CHAPTER 8 : ALDEHYDE,KETONES AND CARBOXYLIC ACID

TEXTUAL EXERCISE
1. What is meant by following terms? Give an example
Cyanohydrin Addition product
obtained by reaction
between aldehyde/
ketones & hydrogen
cyanide is called
Cyanohydrin
Acetal Compound formed
when 2 equivalents of
monohydric alcohol are
added to aldehyde in
presence of dry HCl is
called Acetal
Semicarbazone Addition product
obtained by reaction
between aldehyde/
ketones & hydrogen
Semicarbazide followed
by elimination of water

Aldol β-hydroxy aldehyde

formed by reaction
between 2 same or
different aldehyde
molecules in presence
of dilute alkali
Hemiacetal Intermediate formed
when aldehyde reacts
with one equivalent of
monohydric alcohol in
presence of dry
hydrogen chloride
Oxime Imine obtained from
reaction of carbonyl
compound with
hydroxylamine is Oxime
Ketal Compound formed
when ketone reacts
with 2 equivalent
monohydric alcohols in
presence of dry HCl
Imine A compound containing
carbon-nitrogen double
bond
2,4 DNA Product obtained by
Derivative addition of aldehyde/
ketones & 2,4-
Dinitrophenylhydrazine
followed by elimination
of water molecule

Schiff’s Base N-alkylimine obtained

from reaction of
aldehyde/ketone &
primary amine

2. Name following compounds according to IUPAC names and

nomenclature
CH3CH(CH3)CH2CH2CHO 4-methyl pentanal
CH3CH2COCH(C2H5)CH2CH2Cl 6-chloro-4-ethyl hexan-3-one
CH3CH=CHCHO But-2-en-1-al
CH3COCH2COCH3 Pentane-2,4-dione
CH3CH(CH3)CH2C(CH3)2COCH3 3,3,5-Trimethyl Hexan-2-one
(CH3)2CCH2COOH 3,3-Dimethylbutan-1-oic acid
OHCC6H4CHO-p Benzene-1,4 carbaldehyde
3. Draw structures of following compounds
3-methylbutanal

p-Nitropropiophenone
 p-Methylbenzaldehyde

4-Methylpent-3-en-2-one

4-chloropentan-2-one

3-bromo-4-phenylpentanoic
acid

p,pI -
Dihydroxybenzophenone

Hex-2-en-4-yonic acid

4. Write IUPAC names & common names

CH3CO(CH2)4CH3 IUPAC : Heptan-2-one
Common :Methyl n-pentyl ketone
CH3CH2CHBrCH2CH(CH3)CHO IUPAC : 4-bromo-2-methyl hexanal
Common : ¥-Bromo-∝-Methyl
Caproaldehyde
CH3(CH2)5CHO IUPAC : Heptan-1-al
Ph-CH=CH-CHO IUPAC : 3-Phenyl prop-2-enal
Common : Cinnamaldehyde
IUPAC :
Cyclopentane Carbaldehyde

PhCOPh IUPAC : Benzophenone

Common : Diphenyl Ketone
5. Draw Structures of following derivative
2,4
dinitrophenylhydrazone of
benzaldehyde
 Cyclopropanone Oxime

Actealdehydemitheylacetal

Semicarbazone of
Cyclobutane

Ethylene Ketal of Hexan-3-

one

Methyl Hemiacetal of
Formaldehyde

6. Predict products when cyclohexenecarbaldehyde reacts with

(i) PhMgBr and then H3O+

(ii) Tollen’s Reagent

 (iii) Semicarbazide and Weak acid

(iv) Excess Ethanol and Acid

(v) Zinc amalgam and dilute hydrochloric acid

7. Which of following undergo aldol condensation, Cannizaro and which

neither? Write structures of expected products of aldol condensation

Compound Reaction Expected Products

Methanal Cannizaro
(HCHO)
2-Methyl Aldol
pentanal Condensation

Benzaldehyde Cannizaro

Benzophenone Neither go Cannizaro or aldol condensation

Cyclohexanone Aldol
Condensation

1-Phenyl Aldol
Propanone Condensation

Phenyl Aldol
acetaldehyde Condensation

Butan-1-ol Neither
2,2-dimethyl Cannizaro
butanal Reaction

8. How will you convert Ethanal into following compounds

A. Ethanal to 1,3 -diol

B. Ethanal to But-2-enal

C. Ethanal to But-2-enoic acid

9. Write structural formulas and names of four possible aldol

condensation products from propanal and butanal. In each case,
indicate which aldehyde acts as nucleophile and which as electrophile
10. An organic compound with molecular formula C9H10O forms 2,4-DNP
derivative reduces Tollen’s reagent and undergoes Cannizaro Reaction.
On vigorous oxidation it gives 1,2-benzenedicarboxylic acid. Identify
compound
11. An organic compound (A) (molecular formula : C8H16O2) was
hydrolyzed with dilute sulphuric acid to give carboxylic acid (B) &
alcohol (C). Oxidation of (C) with chromic acid produced (B). (C) on
dehydration gives But-1-ene. Write chemical reactions involved
12. Arrange following in increasing order of property indicated
A. Reactivity towards HCN

B. Acid Strength

C. Acid Strength

13. Give chemical reactions to distinguish between following compounds

A. Propanal and Propanone
 Silver Mirror Test
 Iodoform Test
B. Acetophenone and Benzophenone
 Iodoform Test
C. Phenol and Benzoic Acid
 Sodium Bicarbonate Test
 Ferric Chloride Test
D. Benzoic Acid and Ethyl Benzoate
 Sodium Bicarbonate Test
 Litmus Test
E. Pentan-2-one and Pentan-3-one
 Iodoform Test
F. Benzaldehyde and Acetophenone
 Iodoform Test
 Silver Mirror Test
G. Ethanal and Propanal
 Iodoform Test
14. How will you prepare following compounds from benzene? You may use
any inorganic reagent and any organic reagent having not more than one
carbon atom
A. Benzene to Methyl Benzoate

B. Benzene to m-Nitrobenzoic Acid

C. Benzene to p-Nitrobenzoic Acid

D. Benzene to Phenyl Acetic Acid

E. Benzene to p-Nitrobenzaldehyde

15. How will you bring following conversions

A. Propanone to Propene

B. Benzoic Acid to Benzaldehyde

C. Ethanol to 3-Hydroxybutanal

D. Benzene to m-Nitroacetophenone

E. Benzaldehyde to Benzophenone

F. Bromobenzene to 1-Phenylethanol

G. Benzaldehyde to 3-Phenylpropan-1-ol

H. Benzaldehyde to ∝-Hydroxyphenylacetic acid

 I. Benzoic Acid to m-Nitrobenzyl alcohol

Benzoic Acid m-Nitro benzoic acid m-Nitrobenzylalcohol

16. Describe following

A. Acetylation
 Substitution of active hydrogen atom of alcohols, phenols or
amines by acyl group forming corresponding esters
or amides is called acetylation

B. Cannizaro Reaction
C. Cross Aldol Condensation
D. Decarboxylation
17. Complete each synthesis by giving missing starting material, reagent or
products
18. Give reasons
A. Cyclohexanone forms cyanohydrin in good yield but 2,2,6-
trimethylcyclo-hexanone does not
 Cyclohexanone forms Cyanohydrin

 Reactivity of nucleophilic addition depends on 2 factors :

Steric Factor and Electronic Factor
 There is no steric hinderance allowing nucleophile CN to
attack with ease and hence forms yield in good amount
 2,2,6-Trimethylcyclo-hexanone
  In 2,2,6-trimethylcyclohexanone, there are 3 methyl groups
present which causes steric hinderance to nucleophilic attack
of CN- on carbonyl group. Hence yield is less

B. There are two NH2 group in semicarbazide. However only one is

involved in formation of semicarbazones
 In semicarbazide there are 2 amino groups

 Out of 2 amino groups, only 1 is involved in resonance

 Electron density on -NH2 group involved in resonance

decreases. Hence it cannot act as nucleophile
 As other -NH2 group is not involved in resonance, it act as
nucleophile. Hence its lone pair of electron is available for
nucleophilic attack and formation of semicarbazones

C. During preparation of esters from carboxylic acid and alcohol in

presence of acid catalyst, water on ester should be removed as
soon as it is formed
 Preparation of esters from carboxylic acid and alcohol in
presence of acid catalyst is reversible reaction

 According to Le-Chatelier’s principle, removal of water or

ester shifts reaction in forward direction
 Also due to reversible nature of reaction, there is possibility of
hydrolysis of ester formed
 Hence to avoid this, water on ester should be removed as
soon as it is formed
19. An organic compound contains 69.77 % carbon, 11.63 % hydrogen and
rest oxygen. Molecular mass of compound is 86. It does not reduce
Tollen’s reagent but forms addition compound with sodium
hydrogensulphite and gives positive iodoform test. On vigorous
oxidation it gives ethanoic and propanoic acid. Write possible structure
of compound

% of O = 100 – 69.77 - 11.63

% = 18.60

Element % Atomic No of Simple ratio

mass moles
C 69.77 12 𝟔𝟗.𝟕𝟕 𝟓.𝟖𝟏𝟒
= 5.814 =5
𝟏𝟐 𝟏.𝟏𝟔𝟑
H 11.63 1 𝟏𝟏.𝟔𝟑 𝟏𝟏.𝟔𝟑
= 11.63 = 10
𝟏 𝟏.𝟏𝟔𝟑𝟎
= 1.1630 𝟏. 𝟏𝟔𝟑 = 𝟏
O 18.60 16 𝟏𝟖.𝟔
𝟏𝟔
𝟏. 𝟏𝟔𝟑

Empirical Formula : (C5H10O)n

𝑴𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 𝟖𝟔
n= = =1
𝑬𝒎𝒑𝒊𝒓𝒊𝒄𝒂𝒍 𝑴𝒂𝒂𝒔 𝟖𝟔

 Compound : Pentan-2-one
 Reactions :
20. Although phenoxide ion has more number of resonating structures
than carboxylate ion. Carboxylic acid is more stronger than phenol. Why?
 Higher acidity of carboxylic acids compared to phenols is on basis of
stability of their negative ions i.e conjugate bases
 Conjugate base of carboxylic acid (carboxylate ion) is stabilized by 2
equivalent resonating structures

 In these structures, negative charge is at more electronegative oxygen

atom
 Conjugate base of phenol has non-equivalent resonance structures in
which negative charge is at less electronegative carbon atom

 In Carboxylate ion negative charge is delocalized over 2 electronegative

oxygen atoms whereas it is less effectively delocalized over 1 oxygen
atom & less electronegative carbon atoms in phenoxide ion
 Thus carboxylic acids are more acidic than Phenols