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 ALDEHYDES KETONES
STRUCTURE OF CARBONYL GROUPS :
The >C = O bond in aldehyde and ketones is made up of one  and one  -bond around the carbon
oxygen bond.

..... .........
6 ........ .....
. sp2 – p
C. O.
.... ....
......... .........

The electron cloud of the  -bond lies both above and below the C = O,  bond
O O
|| ||
R — C— H R — C— H
Aldehyde Ketone

NOMENCLATURE OF ALDEHYDE AND KETONES :

The suffix term for aldehyde is ‘al’ and for ketone is ‘one’.

O O
C H3  C H  C H  C HO || ||
4 3 2 1
(a) (b) CH 3  C  C CH3
But  2  en  1  al Butane  2, 3  dione

O
C
(c) O (d) CH3
Benzophenone 2-Methyl-cyclohexanone
Aldehyde and ketones are functional isomers to each, due to which their properties largely resembles to
each other.

GENERAL METHODS OF PREPARATION OF ALDEHYDES AND KETONES:

(1) BY DRY-DISTILLATION OF CALCIUM SALT OF CARBOXYLIC ACIDS :

O
H—C—O
Ca HCHO + CaCO3
H—C—O
(a) formaldehyde
O
Calcium formate

[1]
 O O
H—C—O CH3— C — O
Ca + Ca CH3 – CHO + 2CaCO3
(b) H — C — O CH3 — C — O
O O

2. BY ROSENMUND’S REDUCTION:
Only aldehydes can be synthesised by this reaction.

O
Pd-BaSO4 ,S
R — C — Cl + H2 H — Cl + R — C — H
Boiling Xylene
Acid-chloride O
Aldehydes

Pd  BaSO ,S
4  C H  C H
C6 H5  C Cl  H 2  6 5
|| Boiling xylene ||
O O
Benzoyl chloride

Note : Formaldehydes can’t be obtained by this method. Ketones also can’t be synthesised by this reaction.

3. FROM NITRILES :

O
||
(i) dry ether
CH3 — C  N  R  Mg Br 

 CH 3 — C — R  Mg  OH  Br
(a) Grignard reagent (ii) H3O  Ketone 
 NH3

(i) Dry  ether

HC  N R Mg Br 

 R  C H  Mg  OH  Br
Grignard reagent (ii)H3O ||
(b)  NH3 O
 Aldehyde 

4. BY HYDROBORATION - OXIDATION OF ALKYNES :

B2H6
CH3 — C C — CH3 THF
CH3 — C = C — CH3
B
H H

Tautomerises
CH3 — C — CH2 — CH3 CH3 — C = C — CH3
O OH
2-Butanone
5. WACKER’S PROCESS :
CuCl
2  CH CHO  Pd  2HCl
CH 2  CH 2  H 2O  PdCl2  3 air
6. OXIDATION OF METHYL BENZENE :
O–C–CH3
CH3 H–C O CHO
O–C–CH3
CrO3
O OH –/H2O + 2CH3 – COOH
(CH3CO) 2O

7. ETARD REACTION :
O–Cr–(Cl2)OH
CH3 H–C CHO
O–Cr–(Cl2)OH
2CrO2Cl2
H2O
CCl 4

Physical Properties :
(1) Boiling - point :
Aldehyde and Ketone molecule are polar molecules due to the presence of carbonyl groups.

C=O
Among isomeric aldehydes and ketones, ketone have slightaly higher boiling point value
O=C
Dipole - Dipole
interaction

Chemical properties of aldehyde and ketones :

Aldehydes and ketones are highly reactive due to the presence of polarized carbonyl groups. The reaction of
aldehyde and ketones can be devided into following categories :
(1) Nucleophilic addition reactions :

Nu– Nu +
Nu
slow H, fast
C=O C C
O OH
Tetrahedral
intermediate
The ability of the highly electronegative oxygen to retain the negative charge over it, causes the nucleophilic
addition reaction at carbon. In addition, nucleophilic attack causes the formation of stable tetrahedral
intermediate.
The relative reactivity of aldehydes and ketone is effected by at least given two factors :
(i) Inductive effect (ii) Steric factors

H R R
C=O C=O C=O
H H R
Reactivity increases
SOME IMPORTANT NUCLEOPHILIC ADDITION REACTION :

1. ADDITION OF SODIUM BISULPHITE

R R R OH
– +
C=O + NaHSO3 C – O Na C
H or R Proton H or R
+
SO–3Na
SO3H transfer
 The position of equilibrium lies largely to the right for most aldehyde and for most of ketones it lies
toward left.

2. ADDITION OF ALCOHOL :
Aldehyde with one molecule of R–OH forms ‘hemiacetal’ and with another molecule it forms acetal.

OR'
R – CHO HCl(g) R – CH R''OH/H
+ OR'
+ R – CH
OH
R' – OH OR''
Hemiacetal Acetal
Ketone, similarly forms hemiketal and ketal.

3. WITH DIOL :

R CH2 – OH R O CH2
H – Cl(g)
C=O + C
R CH2 – OH R O CH2
Ketone Glycol cyclic ketal

4. WITH HCN :
Cyanohydrins is formed

R R CN
C =O PH = 9 to 10
C
H or R H or R OH
Cynohydrin

5. ADDITION OF AMMONIA DERIVATIVES :

The addition of ammonia derivative to aldehyde and ketone is catalysed by weak acids.

R
+ slow R +
C=O + H C = OH
+
H or R H or R
R Nu–
C — OH
H or R Nu

 Due to protonation, the ease of nucleophilic addition becomes faster..

6.
AMMONIA DERIVATIVE USED PRODUCT OBTAINED
Strucutre Name Strucutre Name
NH2OH Hydroxylamine C = N – OH Oxime

NH2–NH2 Hydrazine C = N – NH2 Hydrazone

NH2–NH Phenyldrazine C = N – NH Phenylhydrazone

NO2 NO2
2,4 -Dinit ro- 2,4-Dinitrophenyl-
NH2–NH NO2 phenyldrazine C = N – NH NO2 hydrazone

NH2CONHNH2 Semicarbazide C = NNHCONH2 Semicarbazone

7. OXIDATION OF ALDEHYDE AND KETONES

Oxidation

(A) Strong Oxidising agents (B) Weak Oxidizing agents

(1) KMnO4 (2) K2Cr2O7 (i) Fehling solution

(3) HNO3 (ii) Tollen's Reagent
(iii) Benedict solution

(A) Strong Oxidising agents :

KMnO or
4  R  COOH
(a) R  C  H 
|| K 2Cr2O7
O Carboxylic acid
Aldehyde

(B) Oxidation by weak oxidising agents :

The given reactions are also used to distinguish between aldehyde and ketones.
(i) By Tollen’s reagent :


R  CHO  2  Ag  NH3 2   3OH  
 R  COO   2H 2O  4NH 3  2Ag 
Tollen 's Silver
reagent mirror test

(ii) Fehling’s solution :

R  CHO  2Cu 2   5OH 

 R  COO  Cu 2 O 3H 2 O
Brown
(C) Oxidation of methyl ketones by Haloform reaction :
O O
|| || 
NaOX
R — C— CH3 
 R — C— ONa  CHX 3
8. REDUCITON :
(a) To alcohol
Reduction :
(b) To alkane
(A) To alcohols :
LiAlH or
4  R — CH — OH
R — CHO  2
NaBH 4

(B) To alkane :
(i) Clemmenssen’s reduction:
Zn-Hg
C=O HCl
CH2 + H2O
alkane

(ii) Wolff-kishner reduction:

H2N – NH2
C=O –H2O
C = N – NH2
KOH-Glycol

H
C +N2
H
alkane

9. REACTION INVOLVING  -HYDROGEN (ALDOL-CONDENSATION REACTION) :

Aldehyde and Ketones having  H undergoes condensation in presence of these dilute base to form aldol.
Thus reactions are also called as aldol condensation reactions.
dil.NaOH
2CH3  CHO 
 CH3  CH  CH 2  CHO
|
OH
(Acetaldol)
Mechanism :

H O
+
–H /OH
– (..) (..)
– – –
H C C = H + OH H—C—C=O H–C = C–O
(Base)
H H H H H

2nd Step :

H O H O H OH
| | | |
H
H — C —— C + CH2 — CHO H  C C  CH 2  CHO 
 H  C  CH  CH 2OH
– | | |
H H H H H
 Aldol 
 Note: The aldol formed may undergo dehydration in presence of dilute acids, upon heating.
H OH
| |
H SO / 
2 4  H C  CH  CHO  H O
H  C CH  CH 2OH  2 2
|
H
Cross Aldol condensation reaction:
Na  OH

CH3  CHO  CH3  CH 2  CHO 
CH3
|
CH 3  CH  CH 2  CHO  CH3  CH 2  CH  CH  CHO
| |
OH self aldol products OH

 CH3  CH  CH  CHO  CH3  CH 2  CH  CH 2  CHO

| | |
OH CH3 OH
cross aldol products

Electrophilic Substitution reaction :

Aromatic aldehydes and ketones, gives rise to electrophilic substitution reaction at meta position. The carbonyl
groups acts as deactivating, group for incoming electrophiles

– – –
H–C=O H–C–O H–C–O H–C–O H–C=O

+ +

H–C O

Resonance hybrid:

NO2
(1) Nitration:
CHO CHO

HNO3
+
H

NO2