ALDEHYDES, KETONES

AND
CARBOXYLIC ACIDS

Aldehydes: Aldehydes are the organic compounds in which carbonyl group is attached to
one hydrogen atom and one alkyl or aryl group.

Where R can be an alkyl or aryl group

Preparation of aldehydes:

a) By oxidation of alcohols: Oxidation of primary alcohols in presence of oxidizing agent like

K2Cr2O7/H2SO4, KMnO4,CrO3 gives aldehydes.

b) By dehydrogenation of alcohols: When the vapours of primary alcohol passed through

heated copper at 573 K, it forms aldehyde.

c) By hydration of alkynes: Ethyne on hydration with at 333 K forms

acetaldehyde.

d) By Rosenmund reduction: Hydrogenation of acyl chloride over palladium on barium

sulphate gives aldehyde.

e) By reduction of nitriles:
i) Stephen Reaction: Reduction of nitriles in presence of stannous chloride in presence of HCl
gives imine which on hydrolysis gives corresponding aldehyde.

ii) Nitriles are selectively reduced by DIBAL-H (Diisobutylaluminium hydride) to aldehydes.

f) By reduction of ester: Esters are reduced to aldehydes in presence of DIBAL-H

(Diisobutylaluminium hydride)
g) From Hydrocarbons:
(i) By oxidation of methyl benzene: Etard Reaction: Chromyl chloride oxidizes
methyl group to a chromium complex, which on hydrolysis gives corresponding
benzaldehyde.

Using chromium oxide : Toluene or substituted toluene is converted to benzaldehyde

in presence of chromic oxide in acetic anhydride.

(ii) By side chain chlorination followed by hydrolysis:

 Gatterman –Koch reaction:

 Ketones: Ketones are the organic compounds in which carbonyl group is attached to
two alkyl group or aryl group or both alkyl and aryl group.

Where R, R’ may be alkyl or aryl.

 Preparation of ketones:

a) By oxidation of alcohols: Oxidation of secondary alcohols in presence of oxidizing

agent like , gives ketones.

b) By dehydrogenation of alcohols: When the vapours of a secondary alcohol are

passed over heated copper at 573 K, dehydrogenation takes place and a ketone is
formed.
 c) By hydration of alkynes: Alkynes on hydration with at 333
K form ketones.

d) From acyl chloride: Acyl chloride on treatment with dialkyl cadmium (prepared by
reaction of cadmium chloride with Grignard reagent) gives ketone.

e) From nitriles: Nitriles on treatment with Grignard reagent followed by hydrolysis give
ketones.

f) By Friedel Crafts acylation reaction: Benzene or substituted benzene on treatment with

acid chloride in presence of anhydrous aluminium chloride forms ketone.

g) Preparation of aldehydes and ketones by ozonolysis of alkenes:

Reactions of aldehydes and ketones:

1. Aldehydes are generally more reactive than ketones in nucleophilic addition reactions
due to steric and electronic reasons (or inductive effect).

2. Electronic Effect: Relative reactivities of aldehydes and ketones in nucleophilic

addition reactions is due the positive charge on carbonyl carbon. Greater positive
charge means greater reactivity. Electron releasing power of two alkyl groups in
ketones is more than one in aldehyde. Therefore positive charge is reduced in ketones
as compared to aldehydes. Thus ketones are less reactive than aldehydes.

3. Sterric Effect: As the number and size of alkyl group increase, the hindrance to the
attack of nucleophile also increases and reactivity decreases. In aldehydes there is one
alkyl group and one hydrogen atom, whereas in ketones there are two alkyl groups
(same or different).

Nucleophilic addition reactions of aldehydes and ketones:

(a) Addition of hydrogen cyanide (HCN) to form cyanohydrins

(b) Addition of sodium hydrogensulphite to form bisulphate addition compound

(c) Addition of Grignard reagent (RMgX) to form alcohol

(d) Addition of alcohol

(i) Aldehydes on addition of monohydric alcohol in presence of dry HCl forms hemiacetal
and acetal.

(ii) Ketones do not react with monohydric alcohols. Ketones react with ethylene glycol under
similar conditions to form cyclic products known as ethylene glycol ketals.

(e) Addition of ammonia and its derivatives:

 Reduction of aldehydes and ketones:

(a) Reduction to alcohols:
Aldehydes and ketones on catalytic hydrogenation in presence of Ni, Pt or Pd by using
lithium aluminium hydride or sodium borohydride forms primary and
secondary alcohols respectively.
(b) Reduction to hydrocarbons:
(i) Clemmensen reduction: Carbonyl group of aldehydes and ketones is reduced
to group on treatment with zinc amalgam and concentrated hydrochloric acid.

ii) Wolff-Kishner reduction: Carbonyl group of aldehydes and ketones is reduced

to group on treatment with hydrazine followed by heating with sodium or potassium
hydroxide in high boiling solvent such as ethylene glycol.

(iii)

 Oxidation of aldehydes and ketones:

(i) Aldehydes are oxidized to acids in presence of mild oxidising agents HNO3, K2Cr2O7,
KMnO4.
(ii) Ketones are oxidized under drastic conditions i.e. with powerful oxidising agents
like at higher temperature.
In case of unsymmetrical ketones cleavage occurs in such a way that keto group stays with
smaller alkyl group. This is known as Popoff’s rule.

(iii)Haloform reaction: Aldehydes and ketones having at least one methyl group linked to
the carbonyl carbon atom i.e. methyl ketones are oxidised by sodium hypohalite to sodium
salts of corresponding carboxylic acids having one carbon atom less than that of carbonyl
compound. The methyl group is converted to haloform.

 Reactions of aldehydes and ketones due to -hydrogen:

Aldol condensation: Aldehydes and ketones having at least one -hydrogen undergo a
self condensation in the presence of dilute alkali as catalyst to form -hydroxy aldehydes
(aldol) or -hydroxy ketones (ketol), respectively.
(ii) Cross aldol condensation: Aldol condensation between two different aldehydes and
ketones is called aldol condensation. If both of them contain -hydrogen atoms, it gives a
mixture of four products.

 Canizzaro reaction: Aldehydes which do not have an -hydrogen atom undergo

self-oxidation and reduction (disproportionation) reaction on treatment with
concentrated alkali to form alcohol and salt of acid.
  Test to distinguish aldehydes and ketones:
1. Tollen’s test: When an aldehyde is heated with Tollen’s reagent it forms silver mirror.
Tollen’s reagent is ammoniacal solution of silver nitrate.

Ketones do not form silver mirror and hence do not give this test.
2. Fehling’s test: When an aldehyde is heated with Fehling’s reagent it formsreddish
brown precipitates of cuprous oxide.Fehling’s reagent: Fehling solution A (aqueous
solution of ) + Fehling solution B (alkaline solution of sodium potassium
tartarate)

Ketones do not give this test.

 Carboxylic Acids:Carboxylic acids are the compounds containing the carboxyl

functional group (-COOH).

Preparation of carboxylic acid:

(i) From alcohols:

a)
b)

(ii) From aldehydes: Oxidation of aldehydes in presence of mild oxidizing agents like
Tollen’s reagent(ammoniacal solution of ) or Fehling reagent (Fehling solution A
(aqueous solution of ) + Fehling solution B (aqueous solution of sodium potassium
tartarate)) forms carboxylic acids.
1.
2.

(iii) From alkylbenzenes: Aromatic carboxylic acids can be prepared by vigorous oxidation of
alkyl benzenes with chromic acid or acidic or alkaline potassium permanganate.
(iv) From alkenes: Suitably substituted alkenes are oxidised to carboxylic acids on oxidation
with acidic potassium permanganate or acidic potassium dichromate.

1.

2.

(v) From Nitriles:

(vi) From Grignard reagent

(vii) From acyl halides and anhydrides:

(viii) From esters: Acidic

 Physical properties of carboxylic acids:

(i) Solubility: As the size of alky group increases solubility of carboxylic acid decreases
because non-polar part of the acid increases
(ii) Boiling points: Carboxylic acids are higher boiling liquids than aldehydes, ketones and
even alcohols of comparable molecular masses. This is due to extensive association of
carboxylic acid molecules through intermolecular hydrogen bonding.

 Acidity of carboxylic acids:

Carboxylic acids are more acidic than phenols. The strength of acid depends on extent of
ionization which in turn depends on stability of anion formed.

(i) Effect of electron donating substituents on the acidity of carboxylic acids: Electron
donating substituent decreases stability of carboxylate ion by intensifying the negative charge
and hence decreases acidity of carboxylic acids.
(ii) Effect of electron withdrawing substituent on the acidity of carboxylic acids: Electron
withdrawing group increases the stability of carboxylate ion by delocalizing negative charge
and hence, increases acidity of carboxylic acid.
(a) Effect of number of electron withdrawing groups: As the number of electron withdrawing
groups increases –I effect increases, increasing the acid strength

(b) Effect of position of electron withdrawing group: As the distance between electron
withdrawing group and carboxylic group increases, electron withdrawing influence
decreases.

 Reaction of carboxylic acids:\

Reactions involving cleavage of C-OH bond:

Carboxylic acids on heating with mineral acids such as or with give
corresponding anhydride.
(i) Anhydride formation:

(ii) Esterification: Carboxylic acids are esterified with alcohols in the presence of a mineral
acid such as concentrated or HCl gas as a catalyst.

(iii) Carboxylic acids react with PCl5, PCl3 and SOCl2 to form acyl chlorides.
1.
2.
3.
4.
(iv) Reaction with ammonia (NH3): Carboxylic acids react with ammonia to give ammonium
salt which on further heating at high temperature gives amides.
i)

ii)

Reactions involving COOH group:

(i) Reduction: Carboxylic acids are reduced to alcohols in presence of LiAlH4 or B2H6.

(ii) Decarboxylation : Sodium or potassium salts of carboxylic acids on heating with soda
lime (NaOH + CaO in ratio of 3:1) gives hydrocarbons which contain one carbon less than
the parent acid.

(c) Reactions involving substitution reaction in hydrocarbon part:

(i) Hell-Volhard-Zelinsky reaction: Carboxylic acids having an -hydrogen are

halogenated at the -position on treatment with chlorine or bromine in the presence of small
amount of red phosphorus to give -halocarboxylic acids)
(ii) Ring substitution in aromatic acids: Aromatic carboxylic acids undergo electrophilic
substitution reactions. Carboxyl group in benzoic acid is electron withdrawing group and is
meta directing.
i)

ii)

VERY SHORT ANSWER TYPE QUESTIONS (1 MARK EACH)

1. Give a chemical test to distinguish between :

i. Methanal and Ethanal

Ans. Iodoform test :-

Reagent- NaOH,I2
Methanal --- No reaction
Ethanal…. Yellow ppt of iodoform. (CHI3)

ii. Methanal and Propanone

Ans Methanal and Propanone

Iodoform test :-
Reagent- NaOH,I2
Methanal ---No reaction
Propanone…. Yellow ppt of iodoform. (CHI3)

iii. Ethanal and Benzaldehyde

Ans. Iodoform test:-

Reagent:- NaOH/I2.
Ethanal-yellow ppt of Iodoform (CHI3)
Benzaldehyde- No reaction.

iv. Benzaldehyde and Acetophenone

 Ans. Tollen`s test:-
Reagent:- ammoniacal silver nitrate.
Benzaldehyde- Silver mirror along the side of test tube.
Acetophenone- No response.

v Pentan-3-one and Pentan-2-one

Ans. Iodoform test:-

Reagent- NaOH, I2
Pentan-2-one --- Yellow ppt of iodoform. (CHI3)
Pentan-3-one….No response

vi. Propanal and Propanone

Ans. Tollen`s test:-

Reagent:- ammoniacal silver nitrate.
Propanal- Silver mirror along the side of test tube.
Propanone- No response.

vii Methanal and Benzaldehyde

Ans. Fehling test :-

Reagent- Fehling A(aq. Copper sulphate) and B( rochelle salt)
Methanal – red ppt of Cu2O obtained.
Benzaldehyde- no response.

Viii Ethanal and Propanal.

Ans. Iodoform test:-

Reagent- NaOH, I2
Ethanal --- Yellow ppt of iodoform(CHI3)
Propanal….No response

ix. Formic acid and acetic acid

Ans. Tollen`s test:-

Reagent:- ammoniacal silver nitrate.
Formic acid- Silver mirror along the side of test tube.
Acetic acid- No response

x. Benzoic acid and phenol

Ans. Neutral FeCl3 test:-

Benzoic acid- buff ppt of ferric benzoate.
Phenol- violet coloration

xi. Acetic acid and acetaldehyde.

Ans. Iodoform test:-
Reagent- NaOH, I2
Acetaldehyde--- Yellow ppt of iodoform(CHI3)
Acetic acid….No response

xii Benzoic acid and ethyl benzoate

Ans.NaHCO3 test:-
Benzoic acid – effervescence due to formation of CO2
Ethyl benzoate- no reaction.

2. Give equations in favour of the following :

i. Cannizzaro's reaction.

ii. Aldol condensation.

iii. Wolf-Kishner's reduction

iv. Clemmensen's reduction.

v. Stephen's reaction.

vi. Rosenmund's reaction.

vii. Hell-Volhard- Zelinsky reaction.

viii. Gattermann-Koch reaction.

ix. Etard's Reaction.

x. Haloform reaction:-
3. Carryout the following conversions :

i) Ethanal  butanal

Ans.

ii) But-2-ene  2-propanol

Ans.

iii) Phenol  Benzaldehyde

Ans.

iv) Toluene  cinnamaldehyde

Ans.

v) Benzaldehyde  Benzene

Ans.

vi) Tert-butyl alcohol  mesitylene

Ans.

vii) Acetone  crotonaldehyde

Ans.

viii) Iodoform  lactic acid

Ans.

ix) 2-Propanol  mesitylene.

Ans.

x) Benzoic acid to m-nitrobenzyl alcohol

Ans.

xi) Benzoic acid to benzaldehyde.

Ans.
xii) Benzaldehyde to benzophenone.

Ans.

xiii) Benzyl alcohol to phenyl ethanoic acid

Ans.

xiv) 1-bromo-3-nitrobenzene to 3-Nitrobenzoic acid.

Ans.

xv) Propanone to propene.

Ans.

4. Explain why :

(i) Methanal is more reactive than ethanal towards nucleophilic addition.

Ans. In HCHO the carbonyl C is more electron deficient and less sterically
hindered than ethanal.

(ii) Weakly acidic medium is maintained in the formation of oxime and

hydrazone formation.

Ans. presence of H+ ion decreases the availability of lone

pairs on nitrogen for nucleophilic attack.
(iii) Trichloro acetaldehyde does not undergo Cannizzaro's reaction.

Ans. On hydrolysis CCl3- ion hydrolyses to form CHCl3 and HCOO(-) .

(iv) Benzaldehyde is less reactive than propanal towards nucleophilic

addition.

Ans. Steric factor is more in benzaldehyde and also electrophilicity of

carbonyl group is reduced to a large extent due to – R effect.

(v) Out of two NH2 groups only one is involved in the formation of
semicarbazone.

Ans.

Due to resonance the lone pair on Nitrogen is not available for donation

(vi) Oximes are more acidic than hydroxylamine.

Ans.
The conjugated base formed is resonance stabilized in oximes

(vii) Oxidation of toluene to benzaldehyde with CrO3 is carried out in presence

of acetic anhydride and not in presence of sulphuric acid.

Ans. In presence of H2SO4, the benzaldehyde obtained forms benzoic acid due
to H2O present in H2SO4.

(viii) Benzaldehyde reduces Tollen`s reagent but not the Fehling`s solution.

Ans. Due to resonance a partial double bond character is developed between

the carbonyl C and the c of the ring. Cu cannot oxidize the strong bond.

(ix) Tert-Butylbenzne does not give benzoic acid on oxidation with acidic
KMnO4

Ans. Due to absence of benzylic hydrogen

(x) Formic acid is stronger than acetic acid

Ans.
 Polarity of O-H is decreased due to ‘+I’ effect of methyl group in acetic
acid. Electron density on the carboxylate ion is more in acetic acid than
formic acid which in turn reduce the stability of the conjugate base.

(xi) O-hydroxybenzaldehyde is a liquid at room temperature while p-

hydroxybenzaldehyde is a high melting solid.

Ans. o-hydroxybenzaldehyde has intramolecular H-bonding but p-

bydroxybenzaldehyde has intermolecular H-bond.

(xii) Formic acid does not give HVZ reaction

Ans. Due to absence of α-hydrogen

(xiii) Acetic acid is stronger than phenol.

Ans. Conjugate base of acetic acid has 2 equivalent resonance structure

whereas phenoxide ion has non-equivalent resonance structure and has
negative charge on less electronegative atom.

(xiv) Benzoic acid does not undergo Friedel-Crafts reaction.

Ans. Due to deactivation of benzene ring by electron with drawing effect of -

COOH group and also AlCl3 gets bonded to –COOH group

(xv) Carboxylic acids do not exihibit the properties of carbonyl group.

Ans. – COOH group is involved in resonance.

The electrophilic character of carbonyl group is reduced.

(xvi) Cyclohexanone forms cyanohydrins in good yield but 2,2,6

trimethylcyclohexanone does not.

Ans. 2,2,6 – trimethylcyclohexanone due to sterric hindrance does not form

cyanohydrins

(xvii) Alpha- chloropropanoic acid is stronger than beta- chloropropanoic acid.

Ans.

In α-chloropropanoic acid, the conjugate base is stabilized to larger extent

due to – I effect of Cl which is present close to –COOH group.

5. Arrange the following in the order indicated:-

(i) Acetaldehyde, acetone, Di-tert butyl ketone, Methyl tert-butyl

ketone(reactivity towards HCN)

Ans. Di-tert butyl ketone Methyl tert-butyl ketone acetone

Acetaldehyde

(ii) Benzoic acid, 4-Nitrobenzoic acid, 3,4-Dinitrobenzoic acid, 4-Methoxy

benzoic acid.(increasing order of acid strength)

Ans. 4-Methoxy benzoic acid Benzoic acid 4-Nitrobenzoic acid 3,4-

Dinitrobenzoic acid

(iii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH,

(CH3)2CHCOOH,CH3CH2CH2COOH (Increasing order of acid strength)

Ans.(CH3)2CHCOOH CH3CH2CH2COOH CH3CH(Br)CH2COOH

(iv) CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3(increasing order of boiling

point)

Ans. CH3CH2CH3 CH3OCH3 CH3CHO CH3CH2OH

(v) Benzaldehyde, p-Tolubenzaldehyde p-Nitrobenzaldehyde,

Acetophenone.(reactivity towards HCN)

Ans. Acetophenone p-Tolubenzaldehyde Benzaldehyde p-

Nitrobenzaldehyde

6. Complete the reaction:-

 (i) ? (ii) ?
Ans. Ans.

(iii) ? (iv) ?

Ans. Ans.

(v) ? (vi) ?

Ans. Ans.

(vii) ? (viii)

Ans. Ans.

(ix) ? (x) ?
 Ans. Ans.

(xi) ?.

Ans.

(xii) ? xiii)

Ans. Ans.

(xiv) ? (xv)

Ans. Ans.

N H 2 -N H 2
(xvi) C H 3 C H 2 C H O K   
O H , g lyc o l,Δ
(xvii)

Ans. CH3CH2CH3 Ans.

SHORT ANSWER TYPE QUESTIONS (2 OR 3 MARKS EACH)

7. A compound 'A' (C2H4O) on oxidation gives 'B' (C2H4O2). 'A' undergoes
iodoform reaction. On treatment with HCN, 'A' forms a product 'C' which
on hydrolysis gives 2-hydroxypropanoic acid. Give the structures of A, B
and C

Ans.

8. The compound C4H8Cl2 (A) on hydrolysis gives a compound C4H8O(B).

The compound (B) reacts with hydroxylamine and gives negative Tollen's
Test. Give the structural formula of the compounds (A) and (B).

Ans.

9. An organic compound (A), C8H6, on treatment with dilute sulphuric acid

containing mercuric sulphate gives a compound (B), which can also be
obtained from a reaction of benzene with an acid chloride in presence of
anhydrous AlCl3. The compound (B), when treated iodine and aqueous KOH
yields (C) and a yellow compound (D). Identify A – B.
Ans.
1. An organic compound (A) with molecular formula C8H8O forms an orange-red
precipitate with 2,4-DNP reagent and gives yellow precipitate on heating with iodine in
the presence of sodium hydroxide. It neither reduces Tollens’ or Fehlings’ reagent, nor
does it decolourise bromine water or Baeyer’s reagent. On drastic oxidation with chromic
acid, it gives a carboxylic acid (B) having molecular formula C7H6O2. Identify the
compounds (A) and (B) and explain the reactions involved.

Ans.

2. An organic compound with the molecular formula C9H10O forms 2,4-DNP derivative,
reduces Tollens’ reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it
gives 1,2-benzenedicarboxylic acid. Identify the compound.
Ans.

3. 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). (C) on dehydration gives but-1-ene.Write equations for the
reactions involved.

Ans.

4. An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The
molecular mass of the compound is 86. It does not reduce Tollens’ reagent but forms an
addition compound with sodium hydrogen sulphite and give positive iodoform test. On
vigorous oxidation it gives ethanoic and propanoic acid. Write the possible structure of
the compound.

Ans.
5. Propose a mechanism of formation of cyanohydrin by reaction of HCN
with acetaldehyde in presence of alkali.

Ans.

6. Write the mechanism of esterification of carboxylic acid.

Ans.

7. An alkene with molecular formula C5H10 on ozonolysis give a mixture of two

compounds, B and C. Compound B gives positive Fehling test and also reacts with iodine
and NaOH solution. Compound C does not give Fehling solution test but forms iodoform.
Identify the compounds A, B and C.

Ans.
17. A, B, C are three non-cyclic functional isomers of a carbonyl compound with molecular
formula C4H8O. isomers A and C gives positive Tollen’s test whereas isomer (B) does
not give Tollen’s test but gives positive iodoform test. Isomers A and B on reduction
with Zn(Hg)/conc. HCl give the same product D.
(i)Write the structure of A, B, C and D.
(ii).Out of A, B and C isomers which one is least reactive towards of addition of
HCN.

Ans.

(i) (A)

(B)

(C)

(D)

(ii) B is least reactive.

18. Carry out following conversions

i. Benzoic acid to aniline

ii. Bromoethane to ethanol
iii. P-nitrotolune to 2-bromobenzoic acid
iv. Propanoic acid to acetic acid

Ans.

i.

ii.

iii.
iv.