EXERCISE 9

Acyl Compounds,
Soaps and Detergents

Acyl Compounds
O

OH

carboxylic
acid

acid halide

OR

ester

O
R
acid anhydride

NH2

NHR

amide

NR2

Nucleophilic Acyl Substitution

nucleophilic addition to the carbonyl group

is less likely in acyl compounds than in

aldehydes and ketones. The characteristic
reaction of acyl compounds is nucleophilic
acyl substitution
reaction

begin with the addition of a

nucleophile to a polar C=O bond to give a
tetrahedral intermediate. The intermediate
formed from a carboxylic acid derivative
expels a leaving group to give a new carbonyl
compound

Nucleophilic Acyl Substitution

SIMPLIFIED VIEW

1)
:O:

R C Y
+ Nu:
2)

.. :O:
R C Y

carbonyl group
forms again

Nu

slow
addition of
nucleophile

elimination of
leaving group

.. :O :
R C Y
Nu

: O:
R C

Nu
most arent this simple, proton
transfers are usually required

Y: -

Solubility of Carboxylic Acids

Sample

H2O

acetic
acid
benzoic
acid
sodium
benzoate
phenol

+
-

10%
NaOH

10%
NaHCO3

+
-

Solubility of Carboxylic Acids

acetic acid
fully
miscible

with

water
capable of hydrogen
bonding
H3C
acetic acid dissociates
in water
CH3COOH(aq) + H2O(l)
CH3COO-(aq) + H3O+(aq)

O
C
OH

Solubility of Carboxylic Acids

benzoic acid
solubility in

water at 25 C:
3.4 g/L
has large
hydrophobic
aromatic ring
that limits
solubility in
water

HO

O
C

Solubility of Carboxylic Acids

sodium

benzoate
soluble in
water
because of
ion-dipole
interaction

Na

O
C

Acidity of carboxylic acids and

phenols
HO

OH

O
C

O
C
HO

benzoic acid
pKa = 4.19

OH

carbonic acid
pKa = 6.00

phenol
pKa = 9.89

Increasing acidity: lower pKa value,

more acidic

Acidity of carboxylic acids and

phenols
carboxylic acids react with NaOH and

NaHCO3 to give sodium carboxylate

carboxylic acids dissociate to give

carboxylate ion in which the negative

charge is delocalized over two equivalent
oxygen atoms

Acidity of carboxylic acids and

phenols
anything that stabilizes the conjugate base

of an acid will necessarily make that acid

stronger and shift the equilibrium to the
right. Both the carboxyl group and the
carboxylate anion are stabilized by
resonance, but the stabilization of the
carboxylate is greater compared to the
carboxylic acid
carboxylate ion is therefore stabilized by

resonance

Hydrolysis of Acyl
Compounds
Sample
acetyl
chloride
acetic
anhydrid
e
ethyl
benzoate
benzamid
e

Without
heating
+

With
heating

Litmus
test
acidic
acidic

neutral

neutral

Hydrolysis of Acyl
Compounds
O

H2O
OH

Cl

Cl-

H2O

OH

Hydrolysis of Acyl
Compounds
O

H2O

OH
O

NH2

H2O

OH

NH2-

Hydrolysis of Acyl
Compounds

Hydrolysis of Acyl
Compounds
Reactivity trends
Leaving group ability
weak bases are better leaving

groups than strong bases

reactivity of acyl compounds
towards nucleophiles decreases
as the basicity of the leaving
group increases

Hydrolysis of Acyl
Compounds
Sample

Conjugate Base/
Leaving Group

Cl

Cl

pKa

-7

4.76

15.9

Hydrolysis of Acyl
Compounds
Sample

Conjugate Base/
Leaving Group

NH2

NH2

pKa

38

chloride and carboxylate are good leaving groups

because they are weak bases and they are stable in
solution
alkoxides and amide are poor leaving groups since
they are strong bases
heating the mixture gives a drastic condition which
forces the reaction to proceed

Hydrolysis of Acyl
Compounds
Resonance
when a nucleophile attacks

a
acyl compound and a tetrahedral
intermediate is formed, the
energetically
favorable
resonance effect is lost, making
it
least
reactive
towards
nucleophilic acyl substitution

Soaps and Detergents

Triacylglycerols / triglycerides
esters of long-chain carboxylic

acids and glycerols

carboxylic acids attached to
glycerol may be identical or
different
undergo same reactions as
low molecular mass esters

Soaps and Detergents

Saponification
from Latin sapo meaning soap
hydrolysis of an ester such

as
triglycerides when the reaction is
carried out under alkaline conditions,
producing a mixture of soaps and
glycerols

soaps salt from the acid-base reaction

between an ester and a strong base such

as NaOH and KOH

Soaps and Detergents

Saponification reaction

R1

+ 3 NaOH
R2

R3

triglyceride

+
R1

O-Na+

OH

+
R2

O-Na+

R3

O-Na+

sodium salts of fatty acids or soaps

OH

OH

glycerol

Soaps and Detergents

O

O
O

+ 3 NaOH
O

OH

CH2(CH2)9CH3

3 H3C(H2C)9H2C

O-Na+

OH

CH2(CH2)9CH3

CH2(CH2)9CH3

triglyceride of
lauric acid

sodium
laureate

OH

glycerol

Soaps and Detergents

Detergents
cleaning agents characterized by the

presence of the sulfate group

comes from a strong acid (sulfonic acid) and
a strong base
same amphiphatic structure as soap
O

O
S
O
R

O Na

Soaps and Detergents

H2SO4
OH

lauryl
alcohol

HO

NaOH

S
O

lauryl hydrogen
sulfate

Na O

O
S

Comparison of Soaps and

Detergents
Hydrolysis
Reaction
with acid
Reaction
with soft
water
Reaction
with hard
water
Emulsifying
action

Soap
Red to blue
Formation of
precipitate
Clear
solution

Detergent
Neutral
Clear
solution
Clear
solution

Formation of
precipitate

Clear
solution

Comparison of Soaps and

Detergents
Hydrolysis
soaps undergo a hydrolysis

reaction in water. As a
result, soap solutions tend to
be alkaline.
detergent
solutions
are
neutral

Comparison of Soaps and

Detergents
Hydrolysis
soap

O
O

H2O

OH

OHdetergent
R

R
O

H2O

S
O

O
S

O
O

OH

OH-

Comparison of Soaps and

Detergents
Reaction with an acid
soaps are water soluble, but the

fatty acids themselves are not. A

soap can be converted into the
fatty acid by means of a reaction
with a strong acid.
acidification
of
detergents
produces acids which are often
water soluble

Comparison of Soaps and

Detergents
Reaction with acid
soap
O

H+

OH

water - insoluble
detergent
R

R
O

H+

S
O

O
S

O
O

water

OH

Comparison of Soaps and

Detergents
Reaction with hard water
sodium ion in soap is replaced

by
either
magnesium
or
calcium ions to form insoluble
precipitates (scum)
detergents form water-soluble
salts
with
calcium
and
magnesium ions

Comparison of Soaps and

Detergents
Reaction with hard water
Soap
O

Ca2

Ca2+

+
O

Mg

Mg2+ *

calcium and magnesium carborxylates are water insoluble

Comparison of Soaps and

Detergents
Reaction with hard water
Detergent
R

R
O

Ca2

S
O

S
O

Ca2
O

Mg2

O
S
O

Mg2+

S
O

Comparison of Soaps and

Detergents
Emulsifying action
soaps
and detergents form

micelles in water
the nonpolar region of the
soap/detergent interacts with
the grease film while the polar
region interacts with water
molecules, forming a emulsion

Emulsifying/cleaning action
of Soap
When a dirty cloth is put is put in

water containing soap than the

hydrocarbon ends of the soap
molecule in the micelle attach to the
oil or grease particles present on the
surface of dirty cloth. In this way the
soap micelles entraps the oily
particles by using the hydrocarbon
ends. The ionic ends of the soap
molecules remain attached to the
water when the dirty cloth is agitated
in soap solution. The oily particles
presents on its surface gets
dispersed in the water due to which
the cloth gets clean.