Organic CH Emistry Ii CHM301: Carboxylic Acids
Organic CH Emistry Ii CHM301: Carboxylic Acids
Organic CH Emistry Ii CHM301: Carboxylic Acids
CHM301
CHAPTER 3
CARBOXYLIC ACIDS
SUBTOPICS
1.0 General formula of carboxylic acids.
2.0 Nomenclature of carboxylic acids.
3.0 Physical properties of carboxylic acids:
- boiling points
- solubility
4.0 Acidity of carboxylic acids.
5.0 Preparations of carboxylic acids.
6.0 Reactions of carboxylic acids.
1.0 NOMENCLATURE
GENERAL FORMULA OF CARBOXYLIC ACIDS
O
Ar C OH Ar = aryl group
NOMENCLATURE OF CARBOXYLIC ACIDS
IUPAC NAME
• The carbonyl group (-C=O) is always at the
beginning of a carbon chain.
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.
O O
3 4 3 2
2
CH3 CH C OH CH3 CH CH C1 OH
1
Br CH3 CH3
2-bromopropanoic acid 2,3-dimethylbutanoic acid
NOMENCLATURE OF CYCLOALKANES WITH –
COOH SUBSTITUENTS
cyclohexanecarboxylic acid
COOH
12
3 CH3
CH3
3,3-dimethylcyclohexanecarboxylic acid
NOMENCLATURE OF CARBOXYLIC
ACIDS (COMMON NAME)
acetic acid
ethanoic acid formic acid
methanoic acid
IUPAC name
common name IUPAC name
common name
NOMENCLATURE OF AROMATIC
CARBOXYLIC ACIDS
O
C OH COOH COOH
1
OH 6 2
3
5 NO2
4
benzoic acid 2-hydroxybenzoic acid 3-nitrobenzoic acid
NOMENCLATURE OF ALIPHATIC
DICARBOXYLIC ACIDS
COOH COOH
COOH CH2 (CH2)4
COOH
COOH COOH
ethanedioic acid propanedioic acid hexanedioic acid
(oxalic acid) (malonic acid) (adipic acid)
Write the IUPAC name of each compound.
COOH d)
a)
COOH
b)
H OH e)
COOH
HOOC
COOH
c) f)
H COOH
COOH
HO
COOH
2.0 PHYSICAL PROPERTIES
2.1 BOILING POINTS OF
ALIPHATIC CARBOXYLIC ACIDS
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.
O H
R C O H
R C O H δ+ δ-
δ+ δ-
H
- 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.
hydrogen bond
O H O
R C CR
OH O
hydrogen bond
H δ+
H
O H
hydrogen bonds
3.0 ACIDITY OF
CARBOXYLIC ACIDS
The acidity of carboxylic acids compared with 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.
Inductive Effect of the Carbonyl Oxygen
The oxygen atom in the carbonyl group is
electronegative and acts as a powerful electron-
withdrawing atom. Thus, the carbonyl group is
electron-withdrawing.
The withdrawal of electrons away from the
carboxyl hydrogen atoms weakens the O-H bond.
Polarization of carboxylic acid.
Resonance Effect of the Carbonyl Group
The carboxylate anion is a resonance
hybrid of two resonance structure.
O O-
H3C C H3C C
O- O
In the carboxylate anion, the negative
charge is delocalized over the carbon-
oxygen bonds.
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 over two
oxygen atoms.
ii) The negative charge on the carboxylate ions is
delocalised onto more electronegative oxygen atom.
O O
R C R C
O O
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
Cl
COOH COOH Cl COOH COOH
Cl
2-Chlorob utanoic 3-Chlorobutanoic 4-Chlorobutanoic Butan oic
acid acid acid acid
(pK a 2.83) (p Ka 3.98) (pKa 4.52) (pKa 4.82)
3. HYDROLYSIS OF NITRILES
4.1 OXIDATION OF PRIMARY ALCOHOLS,
ALDEHYDES, ALKENES AND ALKYL BENZENE
KMnO4/H+/heat or K2Cr2O7/H+/heat
O
R CH2 OH
R-C-OH
1o alcohol carboxylic acid
Example:
O
KMnO4/H+/heat or K2Cr2O7/H+/heat
CH3(CH2)4-CH2-OH CH3(CH2)4-C-OH
1-hexanol
hexanoic acid
ii) OXIDATION OF ALDEHYDES
O oxidizing agent O
R C H R C OH
aldehyde carboxylic acid
Oxidizing agents:
i) KMnO4 / H+ / heat
ii) K2Cr2O7 / H+ / heat
iii) CrO3 / H+ / heat (Jones’ reagent)
iv) Ag2O, NH3 (aq) (Tollen’s reagent)
* H+ = H2SO4
Examples:
O O
KMnO4/H2SO4/heat
CH3C H CH3-C-OH
ethanal ethanoic acid
O
K2Cr2O7/H2SO4/heat
CHO C-OH
benzaldehyde benzoic acid
iii)OXIDATION OF ALKENES
Reagents:
- Hot, concentrated alkaline KMnO4 or hot, concentrated KMnO4
solution in dilute H2SO4
1. Oxidation of alkenes
R R' R R'
KMnO4/H+ O C
C C C O
H HO OH
H
carboxylic acid carboxylic acid
R R' R R'
KMnO4/H+
C C C O O C
R" H R" OH
ketone carboxylic acid
CH3 H CH3
KMnO4/H+ OH
CH3CH2C CCH3 CH3CH2C O O C CH3
3-methyl-2-pentene 2-butanone ethanoic acid
H OH
KMnO4/H+
CH3CH2C=CH2 CH3CH2C=O CO2 H 2O
1-butene propanoic acid
iv) OXIDATION OF ALKYLBENZENES
Examples:
O
hot, KMnO4 /H+
CH3 C OH
or Na2Cr2O7/H2SO4/heat
O
hot, KMnO4 /H+
CH2 CH3 C OH
or Na2Cr2O7/H2SO4/heat
hot, KMnO4/H+
CH3 COOH
or Na2Cr2O7/H2SO4/heat
CH3 COOH
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).
[O]
No reaction
4.2 C A R B O X Y L A T I O N ( C AR B O N A T I O N ) O F
G R I G N A R D R E AG E N TS
H3O +
RMgX CO2 RCOOH
CO2 = dry ice or bubbling gaseous CO2
O O
R MgX H3O+
O C O R C O- MgX+ R C OH
Examples:
i) CO2
ii) H3O+
MgCl COOH
4.3 HYDROLYSIS OF NITRILES
O
NaCN H 3O+
CH3CH2 Cl CH3CH2 CN CH3CH2 C OH + NH4+
CN H 3O+ COOH
CH3 CH3
BASE HYDROLYSIS
OH -, H2O O
R CN
R C O- + NH3
1. SALT FORMATION
2. REDUCTION
4. CONVERSION TO ESTERS
5. CONVERSION TO AMIDES
5.1 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.
O O
R C O H + NaOH R C O- Na+ + H2O
O O
R C O H + NaHCO3 R C
-
O Na+ + H2O + CO2
O O
2R C O H + Na2CO3 2R C O- Na+ + H2O + CO2
O O
R C O H + NH3 R C O- NH4+
Examples:
O H
(1) LiAlH4 / ether
C OH C OH
(2) H2O
H
benzoic acid
phenylmethanol
O O
R C OH PCl5 R C Cl POCl3 HCl
carboxylic acids acid chlorides white fumes
O O
R C OH SOCl2 R C Cl SO2 HCl
carboxylic acids acid chlorides white fumes
O O
3 R C OH PCl3 3 R C Cl H3PO3
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
5.4 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.
O O
conc. H2SO4
CH3 C OH H OC2H5 CH3 C OC2H5 H2O
ethanoic acid ethanol heat or reflux ethyl ethanoate
O O
conc. H2SO4
C OH H OC2H 5 C OC2H 5 H2O
ethanol heat or reflux
benzoic acid ethyl benzoate
5.5 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-NH + 4 Heat (100-200 °C) RCONH2 +H2O
Ammonium 1° amide
carboxylates
Example:
CH3COOH + NH3 → CH3COONH4 CH3CONH2 + H2O
heat
ammonium ethanamide
ethanoate
ii) Reaction of acid chlorides with ammonia or amines
- best method
O O
R C Cl 2NH3 R C NH2 NH4+ Cl-
ammonia amide ammonium chloride
O O H
R C Cl 2RNH2 R C NR RNH3+ Cl-
amine secondary amide ammonium chloride
O O R
R C Cl 2R2NH R C N R R2NH2+ Cl-
secondary amine tertiary amide ammonium chloride
Examples:
O O
CH3 C Cl 2NH3 CH3 C NH2 NH4+ Cl-
O O CH3
CH3 C Cl 2CH3NH2 CH3 C N H CH3NH3+ Cl-
EXERCISE 1
3
4
EXERCISE 2
5
6
The End….TQ
LoveOrganic Chemistry …in shaaAllah