Organic CH Emistry Ii CHM301: Carboxylic Acids

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O R G ANIC C H EMISTRY II

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

Functional group: carboxyl group, -COOH


O
C OH
 General formulae:
O
R C OH R = alkyl group

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.

• 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.

methane methanoic acid


Examples of carboxylic acids

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

Named as cycloalkanecarboxylic acids.


COOH

cyclohexanecarboxylic acid

COOH
12
3 CH3
CH3
3,3-dimethylcyclohexanecarboxylic acid
NOMENCLATURE OF CARBOXYLIC
ACIDS (COMMON NAME)

 Organic acids are usually known by common


names.
 These names usually refer to a natural source of
the acid.

acetic acid
ethanoic acid formic acid
methanoic acid

IUPAC name
common name IUPAC name
common name
NOMENCLATURE OF AROMATIC
CARBOXYLIC ACIDS

 General formula for the aromatic carboxylic acids:


ArCOOH, where Ar is aryl group (aromatic group).
 Examples:

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

Carboxylic acids containing two c arboxyl


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)
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

 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
ethanoic acid 1-propanol propanone
(RMM: 60) (RMM: 60) (RMM: 58)
bp 118oC bp 97oC bp 56oC

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

- The dimer also increases the van der Waals


dispersion forces makes the boiling point of
carboxylic acids become more higher than alcohols.
2.2 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.
H
δ+
R δ- H O
H δ- δ+ C O
O H O δ-

H δ+
H

O H
hydrogen bonds
3.0 ACIDITY OF
CARBOXYLIC ACIDS
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.
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

acid strength increases

*methoxy substituent (CH3O-) : electron-donating and


decreases the acid strength
*-NO2 : electron-withdrawing and increases the acid
strength
electron-withdrawing substituents near the
carboxyl group increase acidity through
their inductive effect

CH 3 COOH ClCH 2 COOH Cl2 CHCOOH Cl3 CCOOH


A ce ti c C h l o ro ace ti c D i ch l oro ace ti c Tri ch l oro ace ti c
acid acid acid acid
pK a : 4.76 2.86 1.48 0.70
In c re asi n g ac i d stre n g th
the acid-strengthening effect of a halogen
substituent falls off rapidly with increasing distance
from the carboxyl group

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)

Decreas ing acid strength


4.0 PREPARATION

1. OXIDATION OF ALKYL BENZENE, ALKENES, ALCOHOLS,


ALDEHYDES

2. CARBOXYLATION OF GRIGNARD REAGENTS

3. HYDROLYSIS OF NITRILES
4.1 OXIDATION OF PRIMARY ALCOHOLS,
ALDEHYDES, ALKENES AND ALKYL BENZENE

i) OXIDATION OF PRIMARY ALCOHOLS

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

2. Oxidation of terminal alkenes


KMnO4/H+
R CH=CH2 R COOH + CO2 + H2O
terminal alkene
Examples:
H H OH OH
KMnO4/H+
CH3CH2C CCH3 CH3CH2C O O C CH3
2-pentene propanoic acid ethanoic acid

CH3 H CH3
KMnO4/H+ OH
CH3CH2C CCH3 CH3CH2C O O C CH3
3-methyl-2-pentene 2-butanone ethanoic acid

CH3 CH3 CH3 CH3


KMnO4/H+
CH3CH2C CCH3 CH3CH2C O O C CH3
2,3-dimethyl-2-pentene 2-butanone propanone

H OH
KMnO4/H+
CH3CH2C=CH2 CH3CH2C=O CO2 H 2O
1-butene propanoic acid
iv) OXIDATION OF ALKYLBENZENES

• 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.
O
hot, KMnO4 /H+
R C OH
or Na2Cr2O7/H2SO4/heat

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).

CH3 No benzylic hydrogen


H3C C CH3

[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

•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.

O O
R MgX H3O+
O C O R C O- MgX+ R C OH
Examples:

CH3CH2MgCl i) CO2 CH3CH2COOH


ii) H3O+

i) CO2
ii) H3O+
MgCl COOH
4.3 HYDROLYSIS OF NITRILES

 Alkyl halides react with NaCN to form nitriles which in turn


undergo hydrolysis in acidic solution to produce carboxylic
acid.
O
NaCN H 3 O+
R X R CN R C OH + NH4+

 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.
Examples:

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

 The nitrile is heated under reflux with an alkaline solution, NaOH


5.0 REACTIONS

1. SALT FORMATION

2. REDUCTION

3. CONVERSION TO ACID CHLORIDES

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:

CH3COOH (aq) +NaOH (aq) → CH3COONa (aq) +H2O (l)


sodium ethanoate

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


sodium propanoate
CH3CO 2H +NH3 → CH3COO - NH4 +

CH3CH2CO 2H +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 base
Organic compounds
NaOH NaHCO3

Neutral organic Insoluble Insoluble


compounds
Phenol Soluble Insoluble

Carboxylic acids Soluble Soluble


2)Reaction withelectropositive 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) 2Mg(aq) +H2 (g)


magnesium ethanoate
5.2 REDUCTION TO PRIMARY ALCOHOLS
 Reducing agents:
-strong reducing agent i.e. LiAlH4 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.
O H
(1) LiAlH4 / ether
R C OH R C OH
(2) H2O
carboxylic acids H
primary alcohols
Examples:
O H
(1) LiAlH4 / ether
CH3 C OH CH3 C OH
(2) H2O
ethanoic acid H
ethanol

(1) BH3, THF


O2N CH2COOH O2N CH2 CH2OH
(2) H3O+
 The complete reduction process of carboxylic acids:

4RCOOH + 3LiAlH4 ether (RCH2O)4AlLi + 4H2 + 2LiAlO2


H2O
(RCH2O)4AlLi 4RCH2OH + Al(OH)3 + LiOH

Balance chemical equation for reduction process of carboxylic


acids:
O H
(1) LiAlH4 / ether
R C OH 4[H] R C OH H 2O
(2) H2O
H
Example:
H
O
(1) LiAlH4 / ether
4[H] CH3 C OH H2O
CH3 C OH (2) H2O
H
[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.

O H
(1) LiAlH4 / ether
C OH C OH
(2) H2O
H
benzoic acid
phenylmethanol

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


bond.
-COOH is reduced to –CH2OH but the C=C bonds remains
unchanged.

CH3CH2CH=CHCOOH 1) LiAlH4/ ether CH3CH2CH=CHCH2OH


2) H2O
5.3 CONVERSION TO ACYL CHLORIDES / ACID CHLORIDES
 Carboxylic acids reacts with phosphorus (v) chloride (PCl5) 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.
 The liberation of white fumes of hydrogen chloride shows the
presence of the –OH group in the carboxylic acid molecule.

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 

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