and increases the acid strength
 REACTIONS OF CARBOXYLIC ACIDS

i. Salt formation
- neutralisation
- reactions with electropositive metals
ii. Reduction to alcohols
iii. Formation of Acyl Chlorides
iv. Formation of Esters
v. Formation of Acid Anhydrides
vi. Formation of Amides
 i) SALT FORMATION
1) Neutralisation:
- carboxylic acids undergo neutralisation reactions with
bases to form carboxylate salts of carboxylic acids and
water.
- examples:
CH3COOH (aq) + NaOH (aq) → CH3COONa (aq) + H2O (l)
sodium ethanoate

2CH3COOH(aq) + CuO (s) → (CH3COO)2Cu(aq) + H2O (l)

copper(II) ethanoate

CH3CH2COOH + NaOH → CH3CH2COONa + H2O

propanoic acid sodium propanoate

* carboxylate salts are soluble in water

 an aqueous solution of benzoic acid turns blue litmus paper
to red.
 Benzoic acids dissolves readily in alkalis to form salts
(benzoates) and water.
- +
COOH NaOH COO Na H2O

sodium benzoate

 Carboxylic acids react with carbonates and hydrogen

carbonates to form CO2, water and salts of carboxylic acids.
 Examples:

2HCOOH (aq) + Na2CO3 (aq) → 2HCOONa (aq) + CO2 (g) + H2O (l)
sodium methanoate

CH3CH2COOH(aq) + NaHCO3(aq) → CH3CH2COONa (aq) + CO2(g)+ H2O(l)

sodium propanoate

• Phenol is a weak acid compared to carboxylic acids.
• Phenol did not react with NaHCO3 and only react with strong
base such as NaOH to form salt.
• Reactions with NaHCO3 can be used to distinguish carboxylic
acid with phenol and other organic compounds.
• Comparison of the solubility of organic compounds are listed
in table below:

Solubility of carboxylate salts from base

Organic compounds
NaOH NaHCO3

Neutral organic Insoluble Insoluble

compounds
Phenol Soluble Insoluble

Carboxylic acids Soluble Soluble

2) Reaction with electropositive metals

• reactive metals (i.e. metals that are very

electropositive) react with carboxylic acids to
form hydrogen gas and salts of carboxylic acids.
• examples of metals: calcium, magnesium and
iron.

2CH3COOH (aq) + Mg → (CH3COO)2Mg(aq) + H2 (g)

magnesium ethanoate
 ii) REDUCTION TO ALCOHOLS
 Reducing agents: LiAlH4 in dry ether
 Carboxylic acids reduced
primary alcohols
O H
( 1 ) L iA lH 4 / e th e r
R C OH R C OH
(2 ) H 2O
c a r b o x y lic a c id s H
p r im a r y a lc o h o ls
e x a m p le s :
O H
(1 ) L iA lH 4 / e th e r
CH3 C OH CH3 C OH
(2 ) H 2 O
e th a n o ic a c id H
e th a n o l
- B e n z o ic a c id c a n b e r e d u c e d t o p h e n y lm e t h a n o l b y u s in g L iA lH 4 in e t h e r a t
lo w te m p e ra tu r e s .
- A n a lk o x id e in te r m e d ia te is f o r m e d fir s t.
- O n a d d in g w a te r , h y d r o ly s is o f t h e in te r m e d ia t e y ie ld s t h e p r im a r y a lc o h o ls .
O H
( 1 ) L iA lH 4 / e th e r
C OH C OH
(2 ) H 2O
b e n z o ic a c id H
p h e n y lm e th a n o l
  Benzoic acid can be reduced to phenylmethanol by using
LiAlH4 in ether at low temperatures.
 An alkoxide intermediate is formed first.
 On adding water, hydrolysis of the intermediate yields the
primary alcohols.
O H
(1 ) L iA lH 4 / e th e r
R C O H R C O H
(2 ) H 2 O
c a r b o x y lic a c id s H
p r im a ry a lc o h o ls
e x a m p le s :
O H
(1 ) L iA lH 4 / e th e r
C H 3 C O H C H 3 C O H
(2 ) H 2 O
e t h a n o ic a c id H
e th a n o l
- B e n z o ic a c id c a n b e r e d u c e d to p h e n y lm e th a n o l b y u s in g L iA lH 4 in e th e r a t
lo w te m p e r a tu r e s .
- A n a lk o x id e in te rm e d ia te is fo r m e d fir s t.
- O n a d d in g w a te r , h y d r o ly s is o f th e in te r m e d ia t e y ie ld s th e p r im a r y a lc o h o ls .
O H
(1 ) L iA lH 4 / e th e r
C O H C O H
(2 ) H 2 O
b e n z o ic a c id H
p h e n y lm e th a n o l

 LiAlH4 has no effect on the benzene ring or the double bond.

 -COOH is reduced to –CH2OH but the C=C bonds remains
unchanged.
1) LiAlH4
CH3CH2CH=CHCOOH CH3CH2CH=CHCH2OH
2) H2O
 iii) FORMATION OF ACYL CHLORIDES / ACID
CHLORIDE
 Carboxylic acids reacts with phosphorus (v) chloride or
sulphur dichloride oxide (thionyl chloride) or
phosphorus trichloride (PCl3) at room temperature to
form acyl chloride.
 In the case of benzoic acid, the reaction mixture is
heated.
O O
R C OH PCl5 R C Cl POCl3 HCl
carboxylic acids acid chlorides

O O
R C OH SOCl2 R C Cl SO2 HCl
carboxylic acids acid chlorides
 Examples:

O O
CH3 C OH SOCl2 CH3 C Cl SO2 HCl
ethanoic acid ethanoyl chloride

O O
C OH SOCl2 C Cl SO2 HCl
benzoic acid benzoyl chloride
 iv) FORMATION OF ESTERS
 When a carboxylic acid is heated with an alcohol in the
presence of a little concentrated sulphuric acid, an ester
is formed.
 Simple esters have fragrant odours. They are used as
flavouring agents in the food industy.

O O
CH3 C OH H OC2H5 CH3 C OC2H5 H2O
ethanoic acid ethyl ethanoate

O O
C OH H OC2H5 C OC2H5 H2O

benzoic acid ethyl benzoate

 v) FORMATION OF ACID ANHYDRIDES
Preparation of acid anhydrides:
- reaction of sodium carboxylate with an acid chloride.
O O O O
R C O- Na+ Cl C R' R C O C R' NaCl
sodium carboxylate acid chloride acid anhydrides

examples
O O O O
CH3 C O Na
- +
Cl C CH3 CH3 C O C CH3 NaCl
sodium ethanoate ethanoyl chloride acetic anhydride

O O O O

CH3 C O Na
- +
Cl C CH3 C O C NaCl

sodium ethanoate benzoyl chloride acetic benzoic anhydride

• Acid anhydride is also formed when a carboxylic
acid is heated with phosphorus pentoxide (P 2O5) –
dehydration reaction.

• The water is absorbed by P2O5 to form H3PO4.

O O O O
P2O5
CH3 C OH HO C CH3 CH3 C O C CH3 H2O
two molecules of acetic acids acetic anhydride
 vi) FORMATION OF AMIDES
 Amides can be synthesised directly from carboxylic
acids, but the yield is poor.
 A better method of synthesising amides is by using
acid chlorides.
 When ammonium carboxylates are heated in the
presence of the free acid, dehydration occurs to form
the primary amide.
 Ammonium carboxylates are obtained by the reaction
of carboxylic acids with ammonia.
Excess RCOOH
RCOO NH4
- +
RCONH2 + H2O
Heat (100-200 °C)
1° amide
For example:
CH3COOH + NH3 → CH3COONH4 CH3CONH2 + H2O
heat
ammonium ethanamide
ethanoate
Secondary and tertiary amides can be synthesised by using
primary amines and secondary amines respectively.
O H O H
R C OH H N R' o R C N R' H2O
o heat (100-200 C) o
2 amide
1 amine
examples:
O H O H
CH3 C OH H N CH3 o
CH3 C N CH3 H2O
heat (100-200 C)
methylamine N-methylethanamide

O R" O R"
R C OH H N R' R C N R' H2O
o heat (100-200 oC) o
3 amide
2 amine
examples:
O CH3 O CH3
CH3 C OH H N CH3 o CH3 C N CH3 H2O
heat (100-200 C)
dimethylamine N,N-dimethylethanamide
 THE IMPORTANCE OF CARBOXYLIC
ACIDS AND THEIR DERIVATIVES
 Methanoic acid and ethanoic acid: coagulate rubber latex.
 Ethanoic acid:
- used in the food industry as vinegar.
- making cellulose ethanoates for producing artificial fibres.
 Hexanedioic acid, HOOC(CH2)4COOH:
- manufacture of nylon 6,6
 Benzoic acid and sodium benzoate:
- as preservatives in foodstuff.
 2-hydroxybenzoic acid:
- making aspirin
 1,4-benzenedicarboxylic acid:
- making PET plastic
 Coumarin (C9H6O3) and its derivative, coumarinic acid (C9H8O3):
- anti-coagulants in medicine.
 Esters:
- responsible for the smell and flavour of many fruits and flowers.
 Vinyl acetate:
- formation of polyvinyl acetate (PVA) plastic.