chemistry

ALDEHYDES KETONES CARBOXYLIC ACIDS

Sakshi Vora

IIT - Roorkee

10th, 12th CBSE State Topper

7+ Years of Teaching Experience

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SAKSHI SAKSHI
Aldehydes
Methods of
preparation
From Alcohol (By Oxidation) :
● Primary alcohols can be oxidised to aldehydes by using
pyridinium chlorochromate (P.C.C) (C5H5NH CrO3Cl-).
● A stronger oxidising agent (e.g. KMnO4) oxidizes primary
alcohols to carboxylic acids.
From Alcohol (By Catalytic Oxidation) :

When vapours of a primary alcohol are passed over heated copper

(or zinc oxide) at 300o, aldehyde (or ketones) are formed.
From Alkene (Ozonolysis) :
Desired aldehyde and ketones can be obtained by ozonolysis of
appropriate alkenes.
Practice
questions
[Sep. 06, 2020 (I)]
[April 12, 2019 (I)]
From Alkene
Acetaldehyde is formed on passing acetylene in 40% aqueous
solution of H2SO4. It is called Kucherov’s reaction
From Grignard’s Reagent :
From Vicinal Glycols
Carbonyl compounds are obtained on oxidation of vicinal
alkanediols by periodic acid or lead tetraacetate
From carboxylic acid :
When vapours of carboxylic acid are passed on manganese oxide
MnO at 300oC, then carbonyl compounds are formed.
From Alkyne (Hydroboration) :
Practice
questions
[Sep. 04, 2020 (II)]
By the Hydrolysis of oximes and accetals :
Methods of
preparation
only for
aldehydes
Rosenmund Reaction :

Formaldehyde cannot be prepared by Rosenmund reaction,

because HCOCl is not a stable compound
Methods of
preparation
only for
ketones
From Alkyl Cyanide

Alkanones are formed on hydrolysis after reaction of an alkyl

magnesium halide with ethyl cyanide or its higher homologue.

O
Chemical properties
Nucleophilic
Addition/substitution
Nucleophilic Addition/Substitution
PRACTISE QUESTIONS
[Sep. 03, 2020 (II)]
[Sep. 02, 2020 (I)]
[April 9, 2019 (I)]
REACTION WITH HCN
Reaction with Hydrogen Cyanide :
Note

Reaction takes place in presence of mild base which abstract H+

from HCN and produce CN- ion which acts as nucleophile.
Reactions of cyanohydrin
REACTION WITH
sodium bisulphite
Reaction with sodium bisulphite :

Carbonyl compound form a white crystalline addition product with

sodium bisulphite called Aldehyde / Ketone sodium bisulphite
adduct.
Note

A. Bisulphite adduct is an important compound because it gives

carbonyl compound on further hydrolysis.
B. The above reaction is used in purification of carbonyl
compound.
C. The reaction is given by only methyl ketone & aldehyde.
REACTION WITH
Grignard reagent
Reaction with Grignard Reagents
REACTION WITH
Ammonia derivatives
Reaction with Ammonia derivatives :
(i) with Hydroxylamine :

(ii) with Hydrazine :

(iii) with Phenylhydrazine :

(iv) With 2, 4 dinitrophenyl hydrazine :

On reacting a carbonyl compound with 2, 4 - dinitrophenylhydrazine, a

yellow precipitate of 2, 4 - dinitrophenylhydrazone derivative is
obtained.
(v) With Semicarbazide :
REACTION WITH
Alcohols
Reaction with Alcohol :

In the presence of catalyst (HgO.BF3) aldehydes form acetal with

alcohol while ketone from ketal with alcohol.
Reaction with Alkane Thiol :

Aldehyde form thio acetal with alkane thiol while ketone form thio ketal
with alkane thiol.
Aldol
condensation
reaction
Aldol Condensation :

In the presence of small amounts of hydroxide ions two molecules of

the carbonyl compound containing α - hydrogen atoms, give a β -
hydroxy carbonyl compound.

As a source of hydroxide ions, a few drops of very dilute aqueous

solution of K2CO3, Na2CO3, NaOH, KOH, Ca(OH)2, Ba(OH)2 etc. are
added.
Aldol Condensation :
Examples of
aldol
condensation
Cross Aldol Condensation :
Intramolecular aldol condensation
● It is given by dialdehydes or diketones.
● The diketones should be 2, 5; 2, 6; 2, 7; and 2, 8 diketones.
● If the diketone is 2,7 2,8 or 2,9 then inner alpha carbon converts
into carbanion so that a 5 or 6 membered ring is formed
Practise
questions
[Jan. 09, 2020 (II)]
[April 9, 2019 (II)]
[Jan. 08, 2020 (II)]
CANNIZZARO’S
REACTION
Cannizzaro Reaction :
Carbonyl compound in which α - H atom is absent, when react with
strong base like NaOH or KOH then forms sodium and potassium salt
of carboxylic acid and alcohol.
Cross Cannizzaro Reaction :

If two different aldehydes (α - hydrogen less) are used then one of the
aldehyde undergoes oxidation while other aldehyde undergoes
reduction.
Ph - CHO + HCHO

Conc. NaOH

H - COO- Na + Ph - CH2OH

Note : α - hydrogen less aldehyde having more electron deficient

carbonyl carbon undergoes oxidation.
[Sep. 03, 2020 (II)]
[April 10, 2019 (I)]
OXIDATION
REACTIONS
Oxidation :

Aldehyde on oxidation forms respective acid while ketone forms less

carbon carboxylic acid on oxidation according to popoff’s rule
BAEYER VILLIGER
OXIDATION
If the oxidising agent is performic acid then aldehyde oxidises
into respective acid while ketone oxidises into ester. The
reaction is called ‘Baeyer - villiger Oxidation’.
MCPBA ⟶ meta chloroperbenzoic acid

O is inserted according to the migratory order of the group

3o alkyl >> cyclohexyl >> 2o alkyl >> benzyl = phenyl >> vinyl >> 1o >> methyl
Reduction
reactions
Reduction :
Aldehyde on reduction form primary alcohol while ketone on
reduction form secondary alcohol.
Important
name reactions
Note :

A. If reducing agent is Na+C2H5OH then reaction is called

'Bouveault-Blanc Reaction'.

A. If reducing agent is (red P/HI) then product will be alkane.

Note :

A. If reducing agent is Zn-Hg/conc. HCl then product will be alkane.

Reaction is called 'Clemmensen- Reduction'.

A. If reducing agent is alkaline solution of hydrazine, product will

be alkane. Reaction is called 'Wolff - kishner Reduction'.

A. If reducing agent is aluminium isopropoxide (CH3 - CH - O -)3Al,

Then product will be alcohol.
Reaction is called ‘ Meerwein - Ponndorf Verley Reduction’.
Note :

LAH can’t reduce

ALCOHOL, AMINES, ORDINARY ALKENES
It can reduce cinnamic double bonds

SBH reduces
Acid halide, aldehyde, ketones, imines, halides
Note :

DIBAL H
Reduces Ester, acid halides, cyanides, aldehydes to aldehyde,
aldehyde, aldehyde and alcohol resp

Borane/ THF
Reduces acid and esters but not acyl halides
[April 9, 2019 (I)]
[Jan. 08, 2020 (I)]
[Sep. 04, 2020 (II)]
[Jan. 07, 2020 (I)]
Reactions shown
by
aldehydes only
Reactions with Tollen’s Reagent :
Ammoniacal silver nitrate solution is called Tollen’s reagent.
Aldehyde reduce the tollen’s reagent and form silver mirror.
Aldehyde oxidises itself into carboxylic acid.
Reactions with Tollen’s Reagent :

Note : In the above reaction oxidation number of Ag varies from +1 to 0.

Reactions with Fehling solution:

It is the mixture of two solution

Fehling solution A and Fehling solution B.

Fehling Solution A: Aqueous solution of CuSO, (blue)

Fehling Solution B: Alkaline solution of Roschelle salt
(sodium potassium tartarate)
Reactions with Fehling solution:

● By the mixing of both solution we get a dark blue colour solution

called final fehling solution.
● Reacting species of this solution is cupric oxide CuO

NOTE : Oxidation number of copper varies from +2 to +1

[Adv. 2015]
Carboxylic acids
Methods of
preparation
By the oxidation of alcohols, aldehydes and ketones :

[0]
(a) 1o Alcohol corresponding carboxylic acids.

(b) Aldehyde [0] Corresponding acids.

[0]
(c) Ketones mixture of acids of lesser no. of C atoms
than the ketone.
By the hydrolysis of cyanides (nitriles) :

Cyanides on complete hydrolysis in the presence of dilute HCl

form carboxylic acids.
From hydrolysis of acid derivatives :

(a) From acyl halides :

(b) From acid anhydride :

From carboxylic ester (Hydrolysis of Ester) :

Hydrolysis of ester possible in acidic medium as well as in

basic medium.
[Jan 10, 2019 (I)]
[Adv. 2020]
From carboxylation of grignard reagent :

By passing CO2 in ether Solution of Grignard’s reagent

CHEMICAL
PROPERTIES
Acidic Nature :
Carboxylic acids are weakly acidic

Both the acid and anion are resonance stabilised, but

stabilisation is more powerful between exactly equivalent
resonating structures of the carboxylate ion.
Effect of Substituents on Acidity
[Jan 9, 2019 (I)]
[Adv.
2019]
[Sep. 02, 2020 (II)]
Reactions due to alkyl group :
HVZ RECATION : Acids having α - H atom give this reaction. The
α - H atoms are easily replaced by chlorine or bromine atoms,
forming halogen derivatives of acids.
Note :
(i) The reaction is known as Hell - Volhard - Zelinisky (HVZ)
reaction.

(ii) In the presence of phosphorus, monohalo product is formed

as the main product.

(iii) Formic acid does not show HVZ reaction due to absence of
alkyl group or α - H atom.
Due to acidic Hydrogen :
Salt Formation - Carboxylic acids form salts with metals, metal
oxide, hydroxides, carbonates, bicarbonates and compounds
showing basic nature.
Note :
Acids liberate CO2 with NaHCO3. This reaction is used to
distinguish carboxylic acid from phenol which does not react
with NaHCO3.
[Adv.
2013]
Reaction due to (-COOH) group :

(a) Decarboxylation of Carboxylic Acids

On heating carboxylic acids with soda - lime (NaOH and CaO).
an alkane is obtained with one carbon less than the carboxylic
acids.
[Adv. 2019]
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SAKSHI SAKSHI