A2 Chemistry Carboxylic Acids and Their Derivatives

A2 chemistry
Carboxylic Acids
and their Derivatives
35.1 Introduction
35.2 Nomenclature of Carboxylic Acids and their
Derivatives
35.3 Physical Properties of Carboxylic Acids
35.4 Preparation of Carboxylic Acids
35.5 Reactions of Carboxylic Acids
35.6 Reactions of the Derivatives of Carboxylic Acids
35.7 Uses of Carboxylic Acids and their Derivatives
1
New Way Chemistry for Hong Kong A-Level Book 3B
AS recap
General formula of carboxylic acid: RCOOH

Examples:
Carboxylic acid derivatives

Name
Structure
Acyl
chlorides
Acid
anhydrides
Amides
Esters
3
Nomenclature of Carboxylic Acids and their Derivatives
CarboxylicAcids
Acids
Carboxylic
Carboxylic acids are named by replacing the final -e of
the name of the corresponding alkane with -oic acid
When other substituents are present, the carboxyl carbon is
assigned position 1
Examples:
AcylChlorides
Chlorides
Acyl
Acyl chlorides are named by replacing the final -ic acid
of the name of the parent carboxylic acid with -yl
chloride
Examples:
AcidAnhydrides
Anhydrides
Acid
Acid anhydrides are named by dropping the word acid
from the name of the parent carboxylic acid and then
adding the word anhydride
Examples:
Amides
Amides
Amides that have no substituents on the nitrogen atom are named
by replacing -oic acid from the parent carboxylic acid with
amide
Substituents on the nitrogen atom of amides are named and the
named substituent is preceded by N-, or N,NExamples:
Esters
Esters
The names of esters are derived from the names of the
alcohol (with the ending -yl) and the carboxylic acid (with
the ending -oate)
The portion of the name derived from the alcohol comes first
Examples:
Tutorial Question 1
Give the IUPAC names of the following compounds:
(a)
(b)
Solution:
(a) 3-Methylbutanoic acid
(b) N-methylethanamide
(c)
(c) Ethyl benzoate
(d) Benzoic anhydride
(d)
Answer
9
Tutorial Question 2
An ester is formed by reacting an alcohol with a carboxylic
acid. Draw the structural formula of the following ester
molecule and give the name of the alcohol and the
carboxylic acid that form the ester.
(a) Methyl ethanoate
Solution:
Answer
(a) The structural formula of methyl ethanoate is:
It is formed from the reaction of ethanoic acid and

methanol.
10
Example 35-2
An ester is formed by reacting an alcohol with a
carboxylic acid. Draw the structural formula of the
following ester molecule and give the name of the alcohol
and the carboxylic acid that form the ester.
(b) Ethyl methanoate
Solution:
Answer
(b) The structural formula of ethyl methanoate is:
It is formed from the reaction of methanoic acid

and ethanol.
11
Check Point 35-1

Complete the following table by filling in the molecular
formulae, structural
formulae or IUPAC names of the
(a)
carboxylic acids.
Molecular formula Structural formula IUPAC name
C3H7COOH
(c)
(a)
(b) Butanoic
acid
(c)(b)
CH3CH(CH3)CH2COOH
(d)
(d) 3-Methylbutanoic acid
(e) C6H4ClCOOH
(f) 2-Chlorobenzoic acid
(g) CCl3COOH
(e)
(g)
12
(h)
(f)
(h)
Trichloroethanoic acid
Answer
35.4 Preparation of Carboxylic Acids (SB p.39)
Oxidationof
ofAlkybenzenes
Alkybenzenes
Oxidation
1 and 2 alkyl groups (but not 3) directly attached to a
benzene ring are oxidized by hot KMnO4/OH to carboxyl group
e.g.
This oxidation takes place initially at the benzylic carbon

alkyl groups longer than methyl group are ultimately
degraded to benzoic acid
13
ethanoic acid
The acid strength of ethanoic acid is shown by the value of its

acid dissociation constant (Ka)
[CH 3COO - ][H3O ]
Ka
[CH 3COOH ]
pKa is used for convenience as Ka is small for weak acids

pKa = log Ka , the smaller the pKa value, the stronger is the acid
-pKa
K
=
10
smaller
the pK value, the stronger is the acid
14 a
New Way Chemistry afor Hong Kong A-Level Book 3B
Carboxylic acids are stronger acids than

alcohol because
Point 1
a)The carbonyl group weakens the O-H bond..this
means
The very electronegative oxygen in Carbonyl group has an
electron withdrawing effect and polarizes the O-H bond.
Point 2
b) carboxylate ion is stabilized by the delocalization of
electron around the carboxylate ionthis means
The negative charge is spread out in the carboxylate ion
and is less likely to attract the hydrogen ion.
15
Resonance Effect
The greater stability of carboxylic acids is attributed to

resonance stabilization of the carboxylate ions
Example:
16

pKa = log Ka , the smaller the pKa value, the stronger is the acid
Ka = 10 -pKa
The smaller the pKa and larger the Kavalue, the stronger is the
acid
17
Unsubstituted carboxylic acid

pKa increases and acid becomes weaker when no of C
and H atoms in molecule increases.
Alkyl groups are electron donating groups that makes
the O-H bond stronger and less hydrogen ions are
released from carboxylic acid.
Name
Formula
Methanoic acid HCOOH

CH3COOH
Ethanoic acid
18
pKa
3.75
4.76
Propanoic acid
CH3CH2COOH
Butanoic acid
CH3CH2CH2COOH 4.82
Benzoic acid
C6H5COOH
4.87
4.20
35.5 Reactions of Carboxylic Acids (SB p.41)
By the resonance effect, the ethanoate ion can be

stabilized by spreading the negative charge over two
oxygen atoms
No stabilizing resonance structures for alkoxide ions

e.g.
Carboxylic acids are much acidic than alcohols

formation of more stable conjugate base
19
Inductive Effect
Both compounds contain the highly polarized O H

bond due to the difference in electronegativity
The greater acidity of ethanoic acid is due to the
presence of the powerful electron-withdrawing carbonyl
group
20
Two resonance structures for the carbonyl group:
The carbonyl atom of ethanoic acid bears a large

partial positive charge and exerts a powerful electronwithdrawing inductive effect to hydroxyl oxygen atom,
making the hydroxyl hydrogen atom much more
positive
proton dissociate more readily
The electron-withdrawing inductive effect of the
carbonyl group stabilizes the carboxylate ion
carboxylic acids are stronger acid than alcohols
21
Inductive Effects of Other

Groups
1. Electron-withdrawing Groups
The presence of electron-withdrawing groups increase
the acidity of a carboxylic acid
e.g.
22
The chlorine atom withdraws electron from the carbonyl

group and oxygen making the hydroxyl hydrogen more
positive than that of ethanoic acid
The chlorine atom also stabilizes the chloroethanoate ion
to greater extent
23
Effect of electron-withdrawing substituents on the acidity of carboxylic acids

Acidity CH3COOH <
Ethanoic
Chloroethanoic
acid
acid
pKa
4.76
2.86
Acidity CH3COOH <
<
<
<
Dichloroethanoic
acid
1.29
<
CCl3COOH
Trichloroethanoic
acid
0.65
<
Ethanoic Iodoethanoic Bromoethanoic Chloroethanoic

Fluoroethanoic
pKa
acid
acid
acid
acid
acid
4.76 the number
3.17 of electron-withdrawing
2.90
2.86
The greater
groups, the 2.66
stronger is the acid

The more electronegative of halogen substituents (F > Cl >
Br > I), the stronger
is the acid
24
The further away of the substituents from the carboxyl

group, the weaker is the acid
Acidity
<
pKa
25
4-Chlorobutanoic
acid
4.52
<
3-Chlorobutanoic
acid
4.06
2-Chlorobutanoic
acid
2.84
2. Electron-releasing Groups
The presence of electron-releasing groups reduce the
acidity of a carboxylic acid
e.g.
26
Electron-releasing alkyl groups release electrons towards the

electron-deficient carbonyl carbon, thus reducing its charge
Reduce the positive character of the hydroxyl
hydrogen atom
dissociate less readily
Intensify the negative charge on the carboxyl group
destablizes the ethanoate ion
27
Check Point 35-3

(a) Match the Ka values: 2.19 103 M and 1.26 103 M,
to the carboxylic acids: CH2FCOOH and
CH2BrCOOH. Explain your answer briefly.
(a) The greater the Ka value, the stronger is the acid.Answer
CH2FCOOH is a stronger acid than CH2BrCOOH.
This F substituent exerts a stronger inductive effect
than the Br substituent, as fluorine is more
electronegative than bromine. The F substituent
stabilizes the conjugate base (i.e. CH2FCOOH) to a
greater extent than the Br substituent. Therefore,
CH2FCOOH has a Ka value of 2.19 103 M, and
CH2BrCOOH has a Ka value of 1.26 103 M.
28
Check Point 35-3

(b) Arrange the following acids in ascending order of acidity:
CHCl2COOH, CCl3COOH, CH2ClCOOH, CH3COOH
Explain the order briefly.
(b) CH3COOH < CH2ClCOOH < CHCl2COOH
< CCl3COOH
The Cl substituent is an electron-withdrawing
group. An increasing number of the Cl substituent
brings about a greater negative inductive effect.
Thus, the conjugate base will be stabilized more,
and the acidity of the acid increases.
29
Answer
Check Point 35-3

(c) Arrange the following aryl carboxylic acids in descending
order of acidity:
Explain the order briefly.
30

(c)
is more acidic than
,because
contains
the Cl substituent which is an electron-withdrawing group. Thus, it

exerts a negative inductive effect to the conjugate base, and hence
stabilizes the carboxylate ion formed.
is less acidic than
, because
contains
a methyl group which is an electron-releasing group. Thus, it exerts a

positive inductive effect to the conjugate base, and hence destabilizes
the carboxylate ion formed.
31
Check Point 35-3

(d) Which is a stronger acid, CH2ClCOOH or
CH3CHClCOOH? Explain your answer briefly.
Answer
(d) CH2ClCOOH is a stronger acid as CH3CHClCOOH
contains a methyl group which is an electron-releasing
group. It exhibits a positive inductive effect and thus
destabilizes the conjugate base of the acid. Therefore,
CH3CHClCOOH is less acidic.
32
Formationof
ofSalts
Salts
Formation
Reaction with Active Metals
Carboxylic acids react with reactive metals such as Na

or Mg to give the corresponding metal carboxylates and
hydrogen gas
33
Example:
34
Reaction with Bases
Carboxylic acids react with strong alkalis such as NaOH to

form sodium carboxylates and water
Examples:
35
Carboxylic acids also react weak alkalis such as Na2CO3 or

NaHCO3 to form sodium carboxylates, carbon dioxide and
water
36
Examples:
This reaction serves as a test to distinguish carboxylic acids

and other acidic organic compounds
37
NaOH and
Na2CO3 can be
used to separate a
mixture of
alcohols, phenols
and carboxylic
acids
38
Check Point 35-4

(a) Describe how to separate a mixture of benzoic acid
and phenol in the laboratory.
Answer
(a) Sodium hydrogencarbonate, water and diethyl ether are
added to the mixture. Benzoic acid reacts with sodium
hydrogencarbonate to form a water-soluble salt which
dissolves in the aqueous layer. After separation by the use
of a separating funnel, phenol can be recovered by distilling
off the ether. To the aqueous layer, hydrochloric acid is
added to generate the benzoic acid which can be extracted
by diethyl ether. After separation from the aqueous
layer, benzoic acid is obtained by distilling off the
ether.
39
Check Point 35-4

(b) Outline how a mixture of butanone and ethanoic
acid can be separated in the laboratory.
Answer
40

(b)
41
Formationof
ofAcyl
AcylChlorides
Chlorides
Formation
Acyl chlorides are the most reactive amongst the
carboxylic acid derivatives
They can be prepared by the use of SOCl2, PCl3 or
PCl5 in good yields
42
Acyl chlorides can be used to prepare aldehydes, ketones,

esters, amides and acid anhydrides in organic synthesis
Acyl chlorides are extremely sensitive to moisture,
therefore, it must be stored in anhydrous conditions
hydrolyze rapidly to form carboxylic acids
43
Formationof
ofAcid
AcidAnhydrides
Anhydrides
Formation
Acid anhydrides can be prepared by reacting acyl
chlorides with carboxylic acids in the presence of
pyridine
This can be used to prepare mixed anhydrides (R R)
or simple anhydrides (R = R)
44
Acyl chlorides react with sodium salts of carboxylic

acids to give acid anhydrides
45
Formationof
ofAmides
Amides
Formation
Ammonia reacts with carboxylic acids to form ammonium
salts. The dry salts are heated to dehydrate to give amide
The better way to prepare amides is reacting

ammonia or amines with acyl chlorides
46
Formationof
ofEsters
Esters
Formation
Carboxylic acids react with alcohols to form esters
through condensation reactions
Esterification reactions are acid-catalyzed and
reversible
47
Reductionwith
withLithium
LithiumTetrahydridoaluminate
Tetrahydridoaluminate
Reduction
LiAlH4 is a powerful reducing agent which reduces
carboxylic acids to primary alcohols in good yields
Example:
48
Example 35-4
(a) Complete and balance the following acid-base
Solution:
equations:
(a) (i)(i)
(ii)
Answer
(ii)
49
Example 35-4
(b) Draw the structural formulae for the products formed
from the following compounds when they are reduced
with lithium tetrahydridoaluminate.
(i)
Solution:
(ii)
(b) (i)
50
Way Chemistry
for Hong Kong A-Level Book 3B
(ii)New HOCH
2CH2CH2CH2OH
Answer
Example 35-4
Solution:
(c) Complete the following equations:
(c) (i)
(i)
(ii)
(ii)
(iii)
(iii)
Answer
51
35.6 Reactions of the Derivatives of Carboxylic Acids (SB p.50)
Reactionsof
ofAcyl
AcylChlorides
Chlorides
Reactions
Both chlorine and oxygen atoms are electronwithdrawing groups, thus making the acyl carbon much
electron-deficient
acyl carbon is a good nucleophilic site
Chloride ion is a good leaving group which is

substituted by other atoms or groups easily
acyl chlorides are very reactive
52
Benzoyl chloride is much less reactive than aliphatic acyl

chlorides
reduction of electron-deficiency on the acyl carbon
due to delocalization of electrons (resonance effect)
53
Reaction with Water
Acyl chlorides are hydrolyzed by water to form the parent

carboxylic acids and hydrogen chloride
Examples:
54
Reaction with Alcohols
Acyl chlorides react with alcohols to give esters and HCl
Examples:
55
Acyl chlorides react with phenols to give esters in the

presence of base as catalyst
an alkaline medium converts phenol to a powerful
nucleophile, phenoxide ion
Example:
56
Reaction with Ammonia and Amines
Acyl chlorides react with ammonia to form amides rapidly
Example:
57
Acyl chlorides react rapidly with 1 and 2 amines to form

N-, N,N- substituted amides respectively
The reaction takes place at room temperature and produces

amides in high yield
This method is widely used in laboratory for amides synthesis
58
Check Point 35-5

Explain why ethanoyl chloride must be protected from
atmospheric moisture during storage.
Answer
This is because ethanoyl chloride reacts readily
with water (from atmospheric moisture) to form
ethanoic acid.
59
Reactionsof
ofAcid
AcidAnhydrides
Anhydrides
Reactions
Reaction with Water
Acid anhydrides undergo hydrolysis to form carboxylic acids
Example:
60
Reaction with Alcohols
Acid anhydrides react with alcohols to form esters in the

presence of acid catalyst
Example:
61
Reaction with Ammonia and Amines
Acid anhydrides react with ammonia and with 1 and 2

amines in the ways similar to those of acyl chlorides
62
Examples:
63
Reactionsof
ofAmides
Amides
Reactions
Amides are the least reactive among the carboxylic acid
derivatives towards nucleophilic substitution reactions
NH2, NHR or NR2 are strong bases and thus
poor leaving groups
64
Reaction with Water
Amide undergo acid and alkaline hydrolyses to form

carboxylic acids and carboxylates respectively
Acid hydrolysis:
Alkaline hydrolysis:
65
Dehydration
Amides are dehydrated by heating with P4O10 to form nitriles
Useful synthetic method for preparing nitriles that are

not available by nucleophilic substitution reactions
between haloalkanes and cyanide ions
66
Hofmann Degradation
Amides react with a solution of Br2 in NaOH or a solution of

Cl2 in NaOH to give amines through a reaction called Hofmann
degradation
The resulted amines have one carbon less than original amides
Example:
67
Reduction with Lithium Tetrahydridoaluminate
Amides are reduced by LiAlH4 in dry ether to

give 1 amines
68
Reactionsof
ofEsters
Esters
Reactions
Acid-catalyzed Hydrolysis
Acid-catalyzed hydrolysis of esters is the reverse reaction

of esterification
Example:
69
Alkali-catalyzed Hydrolysis
When esters are refluxed with an alkali such as NaOH, the

corresponding alcohol and sodium salt of the carboxylic
acid are produced
Alkali-catalyzed hydrolysis are irreversible
Example:
70
Soap is made by the alkaline hydrolysis of fats or oils

(i.e. triesters) to produce sodium carboxylates (i.e. soap)
The reaction is called saponification
71
Reduction with Lithium Tetrahydridoaluminate
Esters are reduced to alcohols by LiAlH4
Example
:
72
Example 35-5
Draw the structural
formulae of the missing compounds A to
Solution:
M:
(a)
(b)
(c)
(a)
(b)
(c)
Answer
73
Example 35-5
Draw theSolution:
structural formulae of the missing compounds A to
M:
(d)
(d)
(e)
(e)
(f)
(f)
Answer
74
Example 35-5
Draw the structural formulae of the missing compounds A to
Solution:
M:
(g)
(g)
(h)
(h)
(i)
(i)
Answer
75
35.7 Uses of Carboxylic Acids and their Derivatives (SB p.59)
AsFood
FoodPreservatives
Preservatives
As
Benzoic acid and its sodium salt used as food
preservatives
Prevent the microbial growth and spoilage
Used in oyster sauce, fish
sauce, ketchup, non-alcoholic
beverages, fruit juices,
margarine, salad dressings,
jams and pickled products
76
AsRaw
Rawmaterials
materialsfor
forMaking
MakingPolymers
Polymers
As
Nylon-6,6,
condensation polymer
,is a
It is a polyamide made by adding NaOH containing

hexanedioyl dichloride and hexane-1,6-diamine to CH3CCl3
77
Advantages of Nylon6,6
Drip dry easily
Not attack by insects easily
Resist creasing (no ironing required
after washing)
Used for making ropes, thread, cords,
and various kinds of clothing from
stockings to jackets
78
Terylene,
, is a polyester
made from acid-catalyzed condensation polymerization

of benzene-1,4-dicarboxylic acid and ethane-1,2-diol
Terylene is used to make washand-wear garments

79
AsSolvents
Solvents
As
Liquid esters are widely used as solvents for all-purpose
adhesives, thinners for paints and nail varnish removers
80
AsFlavourings
Flavourings
As
Volatile esters often have characteristic sweet and

fruity smells
They are used as artificial flavourings

in food-processing industry
An artificial flavouring
made of esters
81

Some esters and their characteristic flavours
Structure of ester
Characteristic
flavour
Banana
Apple
Apricot
Pineapple
82

Some esters and their characteristic flavours (contd)
Structure of ester
Characteristic flavour
Rum
Grape
Wintergreen
83
The END
84

A2 Chemistry Carboxylic Acids and Their Derivatives

Caricato da

Informazioni sul documento

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

A2 Chemistry Carboxylic Acids and Their Derivatives

Caricato da

Copyright:

Formati disponibili

A2 chemistry

New Way Chemistry for Hong Kong A-Level Book 3B

General formula of carboxylic acid: RCOOH

New Way Chemistry for Hong Kong A-Level Book 3B

Carboxylic acid derivatives

New Way Chemistry for Hong Kong A-Level Book 3B

Nomenclature of Carboxylic Acids and their Derivatives

New Way Chemistry for Hong Kong A-Level Book 3B

Nomenclature of Carboxylic Acids and their Derivatives

New Way Chemistry for Hong Kong A-Level Book 3B

Nomenclature of Carboxylic Acids and their Derivatives

New Way Chemistry for Hong Kong A-Level Book 3B

Nomenclature of Carboxylic Acids and their Derivatives

New Way Chemistry for Hong Kong A-Level Book 3B

Nomenclature of Carboxylic Acids and their Derivatives

New Way Chemistry for Hong Kong A-Level Book 3B

Nomenclature of Carboxylic Acids and their Derivatives

New Way Chemistry for Hong Kong A-Level Book 3B

Nomenclature of Carboxylic Acids and their Derivatives

(a) The structural formula of methyl ethanoate is:

It is formed from the reaction of ethanoic acid and

New Way Chemistry for Hong Kong A-Level Book 3B

Nomenclature of Carboxylic Acids and their Derivatives

(b) The structural formula of ethyl methanoate is:

It is formed from the reaction of methanoic acid

New Way Chemistry for Hong Kong A-Level Book 3B

Nomenclature of Carboxylic Acids and their Derivatives

Check Point 35-1

(f) 2-Chlorobenzoic acid

New Way Chemistry for Hong Kong A-Level Book 3B

35.4 Preparation of Carboxylic Acids (SB p.39)

This oxidation takes place initially at the benzylic carbon

New Way Chemistry for Hong Kong A-Level Book 3B

The acid strength of ethanoic acid is shown by the value of its

pKa is used for convenience as Ka is small for weak acids

Carboxylic acids are stronger acids than

New Way Chemistry for Hong Kong A-Level Book 3B

The greater stability of carboxylic acids is attributed to

New Way Chemistry for Hong Kong A-Level Book 3B

pKa is used for convenience as Ka is small for weak acids

New Way Chemistry for Hong Kong A-Level Book 3B

Unsubstituted carboxylic acid

Methanoic acid HCOOH

New Way Chemistry for Hong Kong A-Level Book 3B

35.5 Reactions of Carboxylic Acids (SB p.41)

By the resonance effect, the ethanoate ion can be

No stabilizing resonance structures for alkoxide ions

Carboxylic acids are much acidic than alcohols

New Way Chemistry for Hong Kong A-Level Book 3B

35.5 Reactions of Carboxylic Acids (SB p.41)

Both compounds contain the highly polarized O H

New Way Chemistry for Hong Kong A-Level Book 3B

35.5 Reactions of Carboxylic Acids (SB p.41)

Two resonance structures for the carbonyl group:

The carbonyl atom of ethanoic acid bears a large

New Way Chemistry for Hong Kong A-Level Book 3B

35.5 Reactions of Carboxylic Acids (SB p.42)

Inductive Effects of Other

New Way Chemistry for Hong Kong A-Level Book 3B

35.5 Reactions of Carboxylic Acids (SB p.42)

The chlorine atom withdraws electron from the carbonyl

New Way Chemistry for Hong Kong A-Level Book 3B

35.5 Reactions of Carboxylic Acids (SB p.41)

Effect of electron-withdrawing substituents on the acidity of carboxylic acids