ORGANIC CHEMISTRY II
CHM301
CHAPTER 3
CARBOXYLIC ACIDS
SUBTOPICS:
• GENERAL FORMULA OF CARBOXYLIC ACIDS.
• NOMENCLATURE OF CARBOXYLIC ACIDS.
• PHYSICAL PROPERTIES OF CARBOXYLIC ACIDS:
- Boiling points
- Solubility
- Acidity
• PREPARATIONS OF CARBOXYLIC ACIDS.
• REACTIONS OF CARBOXYLIC ACIDS.
GENERAL FORMULA OF CARBOXYLIC ACIDS
FUNCTIONAL GROUP:
CARBOXYL GROUP, -COOH
General formulae:
NOMENCLATURE OF CARBOXYLIC ACIDS
IUPAC NAME
• 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
• The iupac name of a carboxylic acid is derived
from the name of the alkane corresponding to
the longest carbon chain that contains the
carboxyl group.
▪ The parent name is formed by changing the –e
ending of the alkane to –oic acid.
methanoic acid
methane
Examples of carboxylic
acids
NOMENCLATURE OF CYCLOALKANES
WITH –COOH SUBSTITUENTS
Named as
cycloalkanecarboxylic
acids.
NOMENCLATURE OF CARBOXYLIC ACIDS
(TRIVIAL/COMMON NAME)
● Organic acids are usually known by
common names.
● These names usually refer to a natural
source of the acid.
NOMENCLATURE OF AROMATIC
CARBOXYLIC ACIDS
•General formula for the aromatic
carboxylic acids: arcooh, where ar is aryl
group (aromatic group).
•Examples:
NOMENCLATURE OF ALIPHATIC
DICARBOXYLIC ACIDS
• Carboxylic acids containing two carboxyl
groups are called dicarboxyl acids.
• Their systematic names have the suffix ‘dioic’.
PHYSICAL PROPERTIES OF CARBOXYLIC
ACIDS
BOILING POINTS OF ALIPHATIC CARBOXYLIC ACIDS
• Aliphatic acids with one to 10 carbon atoms are
liquids.
• The boiling points increase with increasing relative
molecular mass.
• Carboxylicacids 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.
Reasons:
- 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.
δ- δ+
δ- δ+
In the liquid and gaseous states or in non-polar
solvents, carboxylic acids exists as dimers
because a carboxylic acid molecule can form
hydrogen bonds with another carboxylic acid
molecule.
The dimer also
increases the van der
Waals dispersion
forces makes the
boiling point of
carboxylic acids
become more higher
than alcohols.
SOLUBILITY OF ALIPHATIC CARBOXYLIC
ACIDS
• Carboxylic acids of fairly low relative molecular mass
(one to four carbon atoms) – completely miscible in
water.
- reason: the –COOH group is able to form hydrogen
bonds with water molecules.
• 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.
δ+
δ-
δ- δ+
δ-
δ+
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.
- acidity of the carboxylic acids depends
on the stability of its carboxylate ions @
conjugate base.
WHY CARBOXYLIC ACIDS IS MORE
ACIDIC THAN PHENOL?
• Reasons: carboxylate ion is more stable than
phenoxide ion.
• Carboxylate ion is stable because:
i) electron in carboxylate ion are distributed
overNtwo oxygen atoms.
ii) the negative charge on the carboxylate ions
is delocalised onto more electronegative
oxygen atom.
TRENDS IN ACIDITY OF SUBSTITUTED BENZOIC
ACIDS
• methoxy substituent (CH3O-) : electron-donating and
decreases
the acid strength
* -NO2 : electron-withdrawing and increases the acid
strength
PREPARATION OF CARBOXYLIC
ACIDS
• Oxidationof primary alcohols, aldehydes,
alkenes and alkyl benzene
• Hydrolysis of nitriles (addition of carbon)
• Carboxylation of grignard reagents
(addition of carbon)
OXIDATION OF PRIMARY ALCOHOLS, ALDEHYDES,
ALKENES AND ALKYL BENZENE
I) OXIDATION OF PRIMARY ALCOHOLS
Example:
ii) OXIDATION OF ALDEHYDES
Oxidizing agents:
i)KMnO4 / H+ / heat
ii)K2Cr2O7 / H+ / heat
iii)CrO3 / H+ / heat (Jones’ reagent)
iv)Ag2O, NH3 (ag) (Tollen’s reagent)
* H+ = H2SO4
Examples:
iii) OXIDATION OF ALKENES
Reagents:
- Hot, concentrated alkaline KMnO4 or hot,
concentrated
KMnO4 solution in dilute H2SO4
1. Oxidation of alkenes
2. Oxidation of terminal alkenes
Example
s:
iv) OXIDATION OF ALKYL BENZENES
• Alkylbenzenes are oxidized to benzoic acid by heating in
acidic KMnO4 or heating in Na2Cr2O7/H2SO4.
• The benzylic carbon will be oxidized to the carboxylic acid.
In order for alkylbenzene to be oxidised, it must
posses one benzylic hydrogen (hydrogen atom
bonded to c atom which is bonded directly to
benzene ring).
No benzylic hydrogen
No reaction
HYDROLYSIS OF NITRILES
• Alkyl halides react with NACN to form nitriles which in
turn undergo hydrolysis in acidic solution to produce
carboxylic acid.
• Formation of nitriles involves nucleophilic
substitution.
• Primary alkyl halides (Cl, Br, I) – SN2 substitution
• Aromatic nitriles cannot be prepared through this
method but still can hydrolysed to give aromatic
carboxylic acids.
• The nitrile is reflux with a dilute acid such as H2SO4 or
HCl to form carboxylic acid.
Example
s:
The nitrile is heated under reflux with an alkaline solution,
NaOH
CARBOXYLATION
(CARBONATION) OF GRIGNARD
REAGENTS
CO2 = dry ice or bubbling gaseous CO2
• Applicable to primary, secondary, tertiary, allyl, benzyl and
aryl halides.
• Occurs via nucleophilic addition:
- alkyl or aryl magnesium halide is added to a double bond
C=O of CO2 to form carboxylate ion.
- when treated with acid, carboxylic acid is formed.
Examples:
REACTIONS CARBOXYLIC ACIDS
• Salt formation
- neutralisation
- reactions with electropositive metals
• Reduction to alcohols
• Conversion to acyl chlorides or acid
chlorides
• Conversion to esters
• Conversion to amides
SALT FORMATION
1) Neutralisation:
- carboxylic
acids undergo neutralisation
reactions with strong bases or some
weak base such as NaOH, NaHCO3,
Na2CO3, NH3 and amines to form
carboxylate salts of carboxylic acids and
water.
- carboxylate salts are soluble in water.
Examples:
CH3COOH (aq) + NaOH (aq) → CH3COONa (aq) + H2O (l)
sodium
ethanoate
CH3CH2COOH(aq) + NaHCO3(aq) → CH3CH2COONa (aq) +
CO2(g)+ H2O(l) sodium propanoate
CH3CO2H + NH3 → CH3COO- NH4+
CH3CH2CO2H + CH3NH2 → CH3CH2COO- CH3NH3+
Method to distinguish carboxylic acid with phenol
and other organic compounds
• 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
Organic base
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,
zinc and iron.
2CH3COOH(aq) + Mg → (CH3COO)2M(aq) + H2 (g)
magnesium ethanoate
REDUCTION TO PRIMARY ALCOHOLS
• Reducing agents:
- Strong reducing agent i.e. LiAl 4 in dry ether or borane
in tetrahydrofuran (BH3/THF).
- Reaction with borane in tetrahydrofuran allows
selective reduction and prevents the reduction of other
group such as nitro group.
- Cannot used NaBH4 or catalytic hydrogenation.
▪ Reduction of carboxylic acids occurs via
nucleophilic acyl substitution followed by
nucleophilic addition reaction.
▪ The complete reduction process of
carboxylic acids:
ether
4RCOOH + 3LiAlH4 (RCH2O)4AlLi + 4H2 + 2LiAlO2
(RCH2O)4AlLi
H2O 4RCH2OH + Al(OH)3 + LiOH
▪ Balance chemical equation for reduction
process of carboxylic acids:
[H] = does not represent atomic hydrogen.
= used to balance the chemical equation and to signify
that it comes from a reducing agent.
▪ 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.
▪ 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
CONVERSION TO ACYL CHLORIDES / ACID CHLORIDES
• Carboxylic acids reacts with phosphorus (v) chloride
(PCl 5) or sulphur dichloride oxide (thionyl chloride) or
phosphorus trichloride (PCl 3) at room temperature to
form acyl chloride.
• Inthe case of benzoic acid, the reaction mixture is
heated.
• The liberation of white fumes of hydrogen chloride
shows the presence of the –oh group in the carboxylic
acid molecule.
white fumes
white fumes
EXAMPLES:
CONVERSION TO ESTERS
• When a carboxylic acid is heated with an
alcohol in the presence of a little concentrated
sulphuric acid, an ester is formed.
• H2SO4 – acid catalyst
• Known as fischer esterification.
• Since the reaction is reversible, the mixture
must be heated or reflux.
CONVERSION TO AMIDES
I) FROM CARBOXYLIC ACIDS:
• amides can be synthesized directly from carboxylic
acids, but the yield is poor.
• 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 (poor method).
Excess RCOOH
RCOOH + NH3 RCOO-NH4+
RCONH2 + H2O Heat (100-200 °C)
Ammonium
carboxylates
Example:
CH3COOH + NH3 → CH3COONH4 CH3CONH2 + H2O
heat
ammonium ethanamide
ethanoate
II) REACTION OF ACID CHLORIDES WITH AMMONIA OR
AMINES
- BEST METHOD
