NAME REACTIONS,DISTINCTION ,WORD PROBLEMS

ON ALDEHYDES,KETONES & CARBOXYLIC ACIDS

NAME REACTIONS

Describe the following:

(i) Acetylation
(ii) Cannizzaro reaction

(iii) Aldol condensation

(iii) Cross aldol condensation
(iv) Decarboxylation

(v) Clemmensen Reduction

(vi) Esterification

(vii) Etard Reaction

(viii)Gattermann-Koch reaction

(ix) Iodoform Reaction

(x)Wolff-Kishner reduction
(xi) Stephen’s Reduction
(xii) Rosenmund reduction

Ans: (i) Acetylation is the process of introducing an acetyl group into a compound in
presence of a base such as pyridine, dimethylanitine, etc.

Pyridine is used to neutralise HCl produced.

(ii) Cannizzaro reaction : Aldehydes which do not contain an a-hydrogen atom, when
treated with concentrated alkali solution undergo disproportionation, i.e., self
oxidation reduction resulting alcohol & salt of carboxylic acid.

(iii) Aldol condensation

An aldol condensation is a condensation reaction in organic chemistry in which

two carbonyl moieties (of aldehydes or ketones) react to form a β-hydroxyaldehyde or
β-hydroxyketone (an aldol reaction)

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(iii) Cross aldol condensation: Aldol condensation between two different aldehydes is
called cross aldol condensation.If both aldehydes contain a-hydrogens, It gives a
mixture of four products.

(iv) Decarboxylation: The process of removal of a molecule of CO2 from a carboxylic

acid is called decarboxylation. Sodium salts of carboxylic acids when heated with
soda-lime undergoes decarboxylation to yield alkanes.

(v)Clemmensen reduction is a reaction that is used to reduce aldehydes or ketones to

alkanes using hydrochloric acid and zinc amalgam.

(vi)When primary alcohol is treated with a carboxylic acid in the presence of

sulphuric acid a sweet smelling compound ,ester is formed. The chemical
reaction occurring in the formation of the ester is known as an esterification reaction.
CH3COOH + CH3CH2COOH → CH3COOCH2CH3
* When dry HCl gas is used as a catalyst it is called Fischer -speier esterification.
(vii) Etard Reaction: The oxidation of aromatic methyl groups to an aldehyde using
chromyl chloride in CCL4 followed by acid hydrolysis is Etard reaction.

(viii)Gattermann-Koch Reaction
the reaction of benzene with CO and HCl in the presence of Lewis catalysts e.g., AlCl 3 to
form benzaldehyde.

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 (ix) Haloform/Iodoform reaction
Carbonyl compounds with amethyl keto group (R - CO - CH3) or alcohols with
the formula R - CH (OH) - CH3 when reacts with Iodine and aqueous sodium
hydroxide (NaOH) solution produce yellow ppt of iodoform.

(x)Wolff-Kishner reduction
The Wolff-Kishner reduction is a reaction to convert an aldehyde or ketone to an
alkane using hydrazine, base, and heat (~200 °C).

(xi) Stephen’s Reduction

The preparation of aldehydes from nitriles with the help of tin (II) chloride and
hydrochloric acid followed by hydrolysis of the resulting iminium salt with water.

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(xii) Rosenmund reduction
Rosenmund reduction is an organic process in which hydrogen gas is passed through
palladium (Pd) on barium sulfate to transform an acid chloride to an aldehyde
(BaSO4).

DISTINCTION

Q1. Give simple chemical tests to distinguish between the following pairs of
compounds.
(i) PropanalandPropanone
(ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid
(iv) Benzoic acid and Ethyl benzoate
(v) Pentan-2-one and Pentan-3-one
(vi) Benzaldehyde and Acetophenone.
(vii) EthanalandPropanal

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Ans:

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WORD PROBLEM ON ALDEHYDES,KETONES,CARBOXYLIC ACID

Q1. An organic compound with the molecular formula C9H10O forms 2,4-DNP
derivative, reduces Tollen’s reagent, and undergoes Cannizzaro reaction. On
vigorous oxidation, it gives 1,2-benzenedicarboxylic acid. Identify the
compound.
Ans: Since the given compound with molecular formula C9H10O forms a 2,4-DNP
derivative and reduces Tollen’s reagent, it must be an aldehyde. Since it undergoes
Cannizzaro reaction, therefore, CHO group is directly attached to die benzene ring.
Since on vigorous oxidation, it gives 1, 2-benzene dicarboxylic acid, therefore, it must
be an ortho- substituted benzaldehyde. The only o-substituted aromatic aldehyde
having molecular formula C9H10O is o-ethyl benzaldehyde. Ail the reactions can
now be explained on the basis of this structure.

Q2. An organic compound (A) (molecular formula C8H16O2) was hydrolysed

with dilute sulphuric acid to give a carboxylic acid (B} and an alcohol (C).
Oxidation of (C) with chromic acid produced (B). (Q on dehydration gives but-l-
ene. Write equations for the reactions involved.
Ans: Since an ester A with molecular formula C8H16O2 upon hydrolysis gives
carboxylic acid B and the alcohol C and oxidation of C with chromic acid produces
the acid B, therefore, both the carboxylic acid B and alcohol C must contain the same
number of carbon atoms.
Further, since ester A contains eight carbon atoms, therefore, both the carboxylic acid
B and the alcohol C must contain four carbon atoms each.
Since the alcohol C on dehydration gives but-l-ene, therefore, C must be a straight
chain alcohol, i.e., butan-l-ol.
If C is butan-l-ol, then the acid B must be butanoic acid and the ester A must be butyl

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butanoate.The chemical equations are as follows:

Q3. An alkene ‘A’ (Molecular formula C5H10) on ozonolysis gives a mixture of

two compounds ‘B’ and ‘C’. Compound ‘B’ gives positive Fehling’s test and also
forms iodoform on treatment with I2 and NaOH. Compound ‘C’ does not give
Fehling’s test but forms iodoform. Identify the compounds A, B and C. Write the
reaction for ozonolysis and formation of iodoform from B and C.
Solution: Compound B gives positive Fehling’s test. It shows that it is an aldehyde
and gives iodoform test which shows it has -COCH3 group. Compounds C is a ketone
because it does not give Fehling’s test but gives iodoform test which shows it also has
-
COCH3 groups.

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Q4. An aromatic compound ‘A’ (Molecular formula CgHgO) gives positive 2, 4-
DNP test. It gives a yellow precipitate of compound ‘B’ on treatment with iodine
and sodium hydroxide solution. Compound ‘A’ does not give Tollens or
Fehling’s test. On drastic oxidation with potassium permanganate it forms a
carboxylic acid ‘C’ (Molecular formula C7H6O2), which is also formed along
with the yellow compound in the above reaction. Identify A, B and C and write
all reactions involved.
Solution: Molecular formula of compound is C8HgO. As ‘A’ does not give Tollens’
or Fehling’s test. It must be a ketone. It gives positive test with 2, 4-DNP and
iodoform test. It means it is methyl ketone.

Q5. Write down functional isomers of a carbonyl compound with molecular

formula C3H6O. Which isomer will react faster with HCN and why? Explain the
mechanism of the reaction also. Will the reaction lead to the completion with the
conversion of whole reactant into product at reaction conditions? If a strong acid
is added to the reaction mixture what will be the effect on concentration of the
product and why?
Solution: C3H6O will have following isomer.

Compound I will react faster with HCN due to less steric hindrance and greater
positive charge on carbon atom of carbonyl group. Two methyl groups increase
electron density on carbonyl carbon in compounds II hence the rate of nucleophilic
attack is less.
Mechanism of the reaction:

The reaction will not lead to completion since it is a reversible reaction, hence

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equilibrium is established.
If a strong acid is added to reaction mixture, the addition is inhibited because the
formation of CN” ions form HCN is prevented.

Q6. When liquid ‘A’ is treated with a freshly prepared ammoniacal silver nitrate
solution, it gives bright silver mirror. The liquid forms a white crystalline solid
on treatment with sodium hydrogen sulphite. Liquid ‘B’ also forms a white
crystalline solid with sodium hydrogen sulphite but it does not give test with
ammoniacal silver nitrate. Which of the two liquids is aldehyde? Write the
chemical equations of these reactions also.
Solution: Liquid ‘A’ forms a bright silver mirror on treatment with ammoniacal
AgNO3 solution, therefore, liquid ‘A’ is an aldehyde.
Liquid B does not give test with ammoniacal AgNO3 solution, therefore, liquid ‘B’
must be a methyl ketone.

Q7. Compound ‘A’ was prepared by oxidation of compound ‘B’ with alkaline
KMnO4. Compound ‘A’ on reduction with lithium aluminium hydride gets
converted back to compound ‘B’. When compound ‘A’ is heated with compound
‘B’ in the presence of H2SO4 it produces fruity smell of compound ‘C’ to which
family the compounds ‘A’, ‘B’ and ‘C’ belong to?
Solution: