Carboxylic Acids & Their Derivatives

Carboxylic Acids & Their Derivatives

1.

Methods of preparation
(a)
Hydrolysis of nitriles
HCl
R C N HOH R C
or NaOH

OH

(b)

Hydrolysis of Esters

RCOOR' HOH

(c)

Hydrolysis of Anhydrides

O
H O
2 RCOOH NH 4 Cl
NH 2 HCl

Rearrangem
ent
RC

NH

HCl

RCOOH R'OH
OH

Ester

Acid

Alcohol

O
||

CH 3 C
CH 3 C

H / OH

O HOH 2CH 3COOH

Ethanoicacid

||

Ethanoicanhydride

(d)

Hydrolysis of acid chloride and nitro alkane

R C Cl HOH

||

H / OH

RCOOH HCl

R CH 2 NO2

(e)

X 3NaOH R C

RCOOH

OH

H O
OH 2 R C
OH

O
OH

3NaX

From Grignard Reagent

O

O C O RMgX

(g)

85%H 2SO4

Hydrolysis of Trihalogen
RC

(f)

Carbon dioxide

||

Dry ether

R C OMgX

H / H 2O

RCOOH Mg(OH )X

Grignard reagent

Oxidation of alkene and alkyne

RCH CHR [ O] RCOOH RCOOH

Alkene

R C C R
Alkyne

(h)

Hot alkaline
KMnO4

(i)O3

R COOH RCOOH

(ii)H 2O

The Arndt-Eistert synthesis

R C Cl CH 2 N 2 R C CHN 2
||

||

H O

Ag2O

R CH 2 COOH
(i)

From acid amides

RCONH2 H 2O
Amide

Acid

RCOOH NH 3

or Alkali

Acid

RCONH2 HNO2 RCOOH N 2 H 2O

Amide

Nitrousacid

64

Carboxylic Acids & Their Derivatives

2.

PHYSICAL PROPERTIES

The first three members (upto 3 carbon atoms) are colourless, pungent smelling liquids. The next six members are
oily liquids having unpleasant smell. The higher members are colourless and odourless waxy solids.

The lower members of the aliphatic carboxylic acid family (upto C 4) are highly soluble in water. The solubility
decreases with the increase in the size of the alkyl group. All carboxylic acids are soluble in alcohol, ether
and benzene etc. The solubility of lower members of carboxylic acids is due to the formation of hydrogen
bonds between the COOH group and water molecules.

The melting points of carboxylic acids donot vary smoothly from one member to another. The melting point of
the acids having even number of carbon atoms are higher than those containing an odd number
immediately above and below them.

The acids with even number of carbon atoms have the COOH group and the terminal CH 3 group on the
opposite side of the carbon chain.

Boiling point of carboxylic acids increase regularly with increase of molecular mass. Boiling points of carboxylic
acids are higher than those of alcohols of same molecular mass. This is due to intermolecular hydrogen
bonding between two acid molecules.
3.
ACIDIC NATURE OF CARBOXYLIC ACIDS

A molecule of carboxylic acid can be represented as a resonance hybrid of the following structures.

..
O:
||

..
..

..

O:
|

R C O H R C O H

..

(I)
(II)
Due to electron deficiency on oxygen atom of the hydroxyl group (Structure II), their is a displacement of
electron pair of OH bond toward the oxygen atom. This facilitate the release of hydrogen as proton (H +).
The resulting carboxylate ion also stabilized by resonance (As negative charge is dispersed on both the
oxygen atom). This enhance the stability of carboxylate anion and make it weaker base or strong acid.

Effect of substituent on acidic nature

(a)

An electron withdrawing substituent ( I effect) stabilizes the anion by dispersing the

negative charge and therefore increases the acidity.
GC

(b)

GC

(I)
(II)
An electron releasing substituent (+ I effect) stabilizes negative charge on the anion resulting in the
decrease of stability and thus decreased the acidity of acid.
Electron with drawing nature of halogen : F > Cl > Br > I

Thus, the acidic strength decreases in the order :

FCH 2COOH ClCH 2COOH BrCH2COOH ICH 2COOH
CCl 3COOH CHCl 2COOH CH 2ClCOOH CH 3COOH

(iii)

Inductive effect is stronger at -position than -position similarly at -position it is more stronger
than at -position

65

Carboxylic Acids & Their Derivatives

CH 3 CH 2 C H COOH CH 3 C H CH 2 COOH C H 2 CH 2 CH 2 COOH
|

Cl

(iv)

Cl

Cl

Relative acid strength in different compounds

RCOOH HOH ROH HC CH NH 3 RH

4. CHEMICAL PROPERTIES
(a)

Reaction with metals

2CH 3COOH 2Na 2CH 3COONa H 2

(b)

Action with alkalies

CH 3COOH NaOH CH 3COONa H 2O

(c)

Action with carbonates and bicarbonates

Sodiumacetate

Aceticacid

Sodiumacetate

2CH 3COOH Na2CO3 2CH 3COONa CO2 H 2O

Sod.acetate

CH 3COOH NaHCO3 CH 3COONa CO2 H 2O

Sod.acetate

Reaction of carboxylic acid with aqueous sodium carbonates solution produces bricks effervescence.
However most phenols do not produce effervescence. Therefore, this reaction may be used to
distinguish between carboxylic acids and phenols.
(d)
Formation of acid chloride

CH 3COOH PCl5 3CH 3COCl POCl3 HCl

Aceticacid

Acetylchloride

3CH 3COOH PCl3 3CH 3COCl H 3PO3

Aceticacid

Acetylchloride

CH 3COOH SOCl2 CH 3COCl SO2 HCl

Aceticacid

(e)

Acetylchloride

Formation of esters (Esterification)

Conc.H2SO4

CH 3CO OH H

Aceticacid

OC2H 5

CH 3COOC2H5 H 2O

Ethylalcohol

Ethylacetate
(Fruitysmelling)

The reaction is shifted to the right by using excess of alcohol or removal of water by distillation.
The reactivity of alcohol towards esterification.
alcohol

heat

CH 3COOH NH 3 CH 3COONH 4 CH 3CONH 2 H 2O

(f)

Formation of amides

(g)

Formation of acid anhydrides

Aceticacid

CH 3COO H
Heat CH 3CO

CH 3CO OH P2O5 CH 3CO
Reduction :

Amm.acetate

Acetamide

O H 2O

Aceticanhydride

Aceticacid

(h)

tert-alcohol< sec-alcohol < pri-alcohol < methyl

R C OH
||

LiAlH 4

R CH 2 OH

Carboxylic acid are difficult to reduce either by catalytic hydrogenation or Na C2H 5OH
(i)

CaO
NaOH R H Na2CO3
Soda Lime Decarboxylation RCOONa
Sodiumsalt
Alkane
heat

66

Carboxylic Acids & Their Derivatives

H SO (conc.)

(j)

Acid Hydrazoic
acid

Formation of amines (Schmidt reaction)

Primary
amine

In Schmidt reaction, one carbon less product is formed.

(k)

RCOOH N3H 2 4 RNH2 CO2 N2

Hell Volhard-zelinsky reaction

Carboxylic acid having an -hydrogen react with Cl2 or Br2 in the presence of a small amount of red
phosphorus to give chloro acetic acid.
CH 3COOH
Aceticacid

Cl 2 ,red P4

ClCH 2COOH

HCl

Chloroaceticacid

Cl 2 ,redP4

Cl2CHCOOH

HCl

Dichloroaceticacid

Cl 2 , redP4

Cl3CCOOH

HCl

Trichloroaceticacid

CLASSROOM ASSIGNMENT
Q 1.

Which one is called ethanoic acid

(a) HCOOH

(b) CH 3COOH

(c) CH 3CH 2COOH (d)

CH 3CH 2CH 2COOH

Q 2.

Vinegar is
(a) HCHO

Q 3.

(b) HCOOH

(c) CH 3 CHO

(d) CH 3 COOH

Acetic acid is obtained when

(a) Methyl alcohol is oxidised with potassium permanganate
(b) Calcium acetate is distilled in the presence of calcium formate
(c) Acetaldehyde is oxidised with potassium dichromate and sulphuric acid
(d) Glycerol is heated with sulphuric acid

Q 4.

C 2 H 2 HgOH
1 % A [O ] B , B is

Q 5.

(a) An acid
(b) An aldehyde
Formic acid is obtained when

H 2SO4

(c) A ketone

(d) Ethanol

(a) Calcium acetate is heated with conc. H 2 SO4 (b) Calcium formate is heated with calcium acetate
(c) Glycerol is heated with oxalic acid at 110o C (d) Acetaldehyde is oxidised with K 2Cr2O7 and
H 2SO4
Q 6.

Q 7.
Q 8.
Q 9.

The acid formed when propyl magnesium bromide is treated with carbon dioxide is
(a) C3H7COOH
(b) C2H 5COOH
(c) Both (a) and (b)
above
Hydrolysis of acetamide produces
(a) Acetic acid
(b) Acetaldehyde

(c) Methylamine

(d) None of the

(d) Formic acid

Ammonium acetate reacts with acetic acid at 110 C to form

(a) Acetamide
(b) Formamide
(c) Ammonium cyanate (d) Urea
Which reaction is used for the preparation of Bromoacetic acid ?
(a) Kolbes Reaction
(b) Reimer-Tiemann Reaction
67

Carboxylic Acids & Their Derivatives

Q 10.
Q 11.
Q 12.
Q 13.

(c) Hell volhard Zelinsky Reaction

(d) Perkins Reation
Which acid is strongest or Which is most acidic
(a) Cl 2CH .COOH (b) ClCH 2COOH
(c) CH 3COOH

(d) Cl3C.COOH

Hydrolysis of an ester gives a carboxylic acid which on Kolbes electrolysis yields ethane. The ester is
(a) Ethyl methonoate
(b) Methyl ethanoate
(c) Propylamine
(d) Ethylamine
Which of the following reduces Tollen's reagent
(a) Acetic acid
(b) Citric acid
(c) Oxalic acid
(d) Formic acid
2CH 3COOH

MnO

A , product A in the reaction is

300o C

(a) CH 3CH 2CHO

(b) CH 3 CH 2 OH (c) CH 3COCH 3

(d)

CH 3 C O C CH 3

Q 14.

||

||

In the reaction CH 3COOH

(a) C 2 H 5 I

Q 15.
Q 16.

Q 17.

Q 18.

Q 20.

(b) C 2 H 5OH

I 2 NaOH
(B)

Ag(Dust)
(C) the final product (C) is

(c) C 2 H 2

(d) CH 3COCH 3

Formaldehyde and formic acid can be distinguished using

(a) Tollen's reagent
(b) Fehling solution
(c) Ferric chloride
(d) Sodium bicarbonate
Which of the following compounds will react with NaHCO3 solution to give sodium salt and carbon
dioxide
(a) Phenol
(b) n-hexanol
(c) Acetic acid
(d) Both (a) and (b)
The end product B in the sequence of reactions

R X CN A NaOH
B is
(a) An alkane
(b) A carboxylic acid
(c) Sodium salt of carboxylic acid (d) A ketone
NH 3

Name the end product in the following series of reactions CH 3COOH A P O B

2 5

(a) CH 4
Q 19.

LiAlH
4 (A)

(b) CH 3OH

(c) Acetonitrile

(d) Ammonium acetate

Reduction of carboxylic acids gives

(a) Alcohol with hydrogen in presence of palladium

(b) Alcohol with LiAlH 4

(c) Aldehyde with LiAlH 4

(d) Alcohol with 2HI (P )

An acyl halide is formed when PCl 5 reacts with an

(a) Acid

(b) Alcohol

(c) Amide

(d) Ester

68