Chapter

27
Aldehydes and Ketones

Introduction O
||

Carbonyl compounds are of two types, aldehydes and ketones. Both R  CH 2  OH 
 R  C  H
Mild oxidising

Primary alcohol agents Aldehyde

have a carbon-oxygen double bond often called as carbonyl group. Mild oxidising agents are
(a) X 2 (Halogen) (b) Fenton reagent ( FeSO 4  H 2 O2 )
O 
(c) K 2 Cr2 O7 / H (d) Jones reagent
C (e) Sarret reagent (f) MnO 2
Both aldehyde and Carbonyl
ketonesgroup
possess the same general formula (g) Aluminium tertiary butoxide [ Al(O  C(CH 3 )3 )3 ]
Cn H 2n O .  When the secondary alcohols can be oxidised to ketones by
aluminium tert-butoxide, [(CH 3 )3 CO ]3 Al the reaction is known as
Structure : Carbonyl carbon atom is joined to three atoms by sigma
oppenauer oxidation. Unsaturated secondary alcohols can also be oxidised to
bonds. Since these bonds utilise sp 2 -orbitals, they lie in the same plane unsaturated ketones (without affecting double bond) by this reagent.
and are 120° apart. The carbon-oxygen double bond is different than carbon-  The yield of aldehydes is usually low by this methods. The allylic
alcohols can be converted to aldehydes by treating with oxidising agent
carbon double bond. Since, oxygen is more electronegative, the electrons of
the bond are attracted towards oxygen. Consequently, oxygen attains a pyridinium chloro-chromate (C5 H 5 NH  CrO3 Cl  ) . It is abbreviated as
partial negative charge and carbon a partial positive charge making the PCC and is called Collin's reagent. This reagent is used in non-aqueous
  solvents like CH 2 Cl 2 (dichloro methane). It is prepared by mixing
bond polar. The high values of dipole moment, C O
pyridine, CrO3 and HCl in dichloromethane. This is a very good reagent
(2.3 – 2.8D) cannot be explained only on the basis of inductive because it checks the further oxidation of aldehydes to carboxylic acids and
effect and thus, it is proposed that carbonyl group is a resonance hybrid of is suitable method for preparing ,-unsaturated aldehydes.
the following two structures. (ii) Dehydrogenation of 1° and 2° alcohols by Cu/300° or Ag/300°C.
 
O
||
C  O  C O Cu / 300 C
R  CH 2 OH    R  C  H  H 2
OH O
120° | ||
-bond R  CH  R ' Cu / 300 C
 R  C  R '  H 2
120° C O
-bond (2) From carboxylic acids
120°
(i) Distillation of Ca, Ba, Sr or Th salts of monobasic acids
O
||

Preparation of carbonyl compounds (RCOO )2 Ca  (R' COO )2 Ca  2 R  C  R ' 2CaCO 3
(1) From alcohols (i) By oxidation. Thus in the product, one alkyl group comes from one carboxylic acid
OH O and other alkyl group from other carboxylic acid.
| ||
R  CH  R '    R  C  R '
Mild oxidising Calcium salts of dibasic acid (1, 4 and higher) on distillation give
Secondary alcohol agents Ketone cyclic ketones.
 O (iii) Wacker process
|| 
C H2  C O (a) CH 2  CH 2    CH 3  CHO
PdCl2 / HOH

| Ca     
Distillation
O+CaCO 3
Ethene air / Cu 2Cl2

CH 2  C  O
||  Cyclopropanone O
||
O O (b) R  CH  CH 2 
 R  C  CH 3
PdCl 2 / HOH
air/Cu 2 Cl 2
 O  Alkyl ethene

  || 
 (5) From alkynes
 O  C  (CH )
2 5  COO  Ca  
Distillation

  O
 
Cyclohexanone H O/HgSO /H SO
2 4 2 4
R – C – CH 3

(ii) Decarboxylation or Dehydration of acids by MnO/ 300°C.

R–CC–H
(a) This reaction takes place between two molecules of carboxylic (i) SiO BH 2 3

acids. Both may be the same or different. R – CH – CHO

 2

(b) If one of the carboxylic acids is HCOOH then this acid (ii) H O / OH
2 2

undergoes decarboxylation because this acid is the only monobasic acid (6) From Grignard reagents
which undergoes decarboxylation even in the absence of catalyst. O O
Case I : When both molecules are HCOOH R' – C – Cl R' – C – R (Only ketone)
O O
|| || O
H  C  OH  H COO H   CO 2  HOH  H  C  H
MnO

formic acid 300 C formaldehyde HCOOC H 2 5

H–C–R (Aldehyde)
Case II : When only one molecule is formic acid.
O
O O
|| || R' COOC H
MnO / 300 C
R  C  OH  H  COO H  R  C  H  CO 2  HOH 2 5

R – C – R' (Ketone)
formic acid Aldehyde
Carboxylic acid R – MgX O
Case III : When none of the molecule is formic acid. (Excess)
(i) HCN

R–C–H
O O (ii) H O/H
|| ||
MnO / 300 C O
2

R  C  OH  R COO H   R  C  R  CO 2  HOH

Ketone
Carboxylic acid (i) R' – CN

R – C – R'
(3) From gem dihalides : Gem dihalides on hydrolysis give carbonyl (ii) H O/H
2

compounds O

O
(i) R  CHX 2  R  CHO HOH / O H CH = CH – C – H
2

Gemdihalide Aldehyde R – CH – CH – C – H 2 2

X O (7) From acid chloride


| || (i) Acid chlorides give nucleophilic substitution reaction with dialkyl
(ii) R  C  R '    R  C  R '
HOH / O H
cadmium and dialkyl lithium cuprate to give ketones. This is one of the
|
X most important method for the preparation of ketones from acid chlorides.
 This method is not used much since aldehydes are affected by O O
|| ||
alkali and dihalides are usually prepared from the carbonyl compounds. R  C  Cl   R  C  R '
R ' 2 Cd

(4) From alkenes O

O
|| ||
(i) Ozonolysis : Alkenes on reductive ozonolysis give carbonyl R  C  Cl  R  C  R ' R ' 2 CuLi
compounds
(Only used for the preparation of ketones)
R  CH  CH  R   R  CHO  RCHO
(i)O3
In this method product is always ketone because R  H and also
Alkene (ii)H 2O / Zn
R'  H .
R R' O O (ii) Rosenmunds reduction : This reduction takes place in the
(i) O3 || || presence of Lindlars catalyst.
CC   R  C  R  R '  C  R '
(ii)H O / Zn
2 O O
R R' || ||
H 2 / Pd  BaSO 4  CaCO 3
Alkene R  C  Cl   R  C  H
Xylene
 This method is used only for aliphatic carbonyl compounds. O O
|| ||
(ii) Oxo process H 2 / Pd  BaSO 4  CaCO 3
Ar  C  Cl   Ar  C  H
CO 2 (CO )8 Xylene
R  CH  CH 2  CO  H 2   R  CH 2  CH 2  CHO
150 C , 300 atm (Only used for aldehydes)
(8) From cyanides
 Oxo process is used only for the preparation of aldehydes.
 (i) Stephen aldehyde synthesis : Conversion of cyanides into CHO
aldehydes by partial reduction with SnCl 2 / HCl , followed by hydrolysis,
CO/HCl /Anhy. ZnCl /Cu Cl
is known as Stephens aldehyde synthesis. 2 2 2

R  C  N 
 R  CHO (i) SnCl 2 / HCl / ether
Benzene
Alkylcyanide (ii)H 2O /  or steam distillation Aldehyde Benzaldehyde
(Only used for aldehydes) CH 3
CH 3
CH 3

(9) From vic diols

CO/HCl /Anhy. ZnCl /Cu Cl
CHO
OH OH O 2 2 2

+
| | ||
R  CH  C  R   RCHO  R  C  R  H 2 O
HIO 4
| Toluene o-methyl CHO
R benzaldehyde p-methyl
 Pb(OCOCH 3 )4 also gives similar oxidation products. benzaldehyde
(10) From Alkyl halides and benzyl halides Cl Cl Cl
R  CH 2 Cl 
 R  CHO ; DMSO
CO/HCl /Anhy. ZnCl /Cu Cl CHO
+
2 2 2

Cl O
| ||
R  C H  R   R  C  R
DMSO Chloro benzene o-Chloro CHO
DMSO or (i) (CH 2 )6 N 4 benzaldehyde p-Chloro
C 6 H 5  CH 2 Cl  benzaldehyde
  C 6 H 5  CHO
(ii) H 2 O / H or Cu ( NO 3 )2 or Pb( NO 3 )2
(4) Gattermann formylation : This reaction is mainly given by alkyl
(11) From nitro alkanes : Nitro alkanes having at least one  - benzenes, phenols and phenolic ethers.
hydrogen atom give carbonyl compounds on treatment with conc NaOH
CH CH CH
followed by 70% H 2 SO 4 . The reaction is known as Nef carbonyl 3 3 3

synthesis. CHO
(i) Zn(CN) /HCl gas
O O H2 OH 2

+
NaOH (ii) H O/
R  CH 2  N     
Tautomerisation
 R  C H  N 2

O O Toluene o-methyl
CHO
(Aci form) benzaldehyde p-methyl
 R  CHO
70 % H 2 SO 4
benzaldehyde
Aldehyde
OH OH OH
R O O
||
CH  N   R  C  R
(i) NaOH CHO
(i) Zn(CN) /HCl gas
(ii) H 2 SO 4 Ketone 2

+
R O (ii) H O/
2

(Iso - nitro alkane)

(12) Reaction with excess of alkyl lithium : Carboxylic acids react Phenol o-salicylaldehyde CHO
with excess of organo lithium compound to give lithium salt of gem diols
which on hydrolysis give ketones.
OCH3 OCH3 p-salicylaldehyde
OCH3
O O
|| || (i) Zn(CN) /HCl gas CHO
(i) R  Li (excess)
R '  C  OH   R '  C  R
2

(ii) H O/
+
(ii)HOH / H 2

Preparation of only aromatic carbonyl compounds o-methoxy

Anisol
(1) From methyl arenes benzaldehyde CHO
(i) CrO Cl 2 2
p-methoxy
C H CHO (5) Houben – Hoesch reaction : This reaction isbenzaldehyde
given by di and
(ii) HOH (Etard's reaction)
6 5

polyhydric benzenes.
(i) CrO /(CH CO) O/CH COOH
C H – CH
6 5 3
3 3 2 3

C H CHO
6 5 OH OH
Toluene
(ii) H O 2

Air/MnO
500°C
C H CHO
6 5
(i) RCN/HCl gas/Anhy.ZnCl 2

(2) From chloro methyl (ii) H O 2

Cu(NO ) / OH OH
3 2

C H CHO
Resorcinol COR
6 5

Pb(NO ) / 2,4-dihydroxy OH
ketone
C H – CH Cl
6 5 2
3 2

C H – CHO
6 5
OH

(i) (CH ) N /
(i) RCN/HCl gas/Anhy.ZnCl
2 6 4

C H – CHO 2

HO
6 5

(3) Gattermann – Koch(ii) formylation : This reaction is mainly given

2
(ii) H O 2

by aromatic hydrocarbons and halobenzenes. HO OH HO OH

Phloroglucinol COR
2,4,6-trihydroxy ketone
 (6) Reimer – Tiemann reaction : Phenol gives o- and p- hydroxy (1) Nucleophilic addition reactions
benzaldehyde in this reaction. (2) Addition followed by elimination reactions
OH OH OH (3) Oxidation
(4) Reduction
CHO
(i) CHCl /Alc.KOH/
3 (5) Reactions due to -hydrogen
(ii) H O/H + +
2
(6) Condensation reactions and
phenol (7) Miscellaneous reactions
(major) CHO (1) Nucleophilic addition reactions
(Minor) (i) Carbonyl compounds give nucleophilic addition reaction with
Physical properties of carbonyl compounds
those reagents which on dissociation give electrophile as well as nucleophile.
(1) Physical state : Methanal is a pungent smell gas. Ethanal is a
volatile liquid, boiling points 294 K. Other aldehydes and ketones containing (ii) If nucleophile is weak then addition reaction is carried out in the
up to eleven carbon atoms are colourless liquids while higher members are presence of acid as catalyst.
solids. (iii) Product of addition reactions can be written as follows,
(2) Smell : With the exception of lower aldehydes which have 
unpleasant odours, aldehydes and ketones have generally pleasant smell. As O OH
the size of the molecule increases, the odour becomes less pungent and ||   |

more fragrant. In fact, many naturally occurring aldehydes and ketones have R  C  R '  H  Nu  R  C  R '
Addition
 |
been used in blending of perfumes and flavouring agents. Nu
(3) Solubility : Aldehydes and ketones upto four carbon atoms are Adduct
miscible with water. This is due to the presence of hydrogen bonding In addition reactions nucleophile adds on carbonyl carbon and
between the polar carbonyl group and water molecules as shown below : electrophile on carbonyl oxygen to give adduct.

–

 +
 –
 +
O 
+
 –

+ (iv) Relative reactivity of aldehydes and ketones : Aldehydes and
C O H H O=C ketones readily undergo nucleophilic addition reactions. However, ketones
are less reactive than aldehydes. This is due to electronic and stearic effects
With the increase in the size of alkyl group, the solubility decreases as explained below:
and the compounds with more than four carbon atom are practically (a) Inductive effect : The relative reactivities of aldehydes and
insoluble in water. All aldehydes and ketones are, however, soluble in ketones in nucleophilic addition reactions may be attributed to the amount
organic solvents such as ether, alcohol, etc. The ketones are good solvents of positive charge on the carbon. A greater positive charge means a higher
themselves. reactivity. If the positive charge is dispersed throughout the molecule, the
(4) Boiling points : The boiling points of aldehydes and ketones are carbonyl compound becomes more stable and its reactivity decreases. Now,
higher than those of non polar compounds (hydrocarbons) or weakly polar alkyl group is an electron releasing group (+I inductive effect). Therefore,
compounds (such as ethers) of comparable molecular masses. However, electron releasing power of two alkyl groups in ketones is more than that of
their boiling points are lower than those of corresponding alcohols or one alkyl group in aldehyde. As a result, the electron deficiency of carbon
carboxylic acids. This is because aldehydes and ketones are polar atom in the carbonyl group is satisfied more in ketones than in aldehydes.
compounds having sufficient intermolecular dipole-dipole interactions Therefore, the reduced positive charge on carbon in case of ketones
between the opposite ends of C  O dipoles. discourages the attack of nucleophiles. Hence ketones are less reactive than
aldehydes. Formaldehyde with no alkyl groups is the most reactive of the
      aldehydes and ketones. Thus, the order of reactivity is:
C  O C  O C  O 
H R R
However, these dipole-dipole interactions are weaker than the
CO > CO > CO
intermolecular hydrogen bonding in alcohols and carboxylic acids.
Therefore, boiling points of aldehydes and ketones are relatively lower than H H R
Formaldehy de Aldehyde Ketone
the alcohols and carboxylic acids of comparable molecular masses.
Among the carbonyl compounds, ketones have slightly higher boiling (b) Stearic effect : The size of the alkyl group is more than that of
points than the isomeric aldehydes. This is due to the presence of two hydrogen. In aldehydes, there is one alkyl group but in ketones, there are
electrons releasing groups around the carbonyl carbon, which makes them two alkyl groups attached to the carbonyl group. The alkyl groups are larger
more polar. than a hydrogen atom and these cause hindrance to the attacking group.
This is called stearic hindrance. As the number and size of the alkyl groups
CH 3 .. CH 3 .. increase, the hindrance to the attack of nucleophile also increases and the
CO: CO: reactivity of a carbonyl decreases. The lack of hindrance in nucleophilic
attack is another reason for the greater reactivity of formaldehyde. Thus, the
H CH 3
Acetaldehyde Acetone
reactivity follows the order:
  2.52 D   2.88 D
b.pt.  322 K b.pt  329 K H CH 3 CH 3
(5) Density : Density of aldehydes and ketones is less than that of CO > CO > CO >
water. H H CH 3
Formaldehy de Acetaldehyde Acetone
Chemical properties of carbonyl compounds
(CH 3 )2 CH (CH 3 )3 C
Carbonyl compounds give chemical reactions due to carbonyl group
CO > CO
and -hydrogens.
(CH 3 )2 CH (CH 3 )3 C
Chemical reactions of carbonyl compounds can be classified into Di - isopropyl ketone Di - tert. butyl ketone
following categories.
 In general, aromatic aldehydes and ketones are less reactive than the Addition of sodium bisulphite
corresponding aliphatic analogues. For example, benzaldehyde is less All types of aldehydes give addition reaction with this reagent.
reactive than aliphatic aldehydes. This can be easily understood from the
resonating structures of benzaldehyde as shown below: O OH O
|| |   ||
R  C  H   R  C  H 
HSO 3 Na
 R  C  H
H or OH or
| HCHO
. .– . .– SO 3 Na
H O. . : H O. . : H O. . : Adduct; white
crystalline in nature
C C C Only aliphatic methyl ketones give addition reaction with sodium
bisulphite.

O OH  O
|| |  ||
R  C  CH 3  R  C  CH 3  R  C  H
HSO 3 Na H or OH or
 | HCHO
I II . .– III SO 3 Na
H O. . : H O Colourless crystalline
product
C C  This reagent can be used for differentiation between aromatic
and aliphatic methyl ketones, e.g.

O
||
CH 3  CH 2  C  CH 2  CH 3 and
IV
It is clear from the resonating V
structures that due to electron
releasing resonance effect of the benzene ring, the magnitude of the positive O
||
charge on the carbonyl group decreases and consequently it becomes less CH 3  CH 2  CH 2  C  CH 3
susceptible to the nucleophilic attack. Thus, aromatic aldehydes and ketones
are less reactive than the corresponding aliphatic aldehyde and ketones. The O O
order of reactivity of aromatic aldehydes and ketones is, || ||
C6 H 5 CHO > C6 H 5 COCH 3 > C6 H 5 COC 6 H 5 C6 H 5  C  CH 3 and CH 3  CH 2  C  CH 3
Benzaldehyde Acetopheno ne Benzopheno ne
 This reagent can be used for the separation of aldehydes and
Some important examples of nucleophilic addition reactions
Addition of HCN aliphatic methyl ketones from the mixture, e.g.
O OH O
||  | ||
R  C  H  HCN  R  C  CN OH CH 3  CH 2  CHO and CH 3  CH 2  C  CH 2  CH 3
|
H These two compounds can be separated from their mixture by the
Cyanohydri n use of NaHSO . Higher aliphatic ketones and aromatic ketones do not react
3

O OH with NaHSO .
||  |
3

C 6 H 5  C  H  HCN 
OH
C 6 H 5  C  CN Addition of alcohols : Carbonyl compounds give addition reaction
|
Benzaldehyde with alcohols. This reaction is catalysed by acid and base. Nature of product
H
Benzaldehyde cyanohydri n
depends on the catalyst.
 Because HCN is a toxic gas, the best way to carry out this Case I : Addition catalysed by base : In the presence of a base one
reaction is to generate hydrogen cyanide during the reaction by adding HCl equivalent of an alcohol reacts with only one equivalent of the carbonyl
to a mixture of the carbonyl compound and excess of NaCN. compound. The product obtained is called hemiacetal (in case of aldehyde)
 Benzophenone does not react with HCN. and hemiketal (in case of ketone). The reaction is reversible. There is always
 Except formaldehyde, all other aldehydes gives optically active equilibrium between reactants and product.
cyanohydrin (racemic mixture).
 This reaction is synthetically useful reaction for the preparation O  OH
||   HO |
of -hydroxy acids, -amino alcohols and -hydroxy aldehydes. CH 3  C  H  CH 3  O  H CH 3  C  H
|
 OH OCH 3
H O/H/ | Hemiacetal
R  C H  COOH
2

 - Hydroxy acid O OH

|| |
(If R is CH then product is lactic acid)
3
CH 3  C  CH 3  CH 3  O  H
HO
CH 3  C  CH 3
|
OH
| OCH 3
H /Pt
R  CH  CN Hemiketal
2

OH Hemiacetals and hemiketals are -alkoxy alcohols.

|
R  C(i)H SnCl
 CH/HCl2
 NH 2 Case II : Addition catalysed by acid : In the presence of an acid one
 - Amino alcohol
2

equivalent of carbonyl compound reacts with two equivalents of alcohol.

(ii) HOH/ Product of the reaction is acetal (in case of aldehyde) or ketal (in case of
OH
| ketone).
R  C H  CHO
 -hydroxy aldehyde
 O OCH 3 O OH
||  | || |
H
R  C  H  2CH 3 OH R  C  H  H 2O R  C  R '  HOH R  C  R'
| Ketone |
OCH 3 OH
Acetal Gemdiol
R' – N
O OCH 3 Gem diols are highly unstable compounds hence equilibrium favours
|| |
the backward direction. The extent to which an aldehyde or ketone is
R  C  R  2CH 3 OH R  C  R  H 2O
| hydrated depends on the stability of gem diol.
OCH 3
Ketal
Stability of gem diols depend on the following factors: NH 2

(i) Formation of acetals and ketals can be shown as follows: (i) Steric hindrance by +I group around -carbon decreases the Hy

R H  O  CH 3 stability of gem diols. +I group decreases stability of gem diol and hence

H decreases extent of hydration.
C O 
(ii) Stability of gem diols mainly depends on the presence of –I NH – N
H  O  CH 3
2

R
group on -carbon. More is the –I power of the group more will be
R OCH 3 stability of gem diols.
C  H 2O (iii) Intramolecular hydrogen bonding increases stability of gem C H – NH
6 5

R OCH 3 diols. –I groups present on carbon having gem diol group increases strength phe
(ii) Acetals and ketals are gem dialkoxy compounds. of hydrogen bond.
(iii) High yield of acetals or ketals are obtained if the water More is the strength of hydrogen bond more will be the stability of O
eliminated from the reaction is removed as it formed because the reaction is gem diol.
reversible. Addition of terminal alkynes : This reaction is known as ethinylation. R–C–R
(iv) Acetals and ketals can be transformed back to corresponding NH – NH

2

aldehyde or ketone in the presence of excess of water. O ONa 2,4

  || |
OCH 3 O R  C  C Na  R '  C  R  R  C  C  C  R "
|  || |
R  C  R  H 2 O 
H
R  C  R  2CH 3 OH Sod. salt of alkyne
R'
| (Excess)
OCH 3 OH
Ketal  |
This reaction is very useful reaction for the protection of carbonyl  R  C  C  C  R "
HOH / H
NH – NH 2

|
group which can be deprotected by hydrolysis. Glycol is used for this Se
R'
purpose. Suppose we want to carry out the given conversion by LiAlH4 . alkynol

(2) Addition followed by elimination reactions : This reaction is

O
|| given by ammonia derivatives (NH 2  Z) .
CH 3  C  CH 2  COOC 2 H 5  
LiAlH4
(i) In nucleophilic addition reactions poor nucleophile such as
O ammonia and ammonia derivatives requires acid as catalyst.
|| (ii) If the attacking atom of the nucleophile has a lone pair of
CH 3  C  CH 2  CH 2 OH electrons in the addition product, water will be eliminated from the addition
This can be achieved by protection of C  O group and then product. This is called a nucleophilic addition elimination.
Primary amines and derivatives of ammonia react with carbonyl
by deprotection
compounds to give adduct.
Addition of Grignard reagents : Grignard reagents react with In adduct nucleophilic group has lone pair of electrons. It undergoes
carbonyl compounds to give alcohols. Nature of alcohol depends on the elimination to give product known as imine. An imine is a compound with a
nature of carbonyl compound. carbon-nitrogen double bond.
O O 
|| ..  
(i) H – C – H
R – CH OH 1°-alcohol R  C  R  H  N H  Z 
H


2

(ii) HOH/H OH
|
R
O OH  HOH
R  C  R   CNZ
(i) R' – C – H | | An imine
RMgX R' – CH – R N HZ R
 2°-alcohol
Grignard reagent (ii) HOH/H ..
O OH The overall reaction can be shown as follows
| R R
(i) R' – C – R' .. 
R' – C – R'
 3°-alcohol C  O  N H 2  Z  H 2 O 
H
CN R
Addition of water (ii)
: Carbonyl |
HOH/H compounds react with water to give
R
gem diols. This reaction is catalysed by acid. The reaction is reversible R R
An imine
reaction.
Different Imine formation with NH 2  Z is given below
 Benedict's solution and Fehling solutions are used as a reagent for
the test of sugar (glucose) in blood sample.
(c) Tollens reagent : Tollens reagent is ammonical silver nitrate
solution. Its reacting species is Ag  .
 It oxidises aliphatic as well as aromatic aldehydes.

R  CHO  Ag    RCOOH  Ag (as silver mirror)

Redox
reaction

 This reagent has no effect on carbon-carbon multiple bond.

CH 2  CH  CHO  Ag   CH 2  CH  COOH  Ag

In this reaction the oxidation no. of Ag varies from +1 to 0.
 Glucose, fructose give positive test with Tollen's reagents and
Fehling solution.
C5 H11 O5 CHO  Cu 2 O (or) Ag2 O  C5 H11 O5 COOH
Gluconic acid

Fructose contain C  O (keto) group yet give positive test

with Fehling solution due to presence of -hydroxyl keto group. Tollens
reagent also gives positive test with terminal alkynes and HCOOH.
Beckmann rearrangement : Ketoxime when treated with acid at 0°C (d) Reaction with mercuric chloride solution :
it undergoes rearrangement known as Beckmann rearrangement.
Thus acid catalysed conversion of ketoximes to N-substituted amides R  C  H  HgCl2  H 2 O  R  C  OH  HCl  Hg2 Cl 2 ()
|| ||
is called Beckmann rearrangement. Acid catalyst used are proton (White)
O O
acids (H 2 SO 4 , HCl, H 3 PO4 ) and Lewis acids
(PCl5 , SOCl 2 , PhSO 2 Cl, RCOCl , SO 3 , BF3 etc.) R  C  H  Hg2 Cl 2  H 2 O  R  C  OH  HCl  Hg()
|| || (Black)
O O O
||
C 6 H 5  C  CH 3   CH 3  C  NH  C 6 H 5
(i) PCl5
|| (ii) H 2 O N - phenylacetamide (e) Schiff's reagent : Megenta solution  colourless solution
SO 2

N OH
Acetopheno xime  pink colour restored (In cold).
CH 3CHO

O (ii) Oxidation by strong oxidising agents : Main strong oxidising

||
agents are KMnO4 / OH / , KMnO4 / H  / ,
CH 3  C  C 6 H 5  C 6 H 5  C  NH  CH 3
(i) PCl5
||
K 2 Cr2 O7 / H  /  and conc HNO 3 /  . These agents oxidise
(ii) H 2 O N - methyl acetamide
N OH
In short product of the rearrangement can be obtained as aldehydes as well as ketones.
follows: (a) Oxidation of aldehydes : Aldehydes are oxidised into
R R' corresponding acids.
C
||
RCHO  RCOOH
[O ]
C n C n
N OH 
O KMnO 4 / O H / 
||
C6 H 5 CHO 
 C6 H 5 COOH
R ' C  O  H   R '  C  NH  R
Tautomerisation
(b) Oxidation of ketones : Ketones undergo oxidation only in drastic
||
RN conditions. During the oxidation of ketones there is breaking of carbon-
(3) Oxidation of carbonyl compounds carbon bond between -carbon and carbonyl carbon. In this process both
(i) Oxidation by mild oxidising agents : Mild oxidising agents oxidise carbons convert into carboxylic groups. This leads to the formation of two
only aldehydes into carboxylic acids. They do not oxidises ketones. Main moles of monocarboxylic acids.
oxidising agents are: Case I : Oxidation of symmetrical ketones
(a) Fehling solution : It is a mixture of two Fehling solution: Fehling O
solution No. 1 : It contains CuSO 4 solution and NaOH. ||
CH 3  CH 2  CH 2  C CH 2  CH 2  CH 3 
[O ]

Fehling solution No. 2 : It contains sodium potassium tartrate. C=7 

(Roschelle salt). COOH COOH
(b) Benedict's solution : This solution contains CH 3  CH 2  CH 2  COOH  CH 3  CH 2  COOH
C 4 C 3
CuSO 4 , NaOH and sodium or potassium citrate. Total number of C  4  3 7

Thus number of carbons in any product is less than the number of

 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
carbons in ketone.
Case II : Oxidation of unsymmetrical ketones : In case of
unsymmetrical ketones -carbon whose bond breaks always belongs to the
alkyl group which has more number of carbons. This rule is known as Example :
Popoff’s rule. CH 3  CO  CH 2  CH 3   CH 3  COOH  HOOCCH 3
[O ]

O (d) Baeyer- villiger oxidation :

||
CH 3  CH 2  CH 2 C  CH 2  CH 3 H
|
H  C  H  O  O  C  H  H  C  OH
COOH COOH || || ||
O O O

 CH 3  CH 2  COOH  CH 3  CH 2  COOH
[O ]
H
|
Case III : Oxidation of cyclic ketones : Formation of dibasic acid CH 3  C  H  O  O  C  H  CH 3  C  OH
takes place from cyclic ketones. In this case the number of carbons in || || ||
ketone and dibasic carboxylic acid is always same. O O O
 Reaction will be held if the oxidising agent is performic acid.
O (4) Reduction of carbonyl compounds
 COOH  (CH 2 )4  COOH
[O ] O
  Adipic acid |
(i) Reduction of – group
C – into –CH – group : Following three 2

 If both -carbons are not identical then bond breaking takes reagents reduce carbonyl group into CH 2  groups: (a) HI / P /  (b)
place between carbonyl carbon and the -carbon which has maximum 
number of hydrogens. Zn / Hg / Conc. HCl and (c) NH 2  NH 2 / OH .

O HI/P/
R – CH – R'
O
2

H  CH
CH 3 |
3

H H |
R – C – R' Zn/Hg/Conc. HCl
 COOH  (CH 2 )3  CH  COOH
[O ] R – CH – R' (Clemmenson
 2

 - Methyl adipic acid reduction)


2-Methyl cyclohaxanone NH – NH /OH
(iii) Miscellaneous oxidation R – CH – R'
2 2


2

(a) Haloform Reaction (ii) Reduction of carbonyl compounds into hydroxy

(Wolff-kishner reduction)compounds :
O Carbonyl group converts into CHOH  group by
|| 
LiAlH4 , NaBH 4 , Na / C2 H 5 OH and aluminium isopropoxide.
R  C  CH 3    RCOOH  CHX 3
(i) X2 / OH

 methyl carbonyl 
(ii) H R  CHO   R  CH 2 OH
(i) LiAlH4
(ii) NaBH 4
(b) Oxidation at -CH or CH by SeO : SeO oxidises 2 3 2 2
(iii)Aluminium isopropoxi de
  CH 2  group into keto group and   CH 3  group into aldehydic O OH
|| |
group.
R  C  R '   R  CH  R '
(i) LiAlH4

In this oxidation reactivity of CH 2 is more than the CH 3 group (ii) NaBH 4

(iii)Aluminium isopropoxi de
and Oxidation is regio selective in nature.
NaBH 4 is regioselective reducing agent because it reduced only.
CH 3  CHO   CHO  CHO ;
2 SeO
Glyoxal CHO in the presence of other reducible group.
O O Example :
|| ||
CH 3  C  CH 3  CH 3  C  CHO CH 3  CH  CH  CHO   CH 3  CH  CH  CH 2 OH
SeO 2 NaBH 4

Methylglyoxal Crotonalde hyde Crotonyl alcohol

(c) Oxidation by organic peracids : Organic peracids oxidise Hydride ion of NaBH 4 attack on carbonyl carbon during
aldehydes into carboxylic acids and ketones into esters. This oxidation is
known as Baeyer – Villiger oxidation. reduction.
O O O OD
|| || || |
R  C  R    R  C  O  R 
C6 H 5 COOOH
Example : CH 3  C  CH 3 
 CH 3  C  CH 2  CH 3 NaBD4

2-Butanone D2 O |
In case of aldehyde there is insertion of atomic oxygen (obtained D
from peracid) between carbonyl carbon and hydrogen of carbonyl carbon.
In case of ketone, insertion of oxygen takes place between carbonyl OH
carbon and -carbon. Thus the product is ester. This is one of the most |
important reaction for the conversion of ketones into esters. NaBD 4 CH – C – CH – CH
3 2 3

HO |
 Vic dicarbonyl compound also undergo oxidation and product is O 2

anhydride. || D
CH 3  C  CH 3 
O O 2 Butanone
|| || OD
R  C  C  R    R  C  O  C  R
C6 H 5 COOOH
|
|| ||
NaBH 4
CH – C – CH – CH
3 2 3

O O |
DO
 Popoff's rule : Oxidation of unsymmetrical ketones largely take H
2

place in such a way that the smaller alkyl group remains attached to the CO (iii) Reductive amination : In this reduction CO  group converts
group during the formation of two molecules of acids. This is known as
Popoff's rule into CH  NH 2 group
 R R R (a) -hydrogen of carbonyl compounds are acidic in character due
C  O  NH 3  C  NH   
H 2 / Ni
CH  NH 2 to the presence of the electron withdrawing CO  group.
R R R
Imine Primary amine -Hydrogen is acidic due to
(iv) Reduction of ketones by Mg or Mg/Hg : In this case ketones strong –I group; – CO –.
undergo reduction via coupling reaction and product is vic cis diol. H O
| |
O O OH OH
|| || | | –C–C–
R  C  C  R    R  C  C  R
(i) Mg / Hg
(b) Thus| carbonyl compounds having -hydrogen convert into
|| || (ii)HOH | |
R R R R carbanions -in
Carbon
the presence of base. This carbanion is stabilised by
Vic cis diol (pinacol) delocalisation of negative charge.
When this reaction is carried out in the presence of 
Mg / Hg / TiCl4 , the product is vic trans diol. O O O
|| Base  || |

HO CH 3  C  R CH 2  C  R  CH 2  C  R
(i) Hg – Mg – TiCl Carbanion Enolate ion
(less stable)
2 O
4

(more stable)
(ii) HOH
OH (c) The acidity of -hydrogen is more than ethyne. pKa value of
Cyclohexanone Vic trans diol aldehydes and ketones are generally 19 – 20 where as pKa value of ethyne is
(v) Reduction of benzaldehyde by Na/C H OH : Benzaldehyde 2 5
25.
undergoes reduction via coupling reaction and product is vic diol. (d) Compounds having active methylene or methyne group are even
more acidic than simple aldehydes and ketones.
O O
|| || O
C6 H 5  C  C  C6 H 5  
(i) Na/C 2 H 5 OH  ||
| | (ii)HOH C6 H 5  CH 2  C  CH 3 pKa  15.9
H H  - phenyl acetone
OH OH O O
| | ||  ||
C6 H 5  CH  C H  C6 H 5 (Bouveault-blanc reaction) C6 H 5  C  CH 2  C  CH 3 pKa  8.5
vic diol  - benzoyl acetone
 Aldehydes are reduced to 1° alcohols whereas ketones to 2° (ii) Halogenation : Carbonyl compounds having -hydrogens
alcohols. If carbon – carbon double bond is also present in the carbonyl undergo halogenation reactions. This reaction is catalysed by acid as well as
compound, it is also reduced alongwith. However, the use of the reagent 9- base.
BBN (9–borabicyclo (3, 3, 1) nonane) prevents this and thus only the
(a) Acid catalysed halogenation : This gives only monohalo
carbonyl group is reduced
derivative.
Example :
O O
9 BBN
CH  CH  CHO     
HOCH 2CH 2 NH 2 || ||
CH 3  C  CH 3 23 
 CH 3  C  CH 2 Br
Br / CH COOH

Acetone   bromo acetone

Cinnamaldehyde CH  CHCH 2OH (b) Base catalysed halogenation : In the presence of base all -
hydrogens of the same carbon is replaced by halogens.
Cinnamyl alcohol O
 If reducing agent is NaH, reaction is called Darzen's reaction, we   ||  
can also use LiAlH in this reaction.
4
CH 3  CH 2  C  CH 2  CH 3
 If reducing agent is aluminium iso propoxide
–
X2/OH
Excess
(CH 3  C H  O )3 Al . Product will be alcohol. This reaction is called
|
CH 3 O O X
|| || |
Meerwein – pondorff verley reduction (MPV reduction). CH 3  CH  C  CH  CH 3 CH 3  CH 2  C  C  CH 3
 The percentage yield of alkanes can be increased by using | | |
X X X
diethylene glycol in Wolf Kishner reduction. Then reaction is called Huang – Carbonyl compounds having three -hydrogens give haloform
Millan conversion. reaction.
(vi) Hydrazones when treated with base like alkoxide give
O 
O 
hydrocarbon (Wolf – Kishner reduction). || || 
R  C  CH 3  R  C  CX 3 OH
 RCOO  CHX 3
X 2 / OH
O N . NH 2
|| ||
R  C  R '    R  C  R ' 
NH 2 NH 2

 R  CH 2  R
RONa (iii) Deuterium exchange reaction : Deuterium exchange reaction is
Hydrazone  

(vii) Schiff's base on reduction gives secondary amines. catalysed by acid (D  ) as well as base (OD) . In both the cases all the
hydrogens on only one -carbon is replaced by D.
R  CH  O   R  CH  NR ' 
R ' NH 2
  R  CH 2 NHR
H 2 / Ni
Aldehyde Schiff's base Secondary amine O 
O
|| ||
R  C  CH 2  R 
 R  C  CD2  R ;
D 2 O / OD
(5) Reactions due to -hydrogen
(i) Acidity of -hydrogens :
 O O  If substrate and reagent both are carbonyl compounds then one

|| ||
should have at least one -hydrogen and other may or may not have -
R  C  CH 2  R  R  C  CD 2  R
D2 O / D
hydrogen.
(iv) Racemisation : Ketones whose -carbon is chiral undergo Condensation reaction always takes place in the presence of acid or
Racemisation in the presence of acid as well as base. base as catalyst. Best result is obtained with base at lower temp.
O OH
O CH 3 O CH 3 ||  |
|| |  || | R  C  R  CH 3  Z  
 R  C  C H 2  Z
H or
C6 H 5  C  C  C 2 H 5  
 C6 H 5  C  C  C 2 H 5
H or
 | 
|  | OH
R
H OH H
2  methyl-1 - phenyl -1 - one Racemic mixture Condensation is carried out at lower temperature ( 20C)
CH 3 O because product of the reaction is alcohol which has strong –I group at -
| || carbon.
 C 2 H 5  C  C  C6 H 5 Such type of alcohols are highly reactive for dehydration. They
|
H undergo dehydration in the presence of acid as well as base even at 25°C.
They also undergo elimination even on strong heating.
(v) Alkylation : Carbonyl compounds having -hydrogens undergo OH
|  R
HO / 
alkylation reaction with RX in the presence of base. This reaction is S N 2 R  C  CH 2  Z   C  CH  Z
 | β Dehydratio n
reaction. The best result is obtained with CH 3  X . Other halides R R
undergo elimination in the presence of strong base. (i) Aldol condensation
O CH 3 O CH 3
|| ||  (a) This reaction takes place between two molecules of carbonyl
CH 3  C  CH   CH 3  C  C
NaH
 
CH 3 I
compounds; one molecule should have at least two -hydrogen atoms. In
(Small base)
CH 3 Carbanion CH 3 this reaction best result is obtained when
LDA
O CH 3 Both molecule are the same or
(Bulky base) || |
CH 3  C  C  CH 3 One should have no -hydrogen atom and other should have at
least two -hydrogens.
|
CH 3
(Main product) (b) These reactions are practical when base is NaOH and reaction
CH 3 O CH 3 temperature is high ( 100) .
 ||
CH 2  C  CH   CH 3 CH 2  C  CH
CH 3 I
(c) The reaction is two step reaction. First step is aldol formation
||
CH 3 CH 3 and second step is dehydration of aldol.
O
(Main product)
Ethyl- isopropyl ketone

(vi) Wittig reaction : Aldehyde and ketones undergo the wittig  OH 


 | 
reaction to form alkenes. CH 3  CHO  CH 3  CHO CH 3  CH  CH 2  CHO 
NaOH / OH

Ph3 P  CH 2   C  O   C  CH 2  Ph3 P  O  
Aldehyde alkene  
Triphenyl
or ketone Phosphoniu m oxide   CH 3  CH  CH  CHO
Dehydratio n

 a,   unsaturate d aldehyde
Ph3 P  CHR  CHR  Ph3 P  CHR 
1 2 1
|| |
Due to hyper-conjugation in crotonaldehyde further condensation
O O CHR 2 give conjugated alkene carbonyl compound.
Ph3 P  CHR 1  Ph3 P  CHR 1
| | || || CH – CH = CH – CHO + CH – CH = CH – CHO
3 3

O  CHR 2 O CHR 2
NaOH
(6) Condensation reaction of carbonyl compounds : Nucleophilic
addition reaction of compounds having carbonyl group with those OH
compounds which have at least one acidic hydrogen at -carbon is known |
as condensation reaction. In this addition reaction : CH – CH = CH – CH – CH – CH = CH – CHO
3 2

Substrate is always an organic compound having a carbonyl group,

e.g.  –H O 2

O O O O
|| || || || CH – CH = CH – CH = CH – CH = CH – CHO
3

H  C  H , C6 H 5  C  H , R  C  H , R  C  R etc.
Addition always takes place on the carbonyl group.
Reagents of the condensation reaction are also organic compounds CH – (CH = CH –) – CHO
3 3

having at least one hydrogen on -carbon and -carbon should have –I Condensed compound 
OH / 
group, e.g. Mechanism : C 6 H 5  CHO  CH 3  CHO  
  
CH 3  NO 2 , CH 3  CH  CHO , CH 3  CH 2  CN C6 H 5  CH  CH  CHO  HOH
|
CH 3

Step I : HO  H  CH 2  CHO
    Test of aldehydes and Ketones (Distinction)
 O O 
|| |
HOH  CH 2  C  H  CH 2  C  H 
Table : 27.1
  Test Aldehydes Ketones
 
  With Schiff's reagent Give pink colour. No colour.
With Fehling's solution Give red precipitate. No precipitate is formed.
With Tollen's reagent Black precipitate or silver No black precipitate or
O mirror is formed. silver mirror is formed.
||  With saturated sodium Crystalline compound Crystalline compound
Step II : C 6 H 5  C  CH 2  CHO  bisulphite solution in (colourless) is formed. (colourless) is formed.
|
H water
With 2, 4-dinitrophenyl Orange-yellow or red well Orange-yellow or red
 hydrazine defined crystals with well defined crystals
O OH melting points with melting points
| | 
characteristic of individual characteristic of
C 6 H 5  C  CH 2  CHO  C 6 H 5  C  CH 2  CHO  OH
HOH
aldehydes. individual ketones.
| |
H H With sodium hydroxide Give brown resinous mass No reaction.
(formaldehyde does not
Step III :
give this test).
OH
| With sodium A deep red colour Red colour which
C6 H 5  CH  CH  CHO  C6 H 5  CH  CH  CHO  HOH nitroprusside and few (formaldehyde does not changes to orange.
| drops of sodium respond to this test).
H hydroxide

OH Some commercially important aliphatic
In aldol condensation, dehydration occurs readily because the double carbonyl compounds
bond that forms is conjugated, both with the carbonyl group and with the
benzene ring. The conjugation system is thereby extended. Formaldehyde : Formaldehyde is the first member of the aldehyde
series. It is present in green leaves of plants where its presence is supposed
Crossed aldol condensation : Aldol condensation between two
to be due to the reaction of CO 2 with water in presence of sunlight and
different aldehydes or two different ketones or one aldehyde and another
chlorophyll.
ketone provided at least one of the components have -hydrogen atom
(1) Preparation
gives different possible product
(i) 2CH 3 OH  O 2   HCHO
Platinised asbestos
300  400 C
(a) CH 3 CHO  CH 3  CH 2  CHO   
dil NaOH Formaldehy de
Ethanal Propanal
CH 3 OH  [O]  HCHO  H 2 O
K 2 Cr2 O7
H 2 SO 4
OH CH 3
| | (ii) CH 3 OH 
 HCHO
Cu or Ag
CH 3  CH  CH  CHO  CH 3  CH 2  CHOH  CH 2  CHO 300  400 C Formaldehy de

However crossed aldol condensation is important when only it the (iii) Ca(HCOO) 2  HCHO Heat

Calcium formate Formaldehy de

components has -hydrogen atom.
(iv) CH 2  CH 2  O 3 
 HCHO
H2

 Pd Formaldehy de
CH 2 O  CH 3 CHO  CH 2  CH 2  CHO  CH 2  CH  CHO
 H 2O
| (Acrolein)
(v) CH 4  O 2 
 HCHOMo -oxide
OH Methane Catalyst Formaldehy de
(3 - hydroxy propanal)

(vi) CO  H 2    HCHO

Elec.discharge
Intra molecular aldol condensation : One molecule Intramolecular Formaldehy de
condensation give aldol compounds (2) Physical properties
(i) It is a colourless, pungent smelling gas.
Example :
(ii) It is extremely soluble in water. Its solubility in water may be
OH due to hydrogen bonding between water molecules and its hydrate.
(iii) It can easily be condensed into liquid. The liquid formaldehyde
O  CH  (CH 2 )5  CHO   
di. NaOH
boils at – 21°C.
CHO (iv) It causes irritation to skin, eyes, nose and throat.
(ii) Claisen – Schmidt reaction : Crossed aldol condensation between (v) Its solution acts as antiseptic and disinfectant.
aromatic aldehyde and aliphatic ketone or mixed ketone is known as Claisen (3) Uses
– Schmidt reaction. Claisen – Schmidt reactions are useful when bases such
(i) The 40% solution of formaldehyde (formalin) is used as
as sodium hydroxide are used because under these conditions ketones do
disinfectant, germicide and antiseptic. It is used for the preservation of
not undergo self condensation. Some examples of this reaction are :
biological specimens.
O  O
|| OH ||
(ii) It is used in the preparation of hexamethylene tetramine
C6 H 5 CHO  CH 3  C  CH 3   C6 H 5  CH  CH  C  CH 3
100 C
(urotropine) which is used as an antiseptic and germicide.
4  Phenyl  3  buten - 2 - one
 (iii) It is used in silvering of mirror. K 2 SO 4  Cr2 (SO 4 )3  3 CH 3 CHO  7 H 2 O
Potassium Chromic Acetaldehyde Water
(iv) It is employed in manufacture of synthetic dyes such as para- sulphate sulphate

rosaniline, indigo, etc. To recover acetaldehyde, the distillate is treated with dry ammonia
when crystallised product, acetaldehyde ammonia, is formed. It is filtered
(v) It is used in the manufacture of formamint (by mixing
and washed with dry ether. The dried crystals are then distilled with dilute
formaldehyde with lactose) – a throat lozenges.
sulphuric acid when pure acetaldehyde is collected.
(vi) It is used for making synthetic plastics like bakelite, urea-
OH
formaldehyde resin, etc. |
CH 3 CHO  NH 3  CH 3  CH  NH 2  
H 2 SO 4

(vii) Rongalite – a product obtained by reducing formaldehyde Acetaldehyde ammonia

sodium bisulphite derivative with zinc dust and ammonia and is used as a
CH 3 CHO  (NH 4 ) 2 SO 4
reducing agent in vat dyeing. Acetaldehyde

Acetaldehyde (x) Manufacture : Acetaldehyde can be manufactured by one of the

following methods:
Acetaldehyde is the second member of the aldehyde series. It occurs
in certain fruits. It was first prepared by Scheele in 1774 by oxidation of (a) By air oxidation of ethyl alcohol
ethyl alcohol. 2CH 3 CH 2 OH  O 2 
 2CH 3 CHO  2 H 2 O
Ag
300 C
(1) Preparation : It may be prepared by any of the general methods.
The summary of the methods is given below (b) By dehydrogenation of alcohol

(i) By oxidation of ethyl alcohol with acidified potassium dichromate CH 3 CH 2 OH 

 CH 3 CHO
Cu
300 C
or with air in presence of a catalyst like silver at 300°C.
(c) By hydration of acetylene
(ii) By dehydrogenation of ethyl alcohol. The vapours of ethyl alcohol HgSO 4 ,(1%), 60 C
are passed over copper at 300°C. CH  CH  H 2 O   CH 3 CHO
H 2 SO 4 (40 %)

(iii) By heating the mixture of calcium acetate and calcium formate. (d) From ethylene (Wacker process)
(iv) By heating ethylidene chloride with caustic soda or caustic H 2 C  CH 2  O 2    H 3 C  CHO
PdCl2 ,CuCl 2

potash solution. H 2O

(v) By the reduction of acetyl chloride with hydrogen in presence of
a catalyst palladium suspended in barium sulphate (Rosenmund's reaction).
(vi) By the reduction of CH 3 CN with stannous chloride and HCl
in ether and hydrolysis (Stephen's method).
(vii) By hydration of acetylene with dil. H 2 SO 4 and HgSO 4 at
60°C.
(viii) By ozonolysis of butene-2 and subsequent breaking of ozonide.
(ix) Laboratory preparation : Acetaldehyde is prepared in the
laboratory by oxidation of ethyl alcohol with acidified potassium dichromate
or acidified sodium dichromate.
K 2 Cr2 O7  4 H 2 SO 4  K 2 SO 4  Cr2 (SO 4 )3  4 H 2 O  3[O]
[CH 3 CH 2 OH  O  CH 3 CHO  H 2 O]  3
K 2 Cr2 O 7  3 CH 3 CH 2 OH  4 H 2 SO 4 
Potassium Ethyl alcohol Sulphuric acid
dichromate
(2) Physical properties
(i) Acetaldehyde is a colourless volatile liquid. It boils at 21°C.
(ii) It has a characteristic pungent smell.
(iii) It is soluble in water, chloroform, ethyl alcohol and ether. Its
aqueous solution has a pleasant odour. In water, it is hydrated to a
considerable extent to form ethylidene diol.
CH 3 CHO  H 2 O  CH 3 CH (OH )2
(3) Uses : Acetaldehyde is used :
(i) In the preparation of acetic acid, acetic anhydride, ethyl acetate,
chloral, 1,3-butadiene (used in rubbers), dyes and drugs.
(ii) As an antiseptic inhalent in nose troubles.
(iii) In the preparation of paraldehyde (hypnotic and sporofic) and
metaldehyde (solid fuel).
(iv) In the preparation of acetaldehyde ammonia (a rubber
accelerator).

Table : 27.2 Comparative study of formaldehyde and acetaldehyde

S.No. Reaction Formaldehyde HCHO Acetaldehyde CH CHO 3

Similarities
1. Addition of hydrogen Forms methyl alcohol Forms ethyl alcohol
(a) H in presence of catalyst, Ni, Pd or Pt
2
HCHO  H 2  CH 3 OH CH 3 CHO  H 2  CH 3 CH 2OH
(b) LiAlH4 (ether)
Forms methyl alcohol Forms ethyl alcohol
(c) Amalgamated zinc + conc. HCl (Clemmenson Forms methane Forms ethane
reduction)
HCHO  4 H  CH 4  H 2O CH 3 CHO  4 H  C2 H 6  H 2O
2. Addition of NaHSO 3 solution Forms bisulphite addition product Forms bisulphite addition product
HCHO  NaHSO 3  CH 2 (OH )SO 3 Na CH 3 CHO  NaHSO 3 

CH 3 CH (OH )SO 3 Na
3. Addition of HCN Forms formaldehyde cyanohydrin Forms acetaldehyde cyanohydrin
HCHO  HCN  CH 2 (OH )CN CH 3 CHO  HCN 

CH 3 CH (OH )CN
4. Addition of Grignard reagent followed by Forms ethyl alcohol Forms isopropyl alcohol
hydrolysis OMgI CH 3 CHO  CH 3 MgI 
HCHO  CH 3 MgI  CH 2
CH 3
CH 3  C HOMgI 2
H O
 Mg (OH )I
  CH 3 CH 2 OH
H 2O |
 Mg (OH )I CH 3

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  

CH 2  NNH 2 CH 3 CH  NNH 2

7. With phenyl hydrazine (C 6 H 5 NHNH 2 ) Forms formaldehyde phenyl hydrazone Forms acetaldehyde phenyl hydrazone
 H 2O
CH 2  O  H 2 NNHC 6 H 5   CH 3 CH  O  H 2 NNHC 6 H 5
 H 2O
  CH 3 CH  NNHC 6 H 5
CH 2  NNHC 6 H 5
8. With semicarbazide (H 2 NNHCONH 2 ) Forms formaldehyde semicarbazone Forms acetaldehyde semicarbazone
CH 2  O  H 2 NNHCONH 2 
  H 2O CH 3 CH  O  H 2 NNHCONH 2
 H 2O
  CH 3 CH  NNHCONH 2
CH 2  NNHCONH 2
9. With alcohol (C2 H 5 OH ) in presence of acid Forms ethylal Forms acetaldehyde diethyl acetal
H 2 C  O  2C 2 H 5 OH 
HCl
CH 3 CHO  2C 2 H 5 OH 
HCl

OC2 H 5 OC2 H 5
CH 2 CH 3 CH
OC2 H 5 OC2 H 5
10. With thioalcohols (C 2 H 5 SH ) in presence of Forms thio ethylal Forms acetaldehyde diethyl thioacetal
acid H 2 C  O  2C 2 H 5 SH  CH 3 CH  O  2C 2 H 5 SH 

SC 2 H 5 SC 2 H 5
CH 2 CH 3 CH
SC 2 H 5 SC 2 H 5
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 reagent Restores pink colour of Schiff's reagent
13. With Tollen's reagent Gives black precipitate of Ag or silver mirror Gives black precipitate of Ag or silver
Ag2O  HCHO  2 Ag  HCOOH mirror
Ag2O  CH 3 CHO 

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

Cu 2O  CH 3 COOH
15. Polymerisation Undergoes polymerisation Undergoes polymerisation
Evaporation H SO Conc.
nHCHO (HCHO )n 3CH 3 CHO 2 4

Paraformal dehyde dil. H SO . distill

2 4

Room temp.
3 HCHO (HCHO )3 (CH 3 CHO )3
heat Metaformaldehyde
Paraldehyd e H2SO4Conc.

dil. H2SO4. distill

4 CH 3 CHO
(CH 3 CHO )4
Metaldehyde

Dissimilarities
16. With PCl 5
No reaction Forms ethylidene chloride
Cl
CH 3 CHO  PCl5  CH 3 CH
Cl
 POCl3
17. With chlorine No reaction Forms chloral
CH 3 CHO  3Cl 2  CCl 3 CHO

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

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

CH 3 CH (OH )CH 2 CHO

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

CH 3 OH
22. With ammonia Forms hexamethylene tetramine (urotropine) Forms addition product, acetaldehyde
6 HCHO  4 NH 3 (CH 2 )6 N 4  6 H 2 O ammonia
CH 3 CHO  NH 3 

OH
CH 3 CH
NH 2
23. With phenol Forms bakelite plastic No reaction
24. With urea Forms urea-formaldehyde plastic No reaction
25. Condensation in presence of Ca(OH )2 Form formose (a mixuture of sugars) No reaction

Inter conversion of formaldehyde and acetaldehyde

(1) Ascent of series : Conversion of formaldehyde into acetaldehyde
CH 3 CH 2 OH   CH 3 CHO
H 2 SO 4 (dil.)
(i) HCHO   CH 3 OH 
H 2 / Ni
 CH 3 Cl 
PCl5

Alc.
Ethyl alcohol K 2 Cr2 O7 Acetaldehyde
Formaldehy de Methyl Methyl KCN
alcohol chloride 
(ii) HCHO   CH 3 CH 2OMgI 
CH 3 MgI


H 3O
CH 3 CN   CH 3 CH 2 NH 2 
Na / Alcohol

NaNO 2
Formaldehy de Ether
Methyl Ethyl amine HCl
cyanide
CH 3 CH 2 OH 
 CH 3 CHO
Cu

Ethyl alcohol 300 C Acetaldehyde

 Reduction H2, Ni, Pd
HCHO 2 2 
  HCOOH  
K Cr O
Ca (OH )2
(iii) 7
CH 3 CHOHCH 3
Formaldehy de H 2 SO 4 Formic acid or LiAlH4
Amalgamated Zn Isopropyl alcohol

(HCOO )2 Ca    CH 3 CHO CH 3 CH 2 CH 3

3 2 (CH COO ) Ca + conc. HCl
Calcium formate heat Acetaldehyde Propane
NaHSO3 (CH 3 )2 C(OH )SO 3 Na
(2) Descent of series : Conversion of acetaldehyde into formaldehyde Acetone sodium bisulphite derivative
HCN OH
(i) CH 3 CHO 2 2 
  CH 3 COOH  
7 K Cr O NH 3
H 2 SO 4
(CH 3 )2 C
Acetaldehyde Aceticacid CN
CH3MgI Acetone cyanohydri n
CH 3 COONH 4   CH 3 CONH 2 
Heat
 
Br2 / KOH
Ether (CH 3 )3 COH
Amm. acetate Acetamide Tertiary butyl alcohol
NH2OH
(CH 3 )2 C  NOH
CH 3 NH 2  CH 3 OH 
 HCHO
NaNO 2 Cu
Acetoxime
HCl 300 C Formaldehy de NH2NH2
(CH 3 )2 C  NNH 2
Methyl amine

(ii) CH 3 CHO 2 2 

  CH 3 COOH   CH 3 COONa
7 K Cr O NaOH Acetone hydrazone
C6H5NHNH2
Acetaldehyde H 2 SO 4 Aceticacid Sod.acetat e (CH 3 )2 C  NNHC 6 H 5
Acetone phenyl hydrazone
H2NNHCONH2
  CH 4 
Sodalime
 CH 3 Cl 
Cl 2

AgOH
(CH 3 )2 C  NNHCONH 2
heat Methane hv Acetone semicarbazone
PCl5 Cl
CH 3 OH 
 HCHO Cu
(CH 3 )2 C
300 C Formaldehy de Cl
Isopropyli dene chloride
Acetone Cl2
CH 3 COCCl 3
It is a symmetrical (simple) ketone and is the first member of the Trichloroacetone
homologous series of ketones. In traces, it is present in blood and urine. I2 +NaOH CHI 3
(1) Preparation : Iodoform
CH COCH CH 3


(i) (CH 3 COO )2 Ca 
3 3

(Acetone)
calciumacetate
C
Conc. H2SO4 CH CH
500 C
(ii) 2CH 3 CHOHCH 3  O2 
 C
Isopropyl alcohol C
CH CH 3

(iii) CH 3 CHOHCH 3 

Cu CH 3
Mesitylene
300 C
2 propanol (1, 3, 5-trimethyl benzene)
CaOCl2
(iv) (a) CH 3 CH  CH 2  PdCl2  H 2 O  (Bleaching powder)
propene CHCl 3
CH COCH heat Chloroform
(b) CH 3 CH  CH 2  H 2 SO 4 
3 3
K2Cr2O7 + H2SO4
CH 3 COOH  CO 2  H 2 O
propene CHCl 3
(CH 3 )2 C(OH )CCl 3
CH 3 CH (HSO 4 )CH 3 Chloretone
H2O Ba(OH)2
(CH 3 )2 C(OH )CH 2 COCH 3
CH 3 CH (OH )CH 3 

Cu
HNO2
Diacetone alcohol
300 C
Isopropyl alcohol CH 3 COCH  NOH
(Oximino acetone)
(v) 2C3 H 5 OH  H 3 O 
 
Zn (CrO )
2
NH3
500 C (CH 3 )2 C(NH 2 )CH 2 COCH 3
Diacetone amine
(vi) 2CH  CH  3 H 2O   
catalyst
Mg–Hg + H2O OH OH
420 C | |

(vii) From pyroligneous acid : Pyroligneous acid containing acetic acid, (CH 3 )2 C — C (CH 3 )2
Schiff's reagent No reaction Pinacol
acetone and methyl alcohol is distilled in copper vessel and the vapours are Tollen's reagent
passed through hot milk of lime. Acetic acid combines to form nonvolatile No reaction
calcium acetate. The unabsorbed vapours of methanol and acetone are Fehling's solution
No reaction
condensed and fractionally distilled. Acetone distills at 56 o C .
If acetone would be in excess in ketal condensation or catalyst
The acetone thus obtained is purified with the help of sodium
bisulphite. (ZnCl 2 / dry HCl) is used then three moles of acetone undergoes
(2) Physical properties : (i) It is a colourless liquid with characteristic condensation polymerisation and form a compound called ‘Phorone’.
pleasant odour. CH CH
3 3
(ii) It is inflammable liquid. It boils at 56 o C . | |
CH 3  C  O H CH 3  C  CH
(iii) It is highly miscible with water, alcohol and ether. CH
(3) Chemical properties H
CO
CH
3 C=O  
ZnCl 2
dry. HCl
|
CH 3  C  O H
CH 3  C  CH
CH |
H CH 3
Acetone (3 molecule) phoron
 Molecular mass of phorone = 3 mole of acetone – 2 mole of H 2 O (i) As a solvent for cellulose acetate, cellulose nitrate, celluloid,
lacquers, resins, etc.
(ii) For storing acetylene.
Reformatsky reaction: This reaction involves the treatment of aldehyde
and ketone with a bromo acid ester in presence of metallic zinc to form  - (iii) In the manufacture of cordite – a smoke less powder explosive.
hydroxy ester, which can be easily dehydrated into  ,  -unsaturated ester. (iv) In the preparation of chloroform, iodoform, sulphonal and
chloretone.

(a) BrCH 2 COOC 2 H 5  Zn   Br  Zn  CH 2 COOC 2 H 5
Benzene (v) As a nailpolish remover.
Organo zinccompound (vi) In the preparation of an artificial scent (ionone), plexiglass
(b) Addition to carbonyl group (unbreakable glass) and synthetic rubber.
(5) Tests
CH 3 Zn Br CH 3
| | (i) Legal's test : When a few drops of freshly prepared sodium
C  O  CH 2 COOC 2 H 5  CH 3  C  CH 2 CH 2 COOC 2 H 5 nitroprusside and sodium hydroxide solution are added to an aqueous
|
CH 3 OZn Br solution of acetone, a wine colour is obtained which changes to yellow on
standing.
(ii) Indigo test : A small amount of orthonitrobenzaldehyde is added
CH 3 to about 2 ml. of acetone and it is diluted with KOH solution and stirred. A
|
HOH / H  blue colour of indigotin is produced.

 CH 3  C  CH 2
 Br 
 Zn  | | (iii) Iodoform test : Acetone gives iodoform test with iodine and
 OH 
OH COOC 2 H 5 sodium hydroxide or iodine and ammonium hydroxide.
 - hydroxyest ers

CH 3
|
 CH 3  C  CH  COOC 2 H 5
(4) Uses
Table : 27.3 Comparison between Acetaldehyde and Acetone
Reaction Acetaldehyde Acetone
Similarities
1. Reduction with H 2 and Ni or Forms ethyl alcohol Forms isopropyl alcohol
LiAlH4 CH 3 CHO  H 2 
 CH 3 CH 2 OH Ni
CH 3 COCH 3  H 2  CH 3 CHOHCH 3

2. Clemmensen's reduction Forms ethane (an alkane) Forms propane (an alkane)
(Zn/Hg and conc. HCl) 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

3. Addition of HCN Forms acetaldehyde cyanohydrin Forms acetone cyanohydrin

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 followed by Forms isopropyl alcohol Forms tertiary butyl alcohol
hydrolysis
CH 3 CHO  CH 3 MgI (CH 3 )2 CH  OMgI (CH 3 )2 CO  CH 3 MgI (CH 3 )3 COMgI
 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
7. With hydrazine (NH 2 NH 2 ) Forms acetaldehyde hydrazone Forms acetone hydrazone
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 hydrazine Forms acetaldehyde phenylhydrazone Forms acetone phenyl hydrazone
(C6 H 5 NHNH 2 ) CH 3 CHO  H 2 NNHC 6 H 5  (CH 3 )2 CO  H 2 NNHC 6 H 5 
 CH 3 CH  NNHC 6 H 5 (CH 3 )2 C  NNHC 6 H 5
9. With semicarbazide Forms acetaldehyde semicarbazone Forms acetone semicarbazone
(H 2 NNHCONH 2 ) CH 3 CHO  H 2 NNHCONH 2  (CH 3 )2 CO  H 2 NNHCONH 2 
CH 3 CH  NNHCONH 2 (CH 3 )2 C  NNHCONH 2
10. With PCl5 Forms ethylidene chloride (Gem dihalide) Forms isopropylidene chloride (Gem dihalide)
Cl Cl
CH 3 CHO  PCl5  CH 3 CH (CH 3 )2 CO  PCl5 (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
12. With alcohols Forms acetal (a diether) Forms ketal (a diether)
OC2 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
OC2 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

14. Iodoform reaction Forms iodoform Forms iodoform

(I2  NaOH )
15. Bleaching powder Forms chloroform Forms chloroform
16. Aldol condensation with mild Forms aldol Forms diacetone alcohol
alkali
2CH 3 CHO  CH 3 CHOHCH 2CHO 2CH 3 COCH 3 (CH 3 )2 C(OH )CH 2COCH 3
17. Polymerisation Undergoes polymerisation Does not undergo polymerisation but gives condensation
reaction
18. With NH 3 Forms acetaldehyde ammonia Forms diacetone ammonia
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 HNO 2 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
CCl 3
22. With alk. sodium Deep red colour Red colour changes to yellow on standing
nitroprusside
23. With sodium nitroprusside + Blue colour No effect
Pyridine
24. Boiling point 21o C 56 o C
Dissimilarities
25. With Schiff's reagent Pink colour Does not give pink colour
26. With Fehling's solution Gives red precipitate No reaction
27. With Tollen's reagent Gives silver mirror No reaction
28. Oxidation with acidified Easily oxidised to acetic acid Oxidation occurs with difficulty to form acetic acid
K2Cr2O7 CH 3 CHO  O  CH 3 COOH CH 3 COCH 3  O  CH 3 COOH  CO 2  H 2 O
Aromatic Carbonyl Compounds
Aromatic aldehydes are of two types : CH 2 OH 
[O ]
CHO
Benzyl alcohol Benzaldehyde
The compounds in which CHO group is attached directly to an
aromatic ring, e.g., benzaldehyde, C 6 H 5 CHO . This method is used for commercial production of benzaldehyde.
(v) By hydrolysis of benzal chloride :
Those in which aldehyde (CHO ) group is attached to side chain, OH
CHCl 2 CH CHO
e.g., phenyl acetaldehyde, C6 H 5 CH 2 CHO . They closely resemble with OH
( H 2 O )
aliphatic aldehydes. 

NaOH
 
Ca (OH )2
Aromatic ketones are compounds in which a carbonyl group
Benzal Chloride Intermedia te Benzaldehyde
(  C  O) is attached to either two aryl groups or one aryl group and one (unstable)
alkyl group. Examples are : This is also an industrial method.
CHO COCH 3 COC 6 H 5 OH (vi) By oxidation of Toluene
CHO
CH 3 CHO
 O 2    H 2O
2 5V O
Benzaldehyde Acetophenone Benzopheno ne Salicylaldehyde 350 o C
(Methyl phenyl (Diphenyl ketone) toluene benzaldehyde
ketone) Commercially the oxidation of toluene is done with air and diluted
CHO
with nitrogen (to prevent complete oxidation) at 500 o C in the presence
of oxides of Mn, Mo or Zr as catalyst.
Benzaldehyde, C6 H5CHO or Partial oxidation of toluene with manganese dioxide and dilute
sulphuric acid at 35 o C , also forms benzaldehyde.
Benzaldehyde is the simplest aromatic aldehyde. It occurs in bitter H /H O
C6 H 5 CH 3   C6 H 5 CH (OCOCH 3 )2 

3 CrO 2
almonds in the form of its glucoside, amygdalin (C 20 H 27 O11 N ) . When Toluene (CH 3 CO )2 O Benzylidene acetate
amygdalin is boiled with dilute acids, it hydrolyses into benzaldehyde,
C6 H 5 CHO  2CH 3 COOH
glucose and HCN
CN (vii) Etard's reaction : C6 H 5 CH 3  2CrO2 Cl 2 
|
C6 H 5 CH 3 2CrO2 Cl 2 2 C6 H 5 CHO
H O
C 6 H 5 CHOC 12 H 21 O10  2 H 2 O  C 6 H 5 CHO 
Amygdalin Benzaldehyde Brown addition product Benzaldehyde

2C 6 H 12 O 6  HCN (viii) Gattermann-koch aldehyde synthesis : Benzene is converted

Glucose into benzaldehyde by passing a mixture of carbon monoxide and HCl gas
under high pressure into the ether solution of benzene in presence of
Benzaldehyde is also known as oil of bitter almonds. anhydrous aluminium chloride and cuprous chloride.
(1) Method of preparation CHO
(i) Laboratory method : It is conveniently prepared by boiling benzyl  CO  HCl  
AlCl3
 HCl
chloride with copper nitrate or lead nitrate solution in a current of carbon
dioxide. Benzene Benzaldehyde

2C 6 H 5 CH 2 Cl  Cu ( NO 3 )2  2C 6 H 5 CHO  CuCl 2  2 HNO 2

heat
(ix) Gattermann reaction
Benzyl chloride or CO 2 Benzaldehyde

Pb( NO3 )2
HC  N  HCl  AlCl3  H C  NH  AlCl4 ;
 
[2 HNO 2  NO  NO 2  H 2 O]
C 6 H 5 H  HC  NH  C 6 H 5 CH  NH 2
Benzene
(ii) Rosenmund reaction :

C6 H 5 COCl  H 2  C6 H 5 CHO  HCl
Pd / BaSO 4 C6 H 5 CH  NH 2  H 2 O  AlCl4 
xylene
Benzyl chloride Benzaldehyde
C6 H 5 CHO  NH 3  AlCl3  HCl
(iii) By dry distillation of a mixture of calcium benzoate and calcium CHO
formate
Thus,  HCN  HCl  H 2 O  
AlCl3
 NH 4 Cl
O
||
C 6 H 5 COO O CH
(x) Stephen's reaction : Benzaldehyde is obtained by partial
Ca  Ca CH   2C 6 H 5 CHO  2CaCO 3
heat

|| Benzaldehyde reduction of phenyl cyanide with stannous chloride and passing dry HCl
C 6 H 5 COO O (Major product) gas in ether solution followed by hydrolysis of the aldimine stannic chloride
Calcium benzoate
O
Calcium formate with water.
(iv) By oxidation of benzyl alcohol : This involves the treatment of C6 H 5 C  N  [C6 H 5 CH  NH ]2 H 2 SnCl 6
HCl / SnCl 2

Phenyl cyanide Ether Aldimine complex

benzyl alcohol with dil. HNO 3 or acidic potassium dichromate or chromic
  2C6 H 5 CHO
H 2O
anhydride in acetic anhydride or with copper catalyst at 350 o C .
 H2NNH2
C6 H 5 CH  NNH 2  H 2 O
Benzaldehyde hydrazone

H2N.NHC6H5
(xi) By ozonolysis of styrene C6 H 5 CH  N . NHC 6 H 5  H 2 O
O CHO Benzaldehyde phenyl hydrazone

H2NOH
C6 H 5 CH  CH 2 
 C6 H 5 – CH
O3
CH 2  
H 2O
C6 H 5 CH  NOH  H 2 O
Vinyl benzene Benzaldoxime
O O
(Benzaldehyde) H N.NHCONH2
C6 H 5 CH  NNHCONH 2  H 2 O
2

C6 H 5 CHO  HCHO  H 2 O2
Benzaldehyde semicarbazone
(xii) Grignard reaction
O O Br H NC H
2 6 5
C6 H 5 CH  NC 6 H 5  H 2 O
|| || Benzylidine aniline(Schiff's base)
HCOC 2 H 5  BrMgC6 H 5  C 6 H 5 C  H  Mg
Ethyl formate Benzaldehyde
OC 2 H 5 PCl 5

C 6 H 5 CHCl 2  POCl3
Other reagents like carbon monoxide or HCN can also be used in Benzal chloride
place of ethyl formate.
(xiii) From Diazonium salt OCH 3
2CH OH |
N  N  Cl  HCH  NOH  CH  NOH + HCl + N 2
3

C 6 H 5 CH  H 2O
Formaldoxi me
HCl |
Benzaldoxime
OCH 3
HO 2
Methyl acetal of benzaldehyde
(iii) Oxidation : Benzaldehyde is readily oxidised to benzoic acid even
CHO on exposure to air.

(2) Physical properties

Benzaldehyde C 6 H 5 CHO  C 6 H 5 COOH
[O ]

(i) Benzaldehyde is a colourless oily liquid. Its boiling point is Acidified K 2 Cr2 O7 , alkaline KMnO 4 and dilute HNO 3 can be
179 o C .
used as oxidising agents for oxidation.
(ii) It has smell of bitter almonds.
(iii) It is sparingly soluble in water but highly soluble in organic (iv) Reducing properties : Benzaldehyde is a weak reducing agent. It
solvents. reduces ammonical silver nitrate solution (Tollen's reagent) to give silver
(iv) It is steam volatile. mirror but does not reduce Fehling's solution.
(v) It is heavier than water (sp. gr. 1.0504 at 15 o C ).
(vi) It is poisonous in nature. C 6 H 5 CHO  Ag 2 O  2 Ag  C 6 H 5 COOH
Benzaldehyde Benzoic acid
(3) Chemical properties
(i) Addition reaction: The carbonyl group is polar as oxygen is more (v) Clemmensen's reduction : With amalgamated zinc and conc. HCl,
electronegative than carbon, benzaldehyde is reduced to toluene.
 
Zn  Hg
C O C 6 H 5 CHO  4 H    C 6 H 5 CH 3  H 2 O
HCl
Thus, The positive part of the polar reagent always goes to the
carbonyl oxygen and negative part goes to carbonyl carbon. (vi) Schiff's reaction: It restores pink colour to Schiff's reagent
OH OH (aqueous solution of p-rosaniline hydrochloride decolourised by passing
HCN
H
C 6 H 5 CH   C 6 H 5 CH sulphur dioxide).
H 2O
CN COOH (vii) Tischenko reaction : On heating benzaldehyde with aluminium
Benzaldehyde cyanohydri n Mandelic acid
alkoxide (ethoxide) and a little of anhydrous AlCl3 or ZnCl 2 , it
OH
NaHSO3 undergoes an intermolecular oxidation and reduction (like aliphatic
C 6 H 5 CH
aldehydes) to form acid and alcohol respectively as such and react to
CHO SO 3 Na produce benzyl benzoate (an ester).
Benzaldehyde sodium bisulphite
(White solid)
2C 6 H 5 CHO    C 6 H 5 CH 2 OOCC 6 H 5
Al(OC 2 H 5 )3
OMgI OH Benzaldehyde Benzyl benzoate (ester)
(Benzaldehyde) 
CH3MgI C 6 H 5 CH 
 C 6 H 5 CH
H
(viii) Reactions in which benzaldehyde differs from aliphatic
H 2O
CH 3 CH 3 aldehydes
1-Phenyl -1-ethanol
(2o alcohol)
(a) With fehling's solution : No reaction
(b) Action of chlorine : Benzoyl chloride is formed when chlorine is
2[H] C 6 H 5 CH 2 OH passed through benzaldehyde at its boiling point in absence of halogen
LiAlH4 Benzyl alcohol carrier. This is because in benzaldehyde there is no  -hydrogen atom
present which could be replaced by chlorine.
However on reduction with sodium amalgam and water, it gives
hydrobenzoin, o

Na  Hg
C 6 H 5 CHO  Cl 2   C 6 H 5 COCl  HCl
170 C

C6 H 5 CH  O  2 H  O  CHC 6 H 5   
H 2O

C6 H 5 CH  CH  C6 H 5 (c) Cannizzaro's reaction : 2C6 H 5 CHO  

KOH

| Benzaldehyde
|
OH OH C6 H 5 CH 2OH  C6 H 5 COOK
Hydrobenzo in Benzyl alcohol Potassium benzoate
(ii) Reactions involving replacement of carbonyl oxygen
 The possible Mechanism is
First step is the reversible addition of hydroxide ion to carbonyl
group. Benzoin can be readily oxidised to a diketone, i.e, benzil.
H C 6 H 5  CH  C  C 6 H 5  [O]    C6 H 5  C  C  C 6 H 5
CuSO 4
|
 (Fast)  | || Pyridine || ||
C 6 H 5  C  O  OH C6 H 5  C  O OH H 2O O O
| |
O Benzil
Benzoin
H OH
Anion (I)
(e) Perkin's reaction
Second step is the transfer of hydride ion directly to the another
CH COONa
aldehyde molecule, the latter is thus reduced to alkoxide ion and the former C 6 H 5 CH O  H 2 CHCOOCOCH 3 
3


 H 2O
(ion I) is oxidised to an acid. Benzaldehyde Acetic anhydride

H H H C 6 H 5 CH  CHCOOCOCH 3
| | |
C 6 H 5 C  O  C 6 H 5 C  O    C 6 H 5 C  O   C 6 H 5 C  O
Hydride
H O
| ion transfer
(slow)
| | 2 C6 H 5 CH  CHCOOH  CH 3 COOH
OH H OH Cinnamic acid Acetic acid
Alkoxide ion acid

(H exchange)
+
–H +
CH 3
H
|
H H 2 C  CO
| CH CH COONa
C 6 H 5  C  OH  C 6 H 5  C  O C6 H 5 CH  O  O 
3
2
| |
H  CH 3  CH 2 CO
O Propionic anhydride
Benzyl alcohol Benzoate ion

Third Step is exchange of protons to give most stable pair alcohol CH 3

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

NaOH / 100 C
   Benzylidene acetone
H  / H 2O (g) Knoevenagel reaction
CHO CHO COOH CH OH 2 COOH
Pyridine
(d) Benzoin Condensation C6 H 5 CH  O  H 2 C 

COOH
H O H O
| || | ||
 C  C  
Alc. KCN
 C  C (   hydroxy ketone)
Malonic acid
|| |
O
|
C6 H 5 CH  CHCOOH  CO 2  H 2O
H OH Cinnamic acid
Two moleculesof benzaldehyde Benzoin (An aldol)
  hydroxy ketone
(h) Reaction with aniline : Benzaldehyde reacts with aniline and
Benzoin can also be reduced to a number of product i.e., forms Schiff's base
Warm
[H]
C6 H 5  CHOH  CHOH  C6 H 5 C6 H 5 CH  O  H 2 NC 6 H 5 
 C6 H 5 CH  NC 6 H 5
Na-Hg/C H OH Hydrobenzoin Aniline ( H 2 O ) Benzylidene aniline
2 5

(Schiff's base)

Reaction with Dimethylaniline

OH O OH H
| || | |
C6 H 5  C  C  C6 H 5 [H]  H 2O
C 6 H 5  CH  CH  C 6 H 5   
|
H Zn-Hg/HCl
C 6 H 5 CH  CHC 6 H 5
Benzoin
Stilbene

H2

H /Raney Ni C6 H 5  CH 2  CH 2  C6 H 5  2 H 2 O
2
Dibenzyl
 H N (CH 3 )2 AlCl
N (CH 3 )2 C 6 H 5 H  Cl COCH 3 
3
 C 6 H 5 COCH 3  HCl
Conc. H 2 SO 4 Benzene Acetyl chloride Acetopheno ne
CH  O     CH
( H 2 O ) (ii) By distillation of a mixture of calcium benzoate and calcium
H N (CH 3 )2 N (CH 3 )2 acetate.
Dimethyl aniline Tetramethy l diamino
triphenyl methane O
(Malachite green) ||
C 6 H 5 COO O CCH 3
(i) Reaction with Ammonia : Benzaldehyde reacts with ammonia to 
Ca  Ca 
form hydrobenzamide aldehyde other than CH 2O give aldehyde ammonia
C 6 H 5 COO O CCH 3
while CH 2 O forms urotropine. Calcium benzoate ||
O
C6 H 5  CHO H 2 NH O  CH  C H
  

6 5 Calcium acetate
C6 H 5  CHO H 2 NH O
||
C6 H 5  CH  N
CH  C6 H 5 2C6 H 5 CCH 3  2CaCO 3
C6 H 5  CH  N Acetopheno ne
Hydrobenza mide (iii) By methylation of benzaldehyde with diazomethane.
(j) Reformatsky reaction C 6 H 5 CHO  CH 2 N 2  C 6 H 5 COCH 3  N 2

(iv) By treating benzoyl chloride with dimethyl cadmium.
C6 H 5 CH  O  Zn  Br C H 2 COOC 2 H 5 
Benzaldehyde Bromo ethylaceta te 2C6 H5 COCl  (CH 3 )2 Cd  2C6 H5 COCH 3  CdCl 2
C 6 H 5 CHCH 2 COOC 2 H 5  C 6 H 5  CH  CH 2 COOC 2 H 5
H 2O (v) By Grignard reagent
|
|
OH (a) CH 3 C  N  C 6 H 5 MgBr  CH 3 C  NMgBr H2O
OZnBr  -hydroxy ester |
C6 H 5
(k) Reaction of benzene ring
HNO (conc.) CHO C6 H 5 COCH 3  NH 3  Mg(OH)Br
3

O
H SO (conc.)
2 4 ||
NO2 (b) C 6 H 5 MgBr  H 5 C 2 O C CH 3 
m  Nitrobenza ldehyde
Ethyl acetate
O
||
Br
CHO CHO
H SO C 6 H 5 C CH 3  Mg
2 4
OC 2 H 5
fuming SO3H (vi) Commercial preparation : Ethylbenzene is oxidised with air at
m  Benzaldehyde
Benzaldehyde
Sulphonic acid 126 o C under pressure in presence of a catalyst manganese acetate.
CH 2 CH 3 COCH 3
Catalyst
Cl 2
CHO  O2   H 2O
126 o C pressure
FeCl
(4) Uses : Benzaldehyde is used, 3

Cl (2) Physical properties : It is a colourless crystalline solid with

m Chlorobenz aldehyde
(i) In perfumery
melting point 20 o C and boiling point 202 o C . It has characteristic
(ii) In manufacture of dyes pleasant odour. It is slightly soluble in water. Chemically, It is similar to
(iii) In manufacture of benzoic acid, cinnamic acid, cinnamaldehyde, acetone.
(3) Chemical properties :
Schiff's base, etc.
OH
(5) Tests : (i) Benzaldehyde forms a white precipitate with |
HCN C 6 H 5  C  CH 3
NaHSO 3 solution. |
CN
(ii) Benzaldehyde forms a yellow precipitate with 2 : 4 dinitrophenyl Acetopheno ne cyanohydri ne

hydrazine.
CH 3
(iii) Benzaldehyde gives pink colour with Schiff's reagent. H2NOH
|
Rearrangem ent
C 6 H 5  C  NOH 

(iv) Benzaldehyde forms black precipitate or silver mirror with Acetopheno ne oxime or H 2 SO 4
(Methylphenyl ketoxime)
Tollen's reagent.
C6H5COCH3 C 6 H 5 NHCOCH 3
(v) Benzaldehyde on treatment with alkaline KMnO4 and (Acetophenone)
Acetanilide
Clemmensen
subsequent acidification gives a white precipitate of benzoic acid on cooling. reduction C6 H 5 CH 2 CH 3
Ethyl benzene
Acetophenone, C6H5COCH3, Acetyl Benzene Zn(Hg)/HCl
(1) Method of preparation
C 6 H 5 CH OH
(i) Friedel-Craft's reaction : Acetyl chloride reacts with benzene in Reduction |
presence of anhydrous aluminium chloride to form acetophenone. CH 3
Na/C2H5OH
Methyl phenyl carbinol
(2 o alcohol)

[O]
Oxidation C6 H 5 COCOOH 
 C6 H 5 COOH
Cold KMnO4 Phenyl glyoxylicacid Benzoic acid
 Oxidation C 6 H 5 COCHO
SeO2 Phenyl glyoxal

PCl5 C 6 H 5 CCl 2 CH 3
2, 2-Dichloroethylbenzene
(It is relatively harmless but
Cl2 C 6 H 5 COCH 2 Cl powerful lachrymator or tear
C6H5COCH3 Phenacyl chloride
gas and is used by police to
(Acetophenone) (Used as a tear gas) disperse mobs.)
Iodoform
reaction
C 6 H 5 COONa  CHI 3
I2/NaOH Iodoform

Aldol type CH 3 O
condensation | ||
Al-ter-butoxide C 6 H 5  C  CH  C  C 6 H 5
Dypnone (It is used as hypnotic)

Nitration NO 2 C 6 H 4 COCH 3
HNO /H SO m -Nitroacetophenone
3 2 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 producing drug.
Benzophenone, C6H5COC6H5
(1) Method of preparation
(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, 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 COC6 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

 Acidified K Cr O i.e., chromic acid sulphuric acid mixture is known

2 2 7

as Jone’s reagent. When used as an oxidising agent unlike acidified

KMnO it does not diffect a double bond.
4

CH =CHCH OH
2 2
K Cr O /H SO
2 2 7 2 4
CH =CHCHO
2

 Vilsmeyer reaction : this reaction involves the conversion of aromatic

compounds to aldehydes in the presence of a 2 amino and formic
CHOacid.
o

(CH ) NH + HCOOH+POCl
3 2 3

Benzane
 Benzaldehyde although reduces Tollen’s reagent. It does not reduce
Fehling or Benedict solution.