Chapter
20


Carboxylic
Acids
and
Nitriles

 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Oxidizing
benzyl

groups

–  Reactants:


•  1.


–  Solvent:

•  1.
and

–  Products:


•  1.


–  Note:

•  1.


•  2.

 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Oxidizing
benzyl

groups

–  Reactants:


•  1.
Alkyl
benzene

–  Solvent:

•  1.
KMnO4
and
H2O

–  Products:


•  1.
Carboxyl
group
subsBtuted
on
aromaBc
ring

–  Note:

•  1.
Only
occurs
on
benzylic
hydrogens
and
thus
no
mixture
of

products
is
given

•  2.
Primary
and
secondary
only;
terBary
doesn’t
oxidize


 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Oxida&ve
cleavage

of
alkenes

–  Reactants:


•  1.


–  Solvent:

•  1.


•  2.


–  Products:


•  1.


 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Oxida&ve
cleavage

of
alkenes

–  Reactants:


•  1.
MonosubsBtuted
carbon
of
an
alkene

–  Solvent:

•  1.
KMnO4


•  2.
H3O+

–  Products:


•  1.
Carboxylic
acid


 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Oxidizing
primary

alcohols



–  Reactants:


•  1.


•  2.


–  Products:


•  1.


 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Oxidizing
primary

alcohols



–  Reactants:


•  1.
Primary
alcohol


•  2.
CrO3+
(in
H3O+
and
acetone)

–  Products:


•  1.
Carboxylic
acid

 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Oxidizing

aldehydes



–  Reactants:


•  1.


•  2.


–  Products:


•  1.


 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Oxidizing

aldehydes



–  Reactants:


•  1.
Aldehyde

•  2.
CrO3+
(in
H3O+
and
acetone)

–  Products:


•  1.
Carboxylic
acid

 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Tollen’s
Reagent

–  Reactants:


•  1.


•  2.


•  3.
in

•  4.


–  Products:


•  1.


–  Notes:

•  1.


 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Tollen’s
Reagent

–  Reactants:


•  1.
Aldehyde

•  2.
Ag2O

•  3.
NH4OH,
H2O
(combined
=
aq.
NH3)

•  4.
Ethanol

–  Products:


•  1.
Carboxylic
acid

–  Notes:

•  1.
Use
for
acid
sensiBve
compounds
(an
aldehyde
containing

an
alkene,
for
instance)

 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Hydrolysis
of
Nitriles


–  Pre‐reac&on:

•  Reactants:


–  1.


–  2.


•  Products:


–  1.


–  Reactants:


•  1.


•  2.
and,
or

•  3.
and

–  Products:


•  1.

•  2.


 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Hydrolysis
of
Nitriles


–  Pre‐reac&on:

•  Reactants:


–  1.
NaCN
ion

–  2.
Primary
(and
someBmes
secondary;
may
cause
E2)
alkyl
halide


•  Products:


–  1.
Nitrile

–  Reactants:


•  1.
Nitrile


•  2.

–  1.
H3O+
and
heat,
or

–  2.
NaOH
and
H2O

–  Products:


•  1.
Carboxylic
acid


•  2.
NH3

 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Grignard
Reagents


– Reactants:


• 1.


• 2.

– 1.
and

– 2.


– Products:


• 1.


 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
Grignard
Reagents


– Reactants:


• 1.
R‐MgX
(Grignard
reagent)

• 2.

– 1.
CO2
(gas),
ether

– 2.
H3O+

– Products:


• 1.
Carboxylic
acid

 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
From
Ketones

– Reactants:


• 1.

• 2.

– 1.
and

– 2.


– Products:


• 1.


 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Carboxylic
Acids:
From
Ketones

– Reactants:


• 1.Ketone

• 2.

– 1.
I2,
KOH

– 2.
NeutralizaBon

– Products:


• 1.
Carboxylic
acid

 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Nitriles:
SN2
reac&on
of
alkyl
halides

–  Reactants:


•  1.


•  2.

–  Products:


•  1.

 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Nitriles:
SN2
reac&on
of
alkyl
halides

–  Reactants:


•  1.
Primary
(rarely
secondary;
may
cause
E2)
Alkyl
halide


•  2.
NaCN

–  Products:


•  1.
Nitrile

 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Nitriles:
Dehydra&on
of
amides

–  Reactants:


•  1.


•  2.


•  3.

•  4.

–  Products:


•  1.

•  2.


•  3.


 Carboxylic
Acids
and
Nitriles


•  Prepara&on
of
Nitriles:
Dehydra&on
of
amides

–  Reactants:


•  1.
Amide

•  2.
SOCl2

•  3.
Benzene


•  4.
80°C


–  Products:


•  1.
Nitrile

•  2.
SO2

•  3.
2
HCl

 Carboxylic
Acids
and
Nitriles


•  Reac&ons
of
Nitriles:
Hydrolysis
to
Yield
Carboxylic

Acids

– Reactants:


• 1.

• 2.

– 1.
and,
or

– 2.
and

– Products:


• 1.


• 2.


 Carboxylic
Acids
and
Nitriles


•  Reac&ons
of
Nitriles:
Hydrolysis
to
Yield
Carboxylic

Acids

– Reactants:


• 1.
Nitrile


• 2.

– 1.
NaOH
and
H2O,
or

– 2.
H3O+
and
heat

– Products:


• 1.
Carboxylic
acid


• 2.
NH3

 Carboxylic
Acids
and
Nitriles


•  Reac&on
of
Nitriles:
Reduc&on
to
Yield
Primary

Amines

– Reactants:


• 1.


• 2.

– 1.
and

– 2.


– Products:


• 1.


 Carboxylic
Acids
and
Nitriles


•  Reac&on
of
Nitriles:
Reduc&on
to
Yield
Primary

Amines

– Reactants:


• 1.
Nitrile

• 2.

– 1.
LiAlH4,
THF

– 2.
H2O

– Products:


• 1.
Amine

 Carboxylic
Acids
and
Nitriles


•  Reac&ons
of
Nitriles:
Grignard
reagents
to
yield

ketones

– Reactants:


• 1.


• 2.


– 1.
and

– 2.


– Products:


• 1.


• 2.


 Carboxylic
Acids
and
Nitriles


•  Reac&ons
of
Nitriles:
Grignard
reagents
to
yield

ketones

– Reactants:


• 1.
Nitrile


• 2.


– 1.
R‐MgX,
ether

– 2.
H3O+

– Products:


• 1.
Ketone

• 2.
NH3