Live Sahab20

Aldehydes, Ketones &

Carboxylic Acids
By Singh Sahab
Introduction
Aldehyde Ketone Carboxylic Acid

Carboxyl
Group

Ex. Ex. Ex.

CH3 – C – H CH3 – C – C2H5 CH3 – C – OH

|| || ||
O O O
Preparation of Aldehydes
1. By oxidation of alcohols
2. By Ozonolysis

1. O3

2. Zn/H2O
3. By hydration of alkynes:
4. From acyl chloride (acid chloride)

Rosenmund reduction
5. From nitriles and esters

Stephen reaction

1. SnCl2 + HCl
CH3 – CN CH3 – CHO
2. H 2O
Nitriles reduced by (DIBAL-H)
Diisobutylaluminium Hydride
Esters reduced by (DIBAL-H)
 6. From Hydrocarbons

(a) Étard Reaction

1. CrO2Cl2 / CS2
2. H 2O

CrO2Cl2 = Chromyl Chloride

(b)

1. CrO3 + Anhydride

2. H 2O
7. By side chain chlorination
8. By Gatterman – Koch reaction
Preparation of Ketone
1. By oxidation of alcohols

PCC / CrO3
CH3 – CH – CH3 CH3 – C – CH3
| ||
OH O
2. Ozonolysis

1. O3

2. Zn + H2O
3. From acyl chlorides

CH3 – C – Cl + (C2H5)2Cd CH 3 – C – C2H5 + CdCl2

|| ||
O O
4. From nitriles
5. Benzene

Friedel-Crafts acylation reaction

Preparation of Carboxylic Acids
1. By oxidation of alcohols & aldehydes
 Mild O.A.
CH3 – CHO (CrO3)
CH 3 – COOH

Oxidation
Aldehydes Carboxylic Acids

Oxidation Oxidation
CH3 – CH2 – OH CH3 – CHO CH3COOH
2. From alkylbenzenes

KMnO4 / H+

Alkyl Group should be 1o or 2o

3. From nitriles

Hydrolysis of nitriles gives carboxylic acids

4. From amides
5. From acyl halides
6. From anhydrides
7. From esters
8. From Grignard reagents
Chemical Reactions of Aldehydes
and Ketones
1. Nucleophilic addition reactions

a) Mechanism:

H+
Step 1 Step 2

Slow Fast
b.) Reactivity

O O O CH3
|| || || |
CH3 – C – H > CH3 – C – CH3 > CH3 – C – C – CH3
|
CH3

Reactivity  1
Hindrance
Example
c.) Addition of Grignard reagents:

Two Steps:
d.) Reaction with ammonia and its derivatives
Ammonia Imine
Amine Substituted imine
(Schiff’s base)
Hydroxylamine Oxime
Hydrazine Hydrazone
Phenylhydrazine Phenylhydrazone
Semicarbazide Semicarbazone
2. Reduction to hydrocarbons:

a.) Clemmensen Reduction

O
||
Zn-Hg
CH3 – C – H HCl
CH3 – CH2 – H

O
|| Zn-Hg
CH3 – C – CH3 HCl
CH3 – CH2 – CH3
b.) Wolff-Kishner reduction
 O
|| 1. NH2 – NH2 / KOH
CH3 – C – H CH3 – CH2 – H
2. Ethylene Glycol

O
|| 1. NH2 – NH2 / KOH
CH3 – C – CH3 CH3 – CH2 – CH3
2. Ethylene Glycol
3. Reduction to alcohols:

H2
Ni/Pd/Pt
CH3 – CH2 – OH Catalytic Hydrogenation

NaBH4
CH3 – CHO CH3 – CH2 – OH
Aldehyde

LiAlH4
CH3 – CH2 – OH
 OH
H2
|
Ni/Pd/Pt CH3 – CH2 – CH3

O OH
|| |
NaBH4
CH3 – C – CH3 CH3 – CH2 – CH3

Ketone
OH
|
LiAlH4
CH3 – CH2 – CH3
4. Tollens’ test:

Reagent- Ammonical silver nitrate solution

Oxidation

It is also silver mirror test

5. Fehling’s test:

Oxidation

• Aldehyde gives Red Brown ppt with Fehling’s Test

• Aromatic aldehydes do not respond to this test.

Gives Tollen’s Test

Do not give Fehling Test

6. Haloform reaction
Iodoform
7. Aldol condensation

Reactant- presence of at least one α-hydrogen

Reagent- dilute base(NaOH, KOH, Ca(OH)2)

Product- β-hydroxy aldehydes (aldol)

or
β-hydroxy ketones (ketol)
Alcohol Aldehyde α,β-unsaturated
carbonyl compound
ol Ald

Aldol
8. Cross-Aldol Condensation

Two different aldehydes and / or ketones are used.

Dil. NaOH
CH3 – CH=O + CH2 – CHO
|
CH3
1. Ethanal + Ethanal

CH3 – CH=O + CH3 – CH=O CH3 – CH = CH – CHO

2. Propanal + Propanal

CH3 – CH2 – CHO + CH2 – CHO CH3 – CH2 – CH = CH – CHO

| |
CH3 CH3
3. Ethanal + Propanal

CH3 – CHO + CH2 – CHO CH3 – CH = C – CHO

| |
CH3 CH3

4. Propanal + Ethanal

CH3 – CH2 – CH=O + CH3 – CH=O CH3 – CH2 – CH = CH – CHO

 9. Cannizzaro reaction

Reactant- no α-hydrogen

Reagent- conc. Base (NaOH, KOH)

Product- If only one Reactant then it is disproportionate reaction

(Alcohol and Carboxylate salt)
10. Nitration

Electron withdrawing groups (-M Effect)

Chemical Reactions of
Carboxylic Acids
1. Formation of anhydride
2. Esterification
3. Reduction of Carboxylic Acid

Sodium borohydride does not reduce the carboxyl group.

4. Decarboxylation
5. Halogenation

Also known as Hell-Volhard-Zelinsky reaction

6. Some Other Reactions
7. Reaction with ammonia
8. Acidic Nature
Carboxylic acids dissociate in water to give resonance stabilised
RCOO- and H3O+
The effect of the following groups in increasing acidity order is

Ph < I < Br < Cl < F < CN < NO2 < CF3

Acidity

CF3 – COOH > CN – COOH > Cl – COOH

Acidity

< <
OCH3 NO2