Aldehydes and Ketones 1255

60
Chapter

27

E3
Aldehydes and Ketones

Introduction
Carbonyl compounds are of two types, aldehydes
and ketones. Both have a carbon-oxygen double bond
often called as carbonyl group.
ID Preparation of carbonyl compounds
(1) From alcohols (i) By oxidation.
O
U
OH O
| ||
C R  CH  R '    R  C  R '
Mild oxidising
Carbonyl group Secondary alcohol agents Ketone
YG

O
||

Both aldehyde and ketones possess the same R  CH 2  OH    R  C  H

Mild oxidising

Primary alcohol agents Aldehy de

general formula Cn H 2n O . Mild oxidising agents are
(a) X 2 (Halogen) (b) Fenton reagent
Structure : Carbonyl carbon atom is joined to
three atoms by sigma bonds. Since these bonds utilise ( FeSO 4  H 2 O2 )

sp 2 -orbitals, they lie in the same plane and are 120°
D

(c) K 2 Cr2 O7 / H (d) Jones reagent

apart. The carbon-oxygen double bond is different than (e) Sarret reagent (f) MnO 2
carbon-carbon double bond. Since, oxygen is more (g) Aluminium tertiary butoxide
[ Al(O  C(CH 3 )3 )3 ]
U

electronegative, the electrons of the bond are attracted

towards oxygen. Consequently, oxygen attains a partial  When the secondary alcohols can be oxidised to
negative charge and carbon a partial positive charge ketones by aluminium tert-butoxide, [(CH 3 )3 CO]3 Al the
ST

making the bond polar. The high values of dipole reaction is known as oppenauer oxidation. Unsaturated
  secondary alcohols can also be oxidised to unsaturated
moment, C O ketones (without affecting double bond) by this reagent.
(2.3 – 2.8D) cannot be explained only on the basis  The yield of aldehydes is usually low by this
methods. The allylic alcohols can be converted to
of inductive effect and thus, it is proposed that
aldehydes by treating with oxidising agent pyridinium
carbonyl group is a resonance hybrid of the following
chloro-chromate (C 5 H 5 NH  CrO 3 Cl  ) . It is abbreviated as
two structures.
PCC and is called Collin's reagent. This reagent is used
  in non-aqueous solvents like CH 2 Cl 2 (dichloro methane).
C  O  C O
It is prepared by mixing pyridine, CrO3 and HCl in

120°
dichloromethane. This is a very good reagent because it
-bond checks the further oxidation of aldehydes to carboxylic
120° C O
-bond
120°
 1256 Aldehydes and Ketones
acids and is suitable method for preparing ,- O O
|| ||
unsaturated aldehydes. MnO / 300 C
R  C  OH  R COO H  R  C  R  CO 2  HOH
(ii) Dehydrogenation of 1° and 2° alcohols by Carboxy lic acid
Ketone

Cu/300° or Ag/300°C.
O (3) From gem dihalides : Gem dihalides on
||
Cu / 300 C hydrolysis give carbonyl compounds
R  CH 2 OH 
 R  C  H  H 2

OH O (i) R  CHX 2   R  CHO
HOH / O H
| || Gemdihalid e Aldehy de
Cu / 300 C
R  CH  R '    R  C  R '  H 2
X O

(2) From carboxylic acids | ||
(ii) R  C  R '   
 R  C  R '
HOH / O H
|

60
(i) Distillation of Ca, Ba, Sr or Th salts of
X
monobasic acids
 This method is not used much since aldehydes
O
|| are affected by alkali and dihalides are usually prepared

(RCOO )2 Ca  (R ' COO )2 Ca  2 R  C  R' 2CaCO 3 from the carbonyl compounds.
(4) From alkenes

E3
Thus in the product, one alkyl group comes from
one carboxylic acid and other alkyl group from other (i) Ozonolysis : Alkenes on reductive ozonolysis
carboxylic acid. give carbonyl compounds
Calcium salts of dibasic acid (1, 4 and higher) on
R  CH  CH  R   R  CHO  RCHO
(i) O3
distillation give cyclic ketones. Alkene (ii) H 2O / Zn

C H2  C O
|
CH 2  C  O
O
||

||
O


Ca   

 
Distillation

Cyclopropanone
O+CaCO3

O
ID R

R
CC

Alkene
R'

R'

(i) O3

(ii) H O / Zn
2
O
||
 R  C  R  R '  C  R '
O
||
U
 This method is used only for aliphatic carbonyl
 O  compounds.
  || 

O  C  (CH 2 )5  COO  Ca  
Distillation
(ii) Oxo process
 
YG

  CO 2 (CO )8
Cyclohexanone R  CH  CH 2  CO  H 2   R  CH 2  CH 2  CHO
150 C , 300 atm

(ii) Decarboxylation or Dehydration of acids  Oxo process is used only for the preparation of
by MnO/300°C. aldehydes.
(a) This reaction takes place between two (iii) Wacker process
molecules of carboxylic acids. Both may be the same or
(a) CH 2  CH 2    CH 3  CHO
PdCl 2 / HOH
D

different. Ethene air / Cu 2Cl 2

(b) If one of the carboxylic acids is HCOOH then O

||
this acid undergoes decarboxylation because this acid is (b) R  CH  CH 2 
 R  C  CH 3
PdCl 2 / HOH
U

the only monobasic acid which undergoes Alky l ethene air/Cu 2 Cl 2

decarboxylation even in the absence of catalyst. (5) From alkynes

Case I : When both molecules are HCOOH O
ST

O H2O/HgSO4
O R – C – CH3
|| || /H2SO4
H  C  OH  H COO H  CO 2  HOH  H  C  H
MnO

formic acid 300 C formaldehyde R–CC–H

(i) SiO2 BH3
Case II : When only one molecule is formic acid. R – CH2 –

O O (ii) H2O2/ CHO
||
MnO / 300 C
|| OH
R  C  OH  H  COO H   R  C  H  CO 2  HOH (6) From Grignard reagents
formic acid Aldehy de
Carboxy lic acid O O
Case III : When none of the molecule is formic R' – C – Cl (Only
R' – C –
acid. R ketone)
O
HCOOC2H5
H – C – R (Aldehyde)

O
R' COOC2H5
R–C– (Ketone)
R – MgX R'
O
(Excess)
 Aldehydes and Ketones 1257
R  CH 2 Cl   R  CHO ;
DMSO

Cl O
| ||
R  C H  R 
 R  C  R
DMSO

DMSO or (i) (CH 2 )6 N 4

C 6 H 5  CH 2 Cl 
        C 6 H 5  CHO
(ii) H 2 O / H or Cu ( NO 3 )2 or Pb ( NO 3 )2

(11) From nitro alkanes : Nitro alkanes having at

least one  -hydrogen atom give carbonyl compounds
on treatment with conc NaOH followed by 70% H 2 SO 4 .
The reaction is known as Nef carbonyl synthesis.

60
O O H2 OH
NaOH
R  CH 2  N   R  C H  N
Tautomeris ation
O O
(Aciform)

 R  CHO
70 % H 2SO 4

Aldehy de

E3
(7) From acid chloride
R O O
(i) Acid chlorides give nucleophilic substitution ||
reaction with dialkyl cadmium and dialkyl lithium CH  N   R  C  R
(i) NaOH
(ii) H 2 SO 4 Ketone
cuprate to give ketones. This is one of the most R O
(Iso- nitro alkane)
important method for the preparation of ketones from
acid chlorides. (12) Reaction with excess of alkyl lithium :
O
||
R  C  Cl 
O
||
O
 R  C  R '
R ' 2 Cd
||

O
||
ID Carboxylic acids react with excess of organo lithium
compound to give lithium salt of gem diols which on
hydrolysis give ketones.
O
||
O
||
R  C  Cl  R  C  R'
R ' 2 CuLi (i) R  Li (excess)
R'  C  OH   R'  C  R
U
(ii) HOH / H
(Only used for the preparation of ketones)
In this method product is always ketone because Preparation of only aromatic carbonyl
R  H and also R'  H . compounds
YG

(ii) Rosenmunds reduction : This reduction takes (1) From methyl arenes
place in the presence of Lindlars catalyst. (i)
CrO2Cl2 C6H5CHO
O O (ii) HOH (Etard's
|| || reaction)
H 2 / Pd  BaSO 4  CaCO 3
R  C  Cl   R  C  H C6H5 –
(i) CrO3 /(CH3CO)2O/CH3COOH
Xy lene C6H5 CHO
CH3 (ii) H2O
O O Toluene Air/MnO
|| ||
D

H 2 / Pd  BaSO 4  CaCO 3 C6H5 CHO

Ar  C  Cl        Ar  C  H 500°C
Xy lene

(Only used for aldehydes) (2) From chloro methyl

Cu(NO3)2/
(8) From cyanides C6H5CH
U

(i) Stephen aldehyde synthesis : Conversion of O

Pb(NO3)2/
cyanides into aldehydes by partial reduction with C6H5 – C6H5 – CHO
SnCl 2 / HCl , followed by hydrolysis, is known as CH2Cl
ST

(i)
Stephens aldehyde synthesis.
(CH2)6N4 / C6H5 – CHO
R  C  N 
 R  CHO
(i) SnCl 2 / HCl / ether (ii) H2O
Alky l cy anide (ii) H 2O /  or steam distillati on Aldehy de
(3) Gattermann – Koch formylation : This
(Only used for aldehydes)
reaction is mainly given by aromatic hydrocarbons and
(9) From vic diols CHO
halobenzenes.
OH OH O
| | ||
R  CH  C  R  RCHO  R  C  R  H 2 O
HIO4
CO/HCl /Anhy. ZnCl2
| /Cu2Cl2
R
 Pb(OCOCH 3 )4 also gives similar oxidation Benzene Benzaldehyde
products. CH3 CH3 CH3
(10) From Alkyl halides and benzyl halides
CHO
CO/HCl /Anhy. ZnCl2
/Cu2Cl2 +

Toluene
o-methyl CHO
benzaldehyde p-methyl
benzaldehyde

Cl Cl Cl
 1258 Aldehydes and Ketones

(6) Reimer – Tiemann reaction : Phenol gives o-

and p- hydroxy benzaldehyde in this reaction.
OH OH OH

(i) CHCl3 CHO

/Alc.KOH/
(ii) H2O/H+ +

phenol

60
(major) CHO
(Minor)
Physical properties of carbonyl compounds
(4) Gattermann formylation : This reaction is (1) Physical state : Methanal is a pungent smell
mainly given by alkyl benzenes, phenols and phenolic gas. Ethanal is a volatile liquid, boiling points 294 K.

E3
ethers. Other aldehydes and ketones containing up to eleven
CH3 CH3 CH3 carbon atoms are colourless liquids while higher
members are solids.
CHO (2) Smell : With the exception of lower aldehydes
(i) Zn(CN)2 /HCl gas
(ii) H2O/
+ which have unpleasant odours, aldehydes and ketones

Toluene o-methyl
benzaldehyd
e
CHO
p-methyl
ID
benzaldehyd
e
have generally pleasant smell. As the size of the
molecule increases, the odour becomes less pungent
and more fragrant. In fact, many naturally occurring
aldehydes and ketones have been used in blending of
perfumes and flavouring agents.
U
OH OH OH
(3) Solubility : Aldehydes and ketones upto four
CHO carbon atoms are miscible with water. This is due to
(i) Zn(CN)2 /HCl
gas + the presence of hydrogen bonding between the polar
(ii) H2O/
YG

carbonyl group and water molecules as shown below :

–

Phenol o- CHO + – + O + –
salicylaldehyd p- +
e salicylaldehyd C O H H O=C
OCH3 OCH3 e OCH3 With the increase in the size of alkyl group, the
solubility decreases and the compounds with more than
(i) Zn(CN)2 /HCl CHO four carbon atom are practically insoluble in water. All
D

gas
(ii) H2O/ +
aldehydes and ketones are, however, soluble in organic
o-methoxy solvents such as ether, alcohol, etc. The ketones are
Anisol
benzaldehyde CHO good solvents themselves.
U

p-methoxy
(4) Boiling points : The boiling points of
benzaldehyde
aldehydes and ketones are higher than those of non
(5) Houben – Hoesch reaction : This reaction is
polar compounds (hydrocarbons) or weakly polar
ST

given by di and polyhydric benzenes.

compounds (such as ethers) of comparable molecular
OH OH
masses. However, their boiling points are lower than
those of corresponding alcohols or carboxylic acids.
(i) RCN/HCl
gas/Anhy.ZnCl
This is because aldehydes and ketones are polar
(ii) H2O 2

OH compounds having sufficient intermolecular dipole-

OH
dipole interactions between the opposite ends of
Resorcino COR
l C  O dipoles.
2,4-dihydroxy
ketone      
OH OH C  O C  O C  O 
However, these dipole-dipole interactions are
(i) RCN/HCl
gas/Anhy.ZnCl 2
weaker than the intermolecular hydrogen bonding in
(ii) H2O
OH HO OH alcohols and carboxylic acids. Therefore, boiling points
HO
Phloroglucinol COR
2,4,6-trihydroxy
ketone
 Aldehydes and Ketones 1259
of aldehydes and ketones are relatively lower than the charge on the carbon. A greater positive charge means a
alcohols and carboxylic acids of comparable molecular higher reactivity. If the positive charge is dispersed
masses. throughout the molecule, the carbonyl compound
Among the carbonyl compounds, ketones have becomes more stable and its reactivity decreases. Now,
slightly higher boiling points than the isomeric alkyl group is an electron releasing group (+I inductive
aldehydes. This is due to the presence of two electrons effect). Therefore, electron releasing power of two
releasing groups around the carbonyl carbon, which alkyl groups in ketones is more than that of one alkyl
makes them more polar. group in aldehyde. As a result, the electron deficiency
of carbon atom in the carbonyl group is satisfied more
CH 3 .. CH 3 .. in ketones than in aldehydes. Therefore, the reduced
CO: CO:
positive charge on carbon in case of ketones

60
H CH 3
Acetaldehyde Acetone
discourages the attack of nucleophiles. Hence ketones
  2.52 D   2.88 D are less reactive than aldehydes. Formaldehyde with no
b.pt.  322 K b.pt  329 K
alkyl groups is the most reactive of the aldehydes and
(5) Density : Density of aldehydes and ketones is ketones. Thus, the order of reactivity is:
less than that of water.

E3
H R R
Chemical properties of carbonyl compounds CO > CO > CO
Carbonyl compounds give chemical reactions due H H R
to carbonyl group and -hydrogens.
Formaldehy de Aldehy de Ketone

(b) Stearic effect : The size of the alkyl group is

Chemical reactions of carbonyl compounds can be
more than that of hydrogen. In aldehydes, there is one
classified into following categories.
(1) Nucleophilic addition reactions
(2) Addition followed by elimination reactions
(3) Oxidation
ID
alkyl group but in ketones, there are two alkyl groups
attached to the carbonyl group. The alkyl groups are
larger than a hydrogen atom and these cause hindrance
to the attacking group. This is called stearic
(4) Reduction hindrance. As the number and size of the alkyl groups
U
(5) Reactions due to -hydrogen increase, the hindrance to the attack of nucleophile also
increases and the reactivity of a carbonyl decreases. The
(6) Condensation reactions and
lack of hindrance in nucleophilic attack is another reason
YG

(7) Miscellaneous reactions

for the greater reactivity of formaldehyde. Thus, the
(1) Nucleophilic addition reactions reactivity follows the order:
(i) Carbonyl compounds give nucleophilic addition H CH 3 CH 3
reaction with those reagents which on dissociation give
CO > CO > CO >
electrophile as well as nucleophile.
H H CH 3
(ii) If nucleophile is weak then addition reaction Form aldehy de Acetaldehyde Acetone
is carried out in the presence of acid as catalyst.
D

(CH 3 )2 CH (CH 3 )3 C
(iii) Product of addition reactions can be written CO > CO
as follows, (CH 3 )2 CH (CH 3 )3 C
Di- isopropy l ketone Di- tert. buty l ketone
U


O OH In general, aromatic aldehydes and ketones are
||   |
R  C  R '  H  Nu  R  C  R '
Addition
less reactive than the corresponding aliphatic
 |
analogues. For example, benzaldehyde is less reactive
ST

Nu
Adduct
than aliphatic aldehydes. This can be easily understood
In addition reactions nucleophile adds on from the resonating structures of benzaldehyde as
carbonyl carbon and electrophile on carbonyl oxygen to shown below:
give adduct.
(iv) Relative reactivity of aldehydes and ketones
. .– . .–
: Aldehydes and ketones readily undergo nucleophilic H O : H O : H O :
.. .. ..
addition reactions. However, ketones are less reactive
C C C
than aldehydes. This is due to electronic and stearic
effects as explained below: 
(a) Inductive effect : The relative reactivities of
aldehydes and ketones in nucleophilic addition

reactions may be attributed to the amount of positive I II III
 1260 Aldehydes and Ketones
All types of aldehydes give addition reaction with
. .–
O : O this reagent.
H .. H
C C O OH  O
|| |  ||
R  C  H   R  C  H    R  C  H
HSO 3 Na
H or OH or

 | HCHO
SO 3 Na
Adduct; white
cry stalline in nature

IV V Only aliphatic methyl ketones give addition

It is clear from the resonating structures that due reaction with sodium bisulphite.
to electron releasing resonance effect of the benzene
O OH O

60
ring, the magnitude of the positive charge on the || |   ||
carbonyl group decreases and consequently it becomes R  C  CH 3   R  C  CH 3    R  C  H
HSO 3 Na H or OH or
| HCHO
less susceptible to the nucleophilic attack. Thus, SO 3 Na
aromatic aldehydes and ketones are less reactive than Colourless cry stalline
product
the corresponding aliphatic aldehyde and ketones. The
order of reactivity of aromatic aldehydes and ketones  This reagent can be used for differentiation

E3
is,
between aromatic and aliphatic methyl ketones, e.g.
C6 H 5 CHO > C6 H 5 COCH 3 > C6 H 5 COC 6 H 5
Benzaldehy de Acetopheno ne Benzopheno ne O
||
Some important examples of nucleophilic CH 3  CH 2  C  CH 2  CH 3 and
addition reactions
Addition of HCN O
O
||
R  C  H  HCN  R  C  CN
OH

OH

H
|

Cy anohy drin
ID CH 3  CH 2  CH 2  C  CH 3

O
||
C6 H 5  C  CH 3
||

and
O
||
CH 3  CH 2  C  CH 3
U
O OH  This reagent can be used for the separation of
||  |
C 6 H 5  C  H  HCN  OH
C 6 H 5  C  CN aldehydes and aliphatic methyl ketones from the
Benzaldehy de |
H mixture, e.g.
YG

Benzaldehy de cy anohy drin

CH 3  CH 2  CHO and
 Because HCN is a toxic gas, the best way to
carry out this reaction is to generate hydrogen cyanide O
||
during the reaction by adding HCl to a mixture of the CH 3  CH 2  C  CH 2  CH 3
carbonyl compound and excess of NaCN.
These two compounds can be separated from their
 Benzophenone does not react with HCN.
mixture by the use of NaHSO3. Higher aliphatic ketones
 Except formaldehyde, all other aldehydes gives
D

and aromatic ketones do not react with NaHSO3.

optically active cyanohydrin (racemic mixture).
 This reaction is synthetically useful reaction for Addition of alcohols : Carbonyl compounds give
the preparation of -hydroxy acids, -amino alcohols addition reaction with alcohols. This reaction is
U

and -hydroxy aldehydes. catalysed by acid and base. Nature of product depends
 OH on the catalyst.
H2O/H/ |
R  C H  COOH Case I : Addition catalysed by base : In the
 - Hy droxy acid
ST

presence of a base one equivalent of an alcohol reacts

(If R is CH3 then product is lactic acid)
with only one equivalent of the carbonyl compound.
OH
| H2/Pt The product obtained is called hemiacetal (in case of
R  CH  CN aldehyde) and hemiketal (in case of ketone). The
OH reaction is reversible. There is always equilibrium
|
R  C(i)
H  CH 2  NH 2 between reactants and product.
 - Amino
SnCl alcohol
/HCl
(ii) 2HOH/
O  OH
OH ||   |
HO
| CH 3  C  H  CH 3  O  H CH 3  C  H
R  C H  CHO |
 -hy droxy aldehy de OCH 3
Hemiacetal
Addition of sodium bisulphite
 Aldehydes and Ketones 1261
O OH Addition of Grignard reagents : Grignard
||  |
CH 3  C  CH 3  CH 3  O  H HO
CH 3  C  CH 3 reagents react with carbonyl compounds to give
|
alcohols. Nature of alcohol depends on the nature of
OCH 3 O
Hemiketal carbonyl compound.
Hemiacetals and hemiketals are -alkoxy (i) H – C –
R – CH2OH 1°-alcohol
H 
alcohols. (ii)
HOH/H
Case II : Addition catalysed by acid : In the O OH
presence of an acid one equivalent of carbonyl (i) R' – C – |
RMgX H  R' – CH – R 2°-
compound reacts with two equivalents of alcohol. Grignard (ii)
alcohol
Product of the reaction is acetal (in case of aldehyde) reagent HOH/H O

60
OH
or ketal (in case of ketone). |
(i) R' – C –
O OCH 3 R'  R' – C – R' 3°-alcohol
||  | (ii)
H |
R  C  H  2CH 3 OH R  C  H  H 2O HOH/H
| R
OCH 3

E3
Acetal
Addition of water : Carbonyl compounds react
O OCH 3
|| | with water to give gem diols. This reaction is catalysed
R  C  R  2CH 3 OH R  C  R  H 2O by acid. The reaction is reversible reaction.
|
OCH 3
Ketal O OH
|| |
(i) Formation of acetals and ketals can be shown R  C  R '  HOH R  C  R'
as follows:
R

R
C O 
H  O  CH 3

H  O  CH 3

H
ID Ketone

Gem diols are highly unstable compounds hence

|
OH
Gemdiol

equilibrium favours the backward direction. The extent

U
to which an aldehyde or ketone is hydrated depends on
R OCH 3
the stability of gem diol.
C  H 2O
Stability of gem diols depend on the following
R OCH 3
YG

factors:
(ii) Acetals and ketals are gem dialkoxy
(i) Steric hindrance by +I group around -carbon
compounds.
decreases the stability of gem diols. +I group decreases
(iii) High yield of acetals or ketals are obtained if
stability of gem diol and hence decreases extent of
the water eliminated from the reaction is removed as it
hydration.
formed because the reaction is reversible.
(ii) Stability of gem diols mainly depends on the
(iv) Acetals and ketals can be transformed back to
D

presence of –I group on -carbon. More is the –I power

corresponding aldehyde or ketone in the presence of O
of the group more will be stability of gem diols.
excess of water.
OCH 3 (iii) Intramolecular hydrogen bonding increases R–C–
O
U

|  || stability of gem diols. –I groups present on carbon

R  C  R  H 2 O 
H
R  C  R  2CH 3 OH
| (Excess)
having gem diol group increases strength of hydrogen
OCH 3 bond.
Ketal
ST

This reaction is very useful reaction for the More is the strength of hydrogen bond more will
protection of carbonyl group which can be deprotected be the stability of gem diol.
by hydrolysis. Glycol is used for this purpose. Suppose Addition of terminal alkynes : This reaction is
we want to carry out the given conversion by LiAlH 4 . known as ethinylation.

O ONa
|| O
CH 3  C  CH 2  COOC 2 H 5   
LiAlH 4   || |
R  C  C Na  R '  C  R   R  C  C  C  R "
Sod. salt of alky ne |
O R'
||
CH 3  C  CH 2  CH 2 OH
This can be achieved by protection of CO
group and then by deprotection
 1262 Aldehydes and Ketones
OH
 |
  R  C  C  C  R "
HOH / H
|
R'
alky nol

(2) Addition followed by elimination reactions :

This reaction is given by ammonia derivatives
(NH 2  Z) .
Beckmann rearrangement : Ketoxime when
(i) In nucleophilic addition reactions poor treated with acid at 0°C it undergoes rearrangement
nucleophile such as ammonia and ammonia derivatives known as Beckmann rearrangement.
requires acid as catalyst. Thus acid catalysed conversion of ketoximes to N-

60
(ii) If the attacking atom of the nucleophile has a substituted amides is called Beckmann rearrangement.
lone pair of electrons in the addition product, water Acid catalyst used are proton acids (H 2 SO 4 , HCl, H 3 PO 4 )
will be eliminated from the addition product. This is and Lewis acids (PCl 5 , SOCl 2 , PhSO 2 Cl, RCOCl , SO 3 , BF3
called a nucleophilic addition elimination. etc.)
Primary amines and derivatives of ammonia react O

E3
||
with carbonyl compounds to give adduct.
C 6 H 5  C  CH 3  CH 3  C  NH  C 6 H 5
(i) PCl 5
In adduct nucleophilic group has lone pair of || (ii) H 2 O N - pheny lacetamide
N OH
electrons. It undergoes elimination to give product Acetopheno xime
known as imine. An imine is a compound with a O
carbon-nitrogen double bond. ||


CH 3  C  C 6 H 5  C 6 H 5  C  NH  CH 3
(i) PCl 5
O
||  ..

OH
|

R  C  R  H  N H  Z 
H

 HOH
R  C  R  
R
CNZ
ID ||
N OH
(ii) H 2 O

In short product of the rearrangement can be

obtained as follows:
R R'
N - methy l acetamide
U
| An imine C
N HZ R ||
.. N OH

The overall reaction can be shown as follows O

YG

||
R R
..  R ' C  O  H  R '  C  NH  R
Tautomeris ation

C  O  N H 2  Z 
H
H 2O  C N R ||
RN
R R
An imine (3) Oxidation of carbonyl compounds
Different Imine formation with NH 2  Z is given (i) Oxidation by mild oxidising agents : Mild
below oxidising agents oxidise only aldehydes into carboxylic
acids. They do not oxidises ketones. Main oxidising
D

agents are:
(a) Fehling solution : It is a mixture of two
Fehling solution: Fehling solution No. 1 : It contains
U

CuSO 4 solution and NaOH.

Fehling solution No. 2 : It contains sodium
potassium tartrate. (Roschelle salt).
ST

(b) Benedict's solution : This solution contains

CuSO 4 , NaOH and sodium or potassium citrate.

 Reacting species of both solutions is Cu  

oxidation no. of Cu varies from 2 to 1.
 These two oxidising agents oxidise only
aliphatic aldehydes and have no effect on any other
functional groups
Benedict's solution and Fehling solutions are used
as a reagent for the test of sugar (glucose) in blood
sample.
 Aldehydes and Ketones 1263
(c) Tollens reagent : Tollens reagent is ammonical O
||

silver nitrate solution. Its reacting species is Ag . CH 3  CH 2  CH 2  C CH 2  CH 2  CH 3 
[O ]

C=7 
 It oxidises aliphatic as well as aromatic COOH COOH
aldehydes. CH 3  CH 2  CH 2  COOH  CH 3  CH 2  COOH
C 4 C 3
Total number of C  4  3 7
R  CHO  Ag    RCOOH  Ag
Redox
(as silver
reaction
Thus number of carbons in any product is less
mirror) than the number of carbons in ketone.
 This reagent has no effect on carbon-carbon Case II : Oxidation of unsymmetrical ketones :
multiple bond. In case of unsymmetrical ketones -carbon whose bond

60
breaks always belongs to the alkyl group which has
CH 2  CH  CHO  Ag   CH 2  CH  COOH  Ag
more number of carbons. This rule is known as Popoff’s
In this reaction the oxidation no. of Ag varies rule.
from +1 to 0. O
||
 Glucose, fructose give positive test with Tollen's CH 3  CH 2  CH 2 C  CH 2  CH 3

E3
reagents and Fehling solution.
COOH COOH
C5 H11 O5 CHO  Cu 2 O (or) Ag 2 O  C5 H11 O5 COOH
Gluconic acid  CH 3  CH 2  COOH  CH 3  CH 2  COOH
[O ]

Fructose contain C  O (keto) group yet give

Case III : Oxidation of cyclic ketones :
positive test with Fehling solution due to presence of - Formation of dibasic acid takes place from cyclic
hydroxyl keto group. Tollens reagent also gives positive
test with terminal alkynes and HCOOH.
(d) Reaction with mercuric chloride solution :
ID ketones. In this case the number of carbons in ketone
and dibasic O


carboxylic acid is always same.


R  C  H  HgCl 2  H 2 O  R  C  OH  HCl  Hg 2 Cl 2 () 
 COOH  (CH 2 )4  COOH
[O ]
U
|| || (White) Adipic acid
O O
 If both -carbons are not identical then bond
R  C  H  Hg 2 Cl 2  H 2 O  R  C  OH  HCl  Hg() breaking takes place between carbonyl carbon and the -
YG

|| || (Black)
O O carbon which has maximum number of hydrogens.
O
(e) Schiff's reagent : Megenta solution 
SO 2
H  CH3
colourless solution    pink colour restored (In
CH 3CHO

cold). H H
CH 3
(ii) Oxidation by strong oxidising agents : Main |

2-Methyl
 COOH
[O ]
 (CH 2 )3  CH  COOH
D

 cyclohaxanone
strong oxidising agents are KMnO 4 / OH / ,  - Methy l adipic acid
 
KMnO 4 / H / , K 2 Cr2 O 7 / H / and conc HNO3 /  . (iii) Miscellaneous oxidation
These agents oxidise aldehydes as well as ketones. (a) Haloform Reaction
U

(a) Oxidation of aldehydes : Aldehydes are O

|| 
oxidised into corresponding acids.
R  C  CH 3    RCOOH  CHX 3
(i) X2 / OH

 methy l carbony l 
RCHO  RCOOH
[O ]
ST

(ii) H
C n C n
 (b) Oxidation at -CH2 or CH3 by SeO2 : SeO2
KMnO 4 / O H / 
C6 H 5 CHO    C6 H 5 COOH oxidises   CH 2  group into keto group and
(b) Oxidation of ketones : Ketones undergo   CH 3  group into aldehydic group.
oxidation only in drastic conditions. During the In this oxidation reactivity of CH 2 is more than
oxidation of ketones there is breaking of carbon-carbon the CH 3 group and Oxidation is regio selective in
bond between -carbon and carbonyl carbon. In this nature.
process both carbons convert into carboxylic groups.
CH 3  CHO   CHO  CHO ;
2 SeO
This leads to the formation of two moles of Gly oxal

monocarboxylic acids. O O
|| ||
CH 3  C  CH 3   CH 3  C  CHO
SeO
Case I : Oxidation of symmetrical ketones 2

Methy lgly oxal

 1264 Aldehydes and Ketones
(c) Oxidation by organic peracids : Organic R  CHO   R  CH 2 OH
(i) LiAlH4
(ii) NaBH 4
peracids oxidise aldehydes into carboxylic acids and (iii) Aluminium isopropoxi de
ketones into esters. This oxidation is known as Baeyer
– Villiger oxidation. O OH
|| |
O O R  C  R '  R  CH  R '
(i) LiAlH 4
|| || (ii) NaBH 4
R  C  R     R  C  O  R 
C6 H 5 COOOH (iii) Aluminium isopropoxi de

In case of aldehyde there is insertion of atomic NaBH 4 is regioselective reducing agent because it
oxygen (obtained from peracid) between carbonyl reduced only. CHO in the presence of other reducible
carbon and hydrogen of carbonyl carbon. group.
In case of ketone, insertion of oxygen takes place Example :
between carbonyl carbon and -carbon. Thus the

60
product is ester. This is one of the most important CH 3  CH  CH  CHO   CH 3  CH  CH  CH 2 OH
NaBH 4

Crotonalde hyde Crotonyl alcohol

reaction for the conversion of ketones into esters.
 Vic dicarbonyl compound also undergo Hydride ion of NaBH 4 attack on carbonyl carbon
oxidation and product is anhydride. during reduction.
O O

E3
|| || Example :
R  C  C  R    R  C  O  C  R
C6 H 5 COOOH
O OD
|| || || |
O O CH 3  C  CH 3   CH 3  C  CH 2  CH 3
NaBD 4
D2 O |
 Popoff's rule : Oxidation of unsymmetrical 2-Butanone
D
ketones largely take place in such a way that the smaller
alkyl group remains attached to the CO group during the OH
formation of two molecules of acids. This is known as
Popoff's rule
Example :
CH 3  CO  CH 2  CH 3  CH 3  COOH  HOOCCH 3
[O ]
ID O
||
CH 3  C  CH 3 
NaBD4
H2 O
|
CH3 – C – CH2 –
CH3
|
D
OD
U
(d) Baeyer- villiger oxidation : 2 Butanone

H |
NaBH4
| CH3 – C – CH2 –
H  C  H  O  O  C  H  H  C  OH D2 O
CH3
|| || ||
YG

O O O |
H H
| (iii) Reductive amination : In this reduction
CH 3  C  H  O  O  C  H  CH 3  C  OH CO  group converts into CH  NH 2 group
|| || ||
O O O R R R
 Reaction will be held if the oxidising agent is C  O  NH 3  C  NH   
H 2 / Ni
CH  NH 2
performic acid. R R R
D

Imine Primary amine

(4) Reduction of carbonyl compounds
O (iv) Reduction of ketones by Mg or Mg/Hg : In
|| this case ketones undergo reduction via coupling
(i) Reduction of
– C – group into –CH2 – group :
U

reaction and product is vic cis diol.

Following three reagents reduce carbonyl group into
O O OH OH
CH 2  groups: (a) HI / P /  (b) Zn / Hg / Conc . HCl and || || | |
 R  C  C  R 
 R  C  C  R(i) Mg / Hg
|| || (ii) HOH | |
ST

(c) NH 2  NH 2 / OH . R R
R R
Vic cis diol (pinacol)
HI/P/
R – CH2 – R' When this reaction is carried out in the presence
O
|| of Mg / Hg / TiCl4 , the product is vic trans diol.
Zn/Hg/Conc. HCl
R–C– 
R – CH2 – R' (Clemmenso
HO
R'  n reduction) (i) Hg – Mg –
2 O TiCl4HOH
(ii)
NH2 – NH2
/OH R – CH2 – R' OH

(Wolff-kishner Cyclohexanone Vic trans diol
(ii) Reduction of carbonyl
into compounds
reduction)
hydroxy compounds : Carbonyl group converts into (v) Reduction of benzaldehyde by Na/C2H5OH :
CHOH  group by LiAlH 4 , NaBH 4 , Na / C2 H 5 OH and Benzaldehyde undergoes reduction via coupling
aluminium isopropoxide. reaction and product is vic diol.
 Aldehydes and Ketones 1265
O O carbanion is stabilised by delocalisation of negative
|| ||
C6 H 5  C  C  C6 H 5  (i) Na/C 2 H 5 OH charge.
| | (ii) HOH
H H 
O O O
OH OH || Base  || |
| | CH 3  C  R CH 2  C  R  CH 2  C  R
C6 H 5  CH  C H  C6 H 5 (Bouveault-blanc reaction) Carbanion
(less stable)
Enolate ion
(more stable)
vic diol
 Aldehydes are reduced to 1° alcohols whereas (c) The acidity of -hydrogen is more than ethyne.
ketones to 2° alcohols. If carbon – carbon double bond is pKa value of aldehydes and ketones are generally 19 –
also present in the carbonyl compound, it is also reduced 20 where as pKa value of ethyne is 25.
alongwith. However, the use of the reagent 9-BBN (9– (d) Compounds having active methylene or

60
borabicyclo (3, 3, 1) nonane) prevents this and thus only methyne group are even more acidic than simple
the carbonyl group is reduced aldehydes and ketones.
O
Example :  ||

9 BBN
C6 H 5  CH 2  C  CH 3 pKa  15 .9
CH  CH  CHO  
 HOCH 2CH 2 NH 2
 - pheny l acetone

E3
O O
Cinnamaldehy ||  ||
de CH  CHCH 2OH C6 H 5  C  CH 2  C  CH 3 pKa  8 . 5
 - benzoy l acetone
Cinnamyl
(ii) Halogenation : Carbonyl compounds having
 If reducing agent is alcohol
NaH, reaction is called
-hydrogens undergo halogenation reactions. This
Darzen's reaction, we can also use LiAlH4 in this
reaction.
 If reducing agent is aluminium iso propoxide
(CH 3  C H  O )3 Al . Product will be alcohol. This
|
CH 3
IDreaction is catalysed by acid as well as base.
(a) Acid catalysed halogenation : This gives only
monohalo derivative.
O
||
O
||
U
CH 3  C  CH 3 23 
 CH 3  C  CH 2 Br
Br / CH COOH
reaction is called Meerwein – pondorff verley reduction Acetone   bromo acetone
(MPV reduction). (b) Base catalysed halogenation : In the presence
 The percentage yield of alkanes can be increased of base all -hydrogens of the same carbon is replaced
YG

by using diethylene glycol in Wolf Kishner reduction. by halogens.

Then reaction is called Huang – Millan conversion. O
(vi) Hydrazones when treated with base like   ||  
CH 3  CH 2  C  CH 2  CH 3
alkoxide give hydrocarbon (Wolf – Kishner reduction). –
X2/OH
O N . NH 2 Excess
|| ||
R  C  R'    R  C  R' 
NH 2 NH 2

 R  CH 2  R
RONa
O X
D

Hy drazone  O
|| || |
(vii) Schiff's base on reduction gives secondary CH 3  CH  C  CH  CH 3 CH 3  CH 2  C  C  CH 3
| | |
amines. X X
X
U

R  CH  O   R  CH  NR ' 
R ' NH 2
  R  CH 2 NHR
H 2 / Ni
Aldehyde Schiff's base Secondary amine Carbonyl compounds having three -hydrogens
give haloform reaction.
(5) Reactions due to -hydrogen
O O
ST

 
(i) Acidity of -hydrogens : || || 
R  C  CH 3  R  C  CX 3 OH
 RCOO  CHX 3
X 2 / OH

(a) -hydrogen of carbonyl compounds are acidic

(iii) Deuterium exchange reaction : Deuterium
in character due to the presence of the electron
exchange reaction is catalysed by acid (D  ) as well as
withdrawing CO  group. -Hydrogen is acidic due

to strong –I group; – CO base (OD) . In both the cases all the hydrogens on only
–.
H O one -carbon is replaced by D.
| || O O

–C–C– || ||
R  C  CH 2  R 
 R  C  CD2  R ;
D2 O / OD
|
-
Carbon O 
O
(b) Thus carbonyl compounds having -hydrogen || ||
R  C  CH 2  R  R  C  CD2  R
D2 O / D
convert into carbanions in the presence of base. This
 1266 Aldehydes and Ketones
(iv) Racemisation : Ketones whose -carbon is   
CH 3  NO 2 , CH 3  CH  CHO , CH 3  CH 2  CN
chiral undergo Racemisation in the presence of acid as |
well as base. CH 3
O CH 3  If substrate and reagent both are carbonyl
O CH 3
|| |  || | compounds then one should have at least one -hydrogen
C6 H 5  C  C  C 2 H 5  
 C6 H 5  C  C  C 2 H 5
H or
and other may or may not have -hydrogen.
|  |
H OH H Condensation reaction always takes place in the
2  methy l-1 - pheny l -1 - one Racemic mixture presence of acid or base as catalyst. Best result is
CH 3 O obtained with base at lower temp.
| || O OH
 C 2 H 5  C  C  C6 H 5 ||  |
| R  C  R  CH 3  Z  
 R  C  C H 2  Z
H or

60
H  | 
OH
R
(v) Alkylation : Carbonyl compounds having - Condensation is carried out at lower temperature
hydrogens undergo alkylation reaction with RX in the ( 20 C ) because product of the reaction is alcohol
presence of base. This reaction is S N 2 reaction. The which has strong –I group at -carbon.

E3
best result is obtained with CH 3  X . Other halides Such type of alcohols are highly reactive for
undergo elimination in the presence of strong base. dehydration. They undergo dehydration in the presence
O O of acid as well as base even at 25°C. They also undergo
CH 3 CH 3
|| ||  elimination even on strong heating.
CH 3  C  CH   CH 3  C  C
NaH
 
CH 3 I
(Small base) OH
CH 3 Carbanion CH 3  R
|
HO/ 
R  C  CH 2  Z  
 C  CH  Z
LDA
(Bulky
base)
O CH 3
||
CH 3  C  C  CH 3
CH 3
(Main product)
|

|
ID  |
R
(i) Aldol condensation
β Dehy dration

(a) This reaction takes place between two

R
U
CH 3 O CH 3 molecules of carbonyl compounds; one molecule should
 ||
CH 2  C  CH   CH 3 CH 2  C  CH
CH 3 I have at least two -hydrogen atoms. In this reaction
||
CH 3 CH 3 best result is obtained when
O
YG

(Main product)
Ethy l- isopropy l ketone Both molecule are the same or
(vi) Wittig reaction : Aldehyde and ketones One should have no -hydrogen atom and other
undergo the wittig reaction to form alkenes. should have at least two -hydrogens.
Ph 3 P  CH 2   C  O   C  CH 2  Ph 3 P  O (b) These reactions are practical when base is
Aldehy de alkene Tripheny l
or ketone Phosphoniu m oxide NaOH and reaction temperature is high ( 100 ) .
Ph3 P  CHR 1  CHR 2  Ph3 P   CHR 1  (c) The reaction is two step reaction. First step is
D

|| |
O O CHR 2 aldol formation and second step is dehydration of aldol.

Ph 3 P  CHR 1  Ph 3 P  CHR 1

 
U

| | || || OH
O  CHR 2 O CHR 2  | 

CH 3  CHO  CH 3  CHO   CH 3  CH  CH 2  CHO 
NaOH / OH
(6) Condensation reaction of carbonyl 
 
compounds : Nucleophilic addition reaction of  
ST

compounds having carbonyl group with those   CH 3  CH  CH  CHO

Dehydration

compounds which have at least one acidic hydrogen at a,   unsaturate d aldehyde

-carbon is known as condensation reaction. In this
Due to hyper-conjugation in crotonaldehyde
addition reaction :
Substrate is always an organic compound having a further condensation give conjugated alkene carbonyl
carbonyl group, e.g. compound.
O O O O
|| || || || CH3 – CH = CH – CHO + CH3 – CH = CH – CHO
H  C  H , C6 H 5  C  H , R  C  H, R  C  R etc. NaOH
Addition always takes place on the carbonyl
OH
group.
|
Reagents of the condensation reaction are also
CH3 – CH = CH – CH – CH2 – CH = CH – CHO
organic compounds having at least one hydrogen on -
carbon and -carbon should have –I group, e.g.  –H2O

CH3 – CH = CH – CH = CH – CH = CH – CHO

CH3 – (CH = CH –)3 – CHO

Condensed
compound
 Aldehydes and Ketones 1267
Intra molecular aldol condensation : One
molecule Intramolecular condensation give aldol
compounds

Example :


OH
Mechanism : C 6 H 5  CHO  CH 3  CHO  OH /  O  CH  (CH 2 )5  CHO 
 di. NaOH

CHO
C6 H 5  CH  CH  CHO  HOH
(ii) Claisen – Schmidt reaction : Crossed aldol


60
Step I : HO  H  CH 2  CHO condensation between aromatic aldehyde and aliphatic
ketone or mixed ketone is known as Claisen – Schmidt
  
 O O  reaction. Claisen – Schmidt reactions are useful when
|| |
HOH  CH 2  C  H  CH 2  C  H  bases such as sodium hydroxide are used because under
 
  these conditions ketones do not undergo self

E3
  condensation. Some examples of this reaction are :

O  O
|| OH ||
O C6 H 5 CHO  CH 3  C  CH 3   C6 H 5  CH  CH  C  CH 3
100 C
||  4  Pheny l 3  buten - 2 - one
Step II : C6 H 5  C  CH 2  CHO 
|
Test of aldehydes and Ketones (Distinction)

O
|
H

C6 H 5  C  CH 2  CHO  C6 H 5  C  CH 2  CHO  OH

|
HOH
OH
|

|
ID

Test
With Schiff's
Table : 27.1
Aldehydes
Give pink colour.
Ketones
No colour.
U
H H reagent
With Fehling's Give red No precipitate is
Step III :
solution precipitate. formed.
OH
YG

| With Tollen's Black precipitate No black

C6 H 5  CH  CH  CHO  C6 H 5  CH  CH  CHO  HOH reagent or silver mirror is precipitate or
|
H formed. silver mirror is
 formed.
OH
With saturated Crystalline Crystalline
In aldol condensation, dehydration occurs readily sodium compound compound
because the double bond that forms is conjugated, both bisulphite (colourless) is (colourless) is
solution in water formed. formed.
D

with the carbonyl group and with the benzene ring. The
conjugation system is thereby extended. With 2, 4- Orange-yellow or Orange-yellow or
dinitrophenyl red well defined red well defined
Crossed aldol condensation : Aldol condensation hydrazine crystals with crystals with
U

between two different aldehydes or two different melting points melting points
characteristic of characteristic of
ketones or one aldehyde and another ketone provided
individual individual
at least one of the components have -hydrogen atom aldehydes. ketones.
ST

gives different possible product With sodium Give brown No reaction.

hydroxide resinous mass
(a) CH 3 CHO  CH 3  CH 2  CHO   
dil NaOH

Ethanal Propanal
(formaldehyde
does not give this
OH CH 3 test).
| |
CH 3  CH  CH  CHO  CH 3  CH 2  CHOH  CH 2  CHO With sodium A deep red colour Red colour which
nitroprusside (formaldehyde changes to
However crossed aldol condensation is important and few drops of does not respond orange.
sodium to this test).
when only it the components has -hydrogen atom.
hydroxide

CH 2 O  CH 3 CHO  CH 2  CH 2  CHO  CH 2  CH  CHO
|  H 2O (Acrolein) Some commercially important aliphatic
OH carbonyl compounds
(3 - hy droxy propanal)
 1268 Aldehydes and Ketones
Formaldehyde : Formaldehyde is the first Acetaldehyde
member of the aldehyde series. It is present in green
Acetaldehyde is the second member of the
leaves of plants where its presence is supposed to be
due to the reaction of CO 2 with water in presence of aldehyde series. It occurs in certain fruits. It was first
prepared by Scheele in 1774 by oxidation of ethyl
sunlight and chlorophyll.
alcohol.
(1) Preparation
(i) 2CH 3 OH  O 2   HCHO
Platinised asbestos (1) Preparation : It may be prepared by any of
300  400 C Formaldehy de
the general methods. The summary of the methods is
CH 3 OH  [O]   HCHO  H 2 O
K 2 Cr2 O7
given below
H 2 SO 4

60
(ii) CH 3 OH    HCHO
Cu or Ag (i) By oxidation of ethyl alcohol with acidified
300  400 C Formaldehy de
potassium dichromate or with air in presence of a
(iii) Ca(HCOO ) 2   HCHO
Heat
catalyst like silver at 300°C.
Calcium formate Formaldehy de

(iv) CH 2  CH 2  O3 
 HCHO H2 (ii) By dehydrogenation of ethyl alcohol. The
Pd Formaldehy de
vapours of ethyl alcohol are passed over copper at

E3
(v) CH 4  O 2    HCHO
Mo- oxide
300°C.
Methane Catalyst Formaldehy de

(iii) By heating the mixture of calcium acetate and

(vi) CO  H 2 
 HCHOElec. discharge
Formaldehy de calcium formate.
(2) Physical properties
(iv) By heating ethylidene chloride with caustic
(i) It is a colourless, pungent smelling gas.
(ii) It is extremely soluble in water. Its solubility
in water may be due to hydrogen bonding between
water molecules and its hydrate.
ID
soda or caustic potash solution.

(v) By the reduction of acetyl chloride with

hydrogen in presence of a catalyst palladium suspended
(iii) It can easily be condensed into liquid. The in barium sulphate (Rosenmund's reaction).
U
liquid formaldehyde boils at – 21°C.
(iv) It causes irritation to skin, eyes, nose and (vi) By the reduction of CH 3 CN with stannous
throat. chloride and HCl in ether and hydrolysis (Stephen's
YG

(v) Its solution acts as antiseptic and disinfectant. method).

(3) Uses (vii) By hydration of acetylene with dil. H 2 SO 4
(i) The 40% solution of formaldehyde (formalin) and HgSO 4 at 60°C.
is used as disinfectant, germicide and antiseptic. It is
used for the preservation of biological specimens. (viii) By ozonolysis of butene-2 and subsequent
breaking of ozonide.
D

(ii) It is used in the preparation of hexamethylene

tetramine (urotropine) which is used as an antiseptic (ix) Laboratory preparation : Acetaldehyde is
and germicide. prepared in the laboratory by oxidation of ethyl alcohol
U

with acidified potassium dichromate or acidified

(iii) It is used in silvering of mirror. sodium dichromate.
(iv) It is employed in manufacture of synthetic
K 2 Cr2 O7  4 H 2 SO 4  K 2 SO 4  Cr2 (SO 4 )3  4 H 2 O  3[O]
ST

dyes such as para-rosaniline, indigo, etc.

[CH 3 CH 2 OH  O  CH 3 CHO  H 2 O]  3
(v) It is used in the manufacture of formamint (by
mixing formaldehyde with lactose) – a throat lozenges. K 2 Cr2 O7  3CH 3 CH 2 OH  4 H 2 SO 4 
Potassium Ethyl alcohol Sulphuric acid
(vi) It is used for making synthetic plastics like dichromate

bakelite, urea-formaldehyde resin, etc. K 2 SO 4  Cr2 (SO 4 )3  3 CH 3 CHO  7 H 2 O

Potassium Chromic Acetaldehyde Water
sulphate sulphate
(vii) Rongalite – a product obtained by reducing
To recover acetaldehyde, the distillate is treated
formaldehyde sodium bisulphite derivative with zinc
with dry ammonia when crystallised product,
dust and ammonia and is used as a reducing agent in
acetaldehyde ammonia, is formed. It is filtered and
vat dyeing.
washed with dry ether. The dried crystals are then
 Aldehydes and Ketones 1269
distilled with dilute sulphuric acid when pure (i) Acetaldehyde is a colourless volatile liquid. It
acetaldehyde is collected. boils at 21°C.
OH (ii) It has a characteristic pungent smell.
|
CH 3 CHO  NH 3  CH 3  CH  NH 2  H 2 SO 4
(iii) It is soluble in water, chloroform, ethyl
Acetaldehyde ammonia
alcohol and ether. Its aqueous solution has a pleasant
CH 3 CHO  ( NH 4 ) 2 SO 4 odour. In water, it is hydrated to a considerable extent
Acetaldehyde
to form ethylidene diol.
(x) Manufacture : Acetaldehyde can be
manufactured by one of the following methods: CH 3 CHO  H 2 O  CH 3 CH (OH )2

(3) Uses : Acetaldehyde is used :

60
(a) By air oxidation of ethyl alcohol

2CH 3 CH 2 OH  O2 
 2CH 3 CHO  2 H 2 O
Ag (i) In the preparation of acetic acid, acetic
300 C
anhydride, ethyl acetate, chloral, 1,3-butadiene (used in
(b) By dehydrogenation of alcohol rubbers), dyes and drugs.
CH 3 CH 2 OH 
 CH 3 CHO
Cu
(ii) As an antiseptic inhalent in nose troubles.

E3
300 C
(iii) In the preparation of paraldehyde (hypnotic
(c) By hydration of acetylene
and sporofic) and metaldehyde (solid fuel).
HgSO 4 ,(1 %),60 C
CH  CH  H 2 O   CH 3 CHO (iv) In the preparation of acetaldehyde ammonia
H 2 SO 4 (40 %)
(a rubber accelerator).
(d) From ethylene (Wacker process)

H 2 C  CH 2  O 2   

(2) Physical properties

H 2O
 H 3 C  CHO
PdCl 2 ,CuCl 2
ID
Table : 27.2 Comparative study of formaldehyde and acetaldehyde
U
S.No Reaction Formaldehyde HCHO Acetaldehyde CH3CHO
.
YG

Similarities
1. Addition of hydrogen Forms methyl alcohol Forms ethyl alcohol
(a) H2 in presence of catalyst, Ni, HCHO  H 2  CH 3 OH CH 3 CHO  H 2  CH 3 CH 2 OH
Pd or Pt
Forms methyl alcohol Forms ethyl alcohol
(b) LiAlH 4 (ether)
Forms methane Forms ethane
(c) Amalgamated zinc + conc. HCl HCHO  4 H  CH 4  H 2 O CH 3 CHO  4 H  C 2 H 6  H 2 O
D

(Clemmenson reduction)
2. Addition of NaHSO 3 solution Forms bisulphite addition product Forms bisulphite addition
HCHO  NaHSO 3  CH 2 (OH )SO 3 Na product
CH 3 CHO  NaHSO 3 
U

CH 3CH (OH )SO 3 Na

ST

3. Addition of HCN Forms formaldehyde cyanohydrin Forms acetaldehyde

HCHO  HCN  CH 2 (OH )CN cyanohydrin
CH 3 CHO  HCN 

CH 3CH (OH )CN

4. Addition of Grignard reagent Forms ethyl alcohol Forms isopropyl alcohol
followed by hydrolysis OMgI CH 3 CHO  CH 3 MgI 
HCHO  CH 3 MgI  CH 2
CH 3
CH 3  C HOMgI  
H 2O
 CH 3 CH 2 OH
H 2O |  Mg(OH ) I
 Mg(OH ) I CH 3
 1270 Aldehydes and Ketones
CH 3 CH  OH
|
CH 3
5. With hydroxylamine NH 2 OH Forms formaldoxime Forms acetaldoxime
 H 2O  H 2O
CH 2  O  H 2 NOH   CH 3 CH  O  H 2 NOH  

CH 2  NOH CH 3 CH  NOH
6. With hydrazine (NH 2 NH 2 ) Forms formaldehyde hydrazone Forms acetaldehyde hydrazone
 H 2O  H 2O
CH 2 O  H 2 N NH 2   CH 3 CH  O  H 2 NNH 2  

60
CH 2  NNH 2 CH 3CH  NNH 2

7. With phenyl hydrazine Forms formaldehyde phenyl Forms acetaldehyde phenyl

(C6 H 5 NHNH 2 ) hydrazone hydrazone
 H 2O
CH 2  O  H 2 NNHC 6 H 5   CH 3 CH  O  H 2 NNHC 6 H 5

E3
 H 2O
  CH 3 CH  NNHC 6 H 5
CH 2  NNHC 6 H 5
8. With semicarbazide Forms formaldehyde Forms acetaldehyde
(H 2 NNHCONH 2 ) semicarbazone semicarbazone
CH 2  O  H 2 NNHCONH  H 2O
  CH 3 CH  O  H 2 NNHCONH 2

9. With alcohol (C2 H 5 OH ) in presence

ID
CH 2  NNHCONH
Forms ethylal
2
2
 H 2O
 

Forms
 CH 3 CH  NNHCONH

acetal
acetaldehyde
2

diethyl
of acid H 2 C  O  2C 2 H 5 OH 
HCl
U
CH 3 CHO  2C 2 H 5 OH 
HCl

OC 2 H 5
CH 2
YG

OC 2 H 5
OC 2 H 5 CH 3 CH
OC 2 H 5
10. With thioalcohols (C 2 H 5 SH ) in Forms thio ethylal Forms acetaldehyde diethyl
presence of acid H 2 C  O  2C 2 H 5 SH  thioacetal
CH 3 CH  O  2C 2 H 5 SH 
SC 2 H 5
D

CH 2 SC 2 H 5
SC 2 H 5 CH 3 CH
SC 2 H 5
U

11. Oxidation with acidified K2Cr2O7 Forms formic acid Forms acetic acid
HCHO  O  HCOOH CH 3 CHO  O  CH 3 COOH
12. With Schiff's reagent Restores pink colour of Schiff's Restores pink colour of Schiff's
ST

reagent reagent
13. With Tollen's reagent Gives black precipitate of Ag or Gives black precipitate of Ag or
silver mirror silver mirror
Ag 2 O  HCHO  2 Ag  HCOOH Ag 2 O  CH 3 CHO 

2 Ag  CH 3COOH
14. With Fehling's solution or Gives red precipitate of cuprous Gives red precipitate of
Benedict's solution oxide cuprous oxide
2CuO  HCHO  Cu 2 O  HCOOH 2CuO  CH 3 CHO 

Cu 2O  CH 3COOH
15. Polymerisation Undergoes polymerisation Undergoes polymerisation
Evaporatio H2SO4Conc.
n
dil. H2SO4.
Room temp. distill
heat
H2SO4Conc.

dil. H2SO4.
distill
 Aldehydes and Ketones 1271
nHCHO (HCHO )n 3CH 3CHO
Paraformaldehy de

3 HCHO
(CH 3 CHO )3
(HCHO )3 Paraldehy de
Metaformaldehy de
4 CH 3CHO
(CH 3 CHO )4
Metaldehy de

Dissimilarities
16. With PCl5 No reaction Forms ethylidene chloride
Cl

60
CH 3 CHO  PCl 5  CH 3 CH
Cl

 POCl 3

E3
17. With chlorine No reaction Forms chloral
CH 3 CHO  3 Cl 2  CCl 3 CHO

3 HCl
18. With SeO2 No reaction Forms glyoxal
CH 3 CHO  SeO 2  CHO .CHO

19. Iodoform reaction (I2+NaOH) No reaction

ID Se  H 2 O
Forms iodoform
CH 3 CHO  3 I2  4 NaOH 
U
CHl 3  HCOONa  3 NaI  3 H 2 O
20. With dil. alkali (Aldol No reaction Forms aldol
condensation) CH 3 CHO  HCH 2 CHO 
YG

CH 3 CH (OH )CH 2 CHO

21. With conc. NaOH (Cannizzaro's Forms sodium formate and methyl Forms a brown resinous mass
reaction) alcohol
2HCHO  NaOH  HCOONa

CH 3 OH
D

22. With ammonia Forms hexamethylene tetramine Forms addition product,

(urotropine) acetaldehyde ammonia
6 HCHO  4 NH 3 (CH 2 )6 N 4  6 H 2 O CH 3 CHO  NH 3 
U

OH
CH 3 CH
ST

NH 2
23. With phenol Forms bakelite plastic No reaction
24. With urea Forms urea-formaldehyde plastic No reaction
25. Condensation in presence of Form formose (a mixuture of sugars) No reaction
Ca(OH )2

Inter conversion of formaldehyde and acetaldehyde CH 3 CN   CH 3 CH 2 NH 2 

Na / Alcohol

NaNO 2

(1) Ascent of series : Conversion of formaldehyde Methy l Ethy l amine HCl

cy anide
into acetaldehyde
(i) HCHO   CH 3 OH 
H 2 / Ni
 CH 3 Cl 
PCl 5

Alc.
Formaldehy de
CH 3 CH 2 OH   CH 3 CHO
Methy l Methy l KCN H 2 SO 4 (dil.)
alcohol chloride
Ethyl alcohol K 2 Cr2 O7 Acetaldehyde
 1272 Aldehydes and Ketones

(ii) HCHO   CH 3 CH 2OMgI 
CH 3 MgI


H3O The acetone thus obtained is purified with the help
Formaldehy de Ether of sodium bisulphite.
(2) Physical properties : (i) It is a colourless
CH 3 CH 2OH 
 CH 3 CHO
Cu

Ethyl alcohol 300 C Acetaldehyde liquid with characteristic pleasant odour.

(ii) It is inflammable liquid. It boils at 56 o C .
HCHO 2 2 
  HCOOH  
K Cr O
Ca (OH )2
(iii) 7
Formaldehy de H 2 SO 4 Formic acid
(iii) It is highly miscible with water, alcohol and
(HCOO )2 Ca   CH 3 CHO
(CH 3 COO )2 Ca ether.
heat
Calcium formate Acetaldehyde (3) Chemical properties
(2) Descent of series : Conversion of Reduction H2, Ni,
Pd CH 3 CHOHCH 3
acetaldehyde into formaldehyde

60
Isopropy l alcohol
Amalgamated
or LiAlH4 Zn
(i) CH 3 CHO    CH 3 COOH 
K 2 Cr2 O7

NH 3
CH 3 CH 2 CH 3
Acetaldehyde H 2 SO 4 Acetic acid
+ conc. HCl
Propane

CH 3 COONH 4   CH 3 CONH 2 
Heat
 
Br2 / KOH
NaHSO3 (CH 3 )2 C(OH )SO 3 Na
Amm.acetate Acetamide Acetone sodium bisulphit e derivative

CH 3 NH 2   CH 3 OH 
NaNO 2
 HCHO
Cu
OH

E3
HCN
Methyl amine HCl 300 C Formaldehy de (CH 3 )2 C
CN
(ii) CH 3 CHO    CH 3 COOH 
K 2 Cr2 O7
 CH 3 COONa
NaOH Acetone cy anohy drin
Acetaldehyde H 2 SO 4 Acetic acid Sod.acetat e
CH3MgI
(CH 3 )3 COH
Ether Tertiary buty l alcohol
  CH 4 
Sodalime
 CH 3 Cl 
Cl 2

AgOH
heat Methane hv NH2OH
(CH 3 )2 C  NOH

Acetone
It is a symmetrical (simple) ketone and is the first
member of the homologous series of ketones. In traces,
CH 3 OH 
 HCHO Cu
300 C Formaldehy de
ID NH2NH2

C6H5NHNH2
Acetoxime

(CH 3 )2 C  NNH 2
Acetone hy drazone

(CH 3 )2 C  NNHC 6 H 5
Acetone pheny l hy drazone
U
it is present in blood and urine. H2NNHCONH2
(1) Preparation : (CH 3 )2 C  NNHCONH 2
Acetone semicarbazone
(i)
Cl
YG

 PCl5
(CH 3 COO )2 Ca  (CH 3 )2 C
calcium acetate Cl
Isopropy lidene chloride
(ii) Cl2
500 C CH 3 COCCl 3
2CH 3 CHOHCH 3  O2   Trichloro acetone
Isopropyl alcohol
(iii)
I2 +NaOH
CH 3 CHOHCH 3  
Cu CHI 3
2 propanol 300 C Iodoform
(iv) (a)
D

CH3
CH 3 CH  CH 2  PdCl 2  H 2 O  CH3COCH3
propene CH3COCH3 (Acetone
(b) CH 3 CH  CH 2  H 2 SO 4  ) C
propene
CH
U

Conc. H2SO4 CH
CH 3CH (HSO 4 )CH 3
H2O
C
CH 3 CH (OH )CH 3 

Cu
C
Isopropyl alcohol 300 C
CH CH3
ST

CH3
(v) 2C3 H 5 OH  H 3 O   
Zn (CrO 2 )
Mesitylene
500 C (1, 3, 5-trimethyl
CaOCl2 benzene)
(vi)
(Bleaching
2CH  CH  3 H 2O   
catalyst
powder) CHCl 3
420 C heat Chloroform

K2Cr2O7 + H2SO4
(vii) From pyroligneous acid : Pyroligneous acid CH 3 COOH  CO 2  H 2 O
containing acetic acid, acetone and methyl alcohol is CHCl3
(CH 3 )2 C(OH )CCl 3
distilled in copper vessel and the vapours are passed Chloretone
through hot milk of lime. Acetic acid combines to form Ba(OH)2
(CH 3 )2 C(OH )CH 2 COCH 3
nonvolatile calcium acetate. The unabsorbed vapours of Diacetone alcohol
methanol and acetone are condensed and fractionally HNO2
distilled. Acetone distills at 56 o C . CH 3 COCH  NOH
(Oximino acetone)

NH3
(CH 3 )2 C(NH 2 )CH 2 COCH 3
Diacetone amine

Mg–Hg + H2O
OH OH
| |
(CH 3 )2 C — C (CH 3 )2
Pinacol
Schiff's
No reaction
reagent
Tollen's
 Aldehydes and Ketones 1273
CH 3
|
HOH / H 
  
 CH 3  C  CH 2
 Br  |
 Zn  |
 OH 
OH COOC 2 H 5
 - hy droxy esters

CH 3
|
 CH 3  C  CH  COOC 2 H 5
(4) Uses
If acetone would be in excess in ketal (i) As a solvent for cellulose acetate, cellulose
condensation or catalyst (ZnCl 2 / dry HCl ) is used then nitrate, celluloid, lacquers, resins, etc.

60
three moles of acetone undergoes condensation (ii) For storing acetylene.
polymerisation and form a compound called ‘Phorone’.
(iii) In the manufacture of cordite – a smoke less
CH CH powder explosive.
3 3
| |
CH 3  C  O H CH 3  C  CH (iv) In the preparation of chloroform, iodoform,

E3
CH sulphonal and chloretone.
H
(v) As a nailpolish remover.
CO
C = O dry
 

ZnCl 2
CH (vi) In the preparation of an artificial scent
3 . HCl
|
(ionone), plexiglass (unbreakable glass) and
CH 3  C  O H
CH 3  C  CH synthetic rubber.
CH

Acetone (3
molecule)
H
phoron
Molecular mass of phorone = 3 mole of acetone –
2 mole of H 2 O
|
CH 3
ID (5) Tests
(i) Legal's test : When a few drops
prepared sodium nitroprusside and sodium
solution are added to an aqueous solution of
of freshly
hydroxide
acetone, a
U
Reformatsky reaction: This reaction involves the wine colour is obtained which changes to yellow on
treatment of aldehyde and ketone with a bromo acid standing.
ester in presence of metallic zinc to form  -hydroxy (ii) Indigo test : A small amount of
,  -
YG

ester, which can be easily dehydrated into orthonitrobenzaldehyde is added to about 2 ml. of
unsaturated ester. acetone and it is diluted with KOH solution and stirred.

A blue colour of indigotin is produced.
(a) BrCH 2 COOC 2 H 5  Zn   Br  Zn CH 2 COOC 2 H 5
Benzene
(iii) Iodoform test : Acetone gives iodoform test
Organo zinc compound
with iodine and sodium hydroxide or iodine and
(b) Addition to carbonyl group ammonium hydroxide.
Zn Br
D

CH 3
CH 3 | |
C  O  CH 2 COOC 2 H 5  CH 3  C  CH 2 CH 2 COOC 2 H 5
|
CH 3 OZn Br
U

Table : 27.3 Comparison between Acetaldehyde and Acetone

Reaction Acetaldehyde Acetone
ST

Similarities
1. Reduction with H2 Forms ethyl alcohol Forms isopropyl alcohol
and Ni or LiAlH 4 CH 3 CHO  H 2 
 CH 3 CH 2 OH
Ni
CH 3 COCH 3  H 2  CH 3 CHOHCH 3

2. Clemmensen's Forms ethane (an alkane) Forms propane (an alkane)

reduction CH 3 CHO  4 H  CH 3 CH 3  H 2 O CH 3 COCH 3  4 H  CH 3 CH 2 CH 3  H 2 O
(Zn/Hg and conc. HCl)
3. Addition of HCN Forms acetaldehyde cyanohydrin Forms acetone cyanohydrin
 1274 Aldehydes and Ketones
OH OH
CH 3 CHO  HCN  CH 3 CH (CH 3 ) 2 CO  HCN (CH 3 ) 2 C
CN CN
4. Addition of NaHSO 3 White crystalline derivative White crystalline derivative
OH OH
CH 3 CHO  NaHSO 3  CH 3 CH (CH 3 ) 2 CO  NaHSO 3 (CH 3 ) 2 C
SO 3 Na SO 3 Na
5. Grignard reagent Forms isopropyl alcohol Forms tertiary butyl alcohol
followed by hydrolysis CH 3 CHO  CH 3 MgI (CH 3 )2 CH  OMgI (CH 3 ) 2 CO  CH 3 MgI (CH 3 )3 COMgI

60
 CH 3 CHOHCH 3
H 2O
  (CH 3 ) 3 COH
H 2O

6. With hydroxylamine Forms acetaldoxime (an oxime) Forms acetoxime (an oxime)
(NH 2OH ) CH 3 CHO  H 2 NOH  CH 3 CH  NOH (CH 3 ) 2 CO  H 2 NOH  (CH 3 ) 2 C  NOH

E3
7. With hydrazine Forms acetaldehyde hydrazone Forms acetone hydrazone
(NH 2 NH 2 ) CH 3 CHO  H 2 NNH 2  CH 3 CH  NNH 2 (CH 3 ) 2 CO  H 2 NNH 2  (CH 3 ) 2 C  NNH 2
8. With phenyl Forms acetaldehyde phenylhydrazone Forms acetone phenyl hydrazone
hydrazine (C6 H5 NHNH 2 ) CH 3 CHO  H 2 NNHC 6 H 5  (CH 3 ) 2 CO  H 2 NNHC 6 H 5 

9. With semicarbazide
(H2 NNHCONH 2 ) CH 3 CHO  H 2 NNHCONH 2
ID
CH 3 CH  NNHC 6 H 5
Forms acetaldehyde semicarbazone
 (CH 3 ) 2 CO  H 2 NNHCONH
(CH 3 )2 C  NNHC 6 H 5
Forms acetone semicarbazone

2 
CH 3 CH  NNHCONH 2 (CH 3 )2 C  NNHCONH
U
2

10. With PCl5 Forms ethylidene chloride (Gem Forms isopropylidene chloride (Gem
dihalide) dihalide)
YG

Cl Cl
CH 3 CHO  PCl 5  CH 3 CH (CH 3 )2 CO  PCl 5 (CH 3 )2 C
Cl Cl
11. With chlorine Forms chloral (Gem trihalide) Forms trichloro acetone (Gem trihalide)
CH 3 CHO  Cl 2  CCl 3 CHO CH 3 COCH 3  Cl 2  CCl 3 COCH 3
D

12. With alcohols Forms acetal (a diether) Forms ketal (a diether)

OC 2 H 5 OC 2 H 5
CH 3 CHO  2C2 H 5 OH  CH 3 CH (CH 3 )2 CO  2C 2 H 5 OH (CH 3 )2 C
U

OC 2 H 5 OC 2 H 5
13. With SeO 2 Forms glyoxal Forms methyl glyoxal
CH 3 CHO  SeO 2  CHOCHO  Se  H 2 O (CH 3 )2 CO  SeO 2  CH 3 COCHO  Se  H 2 O
ST

14. Iodoform reaction Forms iodoform Forms iodoform

(I2  NaOH )

15. Bleaching powder Forms chloroform Forms chloroform

16. Aldol condensation Forms aldol Forms diacetone alcohol
with mild alkali
2CH 3 CHO  CH 3 CHOHCH 2 CHO 2CH 3 COCH 3 (CH 3 )2 C(OH )CH 2 COCH 3

17. Polymerisation Undergoes polymerisation Does not undergo polymerisation but gives
condensation reaction
18. With NH 3 Forms acetaldehyde ammonia Forms diacetone ammonia
 Aldehydes and Ketones 1275
OH (CH 3 )2 CO  NH 3  OC(CH 3 )2 
CH 3 CHO  NH 3  CH 3 CH (CH 3 )2 C(NH 2 )CH 2COCH 3
NH 2
19. With conc. NaOH Forms brownish resinous mass No reaction
20. With HNO2 No reaction Forms oximino acetone
CH 3 COCH 3  HNO 2  CH 3 COCH  NOH
21. With chloroform No reaction Forms chloretone
OH
(CH 3 )2 CO  CHCl 3 (CH 3 )2 C

60
CCl 3
22. With alk. sodium Deep red colour Red colour changes to yellow on standing
nitroprusside
23. With sodium Blue colour No effect

E3
nitroprusside + Pyridine
24. Boiling point 21 o C 56 o C
Dissimilarities
25. With Schiff's reagent Pink colour Does not give pink colour
26. With
solution
27.
reagent
With
Fehling's

Tollen's
Gives red precipitate

Gives silver mirror

ID No reaction

No reaction
U
28. Oxidation with Easily oxidised to acetic acid Oxidation occurs with difficulty to form
acidified acetic acid
CH 3 CHO  O  CH 3 COOH
K2Cr2O7 CH 3 COCH 3  O  CH 3 COOH  CO 2  H 2 O
YG

Aromatic Carbonyl Compounds

Aromatic aldehydes are of two types : Benzaldehyde is the simplest aromatic aldehyde.
It occurs in bitter almonds in the form of its glucoside,
The compounds in which CHO group is attached
amygdalin (C20 H 27 O11 N ) . When amygdalin is boiled
directly to an aromatic ring, e.g., benzaldehyde,
C6 H 5 CHO . with dilute acids, it hydrolyses into benzaldehyde,
D

glucose and HCN

Those in which aldehyde (CHO ) group is
CN
attached to side chain, e.g., phenyl acetaldehyde, |
C6 H 5 CH 2 CHO . They closely resemble with aliphatic C 6 H 5 CHOC 12 H 21 O10  2 H 2 O  C 6 H 5 CHO 
U

Amy gdalin Benzaldehy de

aldehydes.
2C 6 H 12 O 6  HCN
Aromatic ketones are compounds in which a Glucose
carbonyl group (  C  O) is attached to either two aryl
ST

Benzaldehyde is also known as oil of bitter

groups or one aryl group and one alkyl group. Examples almonds.
are :
(1) Method of preparation
CHO COCH 3 COC 6 H 5 OH
CHO (i) Laboratory method : It is conveniently
prepared by boiling benzyl chloride with copper nitrate
Benzaldehy de Acetopheno ne Benzopheno ne Salicylald ehyde or lead nitrate solution in a current of carbon dioxide.
(M ethyl phenyl (Diphenyl ketone) 2C 6 H 5 CH 2 Cl  Cu ( NO 3 )2  2C 6 H 5 CHO  CuCl 2  2 HNO 2
heat

Benzy l chloride or CO 2 Benzaldehy de

ketone) Pb ( NO 3 )2
CHO

[2 HNO 2  NO  NO 2  H 2 O]
Benzaldehyde, C6 H 5 CHO or
(ii) Rosenmund reaction :
 1276 Aldehydes and Ketones
C6 H 5 COCl  H 2   C6 H 5 CHO  HCl
Pd / BaSO 4 CHO
Benzyl chloride xylene Benzaldehy de
 CO  HCl  
AlCl 3
 HCl
(iii) By dry distillation of a mixture of calcium
benzoate and calcium formate Benzene Benzaldehy de

O
|| (ix) Gattermann reaction
C 6 H 5 COO O CH 
Ca  Ca CH   2C 6 H 5 CHO  2CaCO 3
heat HC  N  HCl  AlCl 3  H C  NH  AlCl 4 ;
|| Benzaldehy de  
C 6 H 5 COO O
Calcium benzoate
O (Major product) C 6 H 5 H  HC  NH  C 6 H 5 CH  NH 2
Calcium formate Benzene

(iv) By oxidation of benzyl alcohol : This C6 H 5 CH  NH 2  H 2 O  AlCl 4 

60
involves the treatment of benzyl alcohol with dil. HNO 3
C6 H5 CHO  NH 3  AlCl 3  HCl
or acidic potassium dichromate or chromic anhydride CHO
in acetic anhydride or with copper catalyst at 350 o C .
Thus,  HCN  HCl  H 2 O  

AlCl 3
 NH 4 Cl

E3
CH 2 OH 
[O ]
CHO
(x) Stephen's reaction : Benzaldehyde is obtained
Benzyl alcohol Benzaldehy de
by partial reduction of phenyl cyanide with stannous
This method is used for commercial production of chloride and passing dry HCl gas in ether solution
benzaldehyde. followed by hydrolysis of the aldimine stannic chloride
(v) By hydrolysis of benzal chloride : with water.

CHCl 2

 
NaOH

Benzal Chloride
CH
OH
OH
( H 2 O )
Ca (OH )2


Intermedia te
CHO

Benzaldehy de
ID C6 H 5 C  N  [C6 H 5 CH  NH ]2 H 2 SnCl 6
HCl / SnCl 2

Phenyl cyanide

(xi) By ozonolysis of styrene

Ether

O

Aldimine complex

 2C 6 H 5 CHO
H 2O
U
(unstable)

This is also an industrial method. C6 H 5 CH  CH 2 

 C6 H 5 – CH
O3
CH 2  
H 2O

Viny l benzene
(vi) By oxidation of Toluene O O
YG

CH 3 CHO C6 H 5 CHO  HCHO  H 2 O2

 O 2    H 2O
2 5 V O
350 o C
(xii) Grignard reaction
O O Br
toluene benzaldehyde || ||

Commercially the oxidation of toluene is done HCOC 2 H 5  BrMgC 6 H 5  C 6 H 5 C  H  Mg

Ethy l formate Benzaldehy de
with air and diluted with nitrogen (to prevent complete OC 2 H 5
oxidation) at 500 o C in the presence of oxides of Mn, Mo
D

Other reagents like carbon monoxide or HCN can

or Zr as catalyst. also be used in place of ethyl formate.
(xiii) From Diazonium salt
Partial oxidation of toluene with manganese
N  N  Cl  HCH  NOH  CH  NOH + HCl + N2
U

dioxide and dilute sulphuric acid at 35 o C , also forms Formaldoxi me

Benzaldoxi
benzaldehyde.
me
H2O
H /H O
C6 H 5 CH 3   C6 H 5 CH (OCOCH 3 )2 

3 CrO 2
ST

Toluene (CH 3 CO )2 O Benzy lidene acetate

CHO
C6 H5 CHO  2CH 3COOH Benzaldehy
(2) Physical properties de
(vii) Etard's reaction : C6 H 5 CH 3  2CrO2 Cl 2 
(i) Benzaldehyde is a colourless oily liquid. Its
C6 H 5 CH 3 2CrO2 Cl 2 2 C6 H 5 CHO
H O
boiling point is 179 o C .
Brown addition product Benzaldehy de
(ii) It has smell of bitter almonds.
(viii) Gattermann-koch aldehyde synthesis : (iii) It is sparingly soluble in water but highly
Benzene is converted into benzaldehyde by passing a soluble in organic solvents.
mixture of carbon monoxide and HCl gas under high (iv) It is steam volatile.
pressure into the ether solution of benzene in presence (v) It is heavier than water (sp. gr. 1.0504 at
of anhydrous aluminium chloride and cuprous chloride. 15 o C ).
(vi) It is poisonous in nature.
(3) Chemical properties
 Aldehydes and Ketones 1277
(i) Addition reaction: The carbonyl group is polar C 6 H 5 CHO  C 6 H 5 COOH
[O ]

as oxygen is more electronegative than carbon,

  Acidified K 2 Cr2 O7 , alkaline KMnO 4 and dilute
C O
HNO 3 can be used as oxidising agents for oxidation.
Thus, The positive part of the polar reagent
always goes to the carbonyl oxygen and negative part (iv) Reducing properties : Benzaldehyde is a
goes to carbonyl carbon. weak reducing agent. It reduces ammonical silver
OH OH nitrate solution (Tollen's reagent) to give silver mirror
HCN H
C 6 H 5 CH 
 C 6 H 5 CH but does not reduce Fehling's solution.
H 2O
CN COOH
Benzaldehy de cy anohy drin Mandelic acid
C 6 H 5 CHO  Ag 2 O  2 Ag  C 6 H 5 COOH
Benzaldehy de Benzoic acid

60
OH
NaHSO3
(v) Clemmensen's reduction : With amalgamated
C 6 H 5 CH
zinc and conc. HCl, benzaldehyde is reduced to toluene.
CHO SO 3 Na
Zn  Hg
Benzaldehy de sodium bisulphit e C 6 H 5 CHO  4 H    C 6 H 5 CH 3  H 2 O
(White solid) HCl

E3
OMgI OH (vi) Schiff's reaction: It restores pink colour to

(Benzaldehy
de) CH3MgI C 6 H 5 CH 
 C 6 H 5 CH
H
Schiff's reagent (aqueous solution of p-rosaniline
H 2O
CH 3 CH 3 hydrochloride decolourised by passing sulphur
1-Pheny l-1-ethanol
(2 o alcohol) dioxide).
(vii) Tischenko reaction : On heating
2[H]
LiAlH4
C 6 H 5 CH 2 OH
Benzy l alcohol

However on reduction with sodium amalgam and

water, it gives hydrobenzoin,
ID benzaldehyde with aluminium alkoxide (ethoxide) and
a little of anhydrous AlCl 3 or ZnCl 2 , it undergoes an
intermolecular oxidation and reduction (like aliphatic
aldehydes) to form acid and alcohol respectively as
U
Na  Hg such and react to produce benzyl benzoate (an ester).
C6 H 5 CH  O  2 H  O  CHC 6 H 5  
H 2O
2C 6 H 5 CHO    C 6 H 5 CH 2 OOCC 6 H 5
Al(OC 2 H 5 )3
C6 H 5 CH  CH  C6 H 5 Benzaldehy de Benzyl benzoate (ester)
| |
YG

OH OH (viii) Reactions in which benzaldehyde differs

Hy drobenzo in
from aliphatic aldehydes
(ii) Reactions involving replacement of carbonyl
(a) With fehling's solution : No reaction
oxygen
H2NNH2
C6 H 5 CH  NNH 2  H 2 O (b) Action of chlorine : Benzoyl chloride is formed
Benzaldehy de hy drazone
when chlorine is passed through benzaldehyde at its
H2N.NHC6H5 boiling point in absence of halogen carrier. This is
C6 H 5 CH  N . NHC 6 H 5  H 2 O
D

CHO Benzaldehy de pheny l hy drazone because in benzaldehyde there is no  -hydrogen atom

H2NOH present which could be replaced by chlorine.
C6 H 5 CH  NOH  H 2O
Benzaldoxi me o
C 6 H 5 CHO  Cl 2   C 6 H 5 COCl  HCl
U

170 C

(Benzaldehyd H2N.NHCONH 
e)
C6 H 5 CH  NNHCONH 2  H 2O
2
Benzaldehy de semicarbazone (c) Cannizzaro's reaction : 2C6 H 5 CHO  
KOH

Benzaldehy de
C6 H 5 CH  NC 6 H 5  H 2 O
ST

H2NC6H
5
Benzy lidine aniline (Schiff's base) C6 H 5 CH 2 OH  C6 H 5 COOK
Benzy l alcohol Potassium benzoate
PCl5
C 6 H 5 CHCl 2  POCl 3 The possible Mechanism is
Benzal chloride
First step is the reversible addition of hydroxide
OCH 3 ion to carbonyl group.
2CH3OH |
C 6 H 5 CH  H 2O H
HCl | |
OCH 3 C 6 H 5  C  O  OH  (Fast
)
C6 H 5  C  O 
Methy l acetal of benzald ehy de | |
H OH
Anion (I)
(iii) Oxidation : Benzaldehyde is readily oxidised
to benzoic acid even on exposure to air. Second step is the transfer of hydride ion directly
to the another aldehyde molecule, the latter is thus
 1278 Aldehydes and Ketones
reduced to alkoxide ion and the former (ion I) is
oxidised to an acid. Benzoin can be readily oxidised to a diketone, i.e,
benzil.
H H H
| | |
C 6 H 5 C  O  C 6 H 5 C  O    C 6 H 5 C  O   C 6 H 5 C  O
Hy dride
C 6 H 5  CH  C  C 6 H 5  [O]    C 6 H 5  C  C  C 6 H 5
CuSO 4
| ion transfer | | | || Py ridine || ||
OH (slow) OH H 2O O O
H OH O Benzil
Alkoxide ion acid Benzoin

+ +
(H –H (e) Perkin's reaction
H
exchange)
CH COONa
H
|
C 6 H 5 CH O  H 2 CHCOOCOCH 3 
3


 H 2O
C 6 H 5  C  OH  C 6 H 5  C  O Benzaldehy de Acetic anhydride

60
| |
H  C6 H 5 CH  CHCOOCOCH 3
O
Benzy l alcohol Benzoate ion
H O
Third Step is exchange of protons to give most 2 C6 H 5 CH  CHCOOH  CH 3 COOH
Cinnamic acid Acetic acid
stable pair alcohol and acid anion.

E3
CH 3
So one molecule of aldehyde acts as hydride donor |
and the other acts as hydride acceptor. In other words, H 2 C  CO
Cannizzaro's reaction is an example of self reduction CH CH COONa
C6 H 5 CH  O  O 
3
2
and oxidation.
CH 3  CH 2 CO
 Two different aldehydes each having no  - Propionic anhydride
hydrogen atom, exhibit crossed Cannizzaro's reaction
when heated in alkaline solution.
C6 H 5 CHO  HCHO 
Benzaldehy de
 C6 H 5 CH 2 OH  HCOONa
Formaldehy de
NaOH
heat Benzyl alcohol Sod. formate
ID CH 3
|
C6 H 5 CH  C  COOH  CH 3 CH 2 COONa
 - Methyl cinnamic acid
U
Aldehyde which do not have  - hydrogen (f) Claisen condensation [Claisen-schmidt reaction]
( C6 H5  CHO, CCl 3 CHO, (CH 3 )3 C  CHO, CH 2O etc.)
CH 3
undergoes Cannizzaro’s reaction. |
C 6 H 5 CHO  H 2 C  CHO  
NaOH
YG

Intramolecular cannizzaro reaction Propionald ehy de (Dil.)

CHO CHO CH2OH COOH CH 3

|
NaOH / 100  C
   
 C6 H 5 CH  C  CHO  H 2O

H / H 2O  -Methyl cinnamic aldehyde
CHO CHO COOH CH2OH NaOH (Dil.)
C6 H 5 CHO  H 2CHCOCH 3 

Acetone
(d) Benzoin Condensation
D

C6 H 5 CH  CHCOCH 3  H 2 O
H O H O Benzylidene acetone
| || | ||
 C  C   
Alc. KCN
 C  C (  (g)
 hydroxy ketone)
Knoevenagel reaction
|| |
U

|
O H OH COOH
Two molecules of benzald ehy de Benzoin (An aldol) Pyridine
  hy droxy ketone C6 H 5 CH  O  H 2 C 

COOH
Benzoin can also be reduced to a number of
ST

product i.e., Malonic acid

[H]
C6 H 5 CH  CHCOOH  CO 2  H 2O
C6 H 5  CHOH  CHOH  C6 H 5 Cinnamic acid
Na-Hg/C2H5OH Hydrobenzoin

(h) Reaction with aniline : Benzaldehyde reacts

with aniline and forms Schiff's base
OH O H Warm
| ||
OH
| | C6 H 5 CH  O  H 2 NC 6 H 5 
 C6 H 5 CH  NC 6 H 5
C6 H 5  C  C  C6 H 5 [H] C 6 H 5  CH  CH  C 6 H 5 
  H 2O
Aniline ( H 2 O ) Benzylidene aniline
|
H Zn-Hg/HCl C6 H 5 CH  CHC 6 H 5 (Schiff' s base)
Benzoin
Stilbene
Reaction with Dimethylaniline

H2
C 6 H 5  CH 2  CH 2  C 6 H 5  2 H 2 O
H2/Raney Dibenzyl
Ni
 Aldehydes and Ketones 1279
H N (CH 3 ) 2 N (CH 3 ) 2 (v) Benzaldehyde on treatment with alkaline
CH  O  
Conc. H 2 SO 4
    CH
KMnO 4 and subsequent acidification gives a white
( H 2 O )
precipitate of benzoic acid on cooling.
H N (CH 3 ) 2 N (CH 3 ) 2
Dimethyl aniline Tetramethy l diamino Acetophenone, C6H5COCH3, Acetyl Benzene
triphenyl methane
(Malachite green) (1) Method of preparation
(i) Reaction with Ammonia : Benzaldehyde reacts (i) Friedel-Craft's reaction : Acetyl chloride
with ammonia to form hydrobenzamide aldehyde other reacts with benzene in presence of anhydrous
than CH 2O give aldehyde ammonia while CH 2 O forms aluminium chloride to form acetophenone.
AlCl
urotropine. C 6 H 5 H  Cl COCH 3 
3
 C 6 H 5 COCH 3  HCl
Benzene Acetyl chloride Acetopheno ne
C 6 H 5  CHO H 2 NH O  CH  C 6 H 5

60
   (ii) By distillation of a mixture of calcium
C 6 H 5  CHO H 2 NH
benzoate and calcium acetate.
C6 H 5  CH  N
CH  C6 H 5 O
C6 H 5  CH  N ||
Hydrobenza mide C6 H 5 COO O CCH 3

E3

(j) Reformatsky reaction Ca  Ca 
 C6 H 5 COO O CCH 3
C6 H 5 CH  O  Zn  Br C H 2 COOC 2 H 5  Calcium benzoate ||
Benzaldehy de Bromo ethylaceta te O
Calcium acetate
C 6 H 5 CHCH 2 COOC 2 H 5  C 6 H 5  CH  CH 2 COOC 2 H 5
H 2O
O
| |
||
OZnBr
(k) Reaction of benzene ring
HNO3(conc.)
H2SO4 (conc.)
OH
 -hy droxy ester

CHO
ID (iii) By
diazomethane.
methylation of
2 C 6 H 5 CCH 3  2 CaCO 3
Acetopheno ne
benzaldehyde with

C6 H 5 CHO  CH 2 N 2  C6 H 5 COCH 3  N 2

U
NO2
m  Nitrobenza ldehy de
(iv) By treating benzoyl chloride with dimethyl
cadmium.
CHO CHO 2C6 H5 COCl  (CH 3 )2 Cd  2C6 H5 COCH 3  CdCl 2
YG

H2SO4
(v) By Grignard reagent
fuming SO3H (a) CH 3 C  N  C6 H 5 MgBr  CH 3 C  NMgBr H2O
Benzaldehy de m  Benzaldehy de |
Sulphonic acid
C6 H 5

Cl2 CHO C6 H 5 COCH 3  NH 3  Mg(OH )Br

O
FeCl3
D

||
Cl (b) C 6 H 5 MgBr  H 5 C 2 O C CH 3 
m Chlorobenz aldehy de
Ethyl acetate
(4) Uses : Benzaldehyde is used, O
U

|| Br
(i) In perfumery C 6 H 5 C CH 3  Mg
OC 2 H 5
(ii) In manufacture of dyes
(vi) Commercial preparation : Ethylbenzene is
(iii) In manufacture of benzoic acid, cinnamic oxidised with air at 126 o C under pressure in presence
ST

acid, cinnamaldehyde, Schiff's base, etc. of a catalyst manganese acetate.

(5) Tests : (i) Benzaldehyde forms a white CH 2 CH 3 COCH 3
Catalyst
precipitate with NaHSO 3 solution.  O2   H 2O
126 o C pressure
(ii) Benzaldehyde forms a yellow precipitate with
2 : 4 dinitrophenyl hydrazine. (2) Physical properties : It is a colourless
(iii) Benzaldehyde gives pink colour with Schiff's crystalline solid with melting point 20 o C and boiling
reagent. point 202 o C . It has characteristic pleasant odour. It is
slightly soluble in water. Chemically, It is similar to
(iv) Benzaldehyde forms black precipitate or
acetone.
silver mirror with Tollen's reagent.
(3) Chemical properties :
OH
|
HCN C 6 H 5  C  CH 3
|
CN
Acetopheno ne cy anohy drine

CH 3
|
H2NOH C 6 H 5  C  NOH 

Rearrangement

Acetopheno ne oxime or H 2 SO 4
(Methy lpheny l ketoxime)
 1280 Aldehydes and Ketones

 Acidified K2Cr2O7 i.e., chromic acid sulphuric acid

mixture is known as Jone’s reagent. When used as an
oxidising agent unlike acidified KMnO4 it does not
K2Cr2O7/H2S
diffect a double bond.

60
O4
CH2 =CHCH2OH CH2=CHCHO
 Vilsmeyer reaction : this reaction involves the
conversion of aromatic compounds to aldehydes in the
presence of a 2o amino and formic acid. CHO

E3
(CH3)2 NH +
HCOOH+POCl3
Oxidation C 6 H 5 COCHO Benzane
Pheny l gly oxal
SeO2
 Benzaldehyde although reduces Tollen’s reagent.
PCl5 C 6 H 5 CCl 2 CH 3 It does not reduce Fehling or Benedict solution.
2, 2-Dichloroethy lbenzene

C6H5COCH3
(Acetophenone)
Cl2

Iodoform
reaction
(Used as a tear gas)
(It
C 6 H 5 COCH 2 Cl harmless
powerful
Phenacy l chloride
lachrymator or tear
gas and is used by
C 6 H 5 COONa  CHI
police
3
to disperse
is
ID
relatively
but
U
I2/NaO mobs.)
Iodoform
H
Aldol type CH 3 O
| ||
condensation
C 6 H 5  C  CH  C  C 6 H 5
Al-ter-
YG

Dy pnone (It is used as hy pnotic)

butoxide
Nitratio NO 2 C 6 H 4 COCH 3
n 3/H2SO m -Nitroaceto phenone
HNO
4
conc. H2SO4 HSO 3 C 6 H 4 COCH 3
Acetopheno ne
m  sulphonic acid

(4) Uses : It is used in perfumery and as a sleep

D

producing drug.
Benzophenone, C6H5COC6H5
(1) Method of preparation
U

(i) From alkyl benzenes

C 6 H 5  CH 2  C 6 H 5  2O   C 6 H 5 COC 6 H 5
HNO 3

(2) Physical properties : It is a colourless,

ST

pleasant smelling solid.

(3) Chemical properties : It shows the
characteristic properties of keto group but does not
give bisulphite compounds.
(i) Reduction :
Na  Hg
C 6 H 5 COC 6 H 5  2 H    C 6 H 5 .CHOHC 6 H 5
Diphenyl carbinol

(ii) Clemmenson reduction :

C6 H 5 COC 6 H 5    C6 H 5 CH 2 C6 H 5  H 2 O
Zn / Hg
HCl Diphenyl methane

(iii) Fusion with KOH :

C6 H 5 COC 6 H 5  KOH   C6 H 5 COOK  C6 H 6
Fuse

C6 H 5 COC 6 H 5  H 2 O    C6 H 5 COOH  C6 H 6

Pot. tert. Butoxide
Ether Benzoic acid