Carboxylic Acid and Its Derivatives - Chemistry

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SUBJECT CHEMISTRY TOPIC CARBOXYLIC ACIDS & ITS DERIVATIVE COURSE CODE AISM-09/C/CAID Trans Web Educational Services Pvt. Ltd
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Contents :- CARBOXYLIC ACIDS & ITS DERIVATIVE

Introduction...3 Nomenclature ....5 General methods of preparation...11 Physical properties..24 Chemical reactions..27 Reactions of RCOOH..28 Salt formation.31 The mechanism of easterification reaction35 Carboxylic acid derivatives.44 Chemical reactions of acid derivatives..47 Base promoted hydrolysis of esters: Saponification.52 Claisen Condensation.55 Amides..57 Answers to excersies66 Miscellaneous..75 Solved examples.83 IIT level questions..87
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INTRODUCTION Carboxylic acids are characterized by the presence of carboxyl group. The COOH group which itself is made up of a carbonyl group (C=O) and a hydroxyl group ( from hydroxyl) OH) is called carboxyl group (carb from carbonyl and oxyl
O C Carbonyl O H Hydroxyl
O C O Carboxyl H
Carboxylic acids may be aliphatic or aromatic
O R C O H Ar C
Aliphatic carboxylic acid (Where R = H or any alkyl group)
Aromatic carboxylic acid (Where Ar is any aryl group)
Comparison
of
resonating
structures
of
carboxylic
group
and
carbonyl group Carbonyl group has two resonance structures (I and II)
C (I)
C (II)

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However, for a carboxyl group, three resonance structures (A, B and C) can be written.
O C O (A) H C
O C O (B) H
O (C)
In both structures (A) and (C), the C atom and the two O atoms have eight electrons in their respective valence shells while in structure (B), C atom has only six electrons. Therefore, structure (B) is less stable than structure (C), in other words the two important resonance structures of carboxyl group are structures (A) and (C). In both these structures, carboxyl carbon is electrically neutral. However in case of aldehydes and ketones, only one structure i.e. I is electrically neutral. As a result, the carboxyl carbon of the resonance hybrid is less positive and hence less electrophilic than the carbonyl carbon of aldehydes and ketones. However, it may be noted that like carbonyl group, carboxyl group is also polar due to resonance structures (B) and (C).

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NOMENCLATURE The aliphatic carboxylic acids are commonly known by their initial names, which have been derived from the source of the particular acid. Examples: HCOOH Formic acid [Latin: Fermica = ant] CH3COOH Acetic acid [Latin: acetum = Vinegar] CH3CH2COOH Propionic acid [Greek: Proton = First; Pion = Fat] CH3(CH2)2COOH Butyric acid [Latin: Butyrum = Butter] CH3(CH2)3COOH Valeric acid CH3(CH2)14COOH Palmitic acid CH3(CH2)16COOH Stearic acid
Alternative system of nomenclature is naming the acids as the derivatives of acetic acids. The only exception being formic acid.

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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 numbering to be started from the side of the carboxyl group.
1 CH3 CH CHCH2 COOH | | CH3 CH3
3, 4-dimethylpentanoic acid
NAMING OF ACYL GROUPS, ACID CHLORIDES AND 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 Trans Web Educational Services Pvt. Ltd
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changing the - ic acid at the end of the name of the carboxylic acid to yl, examples:
O || H C O H
Formic acid
O || H C
Formyl group
O || C OH
Benzoic acid
O || C
Benzoyl group
Acid chlorides are named systematically as acyl chlorides.
O H3C Cl acetyl chloride
An acid anhydride is named by substituting anhydride for acid in the name of the acid from which it is derived.
OH
O
O OH succinic acid O dihydrofuran-2,5-dione

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O COOH O
COOH phthalic acid
O 2-benzofuran-1,3-dione
Naming of 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 of the carboxyl group (in the case of an ester) precedes the name of the acid.
O H3C O
+
O Na 1-phenylethanone Sodium benzoate
CH3 ethyl 4-methylbenzoate
Naming 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.
O O H3C NH2 acetamide NH2 cyclohexanecarboxamide

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If the nitrogen atom of the amide has any alkyl groups as substitutents, 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 O 2N N CH3
CH3 N-ethyl-N-methyl-4-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 H3C NH N-phenylacetamide O N-phenylbenzamide NH
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.
H N
O
NH
pyrrolidine-2,5-dione
O 1N-isoindole-1,3(2H)-dione

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Illustration 1: Give (i) the IUPAC names and (ii) common names of the following
compounds
COOH COOH
COOH HOOC
(iii)
H3C
OH
iv)
HOOC
OH
COOH
HO
COOH
Solution: IUPAC Name (i) (ii) (iii) (iv) Ethanedioic acid Butanedioic acid 2-Hydroxy propanoic acid 2, 3 Dihydroxybutanedioic acid General name Oxalic acid Succinic acid Lactic acid Tartaric acid
Illustration 2: Which is not a hydroxy acid? (A) (C) lactic acid citric acid (B) (D) tartaric acid succinic acid

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Solution: (D)
GENERAL METHODS OF PREPARATION 1. Oxidation of alcohols, aldehydes and ketones Refer AEP & AK Illustration 3: How will you prepare CH3CH2COOH from CH3 CH=CH2 Solution:
CH3
CH
CH2
BH3 / THF H2O2 / OH
CH3
CH2
CH2
OH
MnO4 / H
CH3
CH2
COOH
Illustration 4: Bring about the following transformations

CH 2 OH
MnO2
Ag NH3 OH 2 H

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Solution:
O
A:
CHO
B:
OH
2.
Oxidation of alkyl benzenes Although benzene and alkane are quite unreative towards the usual oxidizing agents (KMnO4, K2Cr2O7 etc). The benzene ring renders an aliphatic side chain quite susceptible to oxidation. The side chain is oxidised down to the ring and only a carboxyl group ( to indicate the position of the original side COOH) remains chain. Potassium
permanganate is generally used for this purpose, although potassium dichromate or dilute nitric acid can also be used. (Oxidation of a side chain is more difficult, however, than oxidation of an alkene and requires prolonged treatment with hot KMnO4)
CH 2CH 2CH 2CH 3 hot KMnO

4
COOH CO 2 Benzoic acid
n - butyl benzene

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This reaction is used for two purposes (a) synthesis of carboxylic acids and (b) identification of alkyl benzenes. 3. Carbonation of Grignard reagents The Grignard synthesis of a carboxylic acid is carried out by bubbling gaseous CO2 into the ether solution of the Grignard reagent or by pouring the Grignard reagent on crushed dry ice (solid CO 2). In the latter method dry ice serves not only as reagent but also as cooling agent. The Grignard reagent adds to the carbon oxygen double bond of CO2 just as in the reaction with aldehydes and keotnes. The product is the magnesium salt of the carboxylic acid, from which the free acid is liberated by treatment with mineral acid.
O R MgX C O R COO Mg X H R COOH Mg

2
Grignard's reagent
The Grignards reagent can be prepared from primary, secondary, tertiary or aromatic halides. The method is limited only by the presence of other reactive group in the molecule. The following synthesis illustrate the application of this method.

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CH3 H3C C CH3 OH HCl H3C CH3 C CH3 Cl Mg H3C CH3 C CH3 MgCl CO 2 H H3C CH3 C CH3 Trimethylacetic acid COOH
Illustration 5: (i)
COOH H3C CH3 Br 2 Fe A Mg Ether B CO 2 H H3C CH3
CH3
CH3
Write A and B (ii)

Br COOH
Mg Ether
CO 2
H3C
CH
H3C
CH C2H5
C2H5 p-bromo-sec-butyl benzene
p-sec-butyl benzoic acid
Write A and B Solution: (i)

H3C
Br CH3 H3C Br 2 CH3 H3C Mg Ether CH3 Mesitylene
MgBr CH3 CO 2 H3C H
COOH CH3
CH3 Bromomesitylene
CH3
CH3 Mesitoic acid ( 2, 4, 6 - trimethyl - benzoic acid)

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(ii)
Br
MgBr
COOMgBr
COOH
Mg Ether
CO 2
H3C
CH
H3C
CH C2H5
H3C
CH C2H5
H3C
CH C2H5
C2H5 p-bromo-sec-butyl benzene
p-sec-butyl benzoic acid
Illustration 6: Bring about the following transformations.

Br O C OH
Solution:
O Br
Mg / Ether
MgBr
CO2
CO 2MgBr
H3O
OH
Bring about the following transformations Exercise 1: (i)

Br
OH
(ii)
OH HC CH O

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Exercise 2: (i) Why we can not get anhydrous formic acid by fractional distillation of the Fatty acids? (ii) CH2=CHCH=CH2
(i) HBr (ii) Mg/ether (iii) CO2 /H3O+
A. Identify A?
4.
Hydrolysis of nitriles Aliphatic nitriles are prepared by treatment of alkyl halides with sodium cyanide in a solvent that will dissolve both reactants. In dimethyl sulfoxide (DMSO), reaction occurs rapidly and exothermically at room temperature. The resulting nitrile is then hydrolysed to the acid by boiling with aqueous alkali or acid.
H
R Cl NaCN
DMSO
COOH
NH 4 NH 3
H2 O
OH
COO
Illustration 7: (i)
NaCN n - C 4H9Br n - butyl bromide
C NH4
Write A, B and C. Trans Web Educational Services Pvt. Ltd

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(ii)
Benzyl chloride
CH 2Cl NaCN A 70% H2SO 4, reflux B NH 4
Write A and B. Solution: (i)
NaCN n - C 4H9Br n - butyl bromide
n - C 4H9CN n - voleonitrile (pentanenitrile) (A)
aq. alc. NaOH, reflux
n - C 4H9COO NH 3 (B) H n - C 4H9COOH NH 4 n - valeric acid (pentanoic acid) (C)
(ii)
CH 2Cl NaCN
CH 2CN 70% H 2SO 4, reflux
CH 2COOH NH 4
Benzyl chloride
Phenyl acetonitrile
Phenyl acetic acid
Exercise 3: Identify the missing reagents or products
O H3C CH3
HCN/OH -
(A)
H 2 O/H +
(B)
conc. H 2 SO4
(C)
i) 3 /THF BH ii) 3 COOH CH
(E)
i) BH3/THF
ii) H2O2/OH (D)

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Exercise 4:
OH
Conc. H 2SO 4
Cl2/H2O
CN
H3O
Cr 2 O72 - /H +
Exercise 5: A pleasant smelling optically active ester (A) has molecular weight 186. it does not react with Br2 in CCl4. Hydrolysis of (A) gives two optically active compounds B and C. Compound (C) gives positive iodoform test and on warming with conc. H 2SO4 gives D (saytzeff product) with no geometrical isomers. (C) on treatment with benzene sulphonyl chloride gives (E) which on treatment with NaBr gives optically active F. When Ag2+ salt of (B) is treated with Br2, racemic F is formed. Give structures of A to F. 5. Use of alkoxide
RO Na CO
dark
RCOONa
RCOOH
CH3 O Na CO
CH3COOH
2100 C, pressure Co CO 8
CH3OH CO
CH3COOH
6.
Carbonylation of alkenes
CH2 CH2 CO H2O
H3PO4 300 4000 C
CH3 CH2COOH

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CH3 CH CH2 CO H2O
H3PO4 300 4000 C
CH3
CH COOH | CH 3
7.
Oxidative cleavage of alkenes, alkynes and cyclo alkenes

RC CR'
i O3 or KMnO4 ii H2O
RCOOH R'COOH
CH3C
RCH
CCH3
CHR
i O3 ii H2O
2CH3COOH
2RCOOH
i Alkaline KMnO4 ii H /
KMnO4 / /H
CH 2COOH CH 2COOH
Illustration 8: Compound A, C5H8O3, when heated with soda lime gives B which reacts with HCN to give C, C reacts with PCl 5 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. Solution:
(C5H8O3)
Soda lim e
Compound B
HCN
Compound (C)
PCl5
KCN
Careful oxidation with K2Cr2O7
Compound E
Compound D,
COOH CH3COOH + CH2 COOH
Alk. hydrolysis Salt

soda lim e
n-butane

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On Oxidation only two COOH groups can be introduced, i.e., one to each carbon undergoing CC 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
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 careful oxidation undergo CC 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 arrangement
C3H7COhas
O ||
CH3 C CH2 CH2
O ||
CH3 C CH2 CH2
structure
and
compound
is
COOH

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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 | CN PCl5 Cl | CH3 C CH2 CH3 | CN KCN CN | CH3 C CH2 CH3 | Alkaline hydrolysis CN COONa | CH3 C CH2 CH3 | COONa
(C)
(D)
Soda lim e
CH3 CH2 CH2 CH3

(n-butane)
Illustration 9: How will you affect the following conversions?

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(i)
CH3
COOH
Cl
(ii)
COOH
Solution: (i)
CH3
COOH
COOH
KMnO 4 OH
Fe/Cl 2
Cl
(ii)
H2O/H Hg
2+
O CH3
NaOH I2
COOH
Illustration 10: An organic compound A (C4H8O3), acidic in nature, is oxidised to give B which on gentle heating produces C, (C3H6O) and CO2. A on heating yields D (C4H6O2) having an acid neutralization equivalent of 86. What are A, B and C? Solution:

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A on heating produces D (C4H6O2). It clearly tells us that it is dehydration reaction and A must be a - hydroxyl acid.
OH
So A is CH3 HC CH2 COOH and D is CH3
CH = CH
COOH
OH CH 3C H CH 2 COOH Oxidation H3C
O C (B) CH 2 COOH
decarboxylation
H3C C O CH3 CO 2
(Because if a carbonyl group is present
to carboxylic group, the
compound undergoes decarboxylation on heating) Illustration 11: Formic acid is obtained when (A) (B) (C) (D) calcium acetate is heated with conc. H 2SO4 glycerol is heated with oxalic acid acetaldehyde is oxidised with K2Cr2O7 and H2SO4 calcium formate is heated with calcium acetate

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Solution: (B) Exercise 6: A neutral organic compound A, C3H6O2 on hydrolysis gives a monobasic acid B and a neutral compound C. The acid B reduces HgCl 2 solution. The compound C gives iodoform test. Write structures of A, B and C and give equations to explain the reactions involved. PHYSICAL PROPERTIES Some important physical properties of carboxylic acids are given below, 1. Solubility As the size of the alkyl group increases, the solubility of the acid decreases and polarity is reduced. 2. Boiling points Due to intramolecular hydrogen bonding dimerization of acid takes place and boiling point of carboxylic acid is higher than expected.

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O R C O H O H O C R
3.
Melting points The melting points of aliphatic carboxylic acids do not show a regular pattern. The first ten members show a alteration effect, i.e. the melting point of an acid containing even number of carbon atoms is higher than the next lower and next higher homologues containing odd number of carbon atoms.
Illustration 12: On the basis of H-bonding explain that the second ionization constant K2 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. Trans Web Educational Services Pvt. Ltd
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O C O H C C H C O
Fumarate monoanion (no H-bonding)
O H C OH H C C O
Maleate monoanion (H-bonding)
C O H O
Since the second ionisable H of the Maleate ion participates in Hbonding more energy is needed to remove this H because the H-bond must be broken. The maleate mono anion is, therefore, the weaker acid. Exercise 7: Explain the following (i) Carbon-oxygen bond length in formic acid are 1.24 and 1.36 but in sodium formate both the carbon-oxygen bonds have same value i.e.1.27 . (ii) Acetic acid in the vapour state shows a relative molecular weight of 120.

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CHEMICAL REACTIONS 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.
H R
O (b) (a) O H
C C (d) (c) H
Carboxylic acids can also show various types of reactions. (i) Removal of H+ (due to cleavage of O base (at a above) (ii) (iii) C O bond breaks at b (by PCl 5, PCl3, SOCl2, NH3/ ) H bond) by reaction with a
Nucleophilic attack at point (c) in carboxyl carbon (Ester formation) Reaction in which OH is replaced by
O R C OH NH 2 R O C NH2
NH2, Cl is SN type

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(iv)
Halogenation at reaction)
C by P/Br2 at point d (Hell Volhard Zelinsky
(v)
Oxidation of
- methylene group by SeO2

O
SeO2 ||
RCH2COOH
R C COOH H2O Se keto acid
Some reactions are summarized below:
RCOONH
RCONH
RCOONa
CO 2
3
NH 3 RCH 2OH RCOOR' RCOOCH H2 RCOONa

3
NH3 ,
NaHCO
LiAlH 4 R'OH/H CH 2N2 Na R O C OH Y X
N3H
S o d a lim e,
N2
CO2
R NH2
RH RCOONa
NaOH
PCl 5
PCl 3 ROCI
SOCl 2
P 2O 5 (RCO) 2O
Reactions of RCOOH 1. Acidity and salt formation
Acidity of Carboxylic Acids Trans Web Educational Services Pvt. Ltd

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The acidity of a carboxylic acid is due to the resonance stabilization of its anion.
O R O (I)
H R
O R
R H
O (II) O (III)
O (IV)
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 acidity, eg. Trans Web Educational Services Pvt. Ltd
-position increases the
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Cl3CCOOH > Cl 2CHCOOH > ClCH2COOH > CH3COOH (b) Increase in the distance of Halogen from COOH decreases the acidity e.g.
H3C COOH Cl H3C
Cl
Cl
COOH
COOH
This is due to the fact that inductive effect decreases with increasing distance. (c) Increase in the electronegativity of halogen increases the acidity. FCH2COOH > BrCH2COOH > ICH2COOH Illustration 13: Which one of the following would be expected to be most highly ionised in water? (A) (C) Solution: (D) CH2ClCH2CH2COOH CH3CH2CHClCOOH (B) (D) CH3CHCl CH2COOH CH3CH2CCl2 COOH

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SALT FORMATION Carboxylic acids are weak acids and their carboxylate anions are strong conjugate bases and are slightly alkaline due to the hydrolysis of carboxylate anion compared to other species, the order of acidity and basicity of corresponding conjugate bases are as follows: Acidity Basicity RCOOH > HOH > ROH > HC RCOO < HO < RO < HC CH > NH3 > RH C < NH2 < R
1.
The carboxylic acids react with metals to liberate hydrogen and are soluble in both NaOH and NaHCO3 solutions. For example. 2CH3COOH + 2Na CH3COOH + NaOH CH3COOH + NaHCO3 2CH3COONa+ + H2 CH3COONa+ + H2O CH3COONa+ + H2O + CO2
Examples:
2CH3 COOH Zn Acetic acid CH3 CH2 lauric acid

COOH NaHCO Benzoic acid
3
10
CH3 COO 2 Zn H2 Zinc acetate
COOH NaOH
CH3 CH2
10
COO Na
H2O
Sodiumlaurate
COO Na CO 2 Sodium benzonate H2 O

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Illustration 14: Arrange the following illustration in order of increasing acidity (i) (ii) (iii) (iv) (v) Solution: (i) (ii) (iii) (iv) (v) CH3COOH HCOOH ClCH2COOH CH3COOH CH3COOH ClCH2CH2COOH Cl3CCOOH HCOOH, ClCH2COOH, CH3COOH CH3COOH, (CH3)2CHCOOH, (CH3)3CCOOH ClCH2COOH, Cl 2CHCOOH, Cl3CCOOH ClCH2COOH, CH3COOH CH3COOH, Cl2CHCOOH, CH3CH2COOH, Cl3CCOOH, ClCH2COOH CH3CH2COOH, ClCH2CH2COOH, (CH3)2CHCOOH,
(CH3)3CCOOH (CH3)2CHCOOH ClCH2COOH
(CH3)2CHCOOH CH3CH2COOH
ClCH2COOH < Cl 2CHCOOH < Cl 3CCOOH
CH3CH2COOH CH3COOH
ClCH2COOH
Cl2CHCOOH
Illustration 15: Acetic acid reacts with chlorine in the presence of catalyst, anhydrous FeCl3 to give (A) acetyl chloride (B) methyl chloride

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(C) Solution: (C) 2.
tri-chloro acetic acid
(D)
chloral hydrate
Conversion into functional derivatives

O R C OH R C Z O (Z = -Cl, -OR', -NH
2)
(a)
Conversion into acid chlorides

O R C OH SOCl 2 PCl 3 PCl 5 O R C
Cl Acid chloride
Examples:
COOH Benzoic acid PCl 5
1000 C
COCl POCl Benzoyl chloride
HCl
n C17H 35 COOH n SOCl2

Stearic acid Thionyl chloride
reflux
n C17H 35COCl SO2

Stearoyl chloride
HCl
CH3 COOH PCl3

Acetic acid
500 C
3CH3 COCl H3PO3

Acetyl chloride
Illustration 16: Benzoyl chloride is prepared from benzoic acid by Trans Web Educational Services Pvt. Ltd
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(A) (C) Solution: (C) (b)
Cl2, h SOCl2
(B) (D)
SO2Cl2 Cl2, H2O
Conversion into esters Conversion into Esters (Esterification): Carboxylic acid on reacting with alcohols in presence of
dehydrating agent (H2SO4 or dry HCl gas) gives esters. The reaction is known as esterification.
O RC
Acid
O
H+
+ R OH OH
R C OR
+ H2O
This reaction is reversible and the same catalyst, hydrogen ion, that catalyzes the forward reaction, esterification, necessarily catalyzes the reverse reaction hydrolysis. The equilibrium is particularly unfavourable when phenols
(ArOH) are used instead of alcohol; yet if water is removed

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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 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.

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O || C CH3
+ H+ OH CH3
+ OH || C OH
Protonation of the carbonyl group
CH3
+ OH || C OH O
OH | CH3 C O H +O
OH | CH3 C O H
-BH
O H B CH3
Tetrahedral intermediate being protonated at another site
CH3
CH3
Nucleophilic attack at the carbonyl group
Deprotonation of the intermediate
H+ + OH B || C O CH3 O H H OH | CH3 C O + H O CH3 H
CH3
O H B+ || C O CH3
CH3 +
Deprotonation of the carbonyl group

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Examples:
H COOH Benzoic acid CH 3OH Methanol Methyl benzoate
O H CH 3COOH Acetic acid Benzyl alcohol CH 2OH H3C C O CH 2
COOCH
H2 O
CH3
3 Trimethyl acetic acid
CCOOH
SOCl2
CH3
CCOCl
C2H5 OH
CH3
2 3 Ethyl trimethyl acetate
CCOOC H5
Illustration 17: Assign a structure to each compound indicated by a letter in the following equations.
O HO C (CH2) 9 O C OH
CH 3OH (excess) H2 SO4 ,
Solution:
A=
O CH3
(CH 2)9 OCH 3
Exercise 8: Trans Web Educational Services Pvt. Ltd

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Assign a structure to each compound indicated by a letter in the following equations.

O OH
CH 3CH2 -OH HCl(g),
SOCl2
OH
(c)
Conversion into amides
O R C OH SOCl 2 R C
O NH 3 R C
Cl An acid chloride
NH2 An amide
Example:
C6H5 CH2COOH
Phenyl acetic acid SOCl2
C6H5CH2COCl
Phenyl acetyl chloride
NH3
C6H5CH2CONH2
Phenyl acetat amide
Illustration 18: Discuss the reason for that a characteristic reaction of aldehydes and Ketones is one of nucleophilic addition while Acyl compounds yield Nucleophilic substitution product. Solution:

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R C=O R Nu
Nu CO R R
H Nu
Nu COH R R
Aldehyde or Ketone Nucleophilic addition
H R C=O L Nu H R L Nu+ CO R Nu CO HL+ R

Another acyl compound Elimination
Nu C = O + HL
An acyl compound Nucleophilic addition (L = OH, Cl, NH2, OR etc.) Nucleophilic substitution
The initial step in both reactions involves nucleophilic addition at the carbonyl carbon atom. 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 additionelimination Trans Web Educational Services Pvt. Ltd
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mechanism. Acyl compounds react as they do so because they all have good leaving groups attached to the carbonyl carbon atom. 3. Reduction
R COOH
LiAlH4
R CH2OH
10 Alcohol
Examples:
4(CH 3)3CCOOH
3LiAlH 4
Ether
[(CH 3)3CCH 2O] 4AlLi
2LiAlO 2
4H2
(CH 3)3CCH 2OH Neopentyl alcohol ( 2, 2 - dimethyl - 1 - propanol)

COOH CH 2OH
LiAlH 4 CH3 m - methyl benzyl alcohol
m - toluic acid
CH3
4. (a)
Substitution in alkyl or aryl group Halogenation Reaction) of Aliphatic Acids (Hell-Volhard-Zelinsky

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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. -
CH3
COOH
Cl2 /,P
Cl CH2
COOH
Cl2 ,/ P
Cl2CH COOH
Cl2 ,/ P
Cl3CCOOH
The function of the phosphorus is ultimately to convert a little of the acid into acid halide so that it is the acid halide, not the acid itself, that undergoes this reaction. P + X2 PX3 RCH2 COX
COX R COX CO 2H
R CH2 COOH + PX3

X2
R X
HX
H2O
R X
The halogen of these halogenated acid undergoes nucleophilic displacement and elimination same 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.

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COOH R Br COOH
NH3
ha log enated acid
COOH
R NH2
An
An
a min o acid
COOH
R Cl
NaOH
R OH
An
hydroxy acid
Examples:
CH 3COOH Acetic acid Cl 2/P Cl 2/P ClCH 2COOH Chloroacetic acid Cl 2CHCOOH Dichloroacetic acid Cl 2/P Cl 3CCOOH Trichloroacetic acid
CH3 CH 3CHCH 2COOH Isovaleric acid Br 2/P
CH3 CH 3CH CHCOOH Br

Bromoisovaleric acid
(b)
Ring substitution in aromatic acids: COOH position. deactivates and directs incoming electrophilic to meta
Example:

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COOH COOH HNO 3/H 2SO 4/Heat NO 2 m - nitrobenzoic acid
benzoic acid
Illustration 19: Hydrolysis of a compound A (C7H3Cl5) gives an acid B of the formula C7H4Cl2O2. Decarboxylation of acid yields a neutral substance (C), the nitration of which forms only one mono derivative (D). Identify A, B, C and D. Solution:
Cl CCl 3 A= B=
Cl COOH
Cl
Cl
Cl
Cl NO 2
C=
D=
Cl
Cl

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Illustration 20. Which of the following will not undergo HVZ reaction? (A) (B) (C) (D) Solution: (A) 2, 2-dimethyl propanoic acid propanoic acid acetic acid 2-methyl propanoic acid
CARBOXYLIC ACID DERIVATIVES There are four carboxylic acid derivatives. These are generally represented
O
as R C Z , where Z is halogen (usually Cl), OCOR , OR or NH2 (or NHR or NR2 ). (a) When Z is halogen (usually Cl), the derivatives are called as acid chlorides.
O R C Cl
||
(b)
When Z is
OR , the derivatives are called as esters. Trans Web Educational Services Pvt. Ltd
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O
(c) (d)
When Z is O C R' , the derivatives are called carboxylic anhydrides. Where Z is or NH2, the derivatives are called amides. When Z is NHR
||
NR2 they are called N substituted amides.
Synthesis of acid derivatives Carboxylic acid derivatives are exclusively prepared from carboxylic acids. The preparation methods of carboxylic acid derivatives are already discussed under the chemical reactions of carboxylic acids. Illustration 21: (a) (b)
PhLi
CH3
3
1. Excess CO2 2. H
A
2 eq. CH3Li H
COOH
CH3
COOH
Ag2 O Br2 ,
Solution: (a)
Ph O C O Ph
O C O H Ph
O C (A) OH
(b)
CH3
CH3
3
O
||
CCOOH
CCOOH
Ag2 O Br2 ,
CH3
C C OCH3 B
3
CH3
CBr
CO2

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Illustration 22: Suggest a likely mechanism for each of the following reactions. (a)
OH
C O
CX 3
H2O
RCOO
CHX 3
(b)
O C NH 2 NH 3 F
O C NH2
Solution: (a)
OH R
O C CX 3 R
O C OH CX 3
O NH 3 NH 2 C NH2
(b)
F
O C
O C NH2

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Exercise 9: (i)
O AlCl3 Zn(Hg) HCl
O
O (C10H10) F NBS G alc. KOH H2SO 4
A(C10H10O3)
B(C10H12O 2) SOCl 2
(C10H12O)E
LiAlH4
(C10H10O) D
AlCl3
H(C10H8)
(ii)
When heated with acid (e.g. conc. H 2SO4), O benzoyl benzoic acid yields a product of the formula C14H8O2. What is the structure of this product?
CHEMICAL REACTIONS OF ACID DERIVATIVES (i) Acyl chloride We have already seen that acyl chlorides are the most reactive of all acid derivatives. As a result, acyl chlorides are often selected as the starting material for the preparation any other acid derivative. Let us see how this is done.
O R C Cl R O C O Na R O C O O C R'

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O R C
O R C
O R C Cl R'NH 2 R
O Cl R OH R
O Cl NH 3 R C
O C NHR'
R'
NH2
O R C
O H3C C Cl H2NC 6H5
O Cl R'R"NH R C
O C6H5NHC Acetanilide
O OH CH 3COCl COOH COOH Acetyl salicylic acid (aspirin) O C CH3
NR'R"
CH3
HCl
Reaction of acetyl chloride with olefins Acetyl chlorides add on to the double bond of an olefin in the presence of a catalyst (AlCl 3 or ZnCl2) to form a chloro ketone which on heating, eliminates a molecule of hydrogen chloride to form an unsaturated ketone.

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O H3C CH CH2 CH 3COCl ZnCl 2 H3C CH Cl CH 2 C CH3
O H3C CH CH C CH3 HCl
Conversion into acids: Hydrolysis.

O R C Cl H2O R O C OH HCl An acid
Illustration 23: 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 CH 3COCl, 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. Trans Web Educational Services Pvt. Ltd
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O C CH3 +H2O Cl OC CH3 Cl +OH2
Transition state
O C CH3 Cl +OH2
Intermediate
O Cl + OH2
H
+
C CH3
C CH3
+Cl OH
Transition state
Product
Illustration 24: Hydrogenation of benzoyl chloride in the presence of Pd and BaSO4 gives (A) (C) Solution: (B) (ii) Carboxylic acid anhydrides Carboxylic acid anhydrides can be used to prepare esters and amides. benzyl alcohol benzoic acid (B) (D) benzaldehyde phenol

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O R C O O C R R'OH R O C OR' R O C OH
NH 3 excess O R C NH 2 R O C O NH 4
Anhydrides can be hydrolysed to get back acids.

O R C O O C R H2O 2R O C OH
Illustration 25:
MeO
CHO
(X)
CH3 COONa H3 O
COOH
The compound (X) is (A) (C) Solution: (C) Exercise 10: CH3COOH (CH3CO)2O (B) (D) BrCH2 COOH CHO COOH

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O O
CH3 -CH2 -OH TsOH
(iii) Esters Ester hydrolysis Acid catalysed esterification is an essentially reversible reaction. If you follow the backward course of reactions of esterification it gives you the mechanism for ester hydrolysis.
O R C OR' H2O H R
O C OH R'OH
Base promoted hydrolysis of esters: Saponification Esters undergo base promoted hydrolysis also. This reaction is known as saponification, because it is the way most of the soaps are manufactured. Refluxing an ester with aqueous NaOH produces an alcohol and the sodium salt of the acid.
O R C OR' NaOH H2O R
O C O Na R'OH

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This reaction is essentially irreversible because carboxylate ion is inert towards nucleophilic substitution. Mechanism
O R C OH OR' R
O C OH OR' R
O C OH R'O
O R C O ROH
If an ester is hydrolysed in a known amount of base (taken in excess), the amount of base used up can be measured and used to calculate the saponification equivalent; the equivalent weight of the ester, which is similar to the neutralization equivalent of an acid. Transesterification Esters can also be prepared by transesterification (an alcohol displacing another from an ester)
O C R OR' R" OH HA heat
O C R OR" R' OH
The mechanism of this reactions is quite similar to esterification. Trans Web Educational Services Pvt. Ltd
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O H2C CHCOCH 3 CH 3CH 2CH 2CH 2OH H2C O CHCOCH 2CH 2CH 2CH 3
Transesterification is an equilibrium reaction. To shift the equilibrium to right, it is necessary to use a large excess of the alcohol whose ester we wish to make or else to remove one of the products from the reaction mixture. Reduction of esters (i) Catalytic hydrogenation
O
||
CH3 CH2CH2 C O CH3
H2 , CuO, Hg / H 1500 C high pressure
CH3CH2CH2CH2OH CH3OH
(ii)
Chemical reduction
O
||
CH3 CH2CH2 C O CH3
LiAlH4 / H or Na / C2H5 OH
CH3CH2CH2CH2OH CH3OH
Reaction of esters with Grignard reagents The reaction of carboxylic esters with Grignards reagent is a good method for the preparation of 3 alcohols.

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O R C OR' R"MgX R O C R" R"MgX R OMgX C R" R" H R OH C R" R"
Initially ketones are formed. However, as we know, ketones themselves readily react with Grignard reagent to yield teriary alcohols. Claisen Condensation When ethyl acetate reacts with sodium ethoxide, it undergoes a
condensation reaction. After acidification, the product is a ethyl aceto acetate (commonly known as aceto acetic ester)
- keto ester,
O 2CH 3COC 2H5 NaOC 2H5 H3C
O C
O CH C Na OC 2H5 C2H5OH HCl
CH 3 CCH 2 COC 2H5
Condensation of this type is known as Claisen Condensation. For esters, it is the exact counterpart of the Aldol Condensation. Like the Aldol Condensation, the Claisen Condensation involves nucleophilic attack by a carbanion on an electron deficient carbonyl compound. In the Aldol Condensation, nuclephilic attack leads to addition (the typical reaction of aldehydes and ketones). In the Claisen Condensation, nucleophilic attack leads to substitution (the typical reaction of acyl compounds)

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Mechanism
O Step- 1 R CH H C OC 2H5 OC 2H5
O OC 2H5 RCH C OC 2H5
RCH
O Step- 2 R CH 2C OC 2H5 HC R
O C OC 2H5
R CH
O C OC 2H5
RCH 2
OC 2H5
O RCH 2 C CH R
O C OC 2H5 C2H5O
O Step- 3 RCH 2C
H C R
O COC 2H5 C2H5O
O C R C OC 2H5 C2H5OH
RCH 2C
This step is highly favourable and draws the overall equilibrium toward the product formation

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O Step- 4 RCH 2C C R O C OC 2H5 O O OH RCH 2C O CCOC 2H5 R Enol form
H3 O rapid
RCH 2 C CH C OC 2H5 R Keto form
When planning a claisen condensation with an ester it is important to use alkoxide ion that has the same alkyl group as the alkoxyl group of the ester. This is to avoid the possibility of transesterification. An intramolecular claisen condensation is called Dieckmann condensation. In general, the Dieckmann condensation is useful only for the preparation of five and six membered rings. Amides Preparation: In the laboratory amides are prepared by the reaction of ammonia with acid chlorides or, acid anhydrides. Basic Character of Amides: Amides are very feebly basic and form unstable salts with strong inorganic acids. e.g. RCONH2HCl. The structure of these salts may be I or II

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OH RC NH2 I II + O Cl
+ or RC NH3 Cl
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 Exercise 11: (RCONH)2Hg + H2O
PhHC
CH
CH O C
CH3
OH
PhHC
CH
CH OH
CH3
(Optically active)
Optically active
Exercise 12: An ester A (C4H8O2) on treatment with excess methyl magnesium chloride followed by acidification gives an alcohol B as the only Trans Web Educational Services Pvt. Ltd
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organic product. Alcohol B on oxidation with NaOCl followed by acidification, gives acetic acid. Deduce the structures of A & B. Show the reactions involved. (a) Hydrolysis of amides Amides undergo hydrolysis when they are heated with aqueous acid or aqueous base. Acidic hydrolysis
O R C NH2 H3O
H2 O
O R C OH NH 4
Basic hydrolysis
O R C NH2 OH
H2O
O R C O NH 3
(b)
Reduction of amides Amides are reduced by Na/C2H5OH or by LiAlH4 to a primary amine.

O R C NH2 4H
Na / C2H5 OH
CH 2 NH2
H2O
(c)
Reaction with P2O5

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When heated with P2O5 amides are dehydrated to cyanides.

O R C NH2
P2 O5 H2 O
Amides may also be converted to cyanides by PCl 5.

O R C NH2
PCl5
2HCl
RCCl 2NH 2
(d)
Hofmann rearrangement Amides with no substitutents on the nitrogen react with solutions of Br2 or Cl 2 in NaOH to yield amines through a reaction known as Hofmann rearrangement.
O R C NH2 Br 2 4NaOH RNH 2 2NaBr Na 2CO 3 2H2O
Mechanism

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O R C N
H OH H R
O C N Br H Br R
O C
H OH N Br Br
O R N OH C O -Br R C N Br
OH R N C O OH R N C O R
H N C
O Carbamate ion O
OH
RNH2
CO2
OH
HCO3
Illustration 26: Acetamide reacts with NaOBr in alkaline medium to form (A) (C) Solution: Trans Web Educational Services Pvt. Ltd
NH3 CH3CN
(B) (D)
CH3NH2 C2H5NH2
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(B) Illustration 27:
A(C8H8O)
NH 2OH/HCl
B H D
and
C H E
O
Alc. KOH
H3C C Cl
alc. KOH G (C6H7N)
F (C7H6O2)
Keeping in mind the fact that B, C, D and E are all isomers of molecular formula (C8H9NO), identify A to G. Solution:
O C (A) CH3
Ph (B) H3C C N
OH
Ph (C) H3C C N OH
O (D) Ph C NH CH3

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O (E) H3C C NH Ph
(F) Ph COOH
(G)
Ph
NH2
Illustration 28: Formic acid and acetic acid may be distinguished by reaction with (A) (B) (C) (D) Solution: (B) Exercise 13: (a) (b)
CH 2 COOH
NH 3
sodium dilute acidic permanganate 2, 4 dinitrophenylhydrazine sodium ethoxide
CHCOOH H2C CH CH CH2 CHCOOH A
Exercise 14: Identify A, B, C and D? (i) RCOOH

ND3 /
KOH Br2 /

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(ii)
RCOOH
NH3 /
KOD Br2 /
Exercise 15: (i)

Ph
O C OH
SOCl 2
H2/Pd(BaSO4)
C CH2N2 1 eq. DIBALH B H
Find out A, B and C (ii)

ConvertPh O C OH to PhNH2
(iii)
(a)
O CH 3C OH
i 2 eq. CH 3 Li ii H +
(b)
C O C
O
1 eq. CH 3CH 2OH 1. LiAlH4 2. H
B C
What are A, B and C? Exercise 16: 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), C4H6O4. On treatment with excess of Trans Web Educational Services Pvt. Ltd
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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). Exercise 17: An acidic compound (A), C4H8O3 loses its optical activity on strong heating yielding (B), C4H6O2 which reacts readily with KMnO4. (B) forms a compound C with SOCl 2, which on reaction with (CH3)2NH gives (D). The compound (A) on oxidation with dilute chromic acid gives a compound (E) which on gentle heating readily gives (F), C3H6O. Give structures of (A) to (F) with proper reasoning.

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ANSWERS TO EXERCISES Exercise 1: (i)

Br
O
Mg / Ether
MgBr O
OMgBr
H3O
OH
KMnO4 / H
OH
OH
i CO2 ii H3O
(ii)
HC
CH
HBr
CH2
CHBr
Mg / Ether
CH2
CH MgBr
Exercise 2: (i) Boiling points of formic acid (100.3C) and water (100C) are almost equal.
CH2
(ii)
H2C
HBr
H3C
CO2 H3O
Br
Mg / ether
Br H3C Mg H3C COOH
Exercise 3:
OH
OH
A = H3C
CH3
CN
B=
H3C CH3 OH

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O
O
C=
OH H3C CH2
D=
HO
OH
CH3
H3C
E=
H3C OH
Exercise 4:
OH Cl A= B= C=
OH CN D=
OH COOH E=
COOH O
Exercise 5: (A)
(H3C) 2HC CH CH3
O C O CH CH3
COOH
CH(CH 3)2
(B) H3C
CH
CH
CH3 CH3
(C) H3C
CH OH
CH CH3
CH3
(D) H3CHC (E)

H3C CH
C(CH )2 3
CH(CH 3)2
OSO 2C6H5

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(F)
H3C
CH Br
CH CH3
CH3
Exercise 6: Since neutral compound A on hydrolysis gives an acid B and neutral compound C, it must be an ester.
Ester
A
Acid Alcohol
B C
Further since the acid B reduces mercuric chloride, it must be formic acid (HCOOH) which is the only reducing carboxylic acid. So A must be HCOOC2H5.
HCOOC2H5
A
HCOOH C2H5 OH
B C
HCOOH 2HgCl2
C2H5 OH
C NaOH I2
Hg2Cl2
2HCl CO2
HCOOH CHI3
Exercise 7: (i) In formate ion resonance gives rise to identical bond lengths
HCO O O HC = O O
HC

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Whereas no such resonance is noticed in formic acid (H COOH) and thus CO bonds are different in HCOOH (ii) Acetic acid undergoes intermolecular Hbonding to form dimeric state (CH3COOH)2 and thus results in double molecular weight. Exercise 8:
O O (b) A= OH
O O B= Cl CH3
CH3
Exercise 9: (i)
O C A=
O CH 2 CH 2 COH
B=
O CH 2 CH 2 CH 2 COH
O CH 2 CH 2 CH 2 C C=
D Cl =

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E=
F=
OH
Br G=
H=
(ii)
O C
O C
C OH
C O (Friedel - crafts alkylation)
Exercise 10:
O O OH O CH3
(c)
A=
Exercise 11:

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Ph CH CH CH O Ph C O Ph CH3 OH Ph CH CH CH O C O O Ph C O Ph CH CH CH OH CH3 Ph O C OH Ph CH CH CH O CH3 O CH3
Exercise 12:
O A= H C O HC
CH3 B = H3C CH3
OH CH CH3
Exercise 13: (a)
COOH (Diel's - Alder Reaction) COOH (A)
(b)
H2C H2C
O C NH C O

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Exercise 14:
(i) (ii)
RCOOH RCOOH
ND3 ,
RCOND2 (A) RCONH2 (C)
KOH Br2
KOD Br2
RND 2 (B) R NH2 (D)
NH3 ,
Exercise 15: (i)

A = Ph
O C
O C = Ph C H
O OH SOCl 2 Ph C Cl
O Cl B = Ph C OCH 3
(ii)
Ph
O C
O NH 3 Excess OH Br 2 Ph NH 2 Ph C NH 2
(Hoffmann rearrangement)
(iii)
(a)
O CH 3C OH CH 3Li H3C
O C OLi CH 4 CH 3Li H3C
OLi C CH3 H O OH CH3 H3 C C CH3 OH OLi
H3C
C (A)

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(b)
O C O CH 2 CH3 CH 2OH
C O (B)
OH
CH 2OH
(C)
Exercise 16: A is (CH3)2 C = CHCH2CH2COCH3 6methyl5hepten2one B is CH3COCH2CH2CHO 4oxopentanal C is HO2 CCH2 CH2 CO2 H 1, 4butandioic acid D is succinimide

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CH2 CH2 O=C N | H C=O
Exercise 17:
OH
|
A. C. E.
CH3 CH3 CH3
C H CH2 O
||
COOH
B. D. F.
CH3 CH3 CH3
CH CH O
||
CH COOH O
||
CH O
||
CH C Cl O
||
CH C N CH3
C CH2
C OH
C CH3

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MISCELLANEOUS EXERCISES Exercise 1: Suggest a suitable oxidising agent for the conversion.
CH 3
2
C = CHCOCH 3
CH 3
C = CHCO 2 H
Exercise 2: Arrange the following compounds in order of increasing acid strength:

i CH 3CH 2 CH Br COOH,CH 3 CH Br CH 2 COOH, CH 3
2
CHCO 2 H, CH 3CH 2 CH 2 COOH
(ii)
Benzoic acid, 4-nitrobenzoic acid, 3, 4-dinitrobenzoic acid, 4methoxybenzoic acid.
Exercise 3: Why does benzoic acid not undergo Friedel-Crafts reaction? Exercise 4: Why carboxylic acids do not form oximes? Exercise 5:

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Arrange the following in decreasing order of the boiling points: CH3CH2CH2CH2OH, CH3CH2OCH2CH3.CH3CH2CH2COOH. Exercise 6: Why is an amide more acidic than amines? Exercise 7: Identify (A) and (B) in the following sequence of reactions. (i) (ii)
CH CH
CH3 COOH
CH3COOH excess HgSO4
AIPO4 1075K
distil
B CH3CHO
B
CH3 COOH
Exercise 8: Why excess amine is necessary in the reaction of an acyl chloride with an amine? Exercise 9: Write the structure of the products (a) (b) acetic acid + benzyl alcohol propionic acid + isobutanol
Exercise 10: Trans Web Educational Services Pvt. Ltd

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Complete the following:

H 5 C6 O OH
PCl5
OK
heat
H3C O
H2 O
Electrolysis

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ANSWERS TO MISCELLANEOUS EXERCISES Exercise 1: Alkaline KMnO4, acidified K2Cr2O7 or HNO3 can not be used since all of these will cleave the molecule at the site of double bond giving a mixture of ketone/acids. The most suitable reagent for this oxidation is NaOI (I2/NaOH) since methyl ketones on treatment with NaOH undergo Iodoform reaction to give Iodoform alongwith the Na salt of a carboxylic acid having one carbon atom less than the starting methyl ketone.
CH3 H3C C CH
O C CH3 3NaOI H3C
CH3 C CHCOONa
H / H2O
CHI3
2NaOH
4 Methylpent 3 en 2 one (Mesityl oxide)
CH3 H3C C CHCOOH
3 Methylbut 2 en 1 oic acid

( , Dimethylacrylic acid)
Exercise 2: (i) We know that +I, effect decreases while I effect increases the acid
strength of carboxylic acids. Since +I effect of isopropyl group is more than that of propyl group, therefore, (CH 3)2CHCOOH is a weaker acid than CH3CH2CH2COOH. Trans Web Educational Services Pvt. Ltd
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Further
since
effect
decreases
with
distance,
therefore,
CH3CH2CH(Br)COOH is a stronger acid than CH 3CH(Br)CH2COOH. Thus, the overall acid strength increases in the order:
CH3 H3C CH COOH < CH 3 H2C CH 2 COOH
< H3C
CH Br
CH 2 COOH < H3C
CH 2 CH Br
COOH
(ii)
Since electron donating groups decrease the acid strength, therefore, 4methoxybenzoic acid is a weaker acid than benzoic acid. Further since electronwithdrawing groups increase the acid strength, therefore, both 4nitrobenzoic acid and 3, 4dinitrobenzoic acids are stronger acids than benzoic acid. Further due to presence of an addition NO2 at m position w.r.t COOH group, 3, 4dinitrobenzoic acid is a little stronger acid than 4nitrobenzoic acid. Thus the overall acid strength increases in the order:
4 methoxybenzoic acid benzoic acid 4 nitrobenzoic acid 3,4 dinitrobenzoic acid
Exercise 3:

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Due to deactivation of the benzene ring by electrons withdrawing effect of the Exercise 4: Due to resonance between lone pairs of electrons on the O-atom of the OH group and C = O, the carboxyl carbon is less electrophilic than carbonyl carbon in aldehyde and ketones. Therefore, nucleophilic addition of NH2OH to the C = O group of carboxylic acid does not occur and hence carboxylic acids do not form oximes. Exercise 5: CH3CH2CH2COOH > CH3CH2CH2CH2OH > CH3CH2OCH2CH3 Hint: Due to hydrogen bond Exercise 6: COOH group.
O R NH2 R
O NH 2
Firstly due to delocalization of lone pair of electrons of N atom over the C = O group, amino group gets a positive charge which makes NH bond weak. Secondly the anion left after removal of a proton is stabilized by resonance. Trans Web Educational Services Pvt. Ltd
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O R NH R O NH
In amines no such stabilization is possible. Exercise 7: (i) (ii)
CH
Acetylene
CH
CH3 COOH excess HgSO4
CH3
CH OOCCH3
Ethylidene diacetate
distil 2
CH3CO 2 O CH3CHO
Acetic anhydride Acetaldehyde
CH3 COOH
Acetic acid
AIPO4 , 1075K H2 O
CH2
C
Ketone
CH3 COOH
CH3 CO 2 O
Acetic anhydride
Exercise 8:
R NH2
R Cl R NHR'
HCl
The products of this reaction are an amide and HCl. HCl formed in this reaction protonates unreacted amine and since protonated amines are not nucleophiles, the reaction with acyl chloride stops.
R NH2
HCl
RNH3
No nucleophilic site
Cl
O R Cl
RNH3
No reaction

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Hence, reaction must be carried out with twice as much as amine as acyl chloride. Exercise 9: (a) (b) CH3COOCH2Ph CH3CH2COOCH2CH(CH3)2
Hint: Esterification Exercise 10: (a)
COOH
COCl
PCl5
HCl
POCl3
(b)
CH3 COOK H2O
electrolysis
CH3COO
At anode:
CH3
2CH3COO
CH3
2CO2
2e
At cathode:
2e 2H2O 2OH H2

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SOLVED PROBLEMS
Subjective:
Board Type Questions Problem 1: Write chemical reactions to effect the following transformation. (a) (b) (c) (d) Solution: (a) (b) (c) Butan-1-ol to butanoic acid Benzyl alcohol to phenylacetic acid Bromobenzene to benzoic acid p-methylacetophenone to benzene-1, 4-dicarboxylic acid
CH3
CH2
CH2
CH2
OH
Aq. KMnO4
CH3 CH2CH2COOK Pot. Butanoate
Dil. H2 SO4
CH3CH2CH2COOH Butanoic acid
Butan-1-ol
C6H5 CH2 OH
Benzyl alcohol
PBr3 or HBr
C6H5 CH2Br
Benzyl bromide
KCN
C6H5 CH2 CN
Hydrolysis H / H2 O
C6H5 CH2 COOH

Phenylacetic acid
C6H5Br
Bromo benzene
Mg dry ether
C6H5MgBr
i.e. CO 2 (s)
Dry ice
C6H5COOMgBr
H3 O
C6H5COOH
Benzoic acid
Phenyl mag. bromide

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(d)
H3C
COCH 3
KMnO4 / KOH,
KOOC
COOK
Dil. H2SO4
HOOC
COOH
P-methylacetophenone
Dipotassium benzene- 1, 4dicarboxylate
Benzene- 4-dicarboxylic acid 1,
Problem 2: Arrange the following compounds in increasing order of their boiling points: acetic acid, methyl formate, acetamide, propan-1-ol Solution: (i) Out of all these compounds methyl formate does not undergo Hbonding therefore, its boiling point is the lowest. (ii) Amongst the remaining three compounds intramolecular Hbonding is most extensive in acetamide, followed by acetic acid and least in propan-1-ol. Therefore, their boiling points decrease in the same order i.e. acetamide>acetic acid>propan-1-ol. Thus, the overall increasing order of their boiling points is methyl formate<propan-1-ol<acetic acid<acetamide.

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Problem 3:
O H3C C OH SOCl 2 A H2/Pd BaSO 4 B HCN C H3 O D
Solution:
O A = H3C C Cl B = H3C
O C H O C = H3C
OH C H O CH C O CH3 CN
OH D = H3C C H COOH E=
C H3C CH O
Problem 4: A dicarboxylic acid (A), C4H6O4, gave a compound (B), C6H10O4 upon treatment with excess of methanol and a trace of H 2SO4. Subsequent treatment of (B) with LiAlH 4 followed by usual work up gave C, C4H10O2. Heating of A yielded D, C4H4O3. Assign structures to A, B, C and D. Solution:

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O H2C H2C COOH B= COOH O D= H2C H2C C O C O H2C H2C C C O OCH 3 OCH 3 CH 2CH 2OH CH 2CH 2OH
A=
C=

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IIT Level Questions Problem 5: Two organic compounds A and B have vapour densities 15 and 30 respectively. (A) reduces Fehling solution, but does not react with Na2CO3. (B) does not reduce Fehling solution but gives effervescences with Na2CO3. B when treated with a concentrated solution of base followed by prolonged heating gives a compound C(C 3H6O). Identify A, B and C. Solution:
O (A) H C O (B) H3C C OH H
(C) H3C
C O
CH3
Problem 6: An organic acid A, C3H4O3 is catalytically reduced in presence of ammonia to give B, C3H7NO2. B reacts with acetyl chloride,

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hydrochloric acid and alcohols. It can also react with nitrous acid to give another compound C, C3H6O3, 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
H3C
COOH
on catalytic reduction keto group is converted into secondary alcohol which with ammonia will give amino acid, i.e.,
O || CH3 C COOH OH | CH3 CH COOH NH2 | CH3 CH COOH
reduction
HNH 2
H2O
with nitrous acid, B, react to give

NH2 | CH3 CH COOH + HNO2 (B) OH | CH3 CH COOH + N2 + H2O (C)
Problem 7: Compound A (C6H12O2) on reduction yields two compounds B and C. The compound B on oxidation gave D, which on treatment with Trans Web Educational Services Pvt. Ltd
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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 a monobasic acid (mw = 60). Deduce the structures of A to E. Solution:
Re duction
B C
H2/Pt
[O]
F
O
monobasic acid mol. wt. 60
OH
From the molecular weight data F comes out to be CH 3COOH. If we work back B is CH3CH2OH and D is CH3CHO.
CH3 CHO
D OH
CH3
HC
E
CH CHO
H2 / Pt
CH3CH2CH2CH2OH
C
Aldol condensation
From here we can deduce that reduction of A with LiAlH 4 gives two alcohols. So A must be an ester. Hence (A) comes out to be CH3CH2CH2COOC2H5. Problem 8: An organic compound (A) on treatment with acetic acid in the presence of sulfuric acid produces an ester (B). (A) on mild oxidation Trans Web Educational Services Pvt. Ltd
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gives (C). (C) with concentrated KOH followed by acidification with dil. HCl regenerates (A) and produces (D). (D) with phosphorous pentachloride followed by reaction with ammonia gives (E). (E) on dehydration produces hydrocyanic acid. Identify compounds A, B, C, D and E. Solution:
O E -H2O HCN So (E) must be H C NH2
O H C (D) OH PCl 5 H
O C Cl NH 3 H
O C (E) NH2
(A) reacting with acetic acid is giving an ester (B). So (A) must be an alcohol. (A) alcohol on mild oxidation gives (C). Hence (C) is an aldehyde. (C) with conc. KOH followed by acidification is yielding (A)
O
alcohol and H C OH (D). So this reaction is cannizzaro reaction. So A must be CH3OH.

O
||
||
CH3 OH A
CH3 (B)
C O CH3
HCHO C
HCOOH D
HCONH2 E
Problem 9: An aromatic compound A on treatment with CHCl 3 and KOH gives B & C, both of which, in turn give the same compound D when distilled with Zn dust.Oxidation of D yields E of formula C 7H6O2. The sodium Trans Web Educational Services Pvt. Ltd
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salt of E on heating with soda lime gives F which can also be obtained by distilling A with Zn dust. Identify A, B, C, D, E and F. Solution: Molecular formula of (E) is C7H6O2 and reaction of its sodium salt with soda lime (decarboxylation) to form (F) indicates that (E) and (F) should be C6H5COOH and C6H6 respectively. Since (F) is also obtained from (A) by reaction with Zn dust, it indicates that (A) should be phenol. Nature of (A) as phenol is confirmed by the fact that it explains all the given reactions.
OH
OH CHO CHCl
3
OH
KOH (A)
cd
ust ti o n
B&C Zn dust COOH CHO
CHO
Zi n
di s
tilla
NaOH Soda lime (F) (E)
[O]
(D)

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Problem 10: Five isomeric para disubstituted aromatic compounds A to E with molecular formula C8H8O2 were given for identification. Based on the following observations, give structures of the compounds? (i) (ii) (iii) (iv) Solution: (A) and (B) gives tollens test. Hence must contain aldehyde group. But (B) shows phenolic test also. Hence (A) & (B) are
OCH 3 CH 2OH OH
both A and B form a silver mirror with Tollens reagents; B gives a positive test with FeCl 3 solution also. C gives positive iodoform test. D is readily extracted in NaHCO3 solution. E on acid hydrolysis gives 1, 4 dihydroxy benzene.
or
CHO (A)
CHO
CH 2CHO (B)
(C) shows Iodoform test show it must contain Therefore (C) is

COCH
3
||
C CH3
group.
OH (C)

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(D) shows presence of carboxylic group. Hence (D) and (E) are
COOH OH
CH3 (D)
O (E)
CH
CH2
Problem 11: An organic compound A, C8H4O3 in dry benzene in the presence of anhydrous AlCl 3 gives compound B. The compound B on treatment with PCl 5, followed by reaction with H2/Pd (BaSO4) gives compound C, which on reaction with hydrazine gives cyclised compound D (C14H10N2). Identify A, B, C and D. Solution: Nature of reagents in the conversion of A to B indicates that the reaction must be Friedal crafts reaction.

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O C O C (A) O (B) C 6H 6 AlCl 3 C O OH C O H2/Pd BaSO C6H5 O C N N CHO (D) (C) NH 2NH 2 C6H5
4
O C C6H5 PCl 5
O C C6H5
Cl
Problem 12: An organic compound A, C6H10O on reaction with CH3MgBr followed by acid treatment gives compound B. The compound B on ozonolysis gives compound C, which in presence of a base gives 1- acetyl cyclopentene. The compound B on reaction with HBr gives compound D. Write the structures of A, B, C and D. Solution: As B undergoes ozonolysis to form C, if must have a double bond. C in the presence of base gives condensation.
O CH3 O (i) CH 3MgBr (ii) H (A) (B) O3 CH3 H (C) O OH OH COCH 3 -H2O COCH 3
unsaturated ketone, so it is aldol

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CH3 H3C HBr Br
(B)
(D)
Problem 13: A phenolic compound (A), C7H6O2 on mild oxidation gives a highly volatile oil (B). A forms (C) on reaction with dimethyl sulphate in alkali. Oxidation of (C) with hot KMnO4 gives (D), the silver salt of which reacts with bromine water followed by heating gives (E) containing about 72% bromine. Give structures A to E. Sol.
OH
O C H
A can be
CHO
(ortho, meta or para)
But it must be ortho because on oxidation, it gives a highly volatile oil indicating that there is intramolecular hydrogen bonding.

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OH CHO
(A) OH CHO Oxidation OH COOH
(A) OH (CH 3)2SO 4
(B)
OCH 3 CHO Oxidation (C)
OCH 3 Br COOH Ag2O Br 2/H 2O (D)
OCH 3 Br
Br (E)
% of bromine in E
240 100 345
69.56%
Problem 14: An aromatic compound (A) gave a mixture of two isomeric products 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 oxidised with per benzoic acid to G. Hydrolysis of G gave H and E. An anhydride of E and its sodium salt on condensation with PHCHO produced cinnamic acid. H on reaction with phthalic anhydride in H 2SO4 gave phenolphthalein. Suggest structures for A to H.

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Sol.
O C H5C6 (A) per benzoic acid C6H5CO 3H O C H3C H2O H O H3C C (E) OH C6H5OH (H) O C6H5 (G) H3C (C)
H 2 SO 4 ,
H5C6 CH3 H2N OH H3C H5C6 C N C (B) N
OH
OH
CH 3CONHC 6H5 (D)
CH 3CONHC 6H5 (D)

(CH 3CO) 2O
OH H2 O
CH 3COOH (E)
CH 3COONa
C6H5NH 2 (F)
H5C6 COOH
C6H5CHO
Anhydride of (E) (Perkin Reaction) Formation of cinnamic acid proves that the anhydride is acetic anhydride. Hence E is acetic acid.

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Objective:
Problem 1: End products of the following sequence of reactions is

O
1. I 2 + NaOH 2. H + ,
C O
CH3
(A)
CHI 3 ,
(B)
CHI3 ,
COOH
CHO
(C)
CHI 3 ,
(D)
CHI3 ,
COOH COOH
Solution: Intermediate is
O
COOH
which loses CO2 on heating.
(C) Problem 2:

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O
||
O
||
End product of the reaction H3C C CH2 CH2 CH2 COH (A)
O O H3C
O
1. NaBH4 2. H2O, H
is
(B
CH3
) (D
O
(C)
H3CHC OH
CH 2CH 2CH 2CH 2OH
) CH 3CCH 2CH 2CH 2CH 2OH
Solution: NaBH4 reduces ketonic group but not acidic group

H3C CH OH CH 2 CH 2 CH 2 COOH
is the intermediate which forms cyclic ester.

O
O H3C
(A) Problem 3: R (A) (C) CH2 CH2OH can be converted into R (B) (D) CH2CH2COOH. The
correct sequence of reagents is

PBr3 , KCN, H /H2O
PBr3 , KCN, H2
KCN, H
HCN, H
Solution: Trans Web Educational Services Pvt. Ltd

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R CH2 CH2OH
PBr3
R CH2
CH2
Br
KCN
R CH2
CH2
CN
H H2O
R CH2
CH2
COOH
(A) Problem 4: The ease of alkaline hydrolysis is more for (A)

COOCH
3
(B)
COOCH
NO 2
Cl
3
(C)
COOCH
(D)
COOCH
OCH 3
Solution: There is more electron deficiency on carbonyl carbon in

COOCH
3
NO 2
(A) Problem 5: Trans Web Educational Services Pvt. Ltd

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Which of the following undergoes HVZ reaction? (A) (C) Solution: None of these contains (D) Problem 6: The product C in the reaction CH3 COOH (A) (C) Solution: CH3CH = CHCHO CH3CH2CHO (B) (D) - hydrogen. HCOOH C6H5COOH (B) (D) CCl3COOH none
PCl5
H2 / Pd, BaSO4
dil. NaOH
CH3CH = CHCOOH CH3CH2CH2COOH
O CH3 COOH
PCl5
CH3COCl
H2 / Pd, BaSO4
||
CH3
C H
OH
CH3
CH
CHCHO
Problem 7: The end product of the reaction is

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Br 2 A H2, Pt B KCN H3 O C
C is (A) (C) Solution: propanoic acid malonic acid (B) (D) adipic acid succinic acid
Br
Br
COOH
Br (A)
Br (B)
COOH Adipic acid (C)
Problem 8: Find out D in the following sequence

conc. H2SO 4 OH A NBS B KCN C H3O D
(A)
COOH
(B)
CH3
CH3
COOH
(C)
COOH
(D)
COOH
COOH
CH3
Solution: Trans Web Educational Services Pvt. Ltd

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Br
OH
conc. H2SO 4
NBS
KCN COOH CN
Problem 9: The order of the acidic strength of following acids is (i) CH3CH2COOH (A) (C) Solution: sp hybridized carbon is most electronegative and it stabilizes the carboxylate ion. to the maximum extent. Problem 10: i > ii > iii ii > i > iii (ii) CH2 = CHCOOH (B) (D) iii > ii > i iii > i > ii (iii) CH CCOOH
OH COOH H3C CrO3 A
A and B are (A) CH3COCH2COOH, CH3COCH3 Trans Web Educational Services Pvt. Ltd
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(B) (C) (D) Solution:
CH3CH(OH)CH3, CH3COCH3 CH3COCH3, CH3COOH CH3CH = CHCOOH, CH3CH = CH2
OH COOH CrO 3
O COOH (A)
(B)
(A) Problem 11:
CH3 CH2COOH
NaHCO3
A a gas
i Me MgX ii H3 O
B is C is C14 (A) (C)

*
CH3 COOH
*
(B) (D)
CH3COOH
*
CH3CH2 COCH3
CH3 COCH3
Solution:
CH3CH2COOH
*
NaHCO3
CH3CH2COONa H2O CO2

*
CO2
MeMgX
H3 O
CH3 COOH
(A) Trans Web Educational Services Pvt. Ltd

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Problem 12:
OC2H5
C2 H5O
CH2CO2C2H5
A is (A)
O OC2H5
(B)
O CO2C2H5
(C)
(D)
O
O O
Solution:
O C O C2H5
OC 2H5 CH 2CO 2C2H5
C2 H5 O
OC 2H5 CH C O O C2H5
Problem 13: The carboxylic acid which has maximum solubility in water is (A) (C) phthalic acid malonic acid (B) (D) succinic acid salicylic acid

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Solution: Salicylic acid has intramolecular hydrogen bonding. So it is least soluble. Out of the first three acids malonic acid has smallest non polar alkyl part. So it is most soluble. (C) Problem 14:
Br
O H CH3
i Mg/ ether ii CO2 iii H3O
The final product is (A)

COOH
(B)
O
MgBr
CHO
H CH3 O
CH3
(C)
COOH
(D) None of these
CHO CH3
Solution:

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Br MgBr COO COOH
Mg / ether
CO2
O H CH3 H
O H3O H O CH3 CHO
CH3
CH3
Problem 15: In the reaction CH3 CH2COOH Identify C. (A) (C) Solution:
O CH 3CH 2COOH NH 3 H2CH 3C C ONH 4 O
NH3
P2 O5
C,
CH3CH2CN CH3CH2CH2OH
(B) (D)
CH3CH2CH2NH2 (CH3CH2CO)2O
H3C
CH 2 C
NH 2
P2O 5 H3C CH 2 CN
Fill in the blanks Problem 16: Benzoic acid has a.pKa value than phenol. Solution: Trans Web Educational Services Pvt. Ltd
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Lower Problem 17: The acid derivatives are hydrolysed..readily in either alkaline or acidic medium than in neutral medium. Solution: More Problem 18: O-nitrobenzoic acid isacid than p-nitrobenzoic acid. Solution: Stronger Problem 19: Malonic acid on heating with phosphorous pentoxide gives.. Solution: Trans Web Educational Services Pvt. Ltd
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Carbon suboxide (C3O2) Problem 20: Cinnamic acid can be prepared from benzaldehyde
using.reaction and shows..isomerism. Solution: Perkin, geometrical True and False Problem 21: Methanoic acid like ethanoic acid can be halogenated in the presence of red phosphorous and Br2. Solution: False: Due to the absence of - hydrogen, methanoic acid can not be halogenated by using Br2/red P.

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Problem 22: As the number and size of the substituents around the increases the rate of esterification slows down. Solution: True Problem 23: The boiling point of propionic acid is less than that of n-butanol, an alcohol of comparable molar mass. Solution: False: Due to extensive intermolecular hydrogen bonding, and the cyclic dimer formation, propanoic acid has higher b.p. than n-butanol. Problem 24: The conjugate base of chloro acetic acid is more resonance stabilized than the conjugate base of acetic acid. COOH group

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Solution: True: Due to the presence of chlorine atom. Problem 25: The correct order of acid strength of the given acid is
H 2 SO4 > CH3COOH > H 2O > HC CH > C2 H5 OH
Solution: False: The correct order is H2SO4 CH3CO2H H2O C2H5OH HC CH .

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ASSIGNMENT PROBLEMS
Subjective:
Level-O 1. Describe the following: (a) 2. Saponification (b) Decarboxylation
How is acetic acid prepared from? (i) Acetylene (ii) Ethyl alcohol
3. 4.
How is Grignard reagent employed to prepare a carboxylic acid? Explain the following about acetic acid: (i) (ii) (iii) Its boiling point is higher than that of n propanol. It is weaker acid than formic acid. It is stronger acid than phenol.
5.
Acid anhydrides have higher boiling points than the corresponding carboxylic acids.
6.
Give IUAPC name for each of the following compounds. (a) H3CHC CHCOOH (b)
COOH

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(c)
CHCOOH CH3
(d) Cl2CHCOOH
(e)
O HO C(CH 2)3COOH
7.
HOCH2CH2CH2CH2COOH can be prepared from HOCH 2CH2CH2CH2Br in two ways. One is through Grignard synthesis and the other through nitrile synthesis. Which method would you prefer?
8.
Why the bond length of C = O in carboxylic acids is bit longer than in aldehydes?
9.
Acetic acid can be halogenated in presence of phosphorus and chlorine but formic acid cannot be halogenated in the same way.
10.
During the preparation of esters from a carboxylic acid and an alcohol in the presence of an acid catalyst, the water or the ester should be removed as fast as it is formed. Explain.
11.
Identify the products in the following reactions (a)

HCOOCH3
i) CH3CH2MgBr / ether ii) H3O
(b) C6H5CHO CH3CH2CHO
dil. NaOH
12.
Explain why benzamide is less easily hydrolysed than methyl benzoate.

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13.
There are two NH2 groups in semicarbazide. However only one is involved in the formation of semicarbazones. Explain.
14.
Carbon-oxygen bond length in formic acid are 1.24 and 1.36 but in sodium formate both the carbon-oxygen bonds have same value i.e.1.27 .
15.
Acid and acid derivatives although contain >C=O group, do not undergo the usual properties of carbonyl group explain.

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Level I 1. Convert the following: (a) (b)

Acetaldehyde Butane 1 3 diol ,
Acetaldehyde
But 2 enoic acid
2. 3.
Discuss the action of heat on
- hydroxy carboxylic acids.
Compare the Ka1 and Ka2 values of maleic and fumaric acids.
4.
NH2 are soluble in aqueous acids like HCl, H 2SO4 etc but R C NH2
||
are almost insoluble in those acids. Explain. 5. What happens when: (i) (ii) 6. Dry chlorine is passed through acetic acid in presence of sunlight. Formic acid is reacted with ammonical silver nitrate solution.
Complete the following equations by writing the missing A, B, C.

CH3 CH2MgBr A CH3 CH2CH2CH2OMgBr
H3 O
KMnO4
7.
What is A and B?
O
CrO3 warm
C4H8O3
H3C
CH3
CO2

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O
8.
(a) (b)
||
CH3
CH
CH CH2
C OH
2
HO C CH2 || O
C CH3
C OH || O
9. 10.
Cite 2 reasons why malonic acid does not form a cyclic anhydride.
CH CH
H2SO4 HgSO4
SOCl2
C6H6 anhy AlCl3

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Level II 1. A hydrocarbon A, (C8H10), on ozonlysis gives compound B (C4H6O2) only. The compound B can also be obtained from the alkyl bromide, C (C3H5Br) upon treatment with magnesium in dry ether, followed by CO2 and acidification. Identify A, B and C and also gives equations for the reactions. 2. Predict the product of the reaction given below, given that it is formed under high dilute conditions. EtO2C CH2 4 CO2Et
EtO cat
3.
Compound (A), C5H8O2, liberates CO2 on reaction with sodium bicarbonate. (A) 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.
4.
An organic compound (A) reacts with PCl 5 to form a compound (B). A also reacts with NaOH to form a compound (C). Both B and C react together to form a compound D (C6H10O3). What are A, B, C and D?
5.
a
O H3C H3C H CH3

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O b
B2H6 H
H3C
CH 2OH
1 Ag2 O 2. Br2
O 2N
Br
6.
The active ingredient of an insect repellent is N, Ndiethylm toluamide. Outline a synthesis of this compound starting with benzene.
7.
A carboxylic acid (A) of unknown structure was found to contain only C, H and O. 154.5 mg of this acid required 11.9 mL of 0.22 N NaOH to reach equivalence point. Gentle heating of A led to evolution of CO2 and formation of new carboxylic acid (B) with nutralisation equivalent of 74. Suggest structures for A & B.
8.
Compound (A), C5H11NO is not soluble in cold dil. alkaline or acidic solutions. When (A) is refluxed with NaOH solution, a gas (B) is evolved and a salt (C) is formed. Acetyl chloride reacts with (B) to give (D), C4H9NO. (B) reacts with HNO2/HCl to give a yellow oil (E). Give structures of A to E.
9.
Compound (A) (C6H12O2) on reduction with LiAlH4 yielded two compounds B and C. The compound B on oxidation gave (D) which on treatment with aqueous alkali and subsequent heating furnished (E). The latter on catalytic hydrogenation gave C. The compound D was Trans Web Educational Services Pvt. Ltd
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oxidised further to give F which was found to be monobasic acid with molecular weight 60. Deduce the structures of A, B, C, D, E and F. 10. Suggest a mechanism for each of the following tranforamations.
CO 2Et CO 2Et O t - BuO t - BuOH CO 2Et O CO 2Et

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Objective:
Level I 1. Which of the following will not give cyclic anhydride on heating? (A)
H2C COOH COOH
(B) H2C
H2 C
COOH COOH
(C)
H2C
CH 2COOH
(D)
COOH
CH 2COOH
COOH
2.
In the reaction
CH3 CH2COOH
Cl2 / red P
alc. KOH
the compound B is (A) (C) 3. CH3CH2OH CH2 = CH COOH (B) (D) CH3CH2COCl CH3CHClCOOH
Give the structure of the product of the following reaction

CH3
CH 3NH 2

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(A)
CH3
(B)
CH3
CH3
HO
NHCH
(C)
H3C NH
O C CH 2 CH 2 CH OH CH3
(D) None
4.
Malonic and succinic acids are distinguished by (A) (C) heating both A and B (B) (D) NaHCO3 none
5.
Consider the following acids 1. 2. 3. 4. (A) (C) MeCH2COOH Me2CHCOOH Me3CCOOH Et3CCOOH 1>3>2>4 4>3>2>1 (B) (D) 1>2>3>4 3>2>1>4
Correct order of rate of esterification.
6.
Which of the following compound on heating with caustic potash gives ammonia? (A) CH3CONH2 (B) CH3CH2NH2

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O
(C)
(CH3)2C = NOH
(D)
||
CH2
C N CH3
7.
Identify the final product in the following sequence of reactions

O CH 3CH 2MgBr H2 C CH 2 X H Y KMnO 4 Z
(A) (C) 8.
CH3CH2CH2COOH CH3CH2COOH
(B) (D)
CH3CH(CH3)COOH CH3CH2CH2CH2OH
The typical reaction of carbonyl group is suppressed the most in (A) (C) CH3 CHO (B) (D) CH3CONH2 CH3COOCH3 CH3COCH3
9.
Which of the following carboxylic acids undergoes decarboxylation easily? (A) C6H5COCH2COOH (C) C6H5 HC
OH COOH
(B) (D)
C6H5COCOOH
H5C6 CH NH2 COOH
10.
Benzoic acid gives benzene on being heated with X and phenol gives benzene on being heated with Y. Therefore X and Y respectively are (A) (C) sodalime and copper Zn dust sodalime (B) (D) Zn dust and NaOH sodalime and Zn dust
11.
P2 O5
||
R C NH2
Br2 OH

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X and Y respectively are (A) (C) R CN, RCH2NH2 (B) (D) RNH2, RCN RCN, RCH2NH2 RCN, RNH2
12.
2CH3 CHO
Al OC2H5
Product and the name of the reaction respectively are (A) (B) (C) (D) 13. CH3COOCH2CH3, Tisckenko CH3COOH, CH3CH2OH, cannizzaro 2CH3CH2OH, perkin none
Which of the following reactions sounds correct? 1.

HOOC COOH COOH Br COOH Br 2 Br
2.
COOH alk.KMnO COOH Cold
4
HO
COOH
HO (meso)
COOH
Br COOH
3.
HOOC COOH Br 2
Br
COOH

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4.
HOOC COOH alk.KMnO
4
HO
COOH
HO (meso)
COOH
(A) (C) 14.
1 and 2 3&4
(B) (D)
2&3 1&4
O C OH
CH 3ONa
(A)
O C O CH3
(B)
O C O Na CH 3OH
(C)
O C CH3
(D)
O C OH
15.
The reaction of R C NH2 with a mixture of Br2 and KOH gives R as a product. The intermediate involved in this reaction is
O
||
NH2
(A) (C)
||
R C NHBr
(B) (D)
R N C O
O
||
NHBr
R C NBr2

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16.
Among the carboxylic acids:

O O CH3 (a) OH (b) (c) O H OH (d) OH O O and COOH NO 2
the, one or more than one undergoing decarboxylation readily is (are) (A) (C) 17. Only a a, b and d (B) (D) Both a and b a, b and c
In the following reaction,

hydroxy carboxylic acid
i) DIBALH ii) H+
A is (A) (C) lactone a hemiacetal (B) (D) Lactide

, - unsaturated acid
18.
Which of the following can form an anhydride on heating?

O
O
(A) H
OH
O O
(B)
HO HO O
(C)
HO OH
(D)
O HO OH
19.
O
i) ND3 , ii) KOH, Br2 , H2O
Product is
OH

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NH2 ND 2
(A)
(B)
NH2
ND 2
(C)
(D)
20.
Acetamide is treated separately with the following reagents. Which one of these would give methylamine? (A) (C) PCl5 NaOH + Br2 (B) (D) Sodalime None of these

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Level-II
1.
||
Ph C OH CH2N2
Pr oduct
(A) (C) 2.
H
PhCOOCH2N2 PhCH3
(B) (D)
PhCOOCH3 none of these
A C B
O H O H
C C D
(C (A) (C) 3.
O) bond lengths designated by A, B, C, D are in order A=C<B=D A<C=D<B (B) (D) A<B<C=D all are equal
A (monobasic acid)
NH3 /
KBrO
HNO2
(H3C) 3C or (H3C) 3C or H3C
OH Br C CH2 CH3
A is (A)
CH3
3
C COOH
(B)
H3C
CH3 CH CH 2 COOH
(C)
H3C
CH2 CH2
COOH
(D)
H3C
CH3 C CH CH3 COOH

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4.
O on saponification forms
(A)
OH
(B) 2CH3OH, 2HCOOH
OH H O
(C)
OH
HO
(D)
OH H
O C OH
OH HO O
OH
5.
O C NH2
O C CH3
P4 O10
MeMgBr H3 O
i Ca OH
ii I2 , H3 O
(A)
(B)
COOH
(C)
O C
(D)
6.
COOC 2H5
C2H5O / C2H5OH
(A)
i) H3O ii)
(B)
COOC 2H5

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The compound B is (A)

O
(B)
COOH
COOH
COOH
(C)
(D)
COOEt COOEt
COOEt
7.
Which of the following reaction/s will yield carboxylic acid? 1. 2. 3. 4. (A) (C) RMgX + CO2 PhOH + CHCl 3 + NaOH PhCN + H3O+ PhOH + NaOH + CO2 3 and 4 2 only
H
(B) (D)
2 and 4 4 only
8.
An ester (A) with molecular formula C9H10O2 was treated with excess of CH3MgBr and the complex so formed was treated with H 2SO4 to give an olefin (B). Ozonolysis of (B) gave a ketone with molecular formula C4H8O which shows positive iodoform test. The structure of (A) is
O
(A)
C6H5COOC2H5
(B)
||
C2H5 C O C6H5

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O
(C)
C4H9COOC4H9
(D)
||
C5H11 C O C3H7
9.
An ester (A) with molecular formula C11H14O2 was treated with LiAlH4 to give two compounds C9H12O (B) and C2H6O (C). B on heating with an acid forms C9H10(D). Compound (D) on oxidation with KMnO4 forms phthalic acid. Compound A is (A)
CH 2COOC 3H7
(B)
H 2C
O C O C2H5
CH 3
(C)
H2C
O C O C2 H5
(D)
H2C H3C
O C O C2H5
CH3
10.
CH 3CO 2OH
P. P is
(A)
(B)

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(C)
(D)
HO
OH
11.
Identify the product A in the following reaction.

COOH H2C COOH
CH 3COOH
(A) (C) 12.
CO2 CH3OH
(B) (D)
CH3CHO none of theses
Which carboxylic acid of equivalent mass 52 g losses CO2 when heated to give an acid of equivalent mass of 60 g? (A) (B) (C) (D) CH3COOH CH2(COOH)2 CH2(COOH) CH2(COOH) HOOC(CH2)3COOH
13.
CH 3CH 2COOH
NaN 3, conc. H 2SO 4
Br 2/P
X by reaction R 1 Y by reaction R 2
Choose the correct alternate X (A) CH3CH2NH2 Y

CH3 C HCOOH | Br
R1 Curtius
R2 HVZ

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(B) (C) (D) 14.

X
CH3CH2CONH2 CH3CH2NH2 none of these
CH3CH2OBr CH3CH2OBr
HVZ Curtius
Hoffmann HVZ
NaBH 4
O LiAlH 4
X & Y respectively are
(A)
OH
(B)
O
and
and
OH
OH
OH
OH O
(C)
both are
(D)
both are
OH OH
15.
O COOH Prolonged Heating COOH
COOH
(A)
O COOH
(B)
COOH
COOH
COOH

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(C)
O C O C O
(D)
O C O C O
16.
When acetic acid reacts with ketene, product formed (A) (C) ethyl acetate acetic anhydride (B) (D) aceto - acetic ester no reaction
17.
RCH2CH2OH can be converted in RCH2CH2COOH. The correct sequence of reagents is (A) (C) PBr3, KCN, H+ KCN, H+ (B) (D) PBr3, KCN, H2 HCN, PBr3, H+
18.
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) (B) (C) (D) Unionized in the small intestine and in the stomach Completely ionized in the stomach and almost unionized in the small intestine. Ionized in the stomach and almost unionized in the small intestine Ionised in the small intestine and almost unionised in the stomach Trans Web Educational Services Pvt. Ltd
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19.
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) (C) (CH3)2C=CHCH2COOH (CH3)2C=CHCOOH (B) (D) (CH3)2CHCOOH (CH3)2C=CHCOCOOH
20.
The ease of alkaline hydrolysis is more for (A)

COOCH
3
(B)
COOCH
NO 2
Cl
3
(C)
COOCH
(D)
COOCH
OCH 3

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ANSWERS TO ASSIGNMENT PROBLEMS
Subjective:
Level O 1. 2. See the text (i)

CH CH
1% HgSO4 dil. H2 SO4 , 80o C
O H3C H
[O] KMnO4
H3C O
OH
(ii)
CH3 CH2 OH
O
[O] K 2 Cr2 O7 / H2 SO4 ,
H3C H
[O] KMnO4
OH O
H3C
3.
CH3MgBr O C O
(i) Dry ether (ii) H / H2O
O H3C OH
4.
(i) (ii) (iii)
In acetic acid OH bond is more polar so H-bonding will be stronger and boiling point will be high. Due to the presence of +I effect of CH3 group acetic acid is weaker than formic acid. It is stronger acid than phenol due to the presence of symmetrical resonating structure whereas in case of phenoxide ion negative charge comes on less electronegative carbon atom and contributions of resonating structures are less. Trans Web Educational Services Pvt. Ltd
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5.
Due to the high molecular mass of anhydride van der Waals force increases hence boiling point increases.
6.
(a) (b) (c) (d) (e)
But-2-enoic acid 2-Cyclohexenecarboxylic acid 2-Cyclopropylpropanoic acid 2, 2 Dichloroethanoic acid Pentane-1, 5-dioic acid nitrile synthesis. Preparation of Grignard reagent from
7.
HOCH2CH2CH2CH2Br is not possible because of the presence of the acidic hydroxyl group. 8. 9. Due to resonance. This is HVZ reaction. It occurs only in those carboxylic acids which have -hydrogen atoms. Acetic acid posseses three -hydrogen atoms but formic acid does not have even a single formic acid does not undergo this reaction. 10. Because water form can again hydrolyse the ester into acid and alcohol. -hydrogen atom. Thus,

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11.
(a)
H O
O CH3
(i) CH3 CH2MgBr / ether (ii) H3 O
H5 C2 OH
C2 H5
(b)
H5C6 O
H H3C O
H
dil. NaOH
C6H5
CH
CH CH2
CHO
12.
In Benzamide carbonyl group is in resonance with lone pair of N so positive charge decreases therefore nucleophilic attack inhibit.
13.
Lone pair on nitrogen atom adjacent to the carbonyl group will participate in the resonance with the carbonyl group so this lone pair is not available for the attack at carbonyl group.
14.
In formate ion resonance gives rise to identical bond lengths

HCO O O HC = O O HC O
Whereas no such resonance is noticed in formic acid (H COOH) and thus CO bonds are different in HCOOH. 15. It is because of the possibility of resonance which compensates the electron deficiency of carbonyl carbon to some extent for example.
O R C NH 2 R O C NH 2
or
O R C OH R O C OH

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Level I 1. (a)
2CH3
O
H
dil. NaOH (aldol)
OH CH3
OH
dil. NaOH (aldol)
H
LiAlH4
CH3 O OH
CH3 H
OH
(b)
2CH3
O
H CH3
H O
CH3
Tollen's reagent
OH O
2.
- Hydroxy acids are not capable of forming lactones because of presence of strain in three membered ring lactone. But they undergo intramolecular self-esterification to yield a cyclic product containing two carbonyl groups and is called a lactide.
CH 3CHOH COOH COOH
2H2 O
H3C
3
HOCHCH
CH3
3.
Ka1 of maleic acid is more than that of fumaric acid. This is explained by the fact that conjugate base of maleic acid is stabilized by hydrogen bonding
O O C C H C H H O C O
But Ka2 of maleic acid is lesser than that of fumaric acid because it is difficult to remove hydrogen bonded H in the conjugate base of maleic acid.

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4.
This can be explained by the fact that amines are more basic than amides. The less basicity of amides are due to cross conjugation.
5.
(i) (ii)
CH3 COOH
Cl sunlight
CH2ClCOOH
HCOOH Ag(NH3 )2 NO3
Ag 2NH4NO3
CO2
6.
H2 C
CH 2 O
CH3 CH2MgBr
CH3 CH2 CH2 CH2OMgBr (A)
H3 O
CH3 CH2 CH2 CH2 OH (B)

KMnO 4
CH3 CH2 CH2 COOH (C)
7.
(C4H8 O3 )
H3C OH OH
O
CrO3
O CH3 OH
O
warm
CH3
CO2
CH3
(A)
(B)
8.
(a) (b)
CH3
H3C H3C
CH = CH
O
CH3 (A) (decarboxylation)
O (cyclic anhydride formation)
O (B)
9.
1. 2.
The cyclic anhydride of malonic acid would have a strained four membered ring. The heating causes decarboxylation instead. Trans Web Educational Services Pvt. Ltd
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O O HOC CH 2 C OH
HO C CH 3 O
CO 2
10.
A = H3C
O C H O C D= CH3 B = H3C
O C OH C = H3C
O C Cl

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Level II 1.
A=
B=
COOH
C=
Br
2.
High dilute conditions favour intramolecular condensation over inter molecular process.
EtO2C CH2
CO 2Et O OEt
4
CO2Et
EtO
EtO2CCHCH2CH2CH2CO2Et
CO 2Et O
3.
A=
H3C C H
CH3 B = H5 C2 C H
CH3 C COOH (or)
H3C C H
CH3
COOH C CH3
COOH (or) HOOC
C H
C2 H5
4.
A.
O
||
CH3 CH2 COH O

||
B.
CH3 CH2 C Cl O
||
C.
CH3CH2 C O Na

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D.
CH3CH2 C O C CH2CH3 || || O O
5.
(a)
H3C H3C
O CH3 COOH
(b)
H3C
O C COOH
(c)
O 2N COOH
6.
CH 3Cl AlCl 3 anhy
CH3
COOH
COOH
KMnO 4 OH, heat
CH 3Cl Anhy AlCl 3 CH3 SOCl 2 O CH3 C Cl
(C2H5)2NH CH3
C O
N(C 2H5)2
7.
The neutralization equivalent of A can be determined as follows =

154.5 11.9 0.22 59 gm

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The fact that A on gentle heating is giving another carboxylic acid suggests that A is a dicarboxylic acid and that too it must be malonic acid or its derivative.
O HO C
R C R'
O C OH
O C OH CO 2
C R'
Acid (B) has equivalent weight 74. So its molecular weight is 74. It can be deduced that it must be propanoic acid. So
O HO C
CH3 O CH (A) C OH
H3C
CH 2 (B)
COOH
CO 2
8.
||
A.
C2H5 CN CH3
B.
D. CH3
2
CH3
NH
C.
C2H5COONa
NCOCH3
E.
CH3
NNO
9.
||
A.
C.
CH3
C O CH2
CH2
CH2
CH3
B.
D.
CH3CH2OH
CH3CHO
CH3CH2CH2CH2OH
O
||
E.
CH3CH
CH C H
F.
CH3COOH

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10.
Et O2C O
CO 2Et 1. t - BuO Et O 2C O CO 2Et CO 2Et
CO 2Et
CO 2Et
Et O2C O
Et O2C O
Et O2C

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Objective:
LEVEL - I 1. 4. 7. 10. 13. 16. 19. LEVEL II 1. 4. 7. 10. 13. 16. 19. B C A B A C C 2. 5. 8. 11. 14. 17. 20. B B B B B A A 3. 6. 9. 12. 15. 18. A A D B D D A C A D C C D 2. 5. 8. 11. 14. 17. 20. C B B D A C C 3. 6. 9. 12. 15. 18. C A A A B D

Page 145

Carboxylic Acid and Its Derivatives - Chemistry

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Carboxylic Acid and Its Derivatives - Chemistry

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AISM-09/C/CAID

BRINGiiT on Study Pack

Contents :- CARBOXYLIC ACIDS & ITS DERIVATIVE

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Carboxylic acids may be aliphatic or aromatic

Aliphatic carboxylic acid (Where R = H or any alkyl group)

Aromatic carboxylic acid (Where Ar is any aryl group)

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1 CH3 CH CHCH2 COOH | | CH3 CH3

Acid chlorides are named systematically as acyl chlorides.

O H3C Cl acetyl chloride

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COOH phthalic acid

O Na 1-phenylethanone Sodium benzoate

CH3 ethyl 4-methylbenzoate

O O H3C NH2 acetamide NH2 cyclohexanecarboxamide

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O H3C NH N-phenylacetamide O N-phenylbenzamide NH

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BH3 / THF H2O2 / OH

Illustration 4: Bring about the following transformations

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CH 2CH 2CH 2CH 3 hot KMnO

COOH CO 2 Benzoic acid

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O R MgX C O R COO Mg X H R COOH Mg

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Write A and B (ii)

C2H5 p-bromo-sec-butyl benzene

p-sec-butyl benzoic acid

Write A and B Solution: (i)

Br CH3 H3C Br 2 CH3 H3C Mg Ether CH3 Mesitylene

MgBr CH3 CO 2 H3C H

CH3 Mesitoic acid ( 2, 4, 6 - trimethyl - benzoic acid)

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C2H5 p-bromo-sec-butyl benzene

p-sec-butyl benzoic acid

Illustration 6: Bring about the following transformations.

Bring about the following transformations Exercise 1: (i)

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NaCN n - C 4H9Br n - butyl bromide

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CH 2Cl NaCN A 70% H2SO 4, reflux B NH 4

Write A and B. Solution: (i)

NaCN n - C 4H9Br n - butyl bromide

n - C 4H9CN n - voleonitrile (pentanenitrile) (A)

aq. alc. NaOH, reflux

n - C 4H9COO NH 3 (B) H n - C 4H9COOH NH 4 n - valeric acid (pentanoic acid) (C)

CH 2CN 70% H 2SO 4, reflux

Phenyl acetic acid

Exercise 3: Identify the missing reagents or products

i) 3 /THF BH ii) 3 COOH CH

ii) H2O2/OH (D)

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Oxidative cleavage of alkenes, alkynes and cyclo alkenes

Careful oxidation with K2Cr2O7

COOH CH3COOH + CH2 COOH

Alk. hydrolysis Salt