Carboxylic Acids

SANTOSH
CHEMISTRY DEPT
Carboxylic acids:
O
R-COOH, R-CO2H, R C
OH

Common names:
HCO2H formic acid
CH3CO2H acetic acid
CH3CH2CO2H propionic acid
CH3CH2CH2CO2H butyric acid
CH3CH2CH2CH2CO2H valeric acid
 5 4 3 2 1
C—C—C—C—C=O
δ γ β α used in common names

Br CH3
CH3CH2CH2CHCOOH CH3CHCH2COOH

 bromovaleric acid  -methylbutyric acid

isovaleric acid
 COOH

benzoic acid

COOH COOH COOH

CH3

CH3
CH3

o-toluic acid m-toluic acid p-toluic acid

IUPAC nomenclature for carboxylic acids:
parent chain = longest, continuous carbon chain that
contains the carboxyl group  alkane, drop –e, add –oic
acid
HCOOH methanoic acid
CH3CO2H ethanoic acid
CH3CH2CO2H propanoic acid

CH3
CH3CHCOOH 2-methylpropanoic acid

Br
CH3CH2CHCO2H 2-bromobutanoic acid
 Dicarboxylic acids

HOOC-COOH oxalic acid

HO2C-CH2-CO2H malonic acid
HO2C-CH2CH2-CO2H succinic acid
HO2C-CH2CH2CH2-CO2H glutaric acid
HOOC-(CH2)4-COOH adipic acid
HOOC-(CH2)5-COOH pimelic acid
 CO2H CO2H
CO2H

CO2H CO2H
CO2H
phthalic acid isophthalic acid
terephthalic acid

H COOH H COOH
C C
C C
H COOH HOOC H

maleic acid fumaric acid

salts of carboxylic acids:
name of cation + name of acid: drop –ic acid, add –ate

CH3CO2Na sodium acetate or sodium ethanoate

CH3CH2CH2CO2NH4 ammonium butyrate

ammonium butanoate

(CH3CH2COO)2Mg magnesium propionate

magnesium propanoate
 Physical Properties:
polar + hydrogen bond  relatively high mp/bp
water insoluble
exceptions: four carbons or less
acidic turn blue litmus  red
soluble in 5% NaOH
RCO2H + NaOH  RCO2-Na+ + H2O
stronger stronger weaker weaker
acid base base acid
• Two molecules of a carboxylic acid can hydrogen bond
together. H O
O
CH3 C C CH3
O H O
 RCO2H RCO2-
covalent ionic
water insoluble water soluble

Carboxylic acids are insoluble in water, but soluble in 5%

NaOH.

1. Identification.
2. Separation of carboxylic acids from basic/neutral organic
compounds.
The carboxylic acid can be extracted with aq. NaOH and
then regenerated by the addition of strong acid.
General Methods of preparation of Carboxylic Acids:

1. oxidation of 1o alcohols:

CH3CH2CH2CH2-OH + CrO3  CH3CH2CH2CO2H

n-butyl alcohol butyric acid
1-butanol butanoic acid

CH3 CH3
CH3CHCH2-OH + KMnO4  CH3CHCOOH
isobutyl alcohol isobutyric acid
2-methyl-1-propanol` 2-
methylpropanoic acid
2. Oxidation of alkylbenzenes:
KMnO4, heat
CH3 COOH

toluene benzoic acid

COOH
note: aromatic acids
CH3
KMnO4, heat only!

H3C HOOC

p-xylene terephthalic acid

KMnO4, heat
CH2CH3 COOH + CO2

ethylbenzene benzoic acid

3. Carbonation of Grignard Reagents:

O
+
R MgX + CO2 R C O MgX
ether
( R-Li )
H3O+

O
R C OH

+ MgX(OH)
CH3 CH3 CH3
Mg CO2 H+

Br MgBr COOH

p-toluic acid

Br2, hv Mg
CH3 CH2Br CH2MgBr

CO2

H+

CH2 COOH

phenylacetic acid
Hydrolysis of Nitriles

_ DMSO
R CH2 Cl + : C N: R CH2 C N + Cl

H2SO4 H 2O
SN2 heat

O
+
R CH2 C OH + NH4
 Br2, hv NaCN
CH3 CH2Br CH2 CN

toluene
H2O, H+, heat

CH2 COOH

phenylacetic acid

KCN
CH3CH2CH2CH2CH2CH2-Br CH3CH2CH2CH2CH2CH2-CN
1-bromohexane
H2O, H+, heat

CH3CH2CH2CH2CH2CH2-COOH
heptanoic acid
CH2OH

KMnO4

CH3
KMnO4, heat
CO2H

Br MgBr
Mg
CO2; then H+

C N
H2O, H+, heat
 SYNTHESIS OF CARBOXYLIC ACIDS
( benzene = R
R C C R R'
sidechain = R’ )
R R
KMnO4
KMnO4
R CH2 OH
H H KMnO4
CrO3
or KMnO4
H2SO4
O O
CrO3 H2O
R C H R C OH R C N
H2SO4 H2SO4
DIBAL or
NaCN
Rosenmund H2O CO2 KMnO4 acetone
O
H2SO4 R Li R X SOCl2
Li or
R C Cl H2O or Mg R OH
O R Mg X
R R
R C OR
H H
OH OH
 Carboxylate Ion Formation

O O
+
R CH2 C OH + NaOH R CH2 C O Na + H2O

carboxylic acid carboxylate ion

pKa 5
 Protonation and Deprotonation
of a Carboxylic Acid
.. H
+ O
.. ..
:O :O ..
R C O H
.. -
R C O NaOH .. H2SO4 ..
: R C O H
.. .. .. H
:O
H2SO4
+
R C O H
.. ..
:O
..
R C O equivalent structures
H
+ due to resonance
H
 O O
+
X C C OH X C C O + H

• Electron-withdrawing Groups:
– strengthen acids
– weaken bases
• Electron-releasing Groups:
– weaken acids
– strengthen bases
Substituents with Electron-Withdrawing
Resonance ( - R ) Effects
X Y
O
C OH carboxyl NO2 nitro

O
C OR alkoxycarbonyl C N cyano

O
C R acyl SO3H sulfo

-R substituents strengthen acids and weaken bases

 Substituents with Electron-Releasing
Resonance ( + R ) Effects
.. .. ..
OH
.. hydroxy OR
.. alkoxy Y
.. O
..
SH
.. mercapto O C R acyloxy
..

CH3 methyl CR3 alkyl

.. ..
NH2 amino NR2 dialkylamino

.. ..
.. :
F fluoro Cl
..
: chloro
.. ..
Br : bromo I: iodo
.. ..

+R substituents weaken acids and strengthen bases

Substituents with Electron-Withdrawing
O ( - I ) Inductive Effects
C OH
carboxyl X
O
C N cyano
C OR alkoxycarbonyl
SO3H sulfonic acid
O OR alkoxy
C R acyl
NR2 dialkylamino
OH hydroxyl
F fluoro
SH mercapto Br bromo
NH2 amino
I iodo
Cl chloro +
N(CH3)3 trimethylammonium
NO2 nitro

-I substituents strengthen acids and weaken bases

 Substituents with Electron-Releasing
Inductive ( + I ) Effects

R
CH3 methyl

O
CR3 alkyl C O carboxylate

O oxide

+I substituents weaken acids and strengthen bases

 O pKa = 4.75 O
CH3 C OH I CH2 C OH 3.12
increasing
acidity

O O
O2N CH2 C OH Br CH2 C OH 2.86
3.83

O O
H2N CH2 C OH Cl CH2 C OH 2.86
2.34

O O
HO CH2 C OH 1.68 F CH2 C OH 2.66
 O O
CH3 C OH pKa = 4.75 H C OH 3.77

O O
Cl CH2 C OH 2.86 CH3 C OH 4.75

O O

Cl CH C OH 1.29 CH3 CH2 C OH 4.88

Cl
O
Cl O CH3 CH C OH 4.86
Cl C C OH 0.65 CH3
Cl
CH3 O
CH3 C C OH 5.05
CH3
 COOH pKa = 2.92 COOH
2.16

Cl ortho NO2 ortho

COOH COOH
3.82 3.47

meta meta
Cl NO2

COOH COOH
3.98 3.41

Cl para O2N para

Benzoic Acid: pKa = 4.19

 COOH COOH

4.08 4.06

OCH3 OH

COOH
COOH
4.48
4.46 HO
CH3 O

COOH

Benzoic Acid: pKa = 4.19 2.97

OH
Chemical Properties of Carboxylic Acids:

1. as acids
2. conversion into functional derivatives
a)  acid chlorides
b)  esters
c)  amides
3. reduction
4. alpha-halogenation
5. EAS
1) Salt formation:
a) with active metals
RCO2H + Na  RCO2-Na+ + H2(g)
b) with bases
RCO2H + NaOH  RCO2-Na+ + H2O
c) relative acid strength?
CH4 < NH3 < HCCH < ROH < HOH < H2CO3 < RCO2H < HF
d) quantitative
HA + H2O  H3O+ + A- ionization in water
Ka = [H3O+] [A-] / [HA]
2) Formation of acid chlorides:

O SOCl2 O
R C R C
OH or PCl3 Cl
orPCl5

CO2H + SOCl2 COCl

O PCl3 O
CH3CH2CH2 C CH3CH2CH2 C
OH Cl
3) Formation of esters:

“direct” esterification: H+
RCOOH + R´OH  RCO2R´ + H2O
-reversible and often does not favor the ester
-use an excess of the alcohol or acid to shift equilibrium
-or remove the products to shift equilibrium to completion

“indirect” esterification:
RCOOH + PCl3  RCOCl + R´OH  RCO2R´
-convert the acid into the acid chloride first; not reversible
 O H+ O
C + CH3OH C + H2O
OH O CH3

SOCl2

O CH3OH
C
Cl
4) Formation of amides:

“indirect” only.
RCOOH + SOCl2  RCOCl + NH3  RCONH2
O O
amide
PCl3 NH3 O
OH Cl NH2
3-Methylbutanoic acid

Directly reacting ammonia with a carboxylic acid results in an

ammonium salt:
RCOOH + NH3  RCOO-NH4+
acid base
 O PCl3 O NH3 O
C C C
OH Cl NH2

amide

NH3

O
C ammonium salt
O NH4
5) Reduction:

RCO2H + LiAlH4; then H+  RCH2OH

1o alcohol

LiAlH4 H+
CH3CH2CH2CH2CH2CH2CH2COOH
Octanoic acid
(Caprylic acid)
CH3CH2CH2CH2CH2CH2CH2CH2OH
1-Octanol

Carboxylic acids resist catalytic reduction under normal

conditions.
RCOOH + H2, Ni  No Reaction (NR)
 O H2, Pt
CH2 C NR
OH

LiAlH4

H+

CH2CH2OH
6) Halogenation of alkyl groups (Hell-Volhard-Zelinsky
reaction):

RCH2COOH + X2, P  RCHCOOH + HX

X
α-haloacid
X2 = Cl2, Br2
CH3CH2CH2CH2COOH + Br2,P CH3CH2CH2CHCOOH
pentanoic acid Br
2-bromopentanoic acid

COOH
Br2,P
NR (no alpha H)
RCH2COOH + Br2,P RCHCOOH + HBr
+ Br
n H
H; the
O NH3
Na

RCHCOOH RCHCOOH
aminoacid
NH2
OH

KOH(alc)
RCH2CHCOOH RCH=CHCOOH
Br then H+
5) Aromatic Substitution:
(-COOH is deactivating and meta- directing)
CO2H
HNO3,H2SO4

NO2

CO2H
H2SO4,SO3
CO2H

SO3H

CO2H
benzoic acid Br2,Fe

Br

CH3Cl,AlCl3
NR