Carboxylic acids:

O
R-COOH, R-CO2H, R C
OH

Common names:
HCO2H

formic acid

L. formica ant

CH3CO2H

acetic acid

L. acetum vinegar

CH3CH2CO2H

propionic acid G. first salt

CH3CH2CH2CO2H

butyric acid

L. butyrum butter

CH3CH2CH2CH2CO2H

valeric acid

L. valerans

Carboxylic acids, common names:

CH3(CH2)4CO2H

caproic acid

CH3(CH2)5CO2H

---

CH3(CH2)6CO2H

caprylic acid

CH3(CH2)7CO2H

---

CH3(CH2)8CO2H

capric acid

CH3(CH2)9CO2H

---

CH3(CH2)10CO2H

lauric acid

L. caper goat

oil of lauryl

5 4 3 2 1
CCCCC=O

Br
CH3CH2CH2CHCOOH

bromovaleric acid

used in common names

CH3
CH3CHCH2COOH

-methylbutyric acid
isovaleric acid

COOH

special names
benzoic acid

COOH
CH3

COOH

CH3
o-toluic acid

m-toluic acid

COOH

CH3
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
HO2C-CH2CH2-CO2H

malonic acid
succinic acid

HO2C-CH2CH2CH2-CO2H

glutaric acid

HOOC-(CH2)4-COOH

adipic acid

HOOC-(CH2)5-COOH

pimelic acid

Oh, my! Such good apple pie!

CO2H
CO2H

CO2H

CO2H

CO2H
CO2H

phthalic acid

H
H

C
C

isophthalic acid

terephthalic acid

COOH

COOH

HOOC

maleic acid

C
C

COOH
H

fumaric acid

salts of carboxylic acids:

name of cation + name of acid: drop ic acid, add ate

CH3CO2Na

sodium acetate

CH3CH2CH2CO2NH4

or sodium ethanoate

ammonium butyrate
ammonium butanoate

(CH3CH2COO)2Mg

magnesium propionate
magnesium propanoate

HO

O
C

OH

carbonic acid

HO

O
C

ONa

sodium bicarbonate
sodium hydrogen carbonate
NaHCO3

NaO

O
C

ONa

sodium carbonate
Na2CO3

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
acid

stronger
base

weaker
base

weaker
acid

RCO2H

RCO2-

covalent
water insoluble

ionic
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.

Carboxylic acids, syntheses:

1. oxidation of primary alcohols
RCH2OH + K2Cr2O7 RCOOH
2. oxidation of arenes
ArR + KMnO4, heat ArCOOH
3. carbonation of Grignard reagents
RMgX + CO2 RCO2MgX + H+
RCOOH
4. hydrolysis of nitriles
RCN + H2O, H+, heat RCOOH

1. oxidation of 1o alcohols:

CH3CH2CH2CH2-OH + CrO3 CH3CH2CH2CO2H

n-butyl alcohol
1-butanol

CH3
CH3CHCH2-OH + KMnO4
isobutyl alcohol
2-methyl-1-propanol`

butyric acid
butanoic acid

CH3
CH3CHCOOH
isobutyric acid
2-methylpropanoic acid

2. oxidation of arenes:
CH3

KMnO4, heat

COOH

toluene

CH3

benzoic acid

COOH

KMnO4, heat

note: aromatic
acids only!

HOOC

H3C

terephthalic acid

p-xylene

KMnO4, heat
CH2CH3
ethylbenzene

COOH + CO2
benzoic acid

3. carbonation of Grignard reagent:

Mg
R-X

CO2
RMgX

H+
RCO2MgX

RCOOH

Increases the carbon chain by one carbon.

Mg
CH3CH2CH2-Br
n-propyl bromide

RMgX +

O
C
O

CO2 H+
CH3CH2CH2MgBr

O
R C
O-

CH3CH2CH2COOH
butyric acid
H+

MgX

O
R C
OH

CH3

CH3
Mg

CH3
CO2

Br

H+

MgBr

COOH
p-toluic acid

Br2, hv
CH3

Mg
CH2Br

CH2MgBr
CO2
H+

CH2 COOH
phenylacetic acid

4. Hydrolysis of a nitrile:
H2O, H+
R-CN

R-CO2H
heat
H2O, OH-

R-CN

R-CO2- + H+ R-CO2H
heat

R-X + NaCN R-CN + H+, H2O, heat RCOOH

1o alkyl halide

Adds one more carbon to the chain.

R-X must be 1o or CH3!

CH3

Br2, hv

NaCN
CH2Br

toluene

CH2 CN
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

Mg

MgBr

C N
H2O, H+, heat

CO2; then H+

carboxylic acids, reactions:

1. as acids
2. conversion into functional derivatives
a) acid chlorides
b) esters
c) amides
3. reduction
4. alpha-halogenation
5. EAS

as acids:
a) with active metals
RCO2H + Na RCO2-Na+ + H2(g)
b) with bases
RCO2H + NaOH RCO2-Na+ + H2O
c) relative acid strength?
CH4 < NH3 < HCCH < ROH < HOH < H2CO3 < RCO2H < HF
d) quantitative
HA + H2O H3O+ + AKa = [H3O+] [A-] / [HA]

ionization in water

Ka for carboxylic acids 10-5

Why are carboxylic acids more acidic than alcohols?
ROH + H2O H3O+ + RORCOOH + H2O H3O+ + RCOOGo = -2.303 R T log Keq
The position of the equilibrium is determined by the free
energy change, Go.
Go = H - TS
Go H
Ka is inversely related to H, the potential
energy difference between the acid and its conjugate base. The
smaller the H, the larger the Ka and the stronger the acid.

potential energy

H3O+ + A-

HA + H2O

ionization

The smaller the H, the more the equilibrium lies to the

right, giving a larger Ka ( a stronger acid ).

OR C
O

O
R C
O-

R C

O
O

Resonance stabilization of the carboxylate ion decreases

the H, shifts the ionization in water to the right, increases
the Ka, and results in carboxylic acids being stronger acids.

Effect of substituent groups on acid strength?

CH3COOH

1.75 x 10-5

ClCH2COOH

136 x 10-5

Cl2CHCOOH

5,530 x 10-5

Cl3CCOOH

23,200 x 10-5

-Cl is electron withdrawing and delocalizes the negative

charge on the carboxylate ion, lowering the PE, decreasing
the H, shifting the ionization to the right and increasing
acid strength.

Effect of substituent groups on acid strength of benzoic acids?

Electron withdrawing groups will stabilize the anion, decrease the H, shift
the ionization to the right, increasing the Ka, increasing acid strength.
COOG

Electron donating groups will destabilize the anion, increase the H, shift the
ionization in water to the left, decreasing the Ka, decreasing acid strength.

COOG

-NH2, -NHR, -NR2

-OH
-OR
-NHCOCH3
-C6H5
-R
-H
-X
-CHO, -COR
-SO3H
-COOH, -COOR
-CN
-NR3+
-NO2

electron donating

electron withdrawing

Relative acid strength?

Ka
p-aminobenzoic acid

1.4 x 10-5

p-hydroxybenzoic acid

2.6 x 10-5

p-methoxybenzoic acid

3.3 x 10-5

p-toluic acid

4.2 x 10-5

benzoic acid

6.3 x 10-5

p-chlorobenzoic acid

10.3 x 10-5

p-nitrobenzoic acid

36

x 10-5

2. Conversion into functional derivatives:

acid chlorides
O
R C
OH

SOCl2

O
R C
Cl

or PCl3
orPCl5

CO2H + SOCl2

CH3CH2CH2 C

O
OH

COCl

PCl3
CH3CH2CH2 C

O
Cl

 esters
direct esterification:

H+

RCOOH + ROH 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 + ROH RCO2R
-convert the acid into the acid chloride first; not reversible

O
C
OH

H+
+

CH3OH

SOCl2

O
C
Cl

CH3OH

O
+ H2O
C
O CH3

 amides
indirect only!
RCOOH + SOCl2 RCOCl + NH3 RCONH2
amide
O
OH
3-Methylbutanoic acid

PCl3

NH3
Cl

O
NH2

Directly reacting ammonia with a carboxylic acid results in

an ammonium salt:
RCOOH + NH3 RCOO-NH4+
acid
base

O
C
OH

PCl3

O
C
Cl

NH3

O
C
NH2
amide

NH3

O
C
O

NH4

ammonium salt

3. Reduction:
RCO2H + LiAlH4; then H+ RCH2OH
1o alcohol
CH3CH2CH2CH2CH2CH2CH2COOH
Octanoic acid
(Caprylic acid)

LiAlH4

H+

CH3CH2CH2CH2CH2CH2CH2CH2OH
1-Octanol

Carboxylic acids resist catalytic reduction under normal

conditions.
RCOOH + H2, Ni NR

O
CH2 C
OH

H2, Pt

LiAlH4
H+

CH2CH2OH

NR

4. Alpha-halogenation: (Hell-Volhard-Zelinsky reaction)

RCH2COOH + X2, P RCHCOOH + HX
X
-haloacid
X2 = Cl2, Br2
CH3CH2CH2CH2COOH

Br2,P

pentanoic acid
COOH
Br2,P

NR (no alpha H)

CH3CH2CH2CHCOOH
Br
2-bromopentanoic acid

RCH2COOH + Br2,P

RCHCOOH + HBr
Br
NH3
RCHCOOH

RCHCOOH

NH2

OH

KOH(alc)
RCH2CHCOOH
Br

then H+

RCH=CHCOOH

aminoacid

5. EAS: (-COOH is deactivating and meta- directing)

CO2H
HNO3,H2SO4
NO2
CO2H
CO2H

H2SO4,SO3
SO3H
CO2H

benzoic acid

Br2,Fe
Br
CH3Cl,AlCl3

NR

spectroscopy:

IR:

-COOH

OH stretch 2500 3000 cm-1 (b)

C=O stretch

nmr: -COOH

10.5 12 ppm

1680 1725 (s)

p-toluic acid

-COOH
stretch

C=O

COOH c
b
CH3

Carboxylic acids, syntheses:

1. oxidation of primary alcohols
RCH2OH + K2Cr2O7 RCOOH
2. oxidation of arenes
ArR + KMnO4, heat ArCOOH
3. carbonation of Grignard reagents
RMgX + CO2 RCO2MgX + H+
RCOOH
4. hydrolysis of nitriles
RCN + H2O, H+, heat RCOOH

carboxylic acids, reactions:

1. as acids
2. conversion into functional derivatives
a) acid chlorides
b) esters
c) amides
3. reduction
4. alpha-halogenation
5. EAS