Carboxylic Acids & Acid Derivatives Explained

CARBOXYLICACIDS &ACID DERIVATIVES
By Anand Kumar Rai

IIT Kharagpur
Pradeep Agarwal Academy

(Taught By IITians.....)
By: Anand Kumar Rai (IITian...)

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CHEMISTRY
CARBOXYLIC ACIDS & ACID DERIVATIVES

Introduction :
Compounds containing the carboxyl group are distinctly acidic and are called carboxylic acids.
O
RCOH
Carboxylic acid
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
There have general formula CnH2nO2

Carboxylic acid derivatives are compounds with functional groups that can be converted to carboxylic
acids by a simple acidic or basic hydrolysis. The most important acid derivatives are esters, amides,
nitriles, acid halides and anhydrides.
RCOCR
anhydride
RCX
acid halide
R C O R' R C NH2
ester
amide
RCO R'
RCONH
RC N
nitrile
Esters and amides are particularly common in nature. For example, isoamyl acetate found in ripe bananas
and geranyl acetate is found in the oil of roses, geraniums and many other flowers. N, N-diethyl-metatoluamide (DEET) is one of the best insect repellents known and penicillin G is one of the antibiotics that
revolutionized modern medicine.
O C CH3
O C CH3
isoamyl acetate
(banana oil)
geranyl acetate
(geranium oil)
H3C
PhCH2 C NH
N(CH2CH3)2
N, N-diethyl-meta-toluamide

CH3
CH3
COOH
Penicillin G

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IUPAC Nomenclature of Acid and Acid derivatives:Table- 1
Compound
IUPAC Name
O
Methanoic acid
(1) H C OH
O
Ethanoic acid
(2) CH3 C OH
O
2-Cyclohexylpropanoic acid
(3) CH3 CH C OH
O
(4) CH3CCH C OH
3-Oxo-2-propylbutanoic acid
CH2CH2CH3
NH2
(5) CH2 CH2 CH2 C OH

Ph
4-Aminobutanoic acid
(6) CH3CH2CH CH2 C OH

CH3
3-Phenylpentanoic acid
(7) CH3 CH CH 2 C OH
3-Methylbutanoic acid
O
Ethanoylfluoride
(8) CH3 C F
O
Propanoylchloride
(9) CH3 CH2 C Cl

O
Br
(10) CH3 CH CH2 C Br
3-Bromobutanoylbromide
O
(11)
Cyclopentanecarbonyl
chloride
C Cl
O
(12) CH3 C O C CH 3
O
Ethanoic anhydride
(13) CF3 C O C CF3
Trifluoroethanoic anhydride
O
O
(14)
1,2-Benzenedicarboxylic
anhydride


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O
CH3 C O C H
Ethanoic methanoic
anhydride
CH3CH2 C O C CF3
C N
Trifluoroethanoic propanoic
anhydride
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
Cyclopropane carbonitrile
CN
CH3 CH2 CH CH2 COOH
3-Cyanopentanoic acid
C OCH2CH3
Ethyl o-cyanobenzoate
CN
O
C NH2
2-Formylcyclohexane
carboxamide
CH
OH
CH3 CH2 CH C N
2-Hydroxybutane nitrile
Dicarboxylic acids
If the substituent is a second carboxyl group, we have a dicarboxylic acid. For example :
HOOCCH2COOH
Malonic acid
Propanedioic acid
HOOCCH2CH2COOH
Succinic acid
Butanedioic acid
HOOCCH2CH2CHCOOH
|
Br
Bromogluta ric acid
2 Bromopen tan edioic acid
CH3
|
HOOCCH2CCH2COOH
|
CH3
HOOCCH2CH2CH2CH2COOH
Adipic acid
Hexanedioic acid
, Dimethyglu taric acid

3,3 Dimethyl pen tan edioic acid

HOOCCHCH2CHCOOH
|
|
Cl
Cl
, Dichloroglutaric acid
2,4 Dichloro pen tan edioic acid

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Physical properties of acids and acid derivatives :

(1) First three members are colourless pungent smelling liquid. The next three members also colurless oily
liquid with unpleasant smell. Higher member (> 7) are colourless waxy solids.
(2) Boiling points:
The boiling point of carboxylic acids are higher than that of alcohols, ketones or aldehydes of similar
molecular weight.
O
O
CH 3CH2CH2OH
1-propanol
bp 97C
CH3 C OH
acetic acid,
bp 118C
CH3CH3CH
Propionaldehyde
bp 49C
The high boiling points of carboxylic acids is the result of formation of a stable hydrogen-bonded dimer.
O ----- H O
RC
CR
O H ----- O
hydrogen bonded acid dimer
Carboxylic acids have higher boiling points than corresponding molucular mass alcohols because of (i) OH bond in carboxylic acid is more polar than alcohol due to the presence of
(ii) Carboxylic acid molecules are held together by two H-bonds.
group.
Esters and acid chlorides have boiling points near those of the unbranched alkanes with similar molecular
weights.
Nitriles also have higher boiling points than esters and acid chlorides of similar molecular weight. This effect
results from a strong dipolar association between adjacent cyano groups.

+
(dipolar association of nitriles)

:N CR
R C N:
These acid derivatives contain highly polar carbonyl groups, but the polarity of the carbonyl group has only a
small effect on the boiling points.
300
Examples
(MW 55 60)
1 amides
bp(C)
200
222
O
CH3COH
CH3CH2CH2OH
CH3CH2CN
O
118
97
97
Boiling point (C)
CH3CNH2
N-methyl 2amides
CH3CH2CH2CH3
acids
32
0
0
nitriles
methyl
esters
100
N,N-dimethyl 3 amides
1 aocohol
HCOCH3
acid
chlorides
100
n-alkanes
20
60
100
140
180
Molecular weight


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(3) Melting points :
Acids containing more than 8 carbon atoms are generally solids, unless they contain double bonds. The
presence of double bonds (especially cis double bond) in a long chain impedes the formation of a stable
crystal lattice resulting in a lower boiling point.
HH
CH3 (CH2)16 C OH
Stearic acid, mp 70C CH3(CH2)4
H
O
C=C
C=C
CH2
(CH2)7 C OH
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
linoleic acid mp 5C
Melting point of carboxylic acids : There is no regular pattern in melting point of carboxylic acid (up to 10
carbon atoms) having even number of C atoms are higher than neighbouring members having odd number of
C atoms because carboxylic acid and methyl group in even members lie in opposite side of zig-zag carbon
chain hence they fit better into crystal lattice resulting in higher melting points.Vice-versa is observed in case
of carboxylic acid having odd no. of carbon atoms.
Amides have surprisingly high boiling points and melting points compared with other compounds of similar
molecular weight. Primary and secondary amides participate in strong hydrogen bonding.
..
:O:
:O:
C
R'
..
N
R'
R'
+
N
R'
+
C=N
H
..
.
O
NH
+
H. . . O
+
C=N
Hydrogen bonding
R'
R
C
R'
+
N+
+
+N
R'
R'
Intermolecular attraction
Strong hydrogen bonding between molecules of primary and secondary amides also results in unusually
high melting points.
CH3
HCN
CH3
dimethylformamide
(DMF) mp 61C
CH3 C N
CH3CH2CN
CH3
N-methylacetamide
m.p. 28C
H
Propionamide
mp 79C
(4) Solubility:
Carboxylic acids form hydrogen bonds with water and the lower molecular - weight carboxylic acids ( upto
4 carbon atoms) are miscible with water.
Acid derivatives (esters, acid chlorides, anhydrides, nitriles and amides) are soluble in common organic
solvents such as alcohols, ethers, chlorinated alkanes and aromatic hydrocarbons. Acid chlorides and
anhydrides cannot be used in nucleophilic solvents such as H2O and alcohols, because they react with
these solvents.


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Physical Properties of Carboxylic Acids
Table -2
IUPAC name
Common Name
Formula
mp
(C)
bp
(C)
Solubility
(g/100 g H2O)
Methanoic
formic
HCOOH
101
(miscible)
Ethanoic
acetic
CH3COOH
17
118
Propanoic
propionic
CH3CH2COOH
21
141
2-Propenoic
acrylic
H2C=CHCOOH
14
141
Butanoic
butyric
CH3(CH2)2COOH
163
2-Methylpropanoic
isobutyric
(CH3)2CHCOOH
46
155
23
Trans-2-butenoic
crotonic
CH3CH=CHCOOH
71
185
8.6
Pentanoic
valeric
CH3(CH2)3COOH
3-Methylbutanoic
isovaleric
(CH3)2CHCH2COOH
2,2-Dimethylpropanoic
pivalic
(CH3)2CCOOH
Hexanoic
caproic
Octanoic
Decanoic
34
186
29
177
3.7
35
164
2.5
CH3(CH2)4COOH
206
1.0
caprylic
CH3(CH2)6COOH
16
240
0.7
capric
CH3(CH2)8COOH
31
269
0.2
Physical Properties of Acid Derivatives

Table -3
Compound
Name
mp (C)
bp (C)
Water
17
118
Solubility
CH3COCl
Ethanoylchloride
(CH3CO)2O
Ethanoic anhydride
CH3COOH
Ethanoic acid
CH3CONH2
Ethanamide
222
O
CH3COCH2CH3
Ethyl acetate
83
77
10%
Dimethylformamide (DMF)
61
153
miscible
Dimethylacetamide (DMA)
20
165
miscible
Acetonitrile
45
82
miscible
O
HCN(CH 3) 2
O
CH 3CN(CH 3)2
CH3C N
Methods of preparation of carboxylic acids

1.
Synthesis of carboxylic acids by the carboxylation of grignard reagents

O
O
||
||
Dry
H / H2O
R C OH
RMgX + O = C = O R C OMgX
ether

Mg (OH) X

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CH3 CHCH2CH3
|
Cl
1. Mg / diethyl ether
2. CO 2
3. H3O+
2 Chlorobu tan e
CH3CHCH2CH3
|
CO 2H
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
2 Methylbu tanoic
acid (76 86%)
1. Mg / diethyl ether
2. CO 2
3. H3O+
CH3 CH COOH
|
CH3
Isobutyric acid (2 methyl propanoic acid)
Ex.
( i ) CO 2
CH3 CH MgBr
( ii ) H2 O / H
|
CH3
2.
Synthesis of Carboxylic acids by the hydrolysis of nitriles

Mechanism :
heat
+ H+
Hydrolysis of cyanides (Acid catalysed) :
Ex.
NaCN
CH2CN
DMSO
Benzyl cyanide (92%)
Ex.

O
||
CH2COH
Phenylacetic acid (77%)
OH
|
CH3CCH2CH2CH3
|
CN

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Note:
(1) Alkyl cyanides needed for the purpose can easily be prepared from the corresponding alkyl halides with
alcoholic KCN or NaCN.
R Cl + KCN R C N + KCl
(2) This reaction is used to ascend the series having one carbon atom more than the corresponding alkyl
halides which are prepared from alcohol on treating with phosphorus halide.
ROH + PX5 R X + POX3 + HX
(3) This hydrolysis of alkyl cyanide provides a useful method to get carboxylic acid having one carbon atom
more than the original alkyl halide and alcohols.
3.
By oxidation of alkylbenzenes - aromatic acids are produced.
KMnO / OH
(i) KMnO / OH
(ii) H / H2O
(ii) H / H2O
K Cr O
7
2 2
Ex.
H2SO 4
Chemical Reactions
1. Acidic Strength :
Acidity of carboxylic acids:-
R C O + H
R C OH
O
(I)
(i) R C O (I) exists as two equivalent canonical structures I(A) and I(B). This ion is resonance stablised
O
and resonance hybrid structure is I(C).
O
O
O
RC
RC
RC
O
O
O
I(A)
I(B)
I(C)
(ii) R C O ion is more stable due to resonance, hence carboxylic acids are acidic in nature.
O
(iii) Electron withdrawing group (I effect) stablises the anion and hence, increases acidic nature.
O
X
Ex.
O
F CH2 COOH > Cl CH2COOH > Br CH2COOH > I CH2COOH
Cl
Ex.
Cl
Cl C COOH > Cl CH COOH > Cl CH2COOH > CH3COOH

Cl


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(iv) Electron releasing group (+ I effect) destablises the anion and hence decreases acidic nature.
O
X
C
O
Ex.
HCOOH > CH3COOH > CH3 CH2 COOH
COOH
Ex.
COOH
COOH
> CH2
CH2 COOH
>
COOH
CH2 COOH
Relative acid strength is:RCOOH > HOH > ROH > HC CH > NH3 > RH
Note Acidity of acids is compared by compairing stability of conjugate base.
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
Ex.
2.
(i)
(ii)
Reaction involving removal of proton from OH group.

Action with blue litmus : All carboxylic acids turn blue litmus red.
Reaction with metals :
2 CH3COOH + 2Na
+ H2
2CH3COOH + Zn
(iii)
+ H2
Reaction with alkalies :

CH3COOH + NaOH CH3COONa + H2O
Reaction with carbonates and bicarbonates :
2CH3COOH + Na2CO3 2CH3COONa + CO2 + H2O
CH3COOH + NaHCO3 CH3COONa + CO2 + H2O
Reaction of carboxylic acid with aqueous sodium carbonate solution produces brisk efferuescence.
However most phenols do not produce effervescence. Therefore, the reaction may be used to distinguish
between carboxylic acids and phenols.
Reaction with grignard reagent :
(iv)
(v)
RCH2MgBr + RCOOH
RCH3 + RCOOMgBr
Note:
A stronger acid displaces a weaker acid from the salt of the weaker acid.
Ex. CH3COOH (Stronger acid) + CH3ONa CH3COONa + CH3OH (Weaker Acid)
Ex. CH3COOH (stronger acid) + NaHCO3 CH3COONa + H2CO3 (Weaker acid) H2O + CO2
(lab. test of carboxylic acid)
3.
Reaction involving replacement of OH group
(i)
Formation of acid chlorides :


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(ii)
Ex.
+ SOCl2
Ex.
+ PCl5
+ SO2 + HCl
+ POCl3 + HCl
Fisher Esterification
Carboxylic acid react with alcohol to form esters through a condensation reaction known as esterification.
General Reaction :
+ R OH
+ H2O
Specific Examples:
+ CH3CH2OH
+ CH3OH
Mechanism : (Acid catalysed esterification)
If we follow the forward reactions in this mechanism, we have the mechanism for the acid catalysed esterification
of an acid. If however, we follow the reverse reactions, we have the mechanism for the acid catalysed
hydrolysis of an ester. Acid catalysed ester hydrolysis.
which resut we obtain will depend on the condition we choose. If we want to esterify an acid, we use an
excess of the alcohol and, if possible remove the water as it is formed. If we want to hydrolyse an ester, we
use a large excess of water that is we reflux the ester with dilute aqueous HCl or dilute aqueous H2SO4.


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(iii)
Formation of amides :
In fact amides can not be prepared from carboxylic acids and amines unless the ammonium salt is heated
strongly to dehydrate it. This is not usually a good method of preparing amides.
Formation of acid anhydride :
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
(iv)
4.
(i)
Decarboxylation reactions :
Soda-lime decarboxylation :
General reaction :
In this reaction carbanion intermediate is formed.

Rate of reaction depends upon the stability of carbanion intermediate.
Electron with drawing group at RCOOH will increases the rate of decarboxylation.
Ex.
Rate of decarboxylation. I > II > III > IV
(ii)
(a) Decarboxylation of -keto carboxylic acids:

Acids whose molecules have a carbonyl group one carbon removed from the carboxylic acid group, called
-keto acids, decarboxylate readily when they are heated to 100150C.
There are two reasons for ease of decarboxylation.

When the acid estelf decarboxylates, it can do so through a six membered cyclic trensition state :
This reaction produces an enol directly and avoids an anionic intermediate. The enol then tautomerises to a
methyl ketone.


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When the carboxylate anion decarboxylates, it forms a resonance stabilized enolate anion.
Alphatic acids that do undergo successful decarboxylation have certain functional groups or double or triple
bonds in the or positions.
(iii)
Kolbes electrolysis
Electrolysis
R R + 2CO2 + H2 + 2KOH
2RCOOK + 2HOH
R CO2 + K+
Mechanism :
R CO2K
At Anode :
R CO2 R CO2 + e
(oxidation)
(I)
R
CO2
R + CO2
(II)
R + R R R
If n is the number of carbon atoms in the salt of carboxylic acid, the alkane formed has 2(n1) carbon atoms.
Ex.
Electrolysis
CH3CH3 + 2CO2 + H2 + 2KOH.

2CH3 COOK + 2H2O


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(iv)
Hunsdiecker Reaction (Bromo-decarboxylation) :

RCOOAg + Br2 RBr + CO2 + AgBr
Mechanism :
Step 1 :
R.COOAg + X2
+ AgX
Step 2 :
Step 3 :
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
Step 4 :
Although bromine is the most often used halogen, chlorine and iodine have also been used.
When iodine is the reagent, the ratio between the reactant is very important and determines the product
A 1 : 1 ratio of salt to iodine gives alkyl halide, as above. A 2 : 1 ratio, however gives the ester RCOOR. This
is called simonini reaction and sometimes used to prepare carboxylic ester.
5.
HVZ Reaction (Halogenation of aliphatic acids and Substituted acids)

In the presence of a small amount of phosphorus, aliphatic carboxylic acids react smoothly with chlorine or
bromine to yield a compound in which -hydrogen has been replaced by halogen. This is the Hell-VolhardZelinsky reaction. Because of its regioselectivity-only alpha halogenation-and the readiness with which it
takes place, it is of considerable importance in synthesis.
Cl , P
Cl , P
Cl , P
2
2
ClCH2COOH 2
Cl3CCOOH
Cl2CHCOOH
CH3COOH
The halogen of these halogenated acids ungergoes nucleophilic displacement and elimination much as it
does in the simpler alkyl halides. Halogenation is therefore the first step in the conversion of a carboxylic
acid into many important substituted carboxylic acids.
+ large excess of NH3 RCHCOOH
|
NH2
An ha log enated
An a min o acid
RCHCOOH
|
Br
acid
H
RCHCOOH NaOH RCHCOONa
RCHCOOH
|
|
|
Br
OH
OH
An hydroxy acid
H
RCH CHCOOH
RCH2CHCOOH KOH (alc ) RCH = CHCOO
An , unsaturate d acid
|
Br


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Summary of reactions of carboxylic acids :
Carboxylic Acid Derivatives

Closely related to the carboxylic acids and to each other are a number of chemical families known as
functional derivatives of carboxylic acids : acid chlorides, anhydrides, amides, and esters, These
derivatives are compounds in which the OH of a carboxyl group has been replaced by CI,OOCR,
NH2, or OR`.


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Acid chloride
Anhydride
Amide
Ester
They all contain the acyl group,
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
Like the acid to which it is related, an acid derivative may be aliphatic or aromatic, substituted or unsubstituted;
whatever the structure of the rest of the molecule, the properties of the functional group remain essentilly the
same.
Characteristic reaction of acid deerivatives (Nucleophilic acyl substitution) :
Nucleophilic acyl substitution usually takes place by an addition-elimination mechanism.The incoming
nucleophile adds to the carbonyl to form a tetrasubstituted intermediate with a tetrahedral carbon.
The tetrahedral intermediate formed when a nucleophile attacks the carbonyl carbon of a carboxylic acid
derivative is not stable and cannot be isolated.
A pair of nonbonding electrons on the oxygen reforms the p bond, and either or
is eliminated with its
bonding electrons. Whether or
is eliminated depends on their relative basicities. The weaker base is
preferentially eliminated because the weaker the base, the better it is a leaving group.
Thus carboxylic acid derivative will undergo a nucleophilic acyl substitution reaction provided that the incoming
nucleophile is a stronger base than the group that is to be replaced. If the incoming nucleophile and the group
attached to acyl group in the starting material have similar basicities, the tetrahedral intermediate can
expect either group with similar ease. A mixture of starting material and substitution product will result.
(i)
(ii)


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(iii)
(iv)
(v)
Condition for acyl nucleophilic substitution reaction :
(i) L must be better leaving group than

(ii)
, i.e., basicity of Nu should be more than that of
must be a strong enough nucleophilic to attack RCOL.
(iii) Carbonyl carbon must be enough electrophilic to react with
(A) Acid halides

Methods of preparation of Acyl halides
(i)
RCOOH + PCl5 RCOCl + POCl3 + HCl
(ii)
3RCOOH + PCl3 3RCOCl + H3PO3
(iii)
RCOOH + SOCl2
RCOCl + SO2 + HCl
Ex.
Distil
3CH3COONa + PCl3
3CH3 COCl Na 3PO 3
Pyridine
Acetyl chloride
Ex.
Distil
2C 6H5 COONa POCl3
2C 6H5 COCl NaCl NaPO 3
Sod. benzoate
Benzoyl chloride
Chemical Reactions
(1) Reaction with carboxylic acids
Acyl chlorides react with carboxylic acids to yield acid anhydrides. When this reaction is used for preparative
purposes, a weak organic base such as pyridine is normally added. Pyridine is a catalyst for the reaction
and also acts as a base to neutralize the hydrogen chloride that is formed.
O
CH3(CH2)5CCl +
Heptanoyl
chloride


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(2) Reaction with alcohols
Acyl chlorides react with alcohols to form esters. The reaction is typically carried out in the presence of
pyridine.
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
(3) Reaction with ammonia and amines
(4) Hydrolysis
Acyl chlorides react with water to yield carboxylic acids. In base, the acid is converted to its carboxylate
salt. The reaction has little preparative value because the acyl chloride is nearly always prepared from the
carboxylic acid rather than vice versa.
+ H2O
water
H2O
water
(5) Reaction of acid halide with organometallic

(a) with Grignard reagent
(b) Reaction with Gilmann reagent


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(6) Reduetion of acid halides
(a) Reduction by LiAIH4
(b) Reduction with H2 /Pd / BaSO4 (Rosenmund reduction)
Summary of reactions of acid halide
(B) Acid amides

Methods of preparation of acids amides
1. By reaction of esters with ammonia and amines
Ex.
Ammonia is more nucleophilic than water, making it possible to carry out this reaction using aqueous
ammonia.
Ex.
O
||
H2C = C COCH3
|
CH3
Methyl 2-methylpropenoate
O
||
H2C = C CNH2 +
|
CH3
2-Methylpropenamide
(75%)
Amines, which are substituted derivatives of ammonia, react similarly :
Ex.


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Ex.
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
Ex.
Ex.
2.
3.
From acid halides

RCOCl + 2NH3
From anhydride
(RCO)2O + 2NH3
4.
6.
RCONH2 + RCOONH4
From esters
RCOOR + NH3
5.
RCONH2 + NH4Cl
RCONH2 + ROH
From ammonium salt of carboxylic acid
RCOONH4
CH3 COONH 4
Amm.cyanides
acetate
From
R C N + H2O
CH3C N H2O
7.
RCONH2 + H2O
CH3CONH2
Acetamide
Conc . HCl
or H2O 2 NaOH
Conc. H SO
4
2
R CONH2
CH3 CONH2
Chemical Reactions
1.
Hoffmann rearrangement
In the Hofmann rearrangement an unsubstituted amide is treated with sodium hydroxide and bromine to give
a primary amine that has one carbon fewer than starting amide
General reaction.
+ NaOH + Br2

RN=C=O
isocyanate
R NH2

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CHEMISTRY
Mech :
OH
CO2R NH
R NH2
(2) Hydrolysis of amides
In acid, however, the amine is protonated, giving an ammonium ion, R2
In base the carboxylic acid is deprotonated, giving a carboxylate ion :
The acid-base reactions that occur after the amide bond is broken make the overall hydrolysis irreversible.
In both cases the amine product is protonated in acid ; the carboxylic acid is deprotonated in base.
Ex.
H2O / H2SO 4
Ex.


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CHEMISTRY
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
Summary of reaction of amide:
Ex.
Ans.
CH3 CH2 C NH2

||
O
(C) Esters
Methods of Preparation
(i)
H
CH3COOC2H5 H2O
CH3 COOH C 2H5 OH
Acetic acid
H
C6H5 COOCH3 H2O
C6H5 COOH CH3OH
Methyl benzoate
Pyridine
(ii)
CH3COCl + C2H5OH
CH3COOC2H5 + HCl
Alcohols react with acyl chlorides by nucleophilic acyl substitution to yield esters. These reactions are
typically performed in the presence of a weak base such as pyridine.
Ex.
Ex.
NaOH
C6H5COCl + CH3CH2OH
C6H5COOCH2CH3 + HCl


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CHEMISTRY
Chemical Reactions
1.
Acid catalysed hydrolysis of ester (AAc2):

Because H2O and ROH have approximately the same basicity, it will be eqully easy for tetrahedral
imtermediate I to collapse to reform the ester as it will be for tetrahedral intermediate II to collapse to form
the carboxylic acid. Consequently, when the reaction has reached equilibrium, both ester and carboxylic
acid will be obtained.
CH3COOH + ROH
Excess water will force the equilibrium to the right.
CH3COOH + ROH
Mechanism:
2.
Base-Promoted Hydrolysis of Esters : Saponification (BAc2):

Esters not only undergo acid hydrolysis, they also undergo base-promoted hydrolysis. Base-promoted
hydrolysis is sometimes called saponification, from the Latin word sapo, soap. Refluxing an ester with
aqueous sodium hydroxide, for example, produces an alcohol and the sodium salt of the acid :
The carboxylate ion is very unreactive toward nucleophilic substitution because it is negatively charged.
Base-promoted hydrolysis of an ester, as a result, is an essentially irreversible reaction.
The mechanism for base-promoted hydrolysis of an ester also involves a nucleophilic addition-elimination at
the acyl carbon.
Mechanism :


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CHEMISTRY
Evidence for this mechanism comes from studies done with isotopically labeled esters. When ethyl propanoate
labled with 18O in the ether-type oxygen of the ester(below) is subjected to hydrolysis with aqueous NaOH
all of the 18O shows up in the ethanol that is produced. None of the 18O appears in the propanoate ion.
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
This labeling result is completely consistent with the mechanism given above . If the hydroxyide ion had
attacked the alkyl carbon instead of the acyl carbon, the alcohol obtained would not have been labled. Attack
at the alkyl carbon is almost never observed.
Although nucleophilic attack at the alkyl carbon seldom occurs with esters of carboxylic acids, it is the
preferred mode of attack with esters of sulfonic acids (e.g. tosylates and mesylates)
Summary of reaction of esters :
(D) Acid anhydrides

Methods of Preparation of acid anhydrides
1. From carboxylic acids
P2O5 ,
CH3 COOH HOOCCH3
CH3 CO . O . CO . CH3 H2O

Acetic acid
Acetic anhydride


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CHEMISTRY
PO ,
2 5
Ex.
PO ,
2 5
Ex.
PO ,
2 5
Ex.
Ex.
PO ,
2 5
five or six membered cyclic anhydride are stable

2. From acid and acid halide
Pyridine
CH3COOH + CH3COCl
CH3CO.O.COCH3 + HCl
Ex.
CH3COCl + CH3COONa CH3CO.O.COCH3 + NaCl
Chemical Reactions
(1) Reaction with aromatic compounds (Friedel crafts acylation)
+ ArH
Ex.
(2) Reaction with alcohols

Acid anhydrides react with alcohols to form esters. The reaction may be carried out in the presence of
pyridine or it may be catalysed by acids. In the example shown, only one acyl group of acetic anhydride
becomes incorporated into the ester ; the other becomes the acyl group of an acetic acid molecule.


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CHEMISTRY
+ CH3COOH
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
Ex.
(3) Reaction with ammonia and amines

Acid anhydrides react with ammonia and amines to form amides. Two molar equivalents of amine are
required. In the example shown, only one acyl group of acetic anhydride becomes incorporated into the
amide and the other becomes the acyl group of the amine salt of acetic acid.
+ CH3COOH
(4) Hydrolysis
Acid anhydrides react with water to yield two carboxylic acid functions. Cyclic anhydrides yield dicarboxylic
acids.
7.
Heating Effects :
(a) Heating effect on monocarboxylic acid
2R COOH


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CHEMISTRY
(b) Heating effect on dicarboxylic acid
CH3 COOH
(c) Heating effects on Hydroxy acids
(1) Hydroxy acid
(2) Hydroxy acid
(3) Hydroxy acid

Since 4 or 8 membered rings are less stable the refore -Hydroxy acids on heating produce unsaturated
carboxylic acid.
(4) Hydroxy acid
(d) Heating effects on esters
R` COOH to R` CH = CH2
Mech :
R` CH = CH2 + R COOH
This reaction follows syn elimination & hoffman product is formed.


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CHEMISTRY
MISCELLANEOUS SOLVED PROBLEMS (MSPS)

Select the correct statement about the following compounds I, II, III.
Ans.
(A) (I) decarboxylates faster than (II) on heating.

(B) Only *CO2 is eliminated on heating of compound (I).
(C) Compound (I) eliminates a mixture of CO2 and *CO2 on heating.
(D) The rate of decarboxylation of (II) is faster than (III).
(A)
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
1.
Sol.
No decarboxylation
CO2 rate of decarboxylation : III > I > II
2.
final product is :
(A)
Ans.
CO2
(B)
(C)
(D)
(B)
Sol.
3.
final product is
(A)
Ans.
(B)
(C)
(D)
(B)
Sol.


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CHEMISTRY
4.
Identify (A), (B), (C) and (D).

( i ) CO
[O ]
Mg / dryether
C3H5Cl (A)
(C)
C8H12(D)
(B) 2
( ii) H2 O / H
Saturated
Ans.
(A) =
; (B) =
; (C) =
; (D) =
5.
Preparation of propanoic acid from ethyl alcohol follows :
Sol.
PCl 5
KCN
H2 O / H
CH3 CH2OH
CH3 CH2 Cl
CH3 CH2 CN
CH3 CH2 COOH
6.
Identify (A), (B) and (C).
KCN
H2 O / OH
C3H6Cl2 (A)
(B)
(C) 2-Methylpropanoic acid
CO2
Sol.
Cl
CN
COOH
|
|
|
KCN
H2 O / OH
CH3 C CH3 CH3 C CH3
CH3 C CH3 2-Methylpropanoic acid

CO2
|
|
|
Cl
CN
COOH
7.
Find the rate of soda-lime decarboxylation.
Sol.
Rate of soda-lime decarboxylation. I > II > III > IV > V
8.
Identify (A), (B) and (C).
Br2 (1 eqV ) / P
KCN
H2 O / H /
CH3 CH2 COOH
(A)
(B)
(C)
Sol.
(A) CH3 CH COOH ;

|
Br
9.
Write the structures of (A) C3H7NO which on acid hydrolysis gives acid (B) and amine (C). Acid (B) gives
(+)ve silvermirror test.
Ans.
A=
10.
Predict A , B , C , D and E.
(B) CH3 CH COOH ;

|
CN
(C) CH3CH2COOH
or
Mesitylene / AlCl3
Acid (A) B
Sol.
(A) = CH3COOH;
(B) = CH3 C O C CH3 ;

||
||
O
O
(C) =
(D) =


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CHEMISTRY
11.
Which of these represents correct reaction ?

(A)
(B)
conc .NaOD
DCOO + DCH2 OD
NaOH
C(CH2OH)4 + HCOO
+
(excess)
P Br2
(C)
(D)
(A,B,C,D)
Sol.
(A)
H2O
Pr
( T ad
au ee
gh p A
tB g
a
y rw
IIT a
ia l A
ns ca
... de
..) m
y
Ans.
conc . H2SO 4
(B)
conc .NaOD
DCOO + DCH2 OD
(Cannizzaro reaction)
NaOH
C(CH2OH)4 + HCOO
(Aldol + Cannizzaro reaction)
(excess)
P Br2
(C)
(D)
12.
(HVZ reaction)
conc . H2SO 4
(Esterification reaction)
H2O
Which are correct against property metioned ?

(A) CH3COCl > (CH3CO)2O > CH3COOEt > CH3CONH2
(Rate of hydrolysis)
(B) CH3CH2COOH >
(Rate of esterification)
(C)
(D)
>
>
>
>
(Rate of esterification)
> PhCH2COOH
(Rate of decarboxylation)
Ans.
(A,B)
13.
Match the product of column II with the reaction of column I.

Column I
Column II
Ans.
(A)
(p) ester with O18
(B)
(q) A -diketone with 18OH group
(C)
(D)
OH /
(r) A cyclic anhydride with 18OH group
(s) A cyclic ester without O18
(A) r ; (B) s ; (C) p ; (D) q.


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Carboxylic Acids & Acid Derivatives Explained

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Carboxylic Acids & Acid Derivatives Explained

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CARBOXYLICACIDS &ACID DERIVATIVES

By Anand Kumar Rai

Pradeep Agarwal Academy

By: Anand Kumar Rai (IITian...)