Beruflich Dokumente
Kultur Dokumente
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
AS recap
Structure
Acyl
chlorides
Acid
anhydrides
Amides
Esters
3
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
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
(a)
(b) Butanoic
acid
(c)(b)
CH3CH(CH3)CH2COOH
(d)
(d) 3-Methylbutanoic acid
(e) C6H4ClCOOH
(g) CCl3COOH
(e)
(g)
12
(h)
(f)
(h)
Trichloroethanoic acid
Answer
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.
13
ethanoic acid
15
Resonance Effect
16
17
Formula
18
pKa
3.75
4.76
Propanoic acid
CH3CH2COOH
Butanoic acid
CH3CH2CH2COOH 4.82
Benzoic acid
C6H5COOH
4.87
4.20
Inductive Effect
22
23
Ethanoic
Chloroethanoic
acid
acid
pKa
4.76
2.86
Acidity CH3COOH <
<
<
<
Dichloroethanoic
acid
1.29
<
CCl3COOH
Trichloroethanoic
acid
0.65
<
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
27
28
29
Answer
30
,because
contains
, because
contains
32
Formationof
ofSalts
Salts
Formation
Reaction with Active Metals
33
Example:
34
Examples:
35
36
Examples:
37
NaOH and
Na2CO3 can be
used to separate a
mixture of
alcohols, phenols
and carboxylic
acids
38
40
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
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
45
Formationof
ofAmides
Amides
Formation
Ammonia reacts with carboxylic acids to form ammonium
salts. The dry salts are heated to dehydrate to give amide
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
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
53
Examples:
54
Examples:
55
56
Example:
57
59
Reactionsof
ofAcid
AcidAnhydrides
Anhydrides
Reactions
Reaction with Water
Example:
60
Example:
61
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
Alkaline hydrolysis:
65
Dehydration
66
Hofmann Degradation
Example:
67
68
Reactionsof
ofEsters
Esters
Reactions
Acid-catalyzed Hydrolysis
Example:
69
Alkali-catalyzed Hydrolysis
Example:
70
71
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
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
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
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
An artificial flavouring
made of esters
81
Structure of ester
Characteristic
flavour
Banana
Apple
Apricot
Pineapple
82
Structure of ester
Characteristic flavour
Rum
Grape
Wintergreen
83
The END
84