Carboxylic Acids & Derivatives

CARBOXYLIC ACIDS & DERIVATIVES
Introduction And Nomenclature

Of the organic compounds that show appreciable acidity, by far the most important are the
carboxylic acids.
These compounds contain the carboxyl group attached to hydrogen (HCOOH) an alkyl
group (RCOOH), or an aryl group (ArCOOH). These are also named as fatty acids because
of some higher members particularly palmitic and stearic acids, occur in natural fats. The
general formula of the carboxylic acids is CnH2nO2.
Only the hydrogen atom of the carboxyl group is replaceable by a metal, therefore the fatty
acids are mono-basic.
Nomenclature
The aliphatic carboxylic acids are commonly known by their initial names, which have been
derived from the source of the particular acid.
Examples:-
i) HCOOH Formic acid [Latin: Fermica = ant]

ii) CH3COOH Acetic acid [Latin: acetum = vinegar]
iii) CH3–CH2–COOH Propionic acid
iv) CH3(CH2)2COOH Butyric acid
v) CH3(CH2)3COOH Valeric acid
vi) CH3(CH2)14COOH Palmitic acid
vii) CH3(CH2)16COOH Stearic acid
Another system of nomenclature, except Formic acid considers acids as acid derivatives of
acetic acid
Example: CH3 – CH2 – COOH Methyl acetic acid

(CH3)3C – COOH Trimethyl acetic acid
According to the IUPAC system of nomenclature, the suffix of the monocarboxylic acid is ‘oic
acid’, which is added to the name of the alkane corresponding to the longest carbon chain
containing the carboxyl group, e.g.
HCOOH methanoic acid

CH3 – CH2 – CH2 – COOH butanoic acid
The positions of side-chains (or substituents) are indicated by numbers, the carboxyl group
always being given number I.
CH3 – CH – CH – CH2 – COOH 3, 4-dimethylpentanoic acid

| |
CH3 CH3
Rankers-JEE by Saurabh Maurya

Illustration 1: Give the IUPAC names of the following compounds
i) (COOH)2 ii) HOOC – (CH2)2 – COOH
iii) CH3 – CH – COOH iv) CH(OH) – COOH
| |
OH CH(OH) – COOH
Solution: IUPAC Name General name

i) Ethanedioic acid Oxalic acid
ii) Butanedioic acid Succinic acid
iii) 2-Hydroxy propanoic acid Lactic acid
iv) 2,3 Dihydroxybutanedioic acid Tartaric acid
Aromatic acids Ar– COOH are usually named as derivatives of the parent
acid i.e. benzoic acid, C6H5COOH.
COOH COOH
 
NO2

Br NO2
p – Bromobenzoic acid 2-4, dinitrobenzoic acid
Naming of Acyl Groups; Acid Chlorides and Acid Anhydrides
The group obtained from a carboxylic acid by the removal of the hydroxyl portion is known
as an acyl group. The name of an acyl group is created by changing the 'ic' at the end of the
name of the carboxylic acid to 'yl', examples:
O O
|| ||
H –C – O – H H –C –
Formic acid Formyl group
O O
|| ||
 C – OH C–
Benzoic acid Benzoyl group
Acid chlorides are named systematically as acyl chlorides.

O
||
CH3  C  Cl
Acetylchloride
An acid anhydride is named by substituting anhydride for acid in the name of the acid from
which it is derived.

O O
O O
O O
Succinic anhydride Phthalic anhydride
Naming Salts and Esters
The name of the cation (in the case of a salt) or the name of the organic group attached to
the oxygen or the carboxyl group (in the case of an ester) preceeds the name of the acid.
The 'ic acid’ part of the name of the acid is converted to 'ate'
O O
|| ||
 C – O– Na+ H2N   COCH2 – CH3
Sodium benzoate
Ethyl-p-aminobenzoate
Name of Amides and Imides:
The names of amides are formed by replacing –oic acid (or –ic acid for common names) by
amide or –carboxylic acid by carboxamide.
CH3 – C – NH2 Ethanamide or acetamide

O
CNH2 Cyclohexanecarboxamide
If the nitrogen atom of the amide has any alkyl group as substituent, the name of the amide
is prefixed by the capital letter N; to indicate substitution on nitrogen, followed by the
name(s) of alkyl group(s).
O CH3
|| |
O2N C – N – CH2 – CH3
N-ethyl-N-methyl-p-nitrobenzamide
If the substituent on the nitrogen atom of an amide is a phenyl group, the ending for the
name of the carboxylic acid is changed to anilide
O O
|| ||
CH3 – C – NH C – NH
Acetanilide Benzanilide

some dicarboxylic acids form cylic amides in which two acyl groups are bonded to the
nitrogen atom. The suffix imide is given to such compounds.
O O
NH NH
O O
succinimide Phthalimide
Exercise -1: Write following isomers of the formula C4H4O4

(a) a dibasic acid that when heated gives acrylic acid
(b) a dibasic acid that forms racemic mixture on reaction with alkaline KMnO 4
(c) a dibsic acid that forms meso compound on reaction with alk. KMnO 4
(d) a cyclic ester
Physical Properties
The molecules of carboxylic acids are polar and exhibit hydrogen bonding. The first four are
miscible with water. The higher acids are virtually insoluble. The simplest aromatic acid,
benzoic acid, contains too many carbon atoms to show appreciable solubility in water.
Carboxylic acids are soluble in less polar solvents like ether, alcohol, benzene etc.
Carboxylic acids have higher boiling points than alcohols. O  H  O

These very high boiling points are due to the fact that a
pair of carboxylic acid molecules are held together not by RC CR
one but by two hydrogen bonds and exist as dimer.
O  H  O
A study of nitrated spectra of formic acid in the liquid and solid states has provided evidence
that this acid, unlike most of the other carboxylic acids, is not dimeric in these states, but is
associated as a polymer.
The first three fatty acids are colourless pungent smelling liquids.
Acidity of Carboxylic Acids

The acidity of a carboxylic acid is due to the resonance stabilization of its anion.
– –
  
O O O O
+
–H
R–C R–C H
+ R–C R–C
 
O H O+ H O O
  
–
I II III IV
Non-Equivalent Equivalent
(Less important resonance) (more important resonance)

Because of the resonance, both the carbon oxygen bond in the carboxylate anion have
identical bond length. In the carboxylic acid, these bond lengths are no longer identical.
The acidity of carboxylic acid depends very much on the substituent attached to – COOH
group. Since acidity is due to the resonance stabilization of anion, substituent causing
stabilization of anion increases acidity whereas substituent causing destabilization of anion
decrease acidity. For example, electron withdrawing group disperses the negative charge of
the anion and hence makes it more stable causing increase in the acidity of the
corresponding acid, on the other hand, electron-releasing group increases the negative
charge on the anion and hence makes it less stable causing the decrease in the acidity. In
the light of this, the following are the orders of a few substituted carboxylic acids.
a) Increase in the number of Halogen atoms on -position increases the acidity, eg.
Cl3CCOOH > Cl2CHCOOH > ClCH2COOH > CH3COOH
b) Increase in the distance of Halogen from COOH decreases the acidity e.g.
CH3 – CH2 – CH – COOH > CH3 – CH – CH2 – COOH > CH2 – CH2 – CH2 – COOH
| | |
Cl Cl Cl
This is due to the fact that inductive effect decreases with increasing distance.
c) Increase in the electro negativity of halogen increases the acidity.
FCH2COOH > BrCH2COOH > ICH2COOH
Exercise-2: Explain the following

i) Carbon-oxygen bond length in formic acid are 1.24 Å and 1.36 Å but in
sodium formate both the carbon-oxygen bonds have same value i.e.1.27 Å.
ii) Acetic acid in the vapour state shows a relative molecular weight of 120.
Illustration 2: On the basis of H-bonding explain that the second ionization constant K 2 for
fumaric acid is greater than for maleic acid.
Solution: We know that H-bonding involving acidic H has an acid weakening effect and
H-bonding in conjugate base has an acid strengthening effect.
Both dicarboxylic acids have two ionisable hydrogen atoms. Considering
second ionization step.
O O
C H C
H
O O
C C
H
C OH C O
H C H C
O O
Fumarate monoanion Maleate monoanion
(no H-bonding) (H-bonding)

Since the second ionisable H of the Maleate ion participates in H-bonding
more energy is needed to remove this H because the H-bond must be
broken. The maleate mono anion is, therefore, the weaker acid.
General Methods Of Preparation
By Oxidation of Alcohols, Aldehydes & Ketones

K2Cr2O7 + H2SO4 K Cr O + H SO
R – CH2OH  RCHO 
2 2 7 2 4
RCOOH
[O] [O]
R
K2Cr2O7 + H2SO4
C = O 
[O]
RCOOH
R
Aldehydes can be oxidized to carboxylic acids with mild oxidizing agents such as Ag(NH3)2+
OH–
1. Ag2O or Ag(NH3)2+
R – CHO 
+
RCO2H
2. H3O
By Oxidation of Alkenes
Alkenes can be oxidized to carboxylic acids with hot alkaline KMnO4.

1. KMnO4, OH–
RCH = CHR  RCO2H + R CO 2H
2. Heat, H2O
By the Hydrolysis of Nitriles (Cyanides)

Acid hydrolysis
R – C  N 
+
R.COOH + NH3
H , HOH
Nitriles can be prepared by nucleophilic substitution reactions of alkyl halides with sodium
cyanide. Hydrolysis of nitriles yields a carboxylic acid with a chain one carbon atom more
than the original alkyl halide.
Example:
NaCN
Br – CH2 – CH2 – CH2 – Br  NC – CH2 – CH2 – CH2– CN
H3O
+ Pentanedinitrile
 HO2C – CH2 – CH2 – CH2 – CO2H
Glutaric acid
This synthetic method is generally limited to the use of primary alkyl halides. Aryl halides
(except for those with ortho and para nitro groups) do not react with sodium cyanide.
By Carbonation of Grignard Reagents
Grignard reagents react with carbon dioxide to yield magnesium carboxylate which on
acidification produces carboxylic acids.

Diethyl ether CO2 H3O+
R – X + Mg  RMgX  RCO2MgX  RCO2H
Diethyl ether CO2 H O+
or Ar – Br + Mg  ArMgBr  ArCO2MgBr 
3
ArCO2H
By the Hydrolysis of Trihalogen Derivatives
Trihalogen derivatives in which the three halogen atoms are all attached to the same carbon
atom yields carboxylic acid on hydrolysis
KOH
RCX3  R – C(OH)3  RCO2H + H2O
By Oxidation of Methyl Ketone
Methyl ketone can be converted to carboxylic acids via the haloform reaction.
O O
|| ||
1. X2/NaOH
Ar – C – CH3 
+ Ar – C – OH + CHX3
2. H3O
By Alkenes (Koch Reaction)
A recent method for manufacturing fatty acids is to heat an olefin with carbon monoxide and
steam under pressure at 300-400° C in the presence of a catalyst, e.g. phosphoric acid.
CH2 = CH2 + CO + H2O  CH3 – CH2 – COOH
By Heating Gem Dicarboxylic Acids
COOH H
CH2  CH2 Acetic acid
– CO2
COOH COOH
The most convenient laboratory preparation for formic acid is to heat glycerol with oxalic
acid at 100 – 110° C.
CH2 – OH CH2O.CO.COOH
| COOH |
100-110°
CH – OH + | CHOH + H2O 
| COOH |
CH2 – OH Oxalic acid CH2OH
Glycerol Glyceryl monoxalate
CH2 – O – COH CH2O.CO.COOH
| (COOH)2 |
CO2 + CH – OH CH – OH + HCO2H
I I
CH2– OH CH2OH
Glyceryl monoformate

Exercise 3: i) Why we can not get anhydrous formic acid by fractional distillation of the
Fatty acids.
(i) HBr
ii) CH2=CH—CH=CH2   A. Identify A?
(ii) Mg/ether
(iii) CO 2 / H3 O 
General Reactions of the Fatty Acids
The characteristic chemical behavior of carboxylic acids is, of course, determined by their
functional group, carboxyl, –COOH. This group is made up of a carbonyl group
(C = O) and a hydroxyl group (–OH). As we shall see, it is the –OH that actually undergoes
nearly every reaction –loss of H+, or replacement by another group but it does so in a way
that is possible only because of the effect of the C = O.
Acidity (Salt formation)
Carboxylic acids are weak acids and their carboxylic anions are strong conjugate bases are
slightly alkaline due to the hydrolysis of carboxylate anion compared to other species, the
order of acidity and basicity or corresponding conjugate bases are as follows:
Acidity RCOOH > HOH > ROH > HC  CH > NH3 > RH
Basicity RCOO– < HO– < RO– < HC  C– < NH 2 < R–
The carboxylic acids react with metals to liberate hydrogen and are soluble in both NaOH
and NaHCO3 solutions. For example.
2CH3COOH + 2Na  2CH3COO–Na+ + H2
CH3COOH + NaOH  CH3COO–Na+ + H2O
CH3COOH + NaHCO3  CH3COO–Na+ + H2O + CO2
Conversion into Functional Derivatives
The –OH of an acid can be replaced by a Cl, OR or NH2 group to yield an acid chloride, an
ester or an amide. These compounds are called functional derivatives of acid they all
contain acyl group.
The functional derivatives are all readily reconverted into the acid by simple hydrolysis.
O O
R–C R–C (Z = –Cl, –OR, –NH2)
OH Z
Illustration3: Discuss the reaction for that a characteristic reaction of aldehydes and
Ketones is one of nucleophilic addition while Acyl compounds yield
Nucleophilic substitution product.

Solution: Nu Nu
R
H – Nu
R=O R–O R–O–H
R R R
Nu– – H R R
Aldehyde or Ketone
Nucleophilic addition
R Nu+ Nu Nu
R=O C–O C–O R = O + HL

L R R R
Nu – H L HL+
An acyl compound Another acyl compound
Nucleophilic addition Elimination

(L = –OH, –Cl, –NH2, OR etc.)
Nucleophilic substitution
The initial step in both reactions involves nucleophilic addition at the carbonyl carbon atom.
With both groups of compound, this initial attack is facilitated by the same factors: the
relative steric opens of the carbonyl oxygen atom to accommodate an electron pair of the
carbon-oxygen double bond. It is after the initial nucleophilic attack has taken place that the
two reactions differ. The tetrahedral intermediate formed from an aldehyde or Ketone
usually accepts a proton to form a stable addition product. By contrast, the intermediate
formed from an acyl compound usually eliminates a leaving group: this elimination leads to
regeneration of the carbon oxygen double bond and to a substitution product. The overall
process in the case of acyl substitution occurs, therefore, by a nucleophilic addition–
elimination mechanism. Acyl compounds react as they do so because they all have good
leaving groups attached to the carbonyl carbon atom:
O O O O O
||
R–C > R–C > R–C >RCOOH >R – C >R – C – O–
Cl O OR NH2
R–C
O
The general order of reactivity of acid derivatives can be explained by taking into account
the basicity of the leaving groups.
Conversion into Acid Chlorides:
An acid chloride is prepared by substitution of –Cl for the –OH in a carboxylic acid. Three
reagents are commonly used for this purpose. Thionylchloride, (SOCl2), phosphorus
trichloride, (PCl3) and phosphorus pentachloride, (PCl5).

O O
reflux
C + SOCl2  C + SO2 + HCl
OH Cl
Benzoic acid Benzoyl chloride
O O
heat
R –C + PCl5  R –C + HCl
OH Cl
Thionyl chloride is particularly convenient, since the product formed besides the acid
chloride are gases and thus easily separated from the acid chloride; any excess of the
thionyl chloride [B.P. = 79°C] is easily removed by distillation.
Conversion into Esters (Esterification)
Carboxylic acid on heating with alcohols in presence of dehydrating agent (H2SO4 or dry HCl
gas) gives esters. The reaction is known as esterification.
O O
H+
R–C + ROH R –C + H2O
OH OR
Acid
This reaction is reversible and the same catalyst, hydrogen ion, that catalyzes the forward
reaction i.e. esterification necessarily catalyzes the reverse reaction i.e. hydrolysis.
The equilibrium is particularly unfavorable when phenols (ArOH) are used instead of alcohol;
yet if water is removed during the reaction, phenolic esters (RCOOAr] are obtained in high
yield.
The presence of bulky group near the site of reaction, whether in alcohol or in the acid,
slows down esterification (as well as its reverse, hydrolysis).
Reactivity CH3OH > 1° > 2° > 3°
In esterification HCOOH > CH3COOH > RCH2COOH > R2CHCOOH > R3CCOOH
Conversion into Amides

O O
|| ||

R – C – OH + NH3  R – C – NH2 + H2O
Conversion into Anhydrides
Lower monocarboxylic acid on heating with dehydrating agent (say P2O5) forms anhydrides
P2O5
2CH3COOH  
(CH3CO)2O + H2O
Note: Anhydride of formic acid is not known, it gives CO and H2O on heating with conc.
H2SO4.

HCOOH    H2O  CO
conc. .H 2 SO 4
Reduction of Acids to Alcohols:
Lithium aluminium hydride can reduce an acid to an alcohol; the initial product is an alkoxide
from which the alcohol is liberated by hydrolysis.
4 R–COOH + 3LiAlH4  4H2 + 2LiAlO2 + (RCH2O)4 AlLi + H2

Hydrolysis of (RCH2O)4  alcohols
Halogenation of Aliphatic Acids (Hell-Volhard-Zelinsky Reaction)
In the presence of phosphorus, aliphatic carboxylic acids react smoothly with chlorine or
bromine to yield a compound in which -hydrogen has been replaced by halogen.
CH 3  COOH   Cl  CH 2  COOH 

Cl2 /,P
 Cl 2 CH  COOH 
Cl2 ,/ P
  Cl 3 CCOOH
Cl2 ,/ P
The function of the phosphorus is ultimately to convert a little of the acid into acid halide so it
is the acid halide, not the acid itself, that undergoes this reaction.
P + X2  PX3
R – CH2 – COOH + PX3  RCH2 – COX
R – CH2 – COX + X2  R – CH – COX + HX   R – CH –CO2H
H2O
X X
The halogen of these halogenated acid undergoes nucleophilic displacement and

elimination much as it does in the simple alkyl halides. Halogenation is therefore the first
step in the conversion of a carboxylic acid into many important substituted carboxylic acid.
R – CH – COOH + NH3  R – CH – COOH
| |
Br NH2
An -halogenated acid An -amino acid

R – CH – COOH + NaOH 
 R – CH – COOH
H
| |
Cl OH
An -hydroxy acid
Illustration 4: How formic acid differs from the rest of the members of the fatty acid series.
Solution: Formic acid is a powerful reducing agent. While other members of the series
are very poor reducing agent, we can explain this by the structure of formic
acid.
O
||
H  C  OH
Formyl group Hydroxy group
A formyl group is present in the structure of formic acid, it indicates the

relationship of formic acid to aldehydes, thus accounting for its reducing
properties. Formic acid reduces ammonical silver nitrate (Tollen’s reagent),
mercuric chloride and acidified KMnO4.

Exercise 4: Identify A  D.
PCl5 NH3 P O5 H2 / Ni
 A  
C6H5CO2H    B 2 
 C   D.
Esters
Esters are usually prepared by the reaction of alcohols or phenols with acids or acid
derivatives.
CH3 CH3
| H
+ |
COOH + HOCH2 – CH – CH3 COO – CH2 – CH – CH3
The Mechanism of the Esterification Reaction
The step in the mechanism for the formation of an ester from an acid and an alcohol are the
reverse of the steps for the acid-catalyzed hydrolysis of an ester, the reaction can go in
either direction depending on the conditions used. A carboxylic acid does not react with an
alcohol unless a strong acid is used as a catalyst, protonation makes the carbonyl group
more electrophilic and enables it to react with the alcohol, which is a weak nucleophile.
H – Cl
+
O O–H
|| || + Cl
C C
CH3 O–H CH3 O–H
Protonation of the
carbonyl group
+
O–H O–H O–H
|| | |
C CH3 – C – O – H CH3 – C – O – H
CH3 O–H
O +O O
+
CH3 H CH3 H CH3 H–B
Nucleophilic attack at the
carbonyl group B Tetrahedral intermediate being
Deprotonation of the protonated at another side
intermediate
O–H
+ |
O H – B– O–H B CH3 – C – O +
–H
|| ||
C C
CH3 O – CH3 CH3 O – CH3 O H
CH3
O
H H
Deprotonation of the carbonyl group

Transesterification:
An alcohol is capable of displacing another alcohol from an ester. This alcoholysis (cleavage
by an alcohol) of an ester is called transesterification.
Transesterification is catalysed by acid (H2SO4 or dry HCl) or base (usually alkoxide ion).
Transesterification is an equilibrium reaction. To shift the equilibrium to the right, it is
necessary to use a large excess of the alcohol.
O
||
CH2 = CH – C – OCH3 + CH3CH2 – CH2– CH2 – OH
H+ or OH–
Methyl acrylate N butylalcohol
(bp 81°C) (bp 117°C)
O
||
CH3OH + CH2 = CH – C – O – CH2 – CH2 – CH2 – CH3
Methanol n-butyl acrylate
(bp 65°C) (bp 145°C)
The difference in the boiling points of the alcohols allows the equilibrium to be shifted toward
the higher molecular weight ester by distilling the methanol out of the reaction mixture.
Exercise 5: Assign a structure to each compound indicated by a letter in the following

equations.
O O
a) || ||
CH3OH (excess)
HO – C – (CH2)9 – C – OH  A
H2SO4
O
||
CH3OH SOCl2
b) CH – C – OH  A  B
| HCl(g),  
OH
O
CH3– CH2 – OH
c) O TsOH 
A
Hydrolysis of esters
Esters are hydrolysed by acids or alkalis
O O
+
H
R–C + H2O H+ R–C + ROH
OR OH
Acidic hydrolysis is reversible and hence the mechanism for hydrolysis is also taken in the
opposite direction of the mechanism for esterification.

When hydrolysis is carried out with alkali the carboxylic acid is obtained as its salt. This
reaction is essentially irreversible, since a resonance stabilized carboxylate anion show little
tendency to react with an alcohol.
–
O O O
–
R–C + OH  R – C – OR  R – C +ROH
OR OH O
Ester Hydroxide Salt Alcohol
Since the alkali salts of the higher acids are soaps, alkaline hydrolysis is known as
saponification; Saponification is far more rapid than acid hydrolysis. If an ester is
hydrolyzed in a known amount of base (taken in excess), the amount of base used up can
be measured and used to give the saponification equivalent; the equivalent weight of the
ester, which is similar to the neutralization equivalent of an acid.
Reduction of Esters
i) Catalytic hydrogenation
CH 3  (CH 2 )10  COOCH 3      CH 3 (CH 2 )10 CH 2 OH  CH 3 OH

H2 , CuO, CuCr2O 4
150° High pressure
Methyl laurate Lauryl alcohol
ii) Chemical reduction is carried out by use of sodium metal and alcohol, or more
usually by use of lithium aluminium hydride.

CH3  (CH 2 )14  COOC 2H5   
LiAlH4
 CH3  (CH 2 )14  CH 2  OH
H
Ethyl palmitate 1–Hexadodecanol
Exercise -6: (i) Lactic acid forms a cyclic double ester Explain its formation?
(ii) How will you convert acetic acid into lactic acid.
Acid Chlorides
Acid chlorides are prepared from the corresponding acids by reaction with thionyl chloride or
phosphorus pentachloride, as discussed earlier.
Acid chlorides are the most reactive of the derivatives of carboxylic acids.
Illustration-5: Acetyl chloride reacts with water more readily than methyl chloride. Explain.
Solution: Alkyl halides are much less reactive than acyl halides in nucleophilic
substitution because nucleophilic attack on the tetrahedral carbon of RX
involves a hindered transition state. Also, to permit the attachment of the
nucleophile a bond must be partly broken. In CH3COCl, the nucleophile,
attack on > C = O involves a relatively unhindered transition of acyl halides
occurs in two steps. The first step is similar to addition to carbonyl compound
and the second involves the loss of chlorine in this case.

O O- O–
C +H2O C C
CH3 Cl CH3 Cl CH3 Cl

+OH2 +OH2
Transition state Intermediate

–
O O
–
 –H
+
C Cl C +Cl–
CH3 + CH3
OH2 OH
Transition state Product
Acylation
Acid Chlorides are important acylating agents for compounds having –OH, –SH, –NH2 and –
NHR group. During acylation, hydrogen atom of these group is replaced by RCO–group.
Acetylation is an example of acylation and is carried out by acetyl chloride.
CH3COCl + HOH  CH3COOH + HCl
CH3COCl + HOC2H5  CH3COOC2H5 + HCl

Acetyl chloride Ethyl acetate
CH3COCl + H2NC6H5  C6H5NHCOCH3 + HCl

Aniline Acetanilide
OH OCOCH3
+ CH3COCl + HCl
COOH COOH
Salicylic acid Acetyl Salicylic acid
(Aspirin)
Reaction of Acetyl Chloride with Olefins
Acetyl chlorides add on to the double bond of an olefin in the presence of a catalyst e.g.,
zinc chloride or aluminium chloride, to form a chloro ketone which, on heating, eliminates a
molecule of hydrogen chloride to form an unsaturated ketone.
CH3 CH3
CH3 – C = CH2 + CH3COCl   CH3 – C – CH2COCH3 

ZnCl 2

heat
CH3
Cl
CH3 – C = CH – COCH3 + HCl

Conversion of Acid Chlorides into Acid Derivatives
Amides and esters are usually prepared from the acid itself. Both the preparation of the acid
chloride and its reaction with ammonia or an alcohol are rapid, essentially irreversible
reactions.
O O
Aqueous NaOH
C + HO C
Cl O
Benzoyl chloride Phenol Phenyl benzoate
O O
RCOCl + R’COONa  R – C – O – C – R  + NaCl

Acid anhydride
Note: Formyl chloride is present in the form of carbon monoxide and hydrogen chloride at
ordinary temperature.
Amides
In the laboratory amides are prepared by the reaction of ammonia with acid chlorides or acid
anhydrides. In industry they are often made by heating the ammonium salts of carboxylic
acids.
Hydrolysis of Amides
It involves nucleophilic substitution, in which the NH2 group is replaced by –OH. Under
acidic conditions hydrolysis involves attack by water on the protonated amide.
O OH OH O–H
H+ H2O +
R–C R–C  R – C – OH2 R–C–O–H
NH2 NH2 NH2 +NH3
+
O–H

RCOOH +NH 4  NH3 + R – C
OH
Under alkaline conditions hydrolysis involves attack by the strongly nucleophilic hydroxide
ion on the amide itself.
–
O O
–
OH
R–C R – C – OH –
RCOO + NH3
NH2 NH2

Basic Character of Amides
Amides are very feebly basic and form unstable salts with strong inorganic acids. e.g.
RCONH2.HCl. The structure of these salts may be I or II
+ +
O–H O
– –
R–C Cl or R–C Cl
NH2 NH3
I II
Acidic Character of Amides:
Amides are also feebly acidic; e.g. they dissolve mercuric oxide to form covalent mercury
compound in which the mercury is probably linked to the nitrogen.
2RCONH2 + HgO  (RCONH)2Hg + H2O
Reduction of Amides
Amides are reduced by sodium ethanol, catalytically, or by lithium aluminium hydride to a

primary amine.
RCONH 2  4H 25 R  CH2  NH 2  H2O

Na / C H OH
Reaction with Phosphorus Pentoxide
When heated with P2O5, amides are dehydrated to alkyl cyanides.

PO
R – CONH2 
2 5
R–CN
–H2O
Alkyl cyanides are also formed when the amides of the higher fatty acids are heated in the
presence of ammonia.
H2 O H2 O
R – CO2H + NH3  RCO2NH4   RCONH2   RCN
Amides may also be converted into cyanides by phosphorus pentachloride.

HCl
RCONH2  RCCl2NH2 
PCl5
 R – CCl = NH 
HCl
 RCN
Reaction with Nitrous Acid
When amides are treated with nitrous acid, nitrogen is evolved and the acid is formed.
RCONH2 + HNO2  RCO2H + N2 + H2O

Exercise -7: Identify A, B,C and D?
ND 3 /  KOH
(i) R—COOH    A   B.
Br2 / 
NH3 /  KOD
(ii) R—COOH   
 C   D
Br2 / 

Answers to Exercises
Exercise-1: (i) COOH



(a) CH2=C CH2=CH—COOH + CO2
COOH acrylic acid
(b) COOH
COOH
H—C
alk
. KMnO H—C—OH
C—H   4

Syn. addition
HO—C—H
COOH
Fumaric acid COOH
(racemic mix)
(c) COOH COOH
H—C H—C—OH
alk
 . KMnO
 
4

H—C syn.addition H—C—OH
COOH COOH
Maleic acid (Meso)
(d) O
CH2 C=O
glycol oxalate
H2C C=O
O
Exercise-2: i) In formate ion resonance gives rise to identical bond lengths

O
H—C—O–  H—C = O H—C
O
–
O O
Whereas no such resonance is noticed in formic acid
(H — COOH) and thus C—O bonds are different in HCOOH
ii) Acetic acid undergoes intermolecular H–bonding to form dimeric state

(CH3COOH)2 and thus results in double molecular weight.
Exercise-3: i) Boiling points of formic acid (100.3°C) and water (100°C) are almost
equal.
HBr Mg / ether
ii) CH2=CH—CH=CH2  CH3—CH=CH—CH2Br    
CO 2
CH3—CH=CH—CH2—Mg—Br  
 CH3—CH=CH—CH2—COOH

H3O

Exercise-4: A = C6H5COCl; B = C6H5CONH2; C = C6H5CN; D = C6H5CH2NH2
Exercise-5: O O
(a) A = CH3—O—C—(CH2)9—C—OCH3
O
(b) A = —CH—C—OCH3
OH
O
B= —CH—C—OCH3
Cl
O
C—OCH2—CH3
(c) A =
C—OH
Exercise6: i) Lactic acid is 2-hydroxy propanoic acid. Water is lost through a double
esterification involving opposite ends of two lactic acid molecules.
O
O
C
C
H3C—HC O
CH3—CH OH 

OH 2H2O
OH
HO O CH—CH3
CH—CH3
C
C
O
O
(ii)
PCl5 H2 / Pd HCN
CH3 COOH  
 CH3COCl   CH3CHO  
 CH3CH(OH)CN
(acetic acid) BaSO 4
H3O+
CH3CH(OH)COOH
(Lactic acid)
ND 3 , KOH
Exercise-7: (i) R—COOH    RCOND 2  
 RNH 2
(A) Br2 (B)
NH3 , KOD
(ii) R—COOH    RCONH 2   R  ND 2

( C) Br2 (D)

Solved Problems
Subjective
Problem 1: Acid and acid derivatives although contain > C = O group, do not undergo the
usual properties of carbonyl group explain.
Solution: It is because of the possibility of resonance which compensates the electron

deficiency of carbonyl carbon to some extent for example.
O O
|| |
+
R – C – NH2 R – C = NH2
or
O O
|| |
+
R – C – OH R – C = OH
Problem 2: The neutralization equivalent of an acid is 116. Fusion of sodium salt of the
acid with sodalime gives a hydrocarbon of which butane monobromo
substitution product is possible. What structural formula may be assigned to
the acid.
Solution: The final product is an alkane derivative, this indicates the acid is mono
carboxylic, RCOOH.
As neutralisation equivalent is 116, therefore, formula weight of alkyl group R
is 116 – 45 (Formula weight of –COOH) = 71.
This corresponds to the pentyl group (C5H11). The formation of butane
derivative suggests a branched alkyl radical containing four carbon atoms in
the largest chain. Therefore, R-should be
CH3 – CH2 – CH – CH2


CH3
and the acid would be
CH3 – CH2 – CH – CH2 – COOH


CH3 (3- methyl pentanoic acid)
Problem 3: Compound A acidic in reaction, having the molecular formula C4H8O3, is

oxidized with mild oxidizing agents to give B which is unstable, syrupy
substance. It easily produces, C, C3H6O and carbon dioxide alone yield D,
C4H6O2 having an acid neutralization equivalent of 104. What are A, B,C and D
give their structural formulas too.
Solution: Compound A has molecular formula C4H8O3 as it is acidic in reaction, hence

it should have –COOH group. The remaining group C3H7O contains oxygen.

The product D, having formula C3H5COOH, an unsaturated acid is obtained
by heating compound A.
-hydroxy substituted acids yield substituted acids on heating. Hence, A

should be -hydroxy substituted acid, i.e.,
OH
|
CH3 – CH – CH2 – COOH (A)
A, on oxidation with mild oxidizing reagents will give
OH O
| ||
CH3 – CH – CH2 – COOH    CH3 – C – CH2 – COOH
Oxidation
B is keto substituted acid, hence, on further decomposition it will eliminate

CO2 to give
O
||
 CO2
CH3 – C – CH2 – COOH   CH3COCH3
(C) Acetone
Problem 4: An organic acid A, C3H4O3 is catalytically reduced in presence of ammonia to

give B, C3H7NO2. B reacts with acetyl chloride, hydrochloric acid and alcohols.
It can also react with nitrous acid to give another compound C, C 3H6O3, along
with the evolution of nitrogen. What are A, B and C. Give reasons.
Solution: Compound A is acid having one –COOH group only, the remaining part
C2H3O can be
O
||
CH3 – C – only. Hence, structural formula of A is
O
||
CH3 – C – COOH
on catalytic reduction keto group is converted into secondary alcohol which

with ammonia will give amino acid, i.e.,
O OH NH2
|| | |
CH3 – C – COOH   CH3 – CH – COOH –H

 
reduction HNH 2
2O
CH3 – CH – COOH
with nitrous acid, B, react to give

NH2 OH
| |
CH3 – CH – COOH + HNO2 CH3 – CH – COOH + N2 + H2O
(B) (C)

Problem 5: Compound A, C5H8O3, when heated with soda lime gives B which reacts with
HCN to give C, C reacts with PCl5 to give D which reacts with KCN to form E. E,
on alkaline hydrolysis gives a salt which is isolated and heated with soda lime
to produce n-butane. A, on careful oxidation with K2Cr2O7 gives acetic acid and
malonic acid. Give structural formulae of A to E.
Soda  lim e
Solution: (C5H8O3)    Compound B  Compound (C)
HCN
PCl5
Compound E   Compound D,
KCN
Careful oxidation with
K2Cr2O7
COOH Alk. hydrolysis
CH3COOH + CH2 soda lim e
Salt     n-butane
COOH 
On Oxidation only two –COOH groups can be introduced, i.e., one to each
carbon undergoing C–C fission, but in the resulting products we have three –
COOH groups. Hence, one –COOH group is already there in compound A,
the remaining portion C4H7O–, resembles with Keto substituted alkyl group
C3H7 – C –
||
O
This indicates that the given organic compound A is Keto substituted acid. To
assign position to Keto group in carbon chain, we know that keto acids on
O
||
careful oxidation undergo C–C bond fission at a place where - C - is situated,
further Keto group is also converted into –COOH and remains with acid
having small number of carbon atoms. From the above discussion it is clear
that acetic acid is formed from.
O O
|| ||
CH3  C  arrangemen t C3H7CO – has CH3  C  CH2  CH2  structure and
O
||
compound A is CH3  C  CH2  CH2  COOH
A, with soda-lime undergoes decarboxylation to give
CH3 – CO – CH2– CH3 (B)
B, being Ketone will give addition product with HCN to form
OH
|
CH3 – C – CH2 – CH3 (C)
|
CN PCl5
Cl
|
CH3 – C – CH2 – CH3 (D)
|
CN KCN
CN
|
CH3 – C – CH2 – CH3
|
Alkaline hydrolysis
CN
COONa
| Soda  lim e
  
CH3 – C – CH2 – CH3 CH3 – CH2 – CH2 – CH3
|  (n-butane)
COONa

Problem 6: An organic compound (A), C8H14O forms an oxime and gives positive haloform
reaction. On ozonolysis it gives acetone and a compound (B), C5H8O2 (B) forms
a dioxime and on subjecting to haloform reaction gives an acid (C), C 4H6O4. On
treatment with excess of ammonia and strong heating (C) gives a neutral
compound (D), C4H5O2N (D) on distillation with Zn dust forms pyrrole. Suggest
structures for (A), (B), (C) and (D). Give the IUPAC names of compounds (A) to
(D).
Solution: A is (CH3)2 C = CH – CH2 – CH2 – COCH3

6 – methyl – 5 – hepten – 2 – one
B is CH3 – CO – CH2 – CH2 – CHO
4 – oxopentanal
C is HO2 CCH2 CH2 CO2 H
1, 4 – butandioic acid
D is succinimide
CH2 – CH2
O=C C=O
N
|
H
Problem 7: a) Can the aromatic ring in benzoic acid stabilize the benzoate anion by -
electron delocalization? Illustrate
–
b) Discuss the electronic effect of the p–NO2 group in p–NO2C6H4COO
Solution: a) The only contributing structure I that delocalizes electron density from
PhCOO– has a positive charge on an O atom with only six electrons.
 +
O



C
 –
O
 

I
The contribution from this extremely high energy resonance structure

is nil.
b) There is no direct resonance interaction between –COO– and –NO2. The

resonance interaction of the NO2 with the ring induces some positive
charge on the ring C bearing the COO– II, from which a strong electron
with drawing inductive effect is generated. This effect is base stabilizing
and thus acid strengthening.
O– O
+
N + C
O– O
II
Problem 8: An aromatic compound A gave a mixture of two isomeric compounds B and C

on reaction with NH2OH. C rearranged to D(C8H9NO) on heating with H2SO4. D
on hydrolysis produced E and F. A was oxidized with perbenzoic acid to G.

Hydrolysis of G gave H and E. Anhydride of E and its sodium salt on
condensation with PhCHO produced cinnamic acid. H on reaction with pthalic
anhydride in H2SO4 gave phenolphthalein. Suggest structures for the
compounds A to H.
Solution: The hydrolysis products (E) and (F) suggests the structure for (D). The
phenyl group in (C) which is anti — OH migrates to give N  phenyl
substituted acetamide.
C6H5 C6H5 OH C6H5

C=O + NH2OH C=N + C=N
CH3 CH3 CH3 OH
A B C
heat H2SO4
perbenzoic
acid
CH3COOH + C6H5CHO H+ CH3CONHC6H5
E F D
CH3—C—OC6H5 H+ CH3COOH + C6H5OH

O
G E H
(CH3CO)2O + C6H5CHO CH3COONa C6H5CH = CHCOOH

Cinnamic acid
Formation of cinnamic acid proves that the anhydride is acetic anhydride.

Hence E is acetic acid.
O OH O
C H2SO4 C
O + O
C C
O H
OH
phthalic
anhydride
OH
Phenolphthalein
Problem 9: A compound X, C18H20O on ozonolysis gives C10H12O, A and C8H8O2, B. A gives

the iodoform reaction and with NH2OH gives the oxime C10H13ON, C. The oxime
undergoes rearrangement to give an amide when treated with PCl 5 in dry ether.
The amide on hydrolysis produces CH 3COOH and a compound C8H11N, D.
o
Compound D with HNO2 at 0 C gives an aromatic alcohol C8H10O, oxidation of
which gives phthalic acid. B on mild oxidation gives a carboxylic acid, C 8H8O3
which is degraded by HI to CH3I and p-hydroxybenzoic acid. Identify X, A to D
and give the reactions involved?

Solution: The compound A must contain CH3CO— group as it shows positive iodoform
test and forms oxime.
The compound D which is obtained after the hydrolysis of amide must

contain aliphatic —NH2 group as it gives alcohol on treatment with HNO2 at
0oC. Since the oxidation of alcohol obtained gives phthalic acid, the alcoholic
substituent must be at ortho position to the another substituent. Guided by
this and the given molecular formulae, we derive the structures as shown in
the following.
COOH CH2OH CH2NH2

[O] HNO2
COOH CH3 CH3
phthalic acid C8H10O D
C8H11N
CH2NHCOCH3 CH3COOH
+ H2O
CH3
amide
Since the amide is obtained by the rearrangement of oxime, we may

formulate, this reaction as
CH2—C=NOH
CH2NHCOCH3
PCl5 in CH3
CH3
CH3 ether
oxime
amide C
Finally the structure of A would be
CH2—C = O
CH2—C=NOH
NH2OH CH3
CH3 CH3
CH3
C A
The given reactions on the compound B are as follows
COOH
[O] HI
B C8H8O3 CH3I +
(C8H8O2) mild carboxylic
acid OH
The intermediate compound C8H8O3 must be an ether. The compound B

must be containing C=O group as it is the ozonolysis product of X. Guided
by these, we formulate the above reactions as

COOH COOH CHO
HI [O]
+ CH3I
OH OCH3 B OCH3
Finally, we write the structure of X as shown in the following:

Ozonolysis
CH2—C = O + OHC— CH3
CH3 CH3
CH2—C = CH— CH3
CH3 CH3 X
Problem 10: a) Convert 2-chlorobutanoic acid into 3-chlorobutanoic acid

b) Prepare malonic acid from acetic acid
c) Prepare 4-p tolylbutanoic acid from toulene and succinic anhydride.
Solution: H H
+ +
a) CH3CH2CHClCOOH alc. KOH CH3CH=CHCOOH H CH3CHCHCOOH –
Cl CH3CHClCHCOOH
 
b) CH3COOH  BrCH2COOH 
Br / PBr 2 3
NCCH 2COOH  CH2 (COOH)2
CN H O 3
C) H2C– CH2
C6H5Me + O = C C=O AlCl3 p-MeC6H4CCH2CH2COOH Zn/HCl p-MeC6H4CH2CH2CH2COOH

O
O

Objective
Problem 1: O
CH3OH
   A A is :-
O
(A) CH2—CH2 (B) CH2—CH2
OH COOCH3 COOH OCH3

(C) both are correct (D) None is correct
Solution: O O
This bond breaks hence intermediate is 

O O–
CH3OH+
O
OCH3
OH
(A)
Problem 2: End product of the following sequence of reaction is

O
1. I2 NaOH,
  
C—CH3 2. H ,3 
O
O
(A) Yellow ppt. of CHI3,
COOH
O
(B) Yellow ppt. of CHI3,
CHO
O
(C) Yellow ppt. of CHI3,
(D) Yellow ppt. of CHI3, COOH

COOH
Solution: O
Intermediate is
COOH
Which loses CO2 on heating (-keto acid)
(C)

O
||
1.NaBH 4
Problem 3: End product of this conversion CH3  C CH2  CH2  CH2  CO 2H    
2.H2O,H
is
CH3
(a) =O
(A) O (B) (b)
=O
CH3 O
CH3—CH—CH2CH2CH2CO2H
(C)
(c) =O (D)
O OH
Solution: NaBH4 reduces reactant to

CH3—CH—CH2—CH2—CH2—CO2H which forms ester
OH
 (A)
Problem 4: On standing in dilute aqueous acid compound A is smoothly converted to
CH3
O O CH3
, the compound A is
CH3CO2H
O O
(A) O CH3 (B) O

OH CH2OH
CH3 O
(C) O O (D) O O
CH3 CH3
CH3 CH3
Solution: Dilute aqueous acid cleaves cyclic acetal linkage forming CH3CHO and
OH OH
CH3
CH2CO2H
 (A)
Problem 5: When acetic acid reacts with ketene, product formed

(A) ethyl acetate (B) aceto - acetic ester
(C) acetic anhydride (D) no reaction
Solution: CH3COOH  C3O2  acetc anhydride

( Ketene )
(C)

Problem 6: R—CH2—CH2OH can be converted in R—CH2CH2COOH. The correct
sequence of reagents is
+
(A) PBr3, KCN, H (B) PBr3, KCN, H2
+ +
(C) KCN, H (D) HCN, PBr3, H
PBr3 KCN
Solution: RCH2CH2OH  
 RCH2CH2Br  
 RCH2CH2CN
H2O / H 
  RCH2CH2COOH
 (A)
Problem 7: The pKa of acetylsalicylic acid (aspirin) is 3.5 . The pH of gastric juice in human
stomach is about 2-3 and pH in the small intestine is about 8. Aspirin will be.
(A) Unionized in the small intestine and in the stomach
(B) Completely ionized in the stomach and almost unionized in the small
intestine.
(C) Ionized in the stomach and almost unionized in the small intestine
(D) Ionised in the small intestine and almost unionised in the stomach
Solution: More ionized in basic medium and less ionized in acidic medium, common
ion effect
 (D)
Problem 8: On subjecting mesityl oxide to the iodoform reaction, one of the products is
the sodium salt of an organic acid. Which acid is obtained?
(A) (CH3)2C=CH—CH2COOH (B) (CH3)2CH—COOH
(C) (CH3)2C=CH—COOH (D) (CH3)2C=CH—CO—COOH
Solution: O O
CH3 NaOH / I2 CH3
C=CH—C—CH3    C=CH—C—OH + CHI3
CH3 mesityl oxide CH3
 (C)
Problem 9: The ease of alkaline hydrolysis is more for

COOCH3 COOCH3
(A) (B)
NO2 Cl
COOCH3 COOCH3
(D)
(C)
OCH3
Solution: COOCH3
Then is more electron deficiency on

carbonyl carbon.
NO2
 (A)

Problem 10: Which of the following does not undergo Hell - Volhard Zelinsky reaction?
(A) HCOOH (B) CCl3COOH
(C) C6H5COOH (D) (CH3)3CCOOH
Solution: None of these contain alpha H atom

 (A), (B), (C) and (D)

Assignments
Subjective
LEVEL – I
1. a) What is glacial acetic acid?
b) Account for the name?
c) what is vinegar and how is it made ?
2. a) Prepare butanoic acid from 1–bromopropane
b) Synthesize HOOC—CH2—CH2—COOH from CH2 = CH2
c) Prepare 2-methylbutanoic acid from 2-butanol
3. Starting with C6H6 and C6H5CH3 prepare
a) C6H5COOH
b) p—CH3—C6H4COOH
c) 2-methyl –5- chlorobenzoic acid
d) p–HOOC—C6H4—COOH
e) 2–Bromo–4–nitrobenzoic acid
Do not repeat the preparation of any needed intermediate compound
4. a) Account for the fact that salicylic acid (o—HOC6H4COOH) is stronger acid than
(o–CH3OC6H4COOH)
b) Explain why highly branched acid such as Me3C—CH2COOH are less acidic than
unbranched acids
5. Name each of the following
(a) CH3—CH2—CH = CH—CH2—COCl
H
(b)
COCl
COCl
(c)
C—Cl
(d)
C—Cl
O
(e) ClCOCH2COCl
(f) H2C = CH—COO—CH—CH3
|
CH3
O
C
OC2H5
(g)
C—OCH3
O

6. Write the structure of the products
a) acetic acid + benzyl alcohol
b) propionic acid + isobutanol
c) acetic acid + n-pentanol
d) salicylic acid + methanol
(e) oxalic acid + ethylene glycol
7. Write the products of the reaction of diazomethane CH2N2, with (A) PhCOOH (B)
CH3—CH2—COOH (C) PhCH2—COOH (D) PhCH2—CH2—COOH
8. What are the structures of A through

HN  H O
i) CH3—CH2—COCl 
3  A  B (C3H5NO) 2 C (C2H7N)
H NOH 
 D (C3H7NO2) 
ii) CH3—CH2—COOCH3 2 OH
 E
9. Carry out the following transformations

a) C2H5OH to CH3CN
b) PhCH3 to PhCH2CN
c) PhCH3 to p.O2NC6H4CN
10. Give the structures of A to D

A lCl
i) CH3CH2COCl + PhH 

3 A
1. AlCl3
(ii) PhH + (CH3CO)2O + B
2. H
1. 2eqi of nB4Li
(iii) PhH3COOH3 + C
2. H
1. PhMgBr
(iv) H2C=CH—CH2CN + D
2. H

LEVEL – II
1. A liquid (X), having a molecular formula, C6H12O2, is hydrolysed with water in

presence of an acid to give a carboxylic acid (Y) and an alcohol (Z). Oxidation of (Z)
with chromic acid gives (Y). What are the structures of (X), (Y) and (Z)?
2. An organic compound (A) on treatment with acetic acid in the presence of sulphuric
acid produces an ester (B). (A) on mild oxidation gives (C). (C) with 50% KOH
followed by acidification with dil. HCl generates (A) and (D). (D) with PCl5 followed by
reaction with ammonia gives (E). (E) on dehydration produces HCN. Identify the
compounds (A), (B), (C), (D) and (E).
3. An organic compound ‘A’ on treatment with ethyl alcohol gives a carboxylic acid ‘B’
and compound ‘C’, Hydrolysis of ‘C’ under acidic conditions gives ‘B’ and ‘D’
Oxidation of ‘D’, with KMnO4 also gives ‘B’. ‘B’ on heating with Ca(OH)2 gives ‘E’
(molecular formula C3H6O). ‘E’ does not give Tollen’s test and does not reduce
Fehling’s solution but forms a 2,4-dinitophenyl hydrazine. Identify ‘A’. B’ ‘C’ ‘D’ and
‘E’.
4. alkaline CrO
   KMnO

4
 A  3 HCN
 B  
 C
CH3COOH +
H3O
 E 
F 
P /
HI
 D
Identify A to F
5. One mole of an organic amide (A) upon alkaline hydrolysis gives one mole of NH3
and one mole of a monobasic acid of equivalent mass 74. What is the molecular
mass of (A)?
6. Compound (A) (C6H12O2) on reduction with LiAlH4 yielded two compounds (B) and
(C). The compound (B) on oxidation gave (D) which on treatment aqueous alkali and
subsequent heating furnished (E). The latter on catalytic hydrogenation gave (C).
The compound (D) was oxidised further to give (F) which was found to be monobasic
acid (molecular mass = 60.0). Deduce the structure of (A), (B), (C), (D) and (E).
7. In the following reactions, identify the compounds (A), (B), (C) and (D)
PCl5 + SO2  (A) + (B)
(A) + CH3COOH  (C) + SO2 + HCl
2(C) + (CH3)2Cd  2(D) + CdCl2
8. Two moles of an ester (A) are condensed in the presence of sodium ethoxide to give
a -keto ester (B) and ethanol. On heating in an acidic solution (B) gives ethanol and
-keto acid (C). On decarboxylation (C) gives 3-pentanone. Identify (A), (B) and (C)
with proper reasoning. Name the reaction involved in the conversion of (A) to (B).
9. What are the structures of A through E

HN3
(i) CH3—CH2—COCl  
 A  HO
B (C3H5NO) 2 C (C2H7N)
H NOH 
(ii) CH3—CH2—COOCH3 2  D (C3H7NO2) 
OH
 E

10. Arrange the following in the increasing order of acidic strength.
COOH COOH COOH COOH COOH
NO2 CH3 NH2 Cl

(I) (II) (III) (IV) (V)

LEVEL - III
1. Compound (A) C5H8O2 liberated carbon dioxide on reaction with sodium bicarbonate.
It exists in two forms neither of which is optically active. It yields compound (B)
C5H10O2 on hydrogenation. Compound (B) can be separated into two enantiomorphs.
Write the structural formulae of (A) and (B) giving reason.
2. A dicarboxylic acid (A), C4H6O4, gave a compound (B), C6H10O4 upon treatment with
excess of methanol and a trace of H2SO4. Subsequent treatment of (B) with lithium
aluminum hydride followed by usual way afforded (C), C4H10O2. Pyrolysis of (A)
yielded (D), C4H4O3. Assign structures to (A), (B), (C) and (D).
3. An organic acid (A), C5H10O2 reacts with Br2 in the presence of phosphorus to give
(B). Compound (B) contains an asymmetric carbon atom and yields (C) on
dehydrobromination. Compound (C) does not show geometric isomerism and on
decarboxylation gives an alkene (D) which one ozonolysis gives (E) and (F).
Compound (E) gives a positive schiff’s test but (F) does not. Give structures of (A) to
(F) with reasons.
4. An acidic compound (A), C4H8O3 loses its optical activity on strong heating yielding
(B), C4H6O2 which reacts readily with KMnO4. (B) forms a derivative (C) with SOCl2,
which on reaction with (CH3)2NH gives (D). The compound (A) on oxidation with
dilute chromic acid gives an unstable compound (E) which decarboxylates readily to
give (F), C3H6O. The compound (F) gives a hydrocarbon (G) on treatment with
amalgamated Zn and HCl. Give structures of (A) to (G) with proper reasoning.
5. An ester (A) is condensed in the presence of sodium methoxide to give a -keto

ester (B) and methanol. On mild hydrolysis with cold conc. HCl, (B) gives methanol
and 3-oxo-acid (C). (C) underwent ready decarboxylation to give cyclopentanone .
a) Identify (A), (B) and (C) .
b) Name the reaction involved in the conversion of (A) to (B).
c) Give the mechanism of condensation. Explain briefly why the 3- oxo-acid
undergoes decarboxylation easily.
6. A pleasant smelling optically active ester (F) has M.W. = 186. It does not react with
Br2 in CCl4. Hydrolysis of (F) gives two optically active compounds, (G) soluble in
NaOH and (H). (H) gives a positive iodoform test and on warming with conc. H2SO4
gives (I) (Saytzeff-product) with no geometrical isomers. (H) on treatment with
benzene sulfonyl chloride gives (J), which on treatment with NaBr gives optically
active (K). When the Ag+ salt of (G) is treated with Br2 racemic (K) is formed. Give
structures of (F) to (K) and explain your choices.
7. Compound (A), M.F C6H12O2 reduces ammonical silver nitrate to metallic silver and
looses its optical activity on strong heating yielding (B), C6H10O which readily reacts
with dilute KMnO4. (A) on oxidation with alkaline KMnO4 gives (C) having M.F
C6H10O3 which decarboxylates readily on heating to 3-pentanone. The compound (A)
can be synthesized from a carbonyl compound having M.F. C3H6O on treatment with
dilute NaOH. Oxidation of (B) with ammonical silver nitrate followed by acidification
gives (D). (D) forms a derivative (E) with SOCl2 which on reaction with

H3CNHCH2CH3 yields (F). Identify (A) to (F) giving proper reaction sequences. What
is the name of the reaction involved in the conversion of C3H6O to (A) ? Give the
IUPAC nomenclature of compounds (A) to (F).
8. A solid organic compound (A), C9H6O2 is insoluble in dilute NaHCO3. It produces a

dibromoderivative (B), C9H6O2Br2 on treatment with Br2/CS2. Prolonged boiling of (A)
with concentrated KOH solution followed by acidification gives a compound (C),
C9H8O3. The compound (C) gives effervescence with aqueous NaHCO3. Treatment
of (C) with equimolar amount of Me2SO4/NaOH gives (D), C10H10O3. The compound
(D) is identical with the compound prepared from ortho-methoxy benzaldehyde by
condensation with acetic anhydride in the presence of sodium acetate. Treatment of
(C) with alkaline C6H5SO2Cl produces (E) which on vigorous oxidation with KMnO4
gives (F). Hydrolysis of (F) gives a steam volatile compound (G) having M.F. C7H6O3.
Give the structures of (A) to (G) giving the proper reaction sequences.
9. A neutral compound (A) C9H16O2 on refluxing with dilute alkali followed by

acidification yields (B) C5H8O2 and (C) C4H10O. (B) liberates CO2 from bicarbonate
solution. (C) on dehydration yields 2-butene as the major product. B on treatment
with OsO4 followed by reductive hydrolysis gives (D) C5H10O4. (D) when treated with
leadtetraacetate furnishes acetone and (E) C2H2O3. (E) is acidic and reduces
Tollen’s reagent. Identify (A), (B), (C), (D) and (E) and write the reactions involved.
10. A neutral compound (A), C16H14O2 on treatment with an excess of boiling aqueous
potash gives a clear solution which when saturated with CO2 affords a liquid turning
to a low melting solid (B), M.F. C6H6O. (B) gives a purple colour with FeCl3 solution
and white precipitate when treated with bromine water. Acidification (with HCl) of the
aqueous solution after removal of (B) yields a solid acid (C), C4H6O4. (C) gives a
neutral compound (D), C6H10O4. (C) when heated loses water to give (E), a neutral
substance with M.F. C4H4O3. Deduce the structure of (A) and explain the formation of
the substances (B) to (E). Give the structures of two products (X) and (Y) when (E)
reacts with anisole in the presence of anhydrous aluminium chloride followed by
acidification.

Objective
LEVEL - I
1. Lemon is sour due to:

(A) citric acid (B) tartaric acid
(C) oxalic acid (D) acetic acid
2. Which of the following is used in baking powder

(A) citric acid (B) lactic acid
(C) tartaric acid (D) oxalic acid
3. Vinegar contains
(A) 10 to 20% acetic acid (B) 10% acetic acid
(C) 6 to 10% acetic acid (D) 100% acetic acid
4. Which of the following is used in preparation of artificial flavours

(A) Lower alcohols (B) esters of higher fatty acid
(C) ester of lower fatty acid (D) lower fatty acid
5. Which are hydroxy acids

(A) lactic acid (B) tartaric acid
(C) citric acid (D) succinic acid
6. Pyroligneous acid contains

(A) 2% acetic acid (B) 50% acetic acid
(C) 10% acetic acid (D) 20% acetic acid
7. An inorganic compound producing an organic compound on heating is

(A) ammonium cyanate (B) sodamide
(C) sodalime (D) potassium cyanide
8. Formic acid is obtained when

(A) calcium acetate is heated with conc. H2SO4
(B) glycerol is heated with oxalic acid
(C) acetaldehyde is oxidised with K2Cr2O7 and H2SO4
(D) calcium formate is heated with calcium acetate
9. When a fat is heated with NaOH, the substances formed are

(A) oil and Na2CO3 (B) soap and glycerol
(C) soap and oil (D) soapless detergent and water
10. Name of the end product in the following series of reactions

NH  P O
CH3COOH  3  (A)  (B) 2
5  (C)
(A) CH4 (B) CH3OH

(C) Acetonitrile (D) ammonium acetate

LEVEL - II
1. Detergent has a common group

(A) RONa (B) RCOONa
(C) RC  CNa (D) RC6H4SO3Na
2. Which one of the following would be expected to be most highly ionised in water?
(A) CH2Cl–CH2–CH2COOH (B) CH3CHCl –CH2–COOH
(C) CH3–CH2–CHCl–COOH (D) CH3CH2–CCl2 –COOH
3. Which of the following will not undergo HVZ reaction

(A) 2,2-dimethyl propanoic acid (B) propanoic acid
(C) acetic acid (D) 2-methyl propanoic acid
4. Formic acid and formaldehyde can be distinguished by treating with

(A) Benedict’s solution (B) Tollen’s reagent
(C) Fehling’s solution (D) NaHCO3
5. Urea react with malonic ester to give

(A) cyanuric acid (B) semicarbazide
(C) urethan (D) barbituric acid
6. Formic acid and acetic acid may be distinguished by reaction with

(A) sodium (B) dilute acidic permangnate
(C) 2,4 dinitrophenylhydrazine (D) sodium ethoxide
7. Which of the following products is formed when adipic acid is heated

CH2 CH2 CH2 CH2
(A) O (B) C= O
CH2 CH2 CH2 CH2
CH2 CH2CO CH2 CH2COOH

(C) O (D)
CH2 CH2COOH
CH2 CH2CO
8. Which one of the following is a strong reducing agent

(A) ethanoic acid (B) benzoic acid
(C) methanoic acid (D) chloroacetic acid
9. Acetic acid reacts with chlorine in the presence of catalyst, anhydrous FeCl3 to give
(A) acetyl chloride (B) methyl chloride
(C) tri-chloro acetic acid (D) chloral hydrate
10. Ammonium acetate on heating gives

(A) N2 gas (B) acetic acid
(C) acetamide (D) NH3 gas

Answers
Subjective
LEVEL - I
1. (A) 100% acetic acid

(C) 5% aqueous solution of HOAc
5. (A) 3–hexenoyl chloride

(B) 2-cyclopentane carboxyl chloride
(C) 2-naphthoyl chloride
(D) pthaloyl dichloride
(E) malonyl dichloride
(F) sec. Butyl acrylate
(G) Ethyl methyl pthalate
6. (A) CH3—COOCH2—Ph
(B) CH3—CH2COOCH2—CH(CH3)2
(C) CH3—COO(CH2)4CH3
COOCH3
OH
(D) (Oil of winter green)
O O
C CH2
(E)
C CH2
O O
7. (A) PhCOOCH3 (B) CH3—CH2—COOCH3
(C) PhCH2—COOCH3 (D) PhCH2CH2COOCH3
8. (A) CH3—CH2CON3 B) CH3CH2NCO

(C) CH3 — CH2 NH2 (D) CH3—CH2.CONHOH
(E) CH3—CH2NH2
10. (A) PhCOCH2CH3 (B) (I–Bu)2CuLi

(C) PhCOH2CH(CH3)2 (D) PhCOCH3
(E) PhCH2C(OH) (n–C4H9)2 (F) H2C = CHCH2COPh

LEVEL -II
1. (X) C2H5COOC3H7 (Y) C2H5COOH

(Z) C3H7OH
2. (A) CH3OH (B) CH3COOCH3

(C) HCHO (D) HCOOH
(E) HCONH2
3. (A) (CH3CO)2O (B) CH3COOH

(C) CH3COOC2H5 (D) C2H5OH
(E) CH3COCH3
5. 73
6. (A) CH3CH2—CH2COOCH2CH3
(B) CH3—CH2—OH
(C) CH3—CH2—CH2—CH2—OH
(D) CH3CHO
(E) CH3—CH = CH.CHO
(F) CH3COOH
7. (A) SOCl2 (B) POCl3

(C) CH3COCl (D) CH3COCH3
8. (A) C2H5COOC2H5 (B) C2H5CO—CH(CH3)COOC2H5

(C) C2H5COCH(CH3)COOH
10. I  V  IV  II  III

LEVEL - III
1. CH3 CH3 CH3 COOH

C=C and C=C
H COOH H CH3
(A) Geometrical isomers

CH3 CH3
C2H5—C—COOH or HOOC—C—C2H5
H H
2. (A) CH2COOH
|
CH2—COOH
(B) CH2COOCH3
|
CH2—COOCH3
(C) CH2—CH2OH
|
CH2—CH2OH
(D) CH2CO
O
CH2CO
3. (A) C3H7CH2COOH
(B) C3H7CHBrCOOH
(C) CH3
C=CHCOOH
CH3
(D) (CH3)2C=CH2
(E) HCHO
(F) CH3COCH3
4. (A) CH3CHOHCH2COOH
(B) CH3CH=CHCOOH
(C) CH3CH = CHCOCl
(D) CH3—CH = HCON(CH3)2
(E) CH3COCH2COOH
(F) CH3COCH3
(G) CH3CH2CH3

5. OMe
O
A= O
OMe
B= =O
CO2Me
O
CO2H
C=
Claisen ester condensation
6. is a saturated monoester with M.W = 186

O
(F) (CH3)2—CH—CH—C—O– CH–CH(CH3)2
CH3 CH3
CH3
(G) CH3 —CH—CHCO2H
CH3
(H) CH3—CH(OH) —CH(CH3)2
(I) CH3—CH=C(CH3)2
OSO2C6H5
(J) CH3—CH—CH(CH3)2
(K) CH3CHBrCH(CH3)2
7. (A) OH
CH3—CH2—CH—CH—CHO
CH3
(B) CH3—CH2CH=C—CHO
CH3
(C) O
CH3—CH2—C—CH —CO2H
CH3
(D)
CH3—CH2—CH = CCO2H
CH3

(E) CH3—CH2—CH=CCOCl
CH3
(F) O
CH3CH2—CH=C—CN(CH3)(CH2CH3)
CH3
8. (A) CH (B) Br
CH
CH
C=O CHBr
O
C=O
O
(C) CH=CHCO2H (D) CH=CHCO2H
OH OCH3
(E) CH=CH–COOH (F) CO2H
OSO2C6H5 OSO2C6H5
(G) CO2H
OH
CH3 CH3
9. A C = CH—C—OCH2CH2CH2CH3 or C = CH—C—O—CH—CH2CH3 ;
CH3 H3C O
O CH3
CH3 CH3CHCH2CH3 CH3CH2CH2CH2OH ;
B C = CHCO2H ; C OH
H3C Dehydration
2 - Butene
CH3
D C—CH—CO2H ; E O=CH—CO2H
H3C MF : C2H2O3
OH OH
M.F C5H10O4

10. (A) O
CH2—C—OC6H5
CH2—C—OC6H5
O
(B) C6H5OH
(C) CH2—CO2H
CH2—CO2H
(D) CH2—CO2Me
CH2—CO2Me
(E) CH2—CO
O
CH2—CO
OMe O
(X)
C—CH2CH2 —CO2H
(Y) OMe
C–CH2CH2COOH

Objective
LEVEL - I
1. A 2. C
3. C 4. C
5. A, B, C 6. C
7. A 8. B
9. B 10. C
LEVEL - II
1. D 2. D
3. A 4. C
5. D 6. B
7. B 8. C
9. C 10. C
6

Carboxylic Acids & Derivatives

Uploaded by

Copyright:

Available Formats

Carboxylic Acids & Derivatives

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Carboxylic Acids & Derivatives

Uploaded by

Copyright:

Available Formats

CARBOXYLIC ACIDS & DERIVATIVES

Introduction And Nomenclature

i) HCOOH Formic acid [Latin: Fermica = ant]

Example: CH3 – CH2 – COOH Methyl acetic acid

HCOOH methanoic acid

CH3 – CH – CH – CH2 – COOH 3, 4-dimethylpentanoic acid

Rankers-JEE by Saurabh Maurya

Solution: IUPAC Name General name

Naming of Acyl Groups; Acid Chlorides and Acid Anhydrides

Benzoic acid Benzoyl group

Acid chlorides are named systematically as acyl chlorides.

Rankers-JEE by Saurabh Maurya

Naming Salts and Esters

Name of Amides and Imides:

CH3 – C – NH2 Ethanamide or acetamide

Rankers-JEE by Saurabh Maurya

Exercise -1: Write following isomers of the formula C4H4O4

Carboxylic acids have higher boiling points than alcohols. O  H  O

Acidity of Carboxylic Acids

Rankers-JEE by Saurabh Maurya

Cl3CCOOH > Cl2CHCOOH > ClCH2COOH > CH3COOH

c) Increase in the electro negativity of halogen increases the acidity.

FCH2COOH > BrCH2COOH > ICH2COOH

Exercise-2: Explain the following

Rankers-JEE by Saurabh Maurya

General Methods Of Preparation

By Oxidation of Alcohols, Aldehydes & Ketones

Alkenes can be oxidized to carboxylic acids with hot alkaline KMnO4.

By the Hydrolysis of Nitriles (Cyanides)

By Carbonation of Grignard Reagents

Rankers-JEE by Saurabh Maurya

By the Hydrolysis of Trihalogen Derivatives

By Oxidation of Methyl Ketone

By Alkenes (Koch Reaction)

CH2 = CH2 + CO + H2O  CH3 – CH2 – COOH

By Heating Gem Dicarboxylic Acids

Rankers-JEE by Saurabh Maurya

General Reactions of the Fatty Acids

Acidity (Salt formation)

Basicity RCOO– < HO– < RO– < HC  C– < NH 2 < R–

2CH3COOH + 2Na  2CH3COO–Na+ + H2

CH3COOH + NaOH  CH3COO–Na+ + H2O

CH3COOH + NaHCO3  CH3COO–Na+ + H2O + CO2

Conversion into Functional Derivatives

Rankers-JEE by Saurabh Maurya

R=O C–O C–O R = O + HL

Nucleophilic addition Elimination

Conversion into Acid Chlorides:

Rankers-JEE by Saurabh Maurya

Conversion into Esters (Esterification)

Reactivity CH3OH > 1° > 2° > 3°

Conversion into Amides

Conversion into Anhydrides

Rankers-JEE by Saurabh Maurya

Reduction of Acids to Alcohols:

4 R–COOH + 3LiAlH4  4H2 + 2LiAlO2 + (RCH2O)4 AlLi + H2

Halogenation of Aliphatic Acids (Hell-Volhard-Zelinsky Reaction)

CH 3  COOH   Cl  CH 2  COOH 

The halogen of these halogenated acid undergoes nucleophilic displacement and

A formyl group is present in the structure of formic acid, it indicates the