f

Aldehydes

1.
2.
3
14 IIT-JEE Syllabus
Introduction
Structure of Carbonyl Group
&
Ketones
4. Nomenclature
5. Physical Properties
6. Preparation
6.1 Preparation of Aldehydes
6.2 Preparation of Ketones In this chapter our attention is focused on the
6.3 Preparation of aldehydes by
oxidation method
6.4 Synthesis from Dithiane preparation of aldehydes and ketones, on
7. Reactions of Aldehydes and
Ketones
7.1 Oxidation their physical properties, chemical reactions,
7.2 Reduction
7.3 Addition Reactions
7.4 Disproportionation specially nucleophilic addition reaction that
7.5 Halogenation
7.6 Aldol Condensation
7.7 Claisen Condensation takes place at their carbonyl groups e.g.
7.8 Acidity of -Hydrogens
7.9 Nucleophilic Edition of Water
8. Reaction related to the Aldol cannizaro reaction, aldol condensation,
condensation
9. Claisen Condensation
10. Decarboxylation of -keto acids reaction with NH2 system, and other
11. Cannizzaro reaction
12. Addition of Ammonia
13. Meerwein Ponndorf – Verley important reactions.
reduction
14. Tischenko Reaction
15. Baeyer-Villiger Oxidation
16. Darzen Glycidic Ester Condensation
17. Claisen Schmidt Reaction
18. Hemiacetal & Acetal
19. Clemensen Reduction
20. Wolff Kischner
21. Schmidt Reaction
22. Pinacole–Pinacolone rearrangement
23. Formaldehyde
24. Benzaldehyde
25. Analysis of Aldehydes & Ketones
26. Solutions to Exercise
27. Solved Problems
28. Assignment
(Subjective problems)
29. Assignment
(Objective Problems
30. Answers to Objective Problems
1. IIT-JEE Syllabus
Aldehydes and Ketones (oxidation, reduction, oxime and hydrazone formation,
Aldol condensation, Perkin reaction, Cannizzaro reaction, haloform and original
reaction only.

2. Introduction
Aldehydes are the compounds which have general formula RCHO, Ketones are
compounds having general formula RRCO. The groups R and R may be aliphatic or
aromatic, similar or different alkyl groups.
R R
C=O C=O
H R
An aldehyde A ketone

Both aldehydes and ketones contain the carbonyl group, >C = O, and are often referred
to collectively as carbonyl compounds.

It is the carbonyl group that governs mainly the chemistry of aldehydes and ketones.

3. Structure of Carbonyl group

The carbonyl carbon atom is sp2 hybridized and bonded to three other atoms through
three coplanar sigma bonds oriented about 120 apart. The unhybridized p orbital
overlaps with a p orbital of oxygen to form a pi bond. The double bond between carbon
and oxygen is similar to an alkene C = C double bond, except that the carbonyl double
bond is shorter and stronger.

R Length Energy
Ketone C = O bond 1.23Å 178 kcal/mol
120 C –– O (745 kJ/mol)
Alkene C = C bond 1.33Å 146 kcal/mol
(611 kJ/mol)
R 120

Another difference between the carbonyl and alkene double bonds is the large dipole
moment of the carbonyl group. Oxygen is more electronegative than carbon, and the
bonding electrons are not shared equally. In particular, the less tightly held pi electrons
are pulled more strongly toward the oxygen atom, giving ketones and aldehydes larger
dipole moments than most alkyl halides and ethers. We can use resonance structures to
symbolize this unequal sharing of the pi electrons.

R R
C=O  C – O–
+

R R
The first resonance structure is clearly more important, since it involves more bonds and
less charge separation. The contribution of the second structure is evident by the large
dipole moments of the ketones and aldehydes shown below.

Cl
O O
|| || O
H–C–H
C C H3C CH3
H CH3 H3C CH3 H
 = 2.7 D  = 2.7 D  = 1.9 D  = 1.30 D
acetaldehyde acetone chloromethane dimethyl ether

This polarization of the carbonyl group contributes to the reactivity of ketones and
aldehydes. The positively polarized carbon atom acts as an electrophile, and the
negatively polarized oxygen acts as a nucleophile.

Illustration 1: What is the simplest structure having one aldehyde and one ketone group?

Solution: H – C – C – CH3
|| ||
O O

Illustration 2: What is the hybridisation state of different carbons in propanone?

1 2 3
Solution: Structure of propanone is H3 C C  C H3
||
O
C1 & C3 carbons are sp3 hybridised. C2 is sp2 hybridised

4. Nomenclature
The common name of aldehydes are derived from the names of the corresponding
carboxylic acids by replacing –oic acid by –al.

The IUPAC names of aldehydes follow the usual pattern. The longest chain containing
the –CHO group is considered the parent structure and named by replacing –e of the
corresponding alkane by –al. The position of the substituent is indicated by a number,
the carbonyl carbon always being considered C-1. Here, as with the carbonyl acids, the
C-2 of the IUPAC name corresponds to alpha of the common name.

H H H H
| | | |
H –– C = O CH3 –– C = O CH3 –– CH2 –– C = O CH3 –– CH2 –– CH2 C = O
Formaldehyde Acetaldehyde Propionaldehyde n-Butyraldehyde
Methanal Ethanal Propanal Butanal

H H
| |
–– C = O O2N –– –– CHO H3C –– –– C =O
Benzaldehyde p-Nitrobenzaldehyde p-Tolualdehyde
 H
| H
C=O |
–– CH2 –– C = O
OH
Salicyaldehyde Phenylacetaldehyde
(o-Hydroxybenzaldehyde) (Phenylethanal)

H H
| |
CH3 –– CH2 –– CH2 –– CH –– C = O CH3 –– CH2 –– CH –– CH2 –– C = O
| |
CH3 CH3
2-Methylpentanal 3-Methylpentanal

H
|
CH3 –– CH –– CH2 –– CH2 –– C = O
|
CH3
4-Methylpentanal

The simple aliphatic ketone has the common name acetone. For most other aliphatic
ketones we name the two groups that are attached to carbonyl carbon and follow these
names by the word ketone. A ketone in which the carbonyl group is attached to a
benzene ring is named as a-phenone, all illustrated below. According to IUPAC system,
the longest chain carrying the carbonyl group is considered the parent structure, and is
named by replacing –e of the corresponding alkane with one. The positions of various
groups are indicated by numbers.

CH3 –– C –– CH3 CH3CH2 –– C –– CH3 CH3 –– CH2CH2 –– C –– CH3

|| || ||
O O O
Acetone Methyl ethyl ketone Methyl-n-propyl ketone
Propanone Butanone 2-Pentanone

CH3
|
CH3 –– CH2 –– C –– CH2CH3 CH3 –– CH –– C –– CH3 CH2 –– C –– CH3
|| || ||
O O O
3–Pentanone 3-Methyl-2-butanone 1-Phenyl-2-propanone

C –– CH3 C –– CH2CH2CH3 C
|| || ||
O O O
Acetophenone n-butyrophenone Benzophenone

5 6 2 3 NO2
H3C ––4 –– C –– 4
||
3 2 6 5
O
3-Nitro-4-methylbenzophenone
Exercise 1: What is the IUPAC nomenclature of
i) PhCH2 – C – CH3
||
O
ii) NO2

H3C C
||
O

5. Physical Properties
Polarization of the carbonyl group creates dipole - dipole interactions between the
molecules of ketones and aldehydes, resulting in higher boiling points than for
hydrocarbons and ethers of similar molecular weights. Ketones and aldehydes have no
O – H or N – H bonds, however, so they cannot form hydrogen bonds with each other.
The following compounds of molecular weight 58 or 60 are ranked in order of increasing
boiling point. The ketones and the aldehyde are more polar and higher-boiling than the
ether and the alkane, but lower boiling than the hydrogen-bonded alcohol.
O O
|| ||
CH 3CH 2CH 2CH 3 CH 3  O  CH 2CH 3 CH 3CH 2  C  H CH 3  C  CH 3
bu tan e bp 0  C methoxyeth ane by 8  C propanal bp 49  C acetone bp 56  C

CH 3CH 2CH 2  OH
1propanol bp 97  C

The melting points, boiling points, and water solubilities of some representative ketones
and aldehydes. Although pure ketones and aldehydes cannot engage in hydrogen
bonding with each other, they have lone pairs of electrons and can act as hydrogen
bond acceptors with other compounds have O – H or N – H bonds. For example, the –
OH of water or an alcohol can form a hydrogen bond with the unshared electrons on a
carbonyl oxygen atom.
O O
H H H R
 
O O
|| ||
C C
H R R R

Because of this hydrogen bonding, ketones and aldehydes are good solvents for polar
hydroxylic substances such as alcohols. They can also remarkably soluble in water. That
acetaldehyde and acetone are miscible (soluble in all proportions) with water, and other
ketones and aldehydes with up to four carbon atoms are appreciably soluble in water.
These solubility properties are similar to those of ethers and alcohols, which also engage
in hydrogen bonding with water.

Formaldehyde and acetaldehyde are the most common aldehydes. Formaldehyde is a

gas at room temperature, so it is often stored and used as a 40 percent aqueous
solution called formalin. When dry formaldehyde is needed, it can be generated by
heating one of the solid derivatives of formaldehyde, usually trioxane units.
Paraformaldehyde is a linear polymer, containing many formaldehyde units. These solid
derivatives form spotaneously when a small amount of acid catalyst is added to pure
formaldehyde.
H H
C
O O
H H heat
O HO OH
C C
H – C – H  H – C – H
H2 O
H O H
Trioxane (metal form Formaldehyde formalin
heat
aldehyde) bp – 21C

 H H H H 
 | | | | 
  C  O  C O C  O  C O  
 | | | | 
 H H H H 
Paraformaldehyde
(a polymer of formaldehyde)

Acetaldehyde boils near room temperature, and it can be handled as a liquid.

Acetaldehyde is also used as a trimer (paraldehyde) and a tetramer (metaldehyde),
formed from acetaldehyde under acid catalysis. Heating either of these compounds
provides dry acetaldehyde. Paraldehyde is used in medicines as a sedative, and
metaldehyde is used as a bailt and poison for snails and slugs.
Illustration 3: Boiling point of aldehydes are in between of corresponding alcohols and
alkane – explain.
Solution: In aldehydes, dipole dipole interaction exists between the molecules. In
alkanes Vander Wall’s interaction exists which is weaker than this and in
alcohols hydrogen bonding exists which is stronger then dipole dipole
interaction. So their boiling points are in between alcohols and alkanes.
H CH3 CH3 H
O O C O H
O O || O C
CH3 CH3  CH 3  C  H 
heat

heat CH3
C CH3
C C Acetaldehyde, bp 20C O
H O H H O C H
Paraldehyde, bp 125C
(a trimer of acetaldehyde)
CH3
Metaldehyde, mp 246C
(a tetramer of acetaldeyde)

6. Preparation
A few of the many laboratory methods of preparation of aldehydes and ketones are
outlined below; (most of these are already familiar to us) Industrial preparation is
generally patterned after these laboratory methods, but with use of cheaper reagents
alcohols are oxidized catalytically with air, or by dehydrogenation over hot copper.

6.1 Preparation of Aldehydes

6.1.1 Oxidation of primary alcohols
 H
| (By special distillation method)
RCH2 OH   R  C  O
K 2Cr2O 7

1° alcohol Aldehyde

RCH2 OH   R  CHO

P.C.C.
CH3Cl

CrO3Cl  (Pyridinium chloro-chromate) (P.C.C.)

N
+
H
Example:
K Cr O , H SO
CH 3CH 2CH 2OH 227
2 
4  CH CH CHO
3 2
warm

6.1.2 Oxidation of methyl benzenes

Cl2 heat h H2O
ArCHCl2
Hydrolysis
ArCH3 –– ArCHO
CrO3, acetic H2O
anhydride ArCH (– OC – CH3)2
||
O
A gem-diacetate
(Not oxidized
Example

Cl , heat
–– CH3  light
2   Br –– –– CHCl2    Br ––
CaCO3 , H2O
Br –– –– CHO
p-Bromotoluene p-Bromobenzaldehyde

–– CH3   –– CH(OAc)22 O2N ––

CrO HO
O2N –– 3
O2N –– – CHO
Ac2O H SO 2 4

p-nitrotoluene p-Nitrobenzaldehyde

6.1.3 Reduction of acid chlorides


–– COCl or RCOCl Pd 
H2
RCHO + HCl
BaSO 4

Poisoned with quinoline-S (trace)

Rosenmund’s reaction

6.1.4 Reimer-Tiemann Reaction-Phenolic Aldehydes

(Discussed under phenol)

6.1.5 By heating a mixture of the calcium salts of formic acid and any one of its
homologues.

(RCO2)2Ca + (HCO2)2 Ca  2RCHO + CaCO3

6.1.6 Stephen’s Method

 R –– C  N   RCHO
1. SnCl2
HCl, 2, H2 O

H2O (Hydrolysis of intermediate) RCH = NH to RCHO and NH3

Illustration 4: What happened when calcium salt of HCO2H undergoes heating?

Δ
Solution: (HCO2)2Ca  CaCO3 + 2HCHO

Illustration 5:
CH = CH – CH2OH   Pdt?
MnO 2

CH2 – CH2 – CH2OH   Pdt?

MnO 2

Solution: MnO2 oxidises alcohol group which is either allylic or benzylic position. So in
the 1st case product will be

CH = CH – CHO but in the 2nd case no reaction takes place

6.2 Preparation of Ketones

6.2.1 Oxidation of Secondary alcohols

R –– CH –– R    R –– C –– R
CrO3 or
K 2Cr2O7 , H2SO4 ||
|
OH O
H
 
K 2Cr2 O7
H2SO 4
OH O

6.2.2 Friedel – Crafts acylation

O
R –– C + ArH  
AlCl3
 R –– C –– Ar + HCl
Cl
or other Lewis acid ||
O
Acid chloride Ketone

CH3 –– C –– Cl +  CH3 –– C ––
AlCl3
||  ||
+ HCl
O O
 Anhy.AlCl
CH3—CH2—C—Cl   
3 CH CH –– C ––
3 2 + HCl
|| ||
O O
Zn–Hg; conc. HCl

CH3CH2CH2 ––
(free from rearrangement)

Anhy .AlCl
–– C –– Cl + 
3 –– C –– + HCl
|| ||
O O
Benzophenone

Anhy .AlCl
(CH3CO)2O +    
3
CH3 –– C –– + CH3CO2H
||
Acetic anhydride
O
O O
|| ||
C C

Zn Hg; c.HCl
O+   
1. AlCl3 , 2. H
  SOCl
  2

F.C. Acylation Clemmensen's Re duction
C CO2H CO2H
||
O

CH2
 
Anh. AlCl3

(Intramolecular F.C. Acylaation)
C – Cl
|| ||
O O

Cl  
Anhy.
AlCl3
|| ||
(Intramolecular
O F.C. Acylation) O

6.2.3 Acylation of Alkenes

R O
| ||
R –– C –– Cl + H2C = CHR [R –– C –– CH2 –– CHCl] R –– C –– CH = CHR
|| ||
O O
 
This is Markovnikov addition initiated by R  C  O :, an acylium cation.

6.2.4 With Organometallics

 a) Reaction of acid chlorides with organocadmium compounds
RMgX R2Cd
+
R –– C –– R or Ar –– C –– R
RCOCI || ||
or O
O
ArCOCI
(R must by aryl or primary alkyl)
Example:

CH3 –– CH2 –– CH2 CH2MgBr (CH3CH2CH2CH2)2Cd + 2CH3 –– CH2 –– C –– Cl

||
O

2CH3CH2CH2CH2 –– C –– CH2 –– CH3

||
O
(2-Methyl-3-heptanone)
Convert
H3C H3C
–– Br  –– COCH2CH2CH3

H3C H3C H3C

Br 
 Cd + 2CH3CH2CH2COCl
Mg
MgBr + CdCl2 
2
H3C
–– CCH2CH2CH3
||
O

H2O
C6H5 –– Mg Br + –– C N  –– C –– C6H5 –– C –– C6H5
||  ||
NM gBr O
6.2.5 By heating the calcium salt of any monocarboxylic acid other than formic
acid

(RCO2)2Ca  R2CO + CaCO3
Example

(CH 3  C  O)2 Ca  CH3COCH3 + CaCO3
||
O
6.2.6 Acetoacetic ester synthesis of ketones
CH3COCH2COOC2H5  CH3COCHCO2CH2CH3 
NaOEt
CH3 –– C –– CHCO2CH2CH3
R X
|| |
Acetoacetic ester
O R

OH
–
H+ 
CH3COCHCO2 CH3 –– CO –– CH –– CO2H CH3COCH2R
| |
R R

6.2 7 Ring Ketones from Dicarboxylic acids and their Derivaties

CO2H
(CH2)n  (CH2)n C = O + BaCO3 + H2O
CO2H
Cyclopentanone or
n = 4 and 5 cyclohexanone

Exercise 2: Pimelic acid (H2OC – (CH2)5 – CO2H) when undergoes heating what will be
product?

6.3 Preparation of aldehydes by oxidation methods

Aldehydes are easily oxidised to carboxylic acids by the same reagent acidic
dichromate, in their syntheses. Hence, removal of aldehyde as fast as it is formed is to
be accomplished. So it is best to use P.C.C. in CH3Cl a selective reagent that does not
further oxidise the aldehydes to the acids.

In the case of toluene , oxidation of the side chain can be interrupted by trapping the
aldehyde in the form a non-oxidisable derivative, the gem-diacetate, which can be
isolated and then hydrolysed.
O –– C –– CH3
||    ArCHO
hydrolysis
ArCH3 anhydride
  ArCH
acetic
O
O –– C –– CH3
||
O
A-gem-diacetate
(Not oxidised)

6.4 Synthesis of Ketones and Aldehydes Using 1,3-Dithianes

1,3-Dithiane is a weak proton acid (pKa = 32) that can be deprotonated by strong bases
such as n-butyllithium. The resulting carbanion is stabilized by the electron withdrawing
effect of two highly polarizable suffer atoms.

+ C4H9Li  + C4H10
S S S  S butane
n-butyllithium
H H
H
1,3-dithiane, pKa = 32
Dithiane anion
Alkylation of the dithiane anion by a primary alkyl halide or tosylate gives a thioacetal
(sulphur acetal) that can be hydrolysed using an acidic solution of mercuric chloride. The
product is an aldehyde bearing the alkyl group that was added by the alkylating agent.
This is a useful synthesis of aldehydes.

+ C4H9 – Li   
H ,HgCl2
O
H2O
S S S S
 Alkylating agent
(primary alkyl halide) H C4H9 H C4H9
H
Dithiane anion thioacetal aldehyde

Alternatively, the thioacetal can be alkylated once more to give a thioketal. Hydrolysis of
the thioketal gives a ketone.

O
 

1. BuLi
 
H ,HgCl2
2. 1 R   X

S H2O
S S S
R R
R H R R
thioacetal thioacetal ketone

For example, 1-phenyl-2-pentanone may be synthesized as shown below:

O
 

1. BuLi
 

1. BuLi



H ,HgCl2
S 2. PhCH2 Br S 2. CH3CH2CH2Br
S S S S H2O
PhCH2 CH2CH2CH3
1,3-dithiane
PhCH2 H PhCH2 CH2CH2CH3 Ketone
thioacetal thioacetal

In each of these sequence, dithiane is alkylated once or twice, then hydrolyzed to give a
carbonyl group bearing the alkyl group(s) used in the alkylation. We often consider
dithiane to be a synthetic equivalent of a carbonyl group that can be made nucleophilic
and alkylated.

7. Reactions of Aldehydes and Ketones

7.1 Oxidation
KMnO or K Cr O / H
a) R CH = O 4 
2 
2 
7  R –– CO2H
or or
Ar –– CH = O ArCO2H
b) Tollen’s Reagent
A specific oxidant for RCHO is [ Ag(NH 3 )2 ]+
R – C – H + Ag(NH 3 ) 2   RCOOH


||
O
Tollen’s test chiefly is used for the detection of aldehydes.
Tollen’s reagent does not attack carbon-carbon double bonds.
 c) Strong Oxidants
Ketones resist mild oxidation, but with strong oxidants at high temperature
they undergo cleavage of C – C bonds on either sides of the carbonyl group.

R – CH2 – C – CH2R   RCO2H + RCH2CO2H + RCH2CO2H + RCO2H

oxidation

|| ( drastic)
From cleavage of bond (a)
O

d) Haloform Reaction
CH 3  C  R
||
O
are readily oxidised by NaOI (NaOH + I2) to iodoform, CHI3, and RCO2Na

Example:

C2H5 –– C –– CH3 + NaOH + I2  C2HCO

5

2
Na+ + CHI3
|| Iodoform yellow;
O mp 119°

7.2 Reduction

a) Reduction to alcohols
H2 + Pt or Pd
| |
–– C = O ––  –– C –– OH
LiAlH4 or NaBH4; |
H
+
then H
Aldehydes  1° alcohols; Ketones  2°alcohols

Example:

CH3 –– CH2CHO   CH3CH2CH2OH

H2 ,Pt

  CH3CH2CH2OH
1. LiAlH4
2. H

Cyclopentanone  2° alcohol

OH

|
–– C –– CH3     

LiAlH4 H
–– C–– CH3
|| |
O H

b) Reduction to hydrocarbons
 |
Zn(Hg). Conc. HCl Clemmensen reduction for compounds
–– C –– H sensitive to base
|
> C = O –– H
|
NH2NH2, base Wolff-Kishner reduction for compounds
–– C –– H sensitive to acids
|
H

Illustration 6: CH3 – C – CH2 – CH2 – C – OEt

|| ||
O O
LiAlH4 NaBH4

What are the products?

Solution: LiAlH4 is a strong reducing agent. It reduces both carbonyl and ester group to
form CH3 CH – CH2 – CH2 – CH2OH
|
OH

NaBH4 can reduce only CH3 – C – group to from

||
O
CH3 CH – CH2 – CH2 – CO2Et
|
OH

7.3 Addition Reactions of Carbonyl Compounds

The C of the carbonyl group is electrophilic

+
C = O  C – O

and initially forms a bond with the nucleophile

a) Addition of cyanide

O CH3 CH3
|| | H2O2 / H2SO 4 |
CH3 – C – CH3 + NaCN   CH3 – C – CN  

H2SO 4

boil
   CH3 – C – CO2H
| |
OH OH
CH3
Acetone cyanohydron |
H O
2 CH2 = C – CO2H
Methylacrylic acid
(2-Methylpropenoic acid)

b) Addition of bisulfite
|
C + NaHSO3  –– C –– SO3 Na Used in purification
(Not for hindered Ketones)
|| |
O OH
Bisulfite addition product
 Example:
H H
| |
–– C = O+ NaHSO3  –– C––
SO 3 Na
|
Benzaldehyde H

CH3 CH3
| |
CH3 –– CH –– C –– CH –– CH3 + NaHSO3  no reaction
||
O

c) Addition of derivative of ammonia.

|
C + H2N – G  –– C –– NH –– G  C = N – G + H2O
|| |
O OH Used for identification

H2N – G Product
H2NOH Hydroxylamine > C = N – OH Oxime
H2N – NH2 Hydrazine > C = N – NH2 Hydrazone
H2N – NH – C6H5 Phenylhydrazine > C = N – NHC6H5 Phenylhydrazone
H2N – NH – C – NH2 Semicarbazide > C = N –NHCONH2 Semicarbazone
||
O
NHNH2 2, 4-Dinitrophenyl NH – N = C 2, 4-
NO2 hydrazine dinitrophenylhydrazone
NO2
(bright orange or yellow
precipitate used for
identifying aldehydes
NO2 NO2 and ketones

sp2 sp3

|
H
C = O + Nu   C – O– 
 – C – OH
| |
Nu Nu

d) Addition of Alcohols; Acetal Formation

H H
| dry HCl
|
R – C = O + 2ROH + R  – C – OR + H2O
H2O |
OR
An acetal (gem-diether)
In H3O+, RCHO is regenerated because acetals undergo acid catalyzed cleavage much
more easily than ethers do. Since acetals are stable in neutral or basic media, they are
used to protect the – CH = O group.

Illustration-7: How you separate carbonyl compounds from non-carbonyl compounds?

Solution: NaHSO3 is used to separate this, it forms white crystalline solids of bisulfite
compounds with carbonyls

OH
C = O + NaHSO3  C
SO3Na
[bisulfite compound]

Also bisulfite compounds can regenerate carbonyl compound when heated

with dilute acid.
1 2 3
Exercise 3: In Semicarbazide NH2  NH  C  NH2 which nitrogen combines with >C =
||
O
O group and why?

7.4. Disproportionation; Cannizaro Reaction

Aldehydes with no H on C undergo self-redox reaction in hot concentrated alkali:

H O
| –
2H—C=O H—C—O + CH3OH
Acid salt Alcohol

Example:

2HCHO  CH3OH + HCO2 –Na+

CHO CH2OH CO2Na+ CHO CO2 CH2OH

2 50% OH–
50% OH–
2 + +
Cl Cl Cl
m-chlorobenzaldehyde m-chloro-benzoate ion + m-chlorobenyl alcohol


C6H5CHO + HCHO    C6H5CH2OH + HCO2 Na+ (Crossed Cannizzaro)
50% OH

Always used Always formed

50% OH–
O2N CHO O2N CH2OH + O2N— —CO2Na

7.5 Halogenation of Ketones

 O O
|| | || |
a)  C  C  X2   C  C  HX
| |
H X
X2 = Cl2, Br2, O2

b) Conversion to dihalides
Cl
O + PCl5  + POCl3
Cl
O F F
||
+ SF4  + SOF2

Illustration 8: >C = O + PCl5  Product

In this reaction what is the attacking reagent?

Solution: Attacking reagent is PCl4+ [solid PCl5 is PCl4+ PCl6–]

7.6 Aldol condensation

| | | | |
C +–C–C=O –C–C–C=O
|| | | |
O H OH
An aldol
(-hydroxycarbonyl compound)

Examples:
H H O H H H
| | || | | |
OH
CH3 – C = O + CH3 – C = O 

 CH3 – C – CH2 – C – H  CH3 – C = C – C = O +H2O
NaHSO 3


| |
H OH
Acetaldehyde (2 mole) Crotonaldehyde (2 - Butenal)

H OH H
| | |
OH
CHO + CH2 – C = O  C – CH2 – C = O  CH = CH – CHO
| |
H H Cinnamaldehyde
(3-phenyl-2-propenal)

Illustration-9: (CH3)2CHCHO does not undergo aldol condensation – justify the statement

Solution: (CH3)2CHCHO undergoes canninzaro reaction though it has  hydrogen

because rate of aldol reaction is much less than that of canninzaro reaction.

(CH3)2CHCHO  (CH3)2CHCO2– + (CH3)2CH – CH2OH

OH
7.7 Claisen (Ester) Condensation: (Discussed later)

O | O | O

–C +–C–C  – C – C – C
OC2H5

OR | OR | OR
H H
A -  Keto ester

Examples:

  O
H3CCO2 – CH2CH3 + CH2 – CO2C2H5     CH3 – C – CH2 – C
NaOC 2H5
Absolute ethanol
| || OC2H5
H O
Ethyl acetate
(2–moles) Ethyl acetoacetate

CO2C2H5 + CH3CO2C2H5  

NaOEt
C – CH2COOC2H5 + C2H5OH
Absoluteethanol
||
O
Ethyl benzoate Ethylacetate Ethylbenzoylacetate

 
CH3 – CH2 – C – OEt + CH3 – CH2 – C – OEt   CH3 – CH2 – C – CH – CO2Et
NaOEt

|| || || |
O O O CH3
(Here CH3 comes in the side chain as the carbanion 
to CO2 Et group attacks the second molecule of ester)

7.8 Acidity of -Hydrogens

Carbonyl group largely determines the chemistry of aldehydes and ketones.

But how the carbonyl group strengthens the acidity of hydrogen atoms attached to the
-carbon and by doing this gives rise to a whole set of chemical reaction?

| | |
– C – C – + :B – C – C + BH
| || ||
H O O
(I)

Aldol Condensation

Substrate  aldehyde or ketone containing  hydrogen

dilute base
Reagent 
(commonly used)

Product  -hydroxyaldehyde or -hydroxyketone

Under the influence of dilute base or dilute acid, two molecules of an aldehyde or ketone
may combine to form a -hydroxy aldehyde or ketone.
The -carbanion generated by the base from one molecule of aldehyde. Or ketone adds
to the carbonyl carbon of the other molecule and the 2-molecules condense and form -
hydroxy aldehyde or ketone. Let us consider the mechanism for the base catalysed aldol
condensation of acetaldehyde:

H
|
– –
HO + H – C – CHO CH2 – CHO + H2O
|
H
+ –
H2C = CH – O

Key step in condensation

H
–
CH3 – C + CH2CHO CH3 – CH – CH2 – CHO
|| |
–
O O

 
CH3 – CH – CH2 – CHO + H – O – H CH3 – CH – CH2 – CHO
| |
O OH
-hydroxyaldehyde

Aldol condensations are reversible, and with ketones the equilibrium is unfavourable for
condensation product. -hydroxycarbonyl compounds are readily dehydrated to give -
-unsaturated carbonyl compounds. With Ar on -carbon, only dehydrated product is
isolated.

Crossed Aldol Condensation

An aldol condensation between two different carbonyl compounds so called crossed

aldol condensation – is not always useful as a mixture of four different possible products
may be obtained.

Under certain condition, a good yield of a single product can be obtained from a crossed
aldol condensation. One reactant contains no -hydrogens and therefore is incapable of
condensing with itself (eg. Aromatic aldehydes or formaldehyde).
 H H H
| | |
CH3CHO, 20°
C=C–C=O
Cinnamaldehyde Crossed Aldol
Condensations

H H H O
|  CH3COCH3 | | ||

OH
—C=C—C—CH3
C=O 100°

H H
C6H5COCH3 20° | |
C=C–C
||
O

7.9 Nucleophilic Addition of Water: Hydrogen of Ketones and aldehydes

In an aqueous solution, a ketone or an aldehyde is in equilibrium with its hydrate, a

geminal diol. With most ketones the equilibrium favors the unhydrated keto form of the
carbonyl.

R R OH
[hydrateO
C = O + H2O C K
[ketone ][H]
R Ketone form R OH
Hydrate
(a geminal diol)

Example
O
OH OH
CH3 – C – CH3 + H2O CH3 – C – CH3 K = 0.002
acetone acetone hydrate

Addition occurs through the nucleophilic addition mechanism, with water (in acid) or
hydroxide ion (in base) serving as the nucleophile.

H
+
O O O–H O–H
+
H3O
C C R – C –R R – C –R
R R R R
O+ O–H
H2O H H
H2O+
H2O
 O O – OH
H2O H–O–H
C HO – C – R HO – C – R + –OH
R R
R R

Aldehydes are more likely than ketones to form stable hydrates. The electrophilic
carbonyl group of aketone is stabilized by its two electron-donating alkyl groups, but an
aldehyde carbonyl has only one stabilizing alkyl group; its partial positive charge is not
as well stabilized. Aldehydes are thus more electrophilic and less stable than ketones.
Formaldehyde, with no electron-donating groups, is even less stable than other
aldehydes.
– – –
O O O


+
 
+ +
C C C
R R R H R H
Ketone two Aldehyde less Formaldehyde
alkyl groups stabilization relatively unstable

These stability effects are apparent in the equilibrium constants for hydrogen of ketones
and aldehydes. Ketones have values of Keq of about 10–4 to 10–2. For most aldehydes,
the equilibrium constant for hydration is close to I. Formaldehyde, with no alkyl groups
bonded to the carbonyl carbon, has a hydration equilibrium constant of about 2000.
Strongly electron withdrawing substituents on the alkyl group of a ketone or aldehyde
also destabilize the carbonyl group and favour of hydrate. Chloral
(trichloroacetaldehyde) has an electron-withdrawing trichloromethyl group that favours
the hydrate. Chloral forms a stable, crystalline hydrate that became famous in the
movies as “knockout drops” or a “Mickey Finn”.
O
OH OH
CH3 – CH2 – C – H + H2O CH3 – CH2 – C – H K = 0.7
propanal propanal hydrate

C HO OH
H H + H2O C K = 2000
formaldehye
H H
O
OH OH
Cl3C – C – CH3 + H2O Cl3C – C – CH3 K = 3000
chloral Chloral hydrate

Exercise 4: Ninhydrin forms very stable hydrate – explain

8. Reactions related to the Aldol Condensation

8.1 A Perkin Condensation

CHO + (CH3CO)2    C6H5CH = CH CO2H

CH3 COONa

Acetic Anhydride Cinnamic acid

 H O
| H H
Ph – C = O + CH3 – C O
| |

O  
OAc   
hydrolysis
 Ph – C = C –C

H3C – C OH
3-Phenylpropenoic acid
O

Ester can be condensed with aromatic aldehydes in the presence of alkoxides; thus
benzaldehyde and ethylacetate in the presence of sodium ethoxide, give ethyl
cinnamate, C6H5CH = CHCOOC2H5.

H
| O
C = O + CH3 – C – OEt 
O Et
CH = CH – C
|| OEt
O
H OH
| |
Ph – C = O + CH2 – C – O Et  Ph—C—CH2—C—OEt OEt
 || | ||   Ph – CH = CH – CO2Et
H O H O CCCO 2Et

Halogenation of Ketones
H or OH
– C – C – + X2 ; 
 – C – C + HX X2 = Cl2, Br2, I2
| || | ||
H O X O
Ketone (a – Halo-Ketone)

Examples:
O O
H
+ Br2 
 + HBr
Br

CH3 CH3 CH3

| | |
OH  
CH3 – C – C – CH3 + I2 + OH  CH3 – C – C – CI3  CH3 – CCO
–
– 2 + CHI3
| || | || |
CH3 O CH3 O CH 3

The Haloform Test depends upon the fact that the three hydrogens on the same carbon
atom are successively replaced by halogen. Taking acetone as an example we see that
the carbon that suffers the initial substitution to the preferred site further substitution.
 H X X X
| | OH– | |
H–C–C–C–H H3C – C – C – H H3C – C = C – H
| || | || – |
H O H O O–
H X
| |
X H–C–C–C–H Not formed
– || |
O H
Electron withdrawal by halogen makes hydrogens on the carbon to which halogen has
already become attached more acidic and hence more ready removed by base to give
further substitution.

OH OH
| |
 –
R – C – CX3  
OH
  R – C – CX3  R – C + CX3  R –
|| | ||
CO 2O+ HCX3
O– O

Electron withdrawal by three halogens makes –CX3 comparatively weakly basic (for a
carbanion) and hence or good leaving group.
Thus both essential aspects of the haloform reaction –– regiospecificity of halogenation,
and cleavage –– are controlled by the same factor; stabilization of a carbanion through
electron withdrawal.
Illustration-10: CHO
OH

  Product A, What is A?

( CH3CO )2 O
CH3CO 2Na

Solution: CHO
OH CH = CH

 
( CH3CO )2 O
C=O
CH3CO 2Na
Δ
OH
HO

O O
(A)
(Coumarine)
 9. Claisen Condensation,Formation of -keto
esters
An –hydrogen in an ester, like an -hydrogen in an aldehyde or ketone, is weakly
acidic, because, the carbonyl group helps accommodate the negative charge of the
carbanaion.
When ethyl acetate is treated with sodium ethoxide, and the resulting mixture is acidified
ethyl 3–oxobutanoate, generally known as ethyl acetoacetate or acetoacetate or
acetoacetic ester is obtained.
C2H2OH
Ethyl acetate Sodium Sodio-acetoacetic ester
+
(2 moles) ethoxide +
H

CH3 – C – CH2 – COOC2H5
||
O
(a, -Keto ester)
Ethyl acetoacetate

Ethyl accetoacetate is the ester of a -Keto acid; its preparation illustrates the reaction
known as the Claisen Condensation.

a) O
||
CH3 – C – OC2H5 + –OC2H5 C2H5OH + –CH2COOC2H5
(I)

b) O O–
|| |
CH3 – C – OC2H5 + –CH2 – COOC2H5 CH3 – C – CH2 COOC2H5
|
OC2H5
O
||
CH3 – C – CH2COOC2H5 + –OC2H5

c) O
||
CH3 – C – CH2COOC2H5 + –OC2H5 CH3COCHCOOC2H5 + HOC2H5
Stronger acid Weaker acid

9.1 Crossed Claisen Condensation

Examples:


CO2C2H5 + CH3CO2 

O C2H5
C – CH2COOC2H5 + C2H5OH
||
O
Ethyl benzoate Ethyl acetate Ethyl benzoyl acetate
Ketones (but not aldehydes) undergo a crossed Claisen Condensation with ester.
Example:
CH3COOC2H5 + CH3COCH3     CH3COCH2COCH3 + C2H5OH
NaOC 2H5

Ethyl acetate Acetone Acetylacetone

10. Decarboxylation of -Keto acids

-Keto esters are normally prepared by Claisen Condensation. Hydrolysis of the -keto
ester gives the -keto acids which are very easy to decarboxylate simply by heating.
Decarboxylation of free acetoacetic acid involves transfer of the acidic hydrogen to the
keto-group followed by loss of carbon-dioxide via a cyclic 6-membered T.S.
CH2
CH3 – C = CH2 + CO2
|
CH3 – C C=O OH
|| |
O H–O
CH3 – C – CH3
||
O

1.H2 O 2  OH
2CH3CO2Et 2  CH3 – C – CH2CO2Et    CH3–C – CH2CO2H
1.NaOEt

.H || 2.H ||
O O
 (Decarboxylation)

CH3 – COCH3 + CO2

O O
||  CO 2 ||
CO2H   

Illustration-11: Give an example of -keto acid which does not undergo decarboxylation easily.

Solution: CF3 – C – CH2 – CO2H

||
O

11. Cannizzaro Reaction

In the presence of concentrated alkali, aldehydes containing no - -hydrogens undergo
self-oxidation and reduction to yield a mixture of an alcohol and a salt of a carboxylic
acid. This reaction is known as Cannizzaro – reaction.

Two successive additions are involved.

a) Addition by hydroxide ion in first step

b) Addition of hydride ion in the next step

 H H
| –
| –
Ar – C = O + OH  Ar – C – O
|
OH
O– H O
| | ||
Ar – C = O + H – C – Ar  Ar – C – H + HO – C – Ar
| |
r.d.s. O–
OH
(Proton exchange)

H O
| ||
Ar – C – H + O– – C – Ar
|
OH

This explains the Crossed Cannizzario reaction involving formaldehyde to take place in
the way that it does.

ArCHO + HCHO  HCO2Na+ + ArCH2OH

On both electronic and steric grounds, the step 1 is faster for HCHO. Hence becomes
the hydride donor in the next step.

H H
| |
H – C = O + –OH H – C – OH
|
O–
H H
| |
–
H – C = O + OH H – C – OH
|
–
O
H H
| |
Ar – C = O + H – C – OH  ArCH2OH + HCO2H
|
–
O

OH 
Illustration-12: H – C – H  Products?
||
O

Solution: Products are H – C – O– + CH3OD

||
O
12. Addition of Ammonia
Aldehydes react with ammonia to form aldehyde ammonia

R R OH
C = O + NH3  C
H H NH2

Aldehyde ammonia

The aldehyde amounts as unstable and lose water immediately to form aldimine. The
dehydration product is not usually obtained because, in most cases, it immediately
polymerises to form cyclic trimers.

CH3 CH3 OH CH3

H2O
C = O + NH3  C   C = NH
H H NH2 H
Aldehyde ammonia Aldimine (very reactive)
(unstable)

CH3
C = NH + NH3  polymerisation
H

When treated with ammonia, formaldehyde does not form an aldehyde – ammonia, but
gives instead hexamethylenetetramine, used in medicine as an urinary antiseptic under
the name Urotropine.

6HCHO + 4NH3  (CH2)6N4 + 5H2O (80%)

N
|
CH2 CH2
CH2
|
N
CH2 CH2
N N

CH2
Hexamethylene tetramine

Ketones also give ketone-ammonia but these cannot be isolated. Acetone reacts slowly
with ammonia to form acetone ammonia and then a complex compound.
 CH3 CH3 OH
C = O + NH3 
low
C
temp
CH3 CH3 NH2
Acetone ammonia

Acetone upon treatment with ammonia at higher temperature give acetoneammonia.

CH3 CH3 CH2COCH3

C = O + NH3 temp
 low
2 C
CH3 CH3 NH2
Acetone ammonia

Aldimines, Schiff’s bases or azomethines are formed when aldehydes react with
aliphatic primary amines, which is removed by slow distillation.

13. Meerwein – Ponndorf – Verley reduction

The carbonyl compound is heated with aluminium isopropoxide in isopropanol solution,
the isopropoxide is oxidised to acetone, which is removed by slow distillation.

R2CO + [(CH3)2CHO)]3Al] R2CHOAl/3 + CH3COCH3 

 R2CHOH
dil.
H2 SO 4

The reducing agent is specific for the carbonyl group, and so may be used for reducing
aldehydes and ketones containing some other functional group that is reducible e.g., a
double bond or a nitro group.

14. Tischenko Reactions

All aldehydes can be made to undergo the Cannizzaro reaction by treatment with
aluminium ethoxide. Under these conditions the acids and alcohols are combined as the
ester, and the reaction is then known as the Tischenko reaction; eg, acetaldehyde gives
ethyl acetate, and propionaldehyde gives propyl propionate.
CH3CHO + Al(OEt)3 – CH3C – OEt + Al(OEt)3
||
O

Hydrolysis

CH3 – C – OH + EtOH
||
O

Illustration- 13: PhCHO   Pdt?

Al( OEt )
3
Solution: Here product is Ph – C – CH2Ph
||
O
This is an example of Tischenko reaction

15. Baeyer-Villger oxidation

Aliphatic ketone undergo the Baeyer – Villiger oxidation to form esters or their
hydrolysed products.

RCOR  RCO2R 
 RCO2H + ROH
H

Reaction is carried out with various organic per acids

e.g. PhCO3H; CH3CO3H. Also H2SO5 canb be used. Mechanism is

R1 R1 R1
+
+
O – O2CR3
H 3 
C=O 2
C = OH  

R CO3
C
R 2
R R2 O–H
slow

R2 – C – OR1 + R3CO2– + H+
||
O
the rearrangement is intramolecular it has been established that the migratory aptitude
of an alkyl group is tertiary  secondary  primary.

For example:
Ph Ph
CHC Me 
 PhCO 3H
CH – OC– – Me
|| ||
Me O Me O

Illustration-14: When benzophenone undergoes reaction with p-nitroperbenzoic acid what

will be product?

Solution: Ph – C – Ph   Ph – C – O – Ph (phenyl benzoate)

per acid

|| ||
O O
This is an example of Baeyer Villiger oxidation

16. Darzen Glycidic Ester Condensation

This reaction involves the condensation of an aldehyde and ketone with an  halogeno
ester to produce ,  epoxy ester. Condensing agent (B) is usually sodium ethoxide or
sodamide.
 ClCH2CO2Et + B CH–ClCO2Et + BH+
R1R2CO

Cl

R1R2C – CH – CO2Et  R1R2C –– CHCO2Et + Cl–

O– O

This is an example of neighbouring group participation

17. Claisen Schmidt Reaction

It is condensation between an aromatic aldohyde and an aliphatic adehyde in presence
of dilute alkali to form an ,  unsaturated compound.

C6H5CHO + CH3CHO   C6H5CH = CHCHO + H2O

NaOH

The mechanism is given below

HO– + H – CH2CHO H2O + CH2CHO

CH2CHO + Ph – CH Ph – CH – CH2CHO

O O–
H2O

HO + Ph – CH – CH2 – CHO

OH
–H2O

PhCH = CHCHO–

18. Hemiacetal and Acetal formation:

Aldehyde combine with alcohols in presence of dry HCl to form first hemiacetal and then
acetal.
HCl R2OH
R1CHO + R2OH R1CH(OH)OR2 R1CH(OR2)2 + H2O

The hemiacetal is rarely isolated since it forms the acetal. Acetals are dieters of unstable
1, 1 dihydroxyalcohols. Unlike the parent dihydroxyl alcohols these acetals are stable.
They are also stable in presence of alkali but are converted into aldehyde by acids. Thus
acetal formation may be used to protect the aldehyde group against alkaline oxidizing
agents. On the other hand the aldehyde group can be protected in acid solution by
merceptal formation.
+
O R OH R OH2
+EtOH +H+
R–C –EtOH
C –H
+
C
H H OEt H OEt

– H2O + H2O

+
R OHEt +EtOH
R
+
C –EtOH C – OEt
H OEt H
+
–H + H+

R OEt
C
H OEt
Illustration-15: O O
CO2Et CO2Et



Solution: O
O O
CO2Et CH2OH

+ CH2OH 

CH2OH
LiAlH4
+ dry HCl

O
O O
CH2OH CH2OH



H

H2 O

19. Clemensen Reduction

The carbonyl compounds are reduced with amalgamated zinc and conc. HCl


R1COR2 
 R1CH2R2
H
 O– OH
+
H
R – C – R + Zn + Cl– R–C–R R–C–R

O ZnCl ZnCl
H+, –H2O

Zn
+
Zn+Cl + R – C– 

Zn
R–C–R

R ZnCl
–
Zn, Cl

 
R – C– – R 
 R – CHR 
H
 RCH2R
H

ZnCl ZnCl

20. Wolff Kishner Reduction

When hydrazones (or semicarbazones) are heated with O–Et at 180°C nitrogen is
eliminated and a hydrocarbon is obtained i.e. by this means carbonyl group is converted
into methylene group.

Δ
C = N – NH2  CH2 + N2

21. Schmidt Reaction

This is the reaction between a carbonyl compound and hydrazoic acid in presence of
concentrated H2SO4. Aldehydes gives a mixture of cyanide and formyl derivatives of
primary amine whereas ketone gives amides.

RCHO + HN3   RCN + RNHCHO + N2

H2 SO4

RCOR + HN3   RCONHR + N2

H2 SO4

Mechanism
 OH
R R R R
 +
C 

H
C 
HN3
R–C–R
||
O +
OH HN – N  N
–H2O

R R
C
+ || +
N– N  N
 N2
R – C = NR 
–H2O


H
O = C – R  H2O+ – CR

NHR NR

22. Pinacol Pinacolone Rearrangement

The conversion of Pinacol into pinacolone is an example of 1, 2 shift and is known as
pinacol pinacolone rearrangement. The pinacol-pinacolone rearrangement is general for
1, 2 glycols under acid conditions.
Mechanism is formulated as follows:
Me2C –– CMe2 + H+ Me2C –– CMe2

OH OH OH OH2
+
I

Me
+
H2O + Me – C ––– CMe2
II
O–H

 +
H
Me – C – CMe3  Me – C – CMe3
||
O
H–O

Kinetic measurement have shown that the conversion of I into II is rate determining step.

23. Formaldehyde, methanal, H-CH=O

1. Preparation

a) By the reduction of carbon monoxide Formaldehyde is produced from carbon-

monoxide when a mixture of these gases (water gas) is passed at low pressure
through an electric discharge of low intensity.
 O
||
CO + H2  H – C – H

b) By oxidation of methyl alcohol - large quantities of formaldehyde are prepared by

passing a mixture of methyl alcohol vapour and air over heated copper or silver.

O
1 ||
CH3OH + O2  H – C – H + H2O
2
Formaldehyde

A catalyst composed of molybdenum trioxide and ferric oxide Converts :

95% of methyl alcohol to formaldehyde. In the oxidation method, the condensate

obtained is a mixture of formaldehyde, methanol and water. It is freed from excess of
methanol by distillation, and the resulting mixture is known as formalin (40%
formaldehyde, 8% methanol, 52% water).

Polymers of Formaldehyde

i) In dilute aqueous solution, formaldehyde is almost 100% hydrated to form methylene

glycol this is believed to be the reason for the stability of dilute formaldehyde
solutions.

CH2O + H2O CH2(OH)2

ii) When formaldehyde solution is evaporated to dryness, white crystalline solid, m.p.-
121-123oC, is obtained this is known as paraformaldehyde, (CH2O)n.H2O, and it
appears to be a mixture of polymers, n having values between 6 and 50.
Paraformaldehyde reforms formaldehyde when heated.

iii) When formaldehyde gas is allowed to stand at rest formaldehyde gas slowly
polymerises to a white solid, trioxymethylene (CH2O)3, mp61-62oC. Trioxan is
prepared by distilling formaldehyde solution (60%) containing a little sulphuric acid.
This trimer is soluble in water and does not show any reducing properties.

Condensation Reactions of Formaldehyde

Formaldehyde can participate in a crossed cannizzaro reaction.

C6H5CHO + HCHO + NaOH  C6H5CH2OH + HCO2Na

Aldehydes with one -hydrogen atom reacts as follow:

 CH2OH
R R CHCHO + HCHO   R'R2C
1 2 NaOH

CHO

Similarly,

CHO CHO
RCH2CHO + HCHO 
 RCH NaOH


HCHO
RC –– CH2OH
CH2OH CH2OH

CH2OH
  R C –– CH2OH + HCO2Na
HCHO
NaOH

CH2OH

Ca ( OH )
CH3CHO + 4CH2O  2  C(CH2OH)4 + HCO2Ca/2

Acetaldehyde (ethanal) is prepared industrially:

i) By the dehydrogenation or air oxidation of ethanol in the presence of silver catalyst

at 300oC.

CH3CHO + H2 
 CH3CH2OH 
Ag
 CH3CHO + H2O
air
Ag

ii) By passing a mixture of ethylene and oxygen, under pressure, into an aqueous
solution of Pd and cupric chlorides at 50oC

CH2 = CH2 + PdCl2 + H2O  CH3CHO + Pd + 2HCl

2CuCl2 + Pd  2CuCl + PdCl2

1
2CuCl + 2HCl + O2  2CuCl2 + H2O
2

Acetaldehyde is a colourless, pungent smelling liquid, b.p, 21oC.

Polymers of Acetaldehyde
When acetaldehyde is treated with a few drops of conc. CH3
H2SO4, a vigorous reaction takes place and the trimer |
paraldehyde, (CH3CHO)3 is formed. It's structure is CH
O O
believed to be (I).
| |
Chloral (trichloroacetaldehyde) is prepared industrially H3C – CH CH – CH3
by the chlorination of ethanol. Chlorine is first passed
O
into cold ethyl alcohol and then at 60o till no further
(I)
absorption of chlorine takes place. The final product is
chloral alcoholate which separates out as a crystalline
solid. This on distillation with concentrated H2SO4 gives
chloral.

CH3CH2OH + Cl2  CH3CHO

OH OH
CH3CHO + HO-C2H5  CH3–CH   CCl3–CH
3Cl2
3HCl

OC2H5 OC2H5
hemiacetal
Conc.
H2SO4

CCl3CHO + C2H5OSO3H

Reaction with Alkalis : with conc. KOH, it yields pure chloroform.

O O– O
|| | ||
– -
CCl3 C–H + OH CCl3 – CH – OH  CCl3 + H–C–OH
H2O
CHCl3

In acids, most aldehydes for nonisolable unstable gem-diols. Chloral hydrate is

stable.

OH
Cl3CCH
OH
H
Cl Cl OH Cl O
+ +
| +  | |
Cl – C – C = O + H2O Cl – C – C – OH Cl – C –– C – H
| | | |
Cl H Cl H Cl O
H
repulsion from adjacent + charges chloral hydrate
less-repulsion
 strong electron withdrawing group on a  - C destabilizes an adjacent carbonyl group
because of repulsion of adjacent + charges. Hydrate formation overcome the forces
of repulsion.

24. Benzaldehyde
Benzaldehyde (and aromatic aldelhydes is general) resemble aliphatic aldehydes in the
following reactions :

i) It gives the Schiff's reaction.

ii) It is readily oxidized, i.e. it is a strong reducing agent : eg. it reduces ammonical
silver nitrate to silver, itself being oxidised to benzoic acid. Benzaldehyde oxidizes to
benzoic acid when exposed to air.

Benzaldehyde differs from aliphatic aldehydes in following ways :

i) It does not reduce Fehling's solution.

ii) It does not readily polymerise eg. it does not resinify with NaOH, but undergoes
cannizzaro reaction.

Benzaldehyde may be prepared by any of the following methods, which are general for
its homologues as well.

1. By hydrolysis of benziledene chloride with aqueous acid (this is also a commercial

method).
C6H5CHCl2 + H2O  C6H5CHO + 2HCl

2. Benzaldehyde may be conveniently prepared in the laboratory by oxidising toluene

with CrO3 in acetic anhydride.

As the benzaldehyde is formed, it is converted into benzilidene acetate, thereby

preventing further oxidation of the benzaldehyde. Hydrolysis of the acetate with dilute
sulphuric acid or hydrochloric acid gives benzaldehyde.

CrO 3 H
C6H5 CH3 C6H5 CH(OCOCH3)2  C6H5CHO + 2CH3CO2H
(CH 3CO )2 O

A better yield of benzaldehyde may be obtained by oxidising benzyl alcohol with CrO 3 in
acetic anhydride.

An interesting oxidising agent is chromyl chloride (Etards reaction). In this method

toluene is treated with chromyl chloride in CCl4 solution and the complex, which is
precipitated is decomposed with water.
H O
C6H5CH3 + 2CrO2Cl2  C6H5 CH(OCrCl2OH)2 2 C6H5 CHO

Gatterman-Koch Aldehyde Synthesis:

Benzaldehyde may be synthesized by bubbling a mixture of carbon-monoxide and

hydrogen chloride through a solution of nitrobenzene or either containing benzene and a
catalyst of AlCl3 and small amount of cuprous chloride.
 AlCl
C6H6 + CO + HCl 

3  C H CHO + HCl
6 5

The mechanism of this reaction is uncertain, but it appears likely that the formyl cation is
the active species.
CO + HCl + AlCl3  [CH+=O  H-CO+] + AlCl4–

It also appears likely that the cuprous chloride forms a complex with the CO, thereby
increasing its local concentration.

The Gatterman - Koch aldehyde synthesis is not applicable to phenols and their
ethers, or when the substituent is strongly deactivating eg. nitrobenzene.

Gattermann Aldehyde Synthesis:

When benzene is treated with a mixture of HCN and HCl in the presence of AlCl3, and
the complex so produced decomposed with water, benzaldehyde is produced.
AlCl H O
C6H6 + HCN + HCl 

3  C H CH = NH + HCl 
6 5
2 C H CHO + NH
6 5 3

Sommelet's Reaction:

Benzaldehyde is produced when benzyl chloride is refluxed with

hexamethylenetetramine in aqueous ethanolic solution followed by acidification and
steam distillation.

C6H5CH2Cl + (CH2)6N4  C6H5CHO

Benzoin Condensation:

When refluxed with aqueous ethanolic potassium cyanide benzaldehyde forms benzoin.

2 C6H5CHO   C6H5CHOHCOC6H5
KCN

O O– OH
|| | |
C6H5 C + CN- C6H5–C–CN C6H5–C––CN
| |
H H

- –
OH O O OH
C6H5CHO | | | |
C6H5 – C–– C – C6H5 C6H5–C––C–C6H5
| | | |
CN H CN H

O OH
|| |
–
C6H5 – C––C – C6H5 + :CN
|
H
25. Analysis of Aldehydes and Ketones
Aldehydes and ketones are characterized through the addition to the carbonyl group of
nucleophilic reagents, especially derivatives of ammonia. All aldehyde or ketone will, for
example react with 2,4-dinitrophenylhydrazine to form an insoluble yellow or red solid.

Aldehydes are characterized, and in particular are differentiated from ketones through
their ease of oxidation: aldehydes give a positive test with Tollen's reagent; ketones do
not.

Aldehydes are also, of course, oxidized by many other oxidizing agents: by cold, dilute,
neutral KMnO4 and by CrO3 in H2SO4.

A highly sensitive test for aldehydes the Schiff test. An aldehyde reacts with the fuachin
aldehyde reagent to form a characteristic magenta colour.

Aldehydes and ketones are generally identified through the melting points of derivatives
like 2,4-dinitrophenylhydrazones, oximes, and semicarbazones.

Methyl Ketone are characterized through the iodoform test.

Aldehydes can be oxidised by Fehling's solution.

Fehling's solution, an alkaline solution of cupric ion complexed with tartarate ion (or
Benedict's solution, in which complexing is with citrate ion); the deep-blue color of the
solution is discharged, and red cuprous oxide precipitates.

Fehling's solution is made by mixing, Fehling A solution, which contains copper sulphate,
+ Fehling B solution, which contains sodium hydroxide and Rochelle salt (Sodium
Potassium Tartarate). During the oxidation of aldehydes to acids, the cupric ions are
reduced to cuprous ions which are precipitated as red cuprous oxide.

RCHO + 2Cu2+ + 3-OH  R-CO-2 + 2Cu+ + 2H2O

2Cu+ + 2-OH  Cu2O + H2O

Cuprous oxide (red)

Exercise 5: How you distinguish

2pentanone and 3 pentanone?
26. Solutions to Exercise
Exercise 1: i) PhCH2 – C – CH3 – IUPAC name is 1-phenyl-2-propanone
||
O

ii) NO2

H3C C
||
O
IUPAC name is 3-nitro-4-methlbenzophenone

Exercise 2: O

Δ
HO2C – (CH2)5 – CO2H  [Cyclohexanone]

(cyclic ketone is formed)

Exercise 3: N1 combines with >C = O group because lone pair on N2 and N3 undergoes
delocalisation with >C = O group.
+
NH2 – NH – C – NH2  NH2 – NH – C  NH2
|| |
O
O

+
NH2 – NH = C  NH2
|
O
So lone pair availability in N1 is highest

Exercise 4: O O
OH
O

 
H 2O
OH

O O
(Ninhydrin) (very stable hydrate due to
intramolecular hydrogen
bodning)

Exercise 5: 2pentanone having CH3 – C – group and undergoes haloform reaction,

||
O
will be oxidised to form O2C – CH2 – CH2 – CH3

3-pentanone having no CH3 – C – group does not undergo haloform

||
O
reaction.
 Solved Problems Subjective
Problem 1: Write down the product with appropriate mechanism for the following reaction:
O

CH2 C

C CH2 CH3 
OH
?
O
Solution: O
O O
CH2 C - OH -
C CH2 CH3 C C CH2 CH2 C CH3

O
O

H2O C
CH2
CH2
C
-
CH3 H3C O

Problem 2: Suggest how you will carry out the following transformation
O

Solution: O3, Zn, H2O

dil NaOH
H3O+, warm

Problem 3: Conversion
O O

Solution: H O H C O
O C
(i) LiAlH4 Ozonolysis H C O dil. NaOH,
(ii) H+

O CH2 CH2Cl CH2 OH

Ozonolysis alc PCl5 H2/Ni

KOH
Problem 4: O
CH3

(i) Ph CHO, OH
(A)
(ii) Zn - Hg, HCl
(iii) O3, Zn/H2O

What is A ?
Solution: O CH3
CH3
O
(i) Ph CHO, OH
(ii) Zn - Hg, HCl
(iii) O3, Zn/H2O
(A)

Problem 5: Write down the mechanism of following reaction:

CH3 CH(CH )
3 2
+ H3C CH(CH3 )2
H
H3C C C C C CH 3
OH O O OH

Solution: CH3 CH3 CH3

+
H +
H3C C C CH(CH3)2 H3C C C C H
OH O OH OH CH3

1,2 -CH3 shift

CH3 CH3
- H+ +
H3C C C CH(CH3)2 H3C C C CH(CH3)2

O OH OH OH

Problem 6: An organic compound C6H8O3 (A) gives an acid C6H8O4 (B) with K2Cr2O7 in acidic
medium. Compound (A) gives yellow predicate with I2 and NaOH. Compound (B)
very easily gives C5H8O2 on heating. Identify the compound A, B and C.

Solution: (A) gives acid on reaction with K2Cr2O7 i.e., it contains – CHO group and it give halo form
test, i.e., it has CH3 – C – group and as [B] releases CO 2 on heating i.e, it is a  - keto
||
O
acid
 (A) is
K2Cr2O7
H3C C CH2 C CH2 CHO H3C C CH2 C CH2 COOH
+
H
O O O O
[A] [B]
-CO2

H3C C CH2 C CH3

O O
[C]
Problem 7: into HO
Convert Cl O

HO O
Solution: CH3 H2C

2C2 H5OH
 Cl O 
KOH (alc.)
O
Cl O HCl  KCl
 H2O
H5C 2 O C 2 H5
O

CH3
HO O C 2 H5 HO OH HO
 H2O

Alkaline
 2H 2 O / H 
 
 
KMnO4 2C2 H5OH
H 2 O  (O)
HO O HO OH HO O

H5C 2

Problem 8: Suggest a mechanism for the following reaction:

CH3

H3C O  H3O  

OH
CH3 CH3
H3C OH
CH3

Solution: The protonated aldehyde is an electrophile, the double bond is a nucleophile, the reaction
between two function closes the ring, hydration of the resulting carbonium ion produces a
diol.
CH3 CH3 CH3 CH3

 H+ 
Ringcolour

H 2O
 H

H H H H
+
O OH OH OH
H3C CH3
H3C CH3 H3C CH3 H3C CH3
OH
Protonated aldehyde t-carbonium ion

Problem 9: What products are formed when acetaldehyde reacts with acetone in presence of a
dilute alkali solution? What happens when each of these is dehydrated with
sulphuric acid?
Solution: Here crossed aldol condensation as well as pure aldol condensation occurs giving four
different aldols.
a) H3C


2CH3CHO 
OH




H
 H3C O
 H2O
Crotonaldehyde
HO O
b) O OH H3C
OH  H
2 H3C 
 H3C 
 H2O

CH3 CH3 CH3 H3C CH3
O O
Diacetone alcohol
 c) O H3C

OH  
H3C  H3C 
 
H
H O
 H3C O
2

O CH3 HO CH3
O CH3
d) H3C OH H3C
  
O  H3C 
OH
 H3C 
H
H O

2

H3C O CH3 O H3C O

Problem 10: Carry out the following transformation in not more than three steps.
H3C O
H3C 


H CH3

Solution: Na in
 H3C 
CH3X
 H3C 
HgSO4
H SO
H3C liquid NH
3
-NaX 2 4

CH
Na CH3
but-1-yne pent-2-yne

H3C O

CH3
pentan-2-one

Solved Problems Objective

Problem 1: Which of the following will react with acetone to give a product containing
C=N–
(A) C6H5NH2 (B) (CH3)3N
(C) C6H5NHC6H5 (D) C6H5NHNH2

Solution: H3C H3C

O  H2N NH 
 N

H3C C6H5 H3C NH C6H5

(D)
O
|| +
H3O
Problem 2: CH3 – C – Cl + R – MgX A; A is
(excess)
O O
|| ||
(A) R – C – CH3 (B) R – C – CH2Cl
OH O
| ||
(C) CH3 – C ( R)2 (D) CH3 – C – H

SOLUTION: (C)

in the reaction HO – CH2 – CHO   dil . NaOH

PROBLEM 3:
how many distinct products (saturated) are possible ?
(A) 1 (B) 2
(C) 3 (D) 4
Solution: (D) Four possible products are
* *
HO – CH2 – CHO 
Aldol condensation
 HO – CH2 CH(OH)CH(OH)CHO
Tetrose
It can be D, L-erythrose and D, L-threose.
Problem 4: What is A in the following reaction?
O

Cl O
t  BuOK
 
t  BuOH
A

O
H5 C 2
O O
H3C
O
(A) C 2 H5 (B)
C 2H5

O
O
OH
(C) (D)
O
O C 2 H5

O
Solution: Cl O Cl O
-
O O
t  BuOK
  CH 
t  BuOH
CH O
O O
Cl C 2 H5
H5C 2 H5 C 2
-
Cl

O
O C 2 H5
 (C)
Problem 5: O

CH3
is the final product obtained when one of the following is reacted with base.
O O O O

(A) (B)
H3C CH3 H3C CH3
O O
O O
(C) H3C (D)
CH3
H3C CH3

O
Solution: O O


Alkali


H3C CH3
CH3

 (A)
Problem 6: End product of the following sequence of reactions is
 CH MgBr CO / H O HgSO / H SO Ag O
CH  CH 
3
 
2 3
 
4 2 4


2

O O
H3C HO O
(A) (B)
OH
O OH
O O
H3C H O
(C) (D)
O OH

Solution: CH  CH + CH3MgBr  CH  C – MgBr

CO2/H3O+

– COOH is (EWG) CH  C  COOH

HgSO4/H2SO4

OHC – CH2 – COOH

Ag2O

HOOC – CH2 – COOH

 (B)

PROBLEM 7: in which of the following substrates, rate of benzoin condensation will be

maximum?

(a)
(A) O2N CHO (b)
(B) H3C CHO

(c)
(C) HO CHO (D) NH2 CHO

Solution: O O O O O O H

N C + CN N C H N C:
O H O O
C N C N
(I) (II) (III)

benzoin condensation is due to stability of intermediate (iii) when negative charge on c is

extensively delocalised in benzene ring, nitro and c  n group. in all other cases, such
dispersal is not extensively possible. on the other hand, NO 2 is also creating a positive
charge center on carbonyl carbon, making it more susceptible to nucleophilic attack of
CN.
 (D)
PROBLEM 8: The following reagent converts C6H5COCHO TO C6H5CHOHCOONA
(A) AQ. NAOH (B) ACIDIC NA2S2O3
(C) NA2CRO4/H2SO4 (D) NANO2/HCL
SOLUTION: (A)
PROBLEM 9: 2CH3  C  CH3 
Mg / Hg

 product. product in the reaction is
|| H
O
CH3 CH3
| |
(A) H3 C  C  C  CH3 (B) CH3  C  O  C  CH3
| | || ||
OH OH O O
(C) CH3  CH CH CH3 (D) none of these
| |
OH OH
CH3 CH3
| |
SOLUTION: (A) 2CH3 - CO – CH3  H3C  C|  C|  CH3
Mg / Hg
H 2O
OH OH
(Pincol)

problem 10: a compound has a vapour density of 29. on warming an aqueous solution of alkali,
it gives a yellow precipitate. the compound is
(A) ch3ch2cho (B) ch3chohch3
(C) ch3coch3 (D) ch3ch2cooh

solution: (C) molecular weight of the compound

= 2  vapour density = 2  29 = 58
molecular weight of ch3ch2cho, ch3chohch3, ch3coch3 and ch3ch2cooh are 58, 60, 58 and
74 respectively. both ch3ch2cho and ch3coch3 have molecular weight 58 but only ketone
O
||
i.e. CH3  C CH3 on warming with aqueous alkali gives yellow precipitate.
 SECTION - I
LEVEL - I Objective Single Choice
1. End products of the following sequence of reaction is
O
i) NaOI, 

ii) H+ , 
 A+B
CH3

O
A & B are
I CO 2H
I O
I and
(A) CH3 (B) I and
I
I O
O
I O I O
(C) I and (D) I and
I CO 2H I

2. Compound A, C5H10O forms a phenyl hydrazone and give negative Tollen’s & iodoform tests.
Compound A, on reduction gives n-pentane. A is
(A) A primary alcohol (B) A secondary alcohol
(C) An aldehyde (D) A ketone

3. Which of the following compound on treatment with LiAlH 4 will give a product that will give
positive iodoform test?
(A) CH3CH2CHO (B) CH3CH2CO2CH3
(C) CH3CH2OCH2CH3 (D) CH3COCH3
4. The product obtained by reaction of PhCHO & MeCHO in basic medium are:
OH OH

(A) and Me O
Ph O
CH3
OH OH

(B) and Ph O
Ph O
Ph
OH OH

(C)
Ph O and Me O
(D) None of these
5. CH3CHO + NH2OH  CH3CH = N – OH
The above reaction is carried out at
(A) pH = 1 (B) pH = 4.5
(C) pH = 12 (D) pH = 14

6. The reagent with which both acetaldehyde and acetone react easily is
(A) Fehling’s reagent (B) Grignard reagent
(C) Schiff’s reagent (D) Tollens reagent
7. Which of the following statements regarding aldehydes is not correct?
(A) the carbonyl functional group is planar
(B) The boiling points of aldehydes is greater than those of alkanes of comparable molar masses
(C) The boiling points of aldeydes is greater than those of alcohols of comparable molar masses
(D) Formaldehyde is gas at room temperature

8. Which of the following statements regarding C=O group is not correct?

(A) The carbon atom of CO group in aldehydes is sp2 hybridized
(B) The carbon atom of CO group in the transition state formed during the addition reaction
across CO group is sp3 hybridized
(C) The aryl group in aromatic aldehydes speeds up the addition reaction across the CO group
(D) An aryl group stabilizes an aldehyde more than the transition state

9. Among the given compounds, the most susceptible to nucleophilic attack at the C=O group is
(A) CH3COCl (B) CH3CHO
(C) CH3COOCH3 (D) CH3COOCOCH3

10. The reagent(s) which can be used to distinguish acetophenone from benzophenone is (are)
(A) 2, 4-dinitrophenylhydrazine (B) aqueous solution of NaHSO3
(C) Benedict reagent (D) I2 and Na2CO3

LEVEL - II More than one choice

1. Base catalysed aldol condensation occurs with

(A) Propanal (B) Benzaldehyde
(C) 2-methylpropanal (D) 2, 2-dimethylpropanal

2. Which of the following compounds will give a yellow precipitate with iodine and alkali?
(A) 2-Hydroxypropane (B) Acetophenone
(C) Methylacetate (D) Acetamide

3. A new carbon-carbon bond formation is possible in

(A) Cannizzaro reaction (B) Friedel-Crafts alkylation
(C) Clemmensen reduction (D) Reimer-Tiemann reaction

4. Which of the following will undergo aldol condensation?

(A) Acetaldehyde (B) Propanaldehyde
(C) Benzaldehyde (D) Trideuteroacetaldehyde

5. Which of the possible compound will be formed in the following sequence of reaction.
HBr Hydrolysis Na 2CO 3
CH2=CH2  X   Y   Z
I2 excess
(A) C2H5I (B) C2H5OH
(C) CHI3 (D) CH3CHO
6. Which of the following compounds will react with ethanolic KCN?
(A) Ethyl chloride (B) Acetyl chloride
(C) Chlorobenzene (D) Benzaldehyde

7. Which of the following are the examples of aldol condensation?

 (A) OH
2CH3CHO 
dil. NaOH
 CHO
H3C
CH3
(B)
2CH 3COCH 3 
dil. NaOH
 H3C CH2COCH3

OH
2HCHO 
 CH3OH dil. NaOH
(C)
C6H5CHO + HCHO 
 C6H5CH2OH dil. NaOH
(D)

8. Which of the following statements are correct?

(A) Benzaldehyde reduces Fehling’s solution
(B) C6H5CHO  C6H5CHO  C6H5CH  CHC6H5  O2 is a Claisen-Schmidt reaction.
NaOH

(C) pKa (formic acid) is less than pKa (acetic acid)

O OH
NaOH
(d) CH3CCH3 + CH3CHO CH3 C CH2CHO is an example of aldol condensation.
CH3

9. CH3  CHO 

OH
 CH3CH(OH)CH2CHO
In the aldol condensation of acetaldehyde represented above, which of the following intermediate
species are obtained?
-
O O
-
(A) H2C (B) H2C
H H
- -
O O

(C) H3C (D) H3C O

H O H CH2

10. Which of the following compounds will give a red precipitate on being heated with Fehling’s
solution.
(A) C6H5CHO (B) CH3CHO
(C) CH3COCH3 (D) C6H5CH2CHO

LEVEL - III Other Engg. Exams

1. During reduction of carbonyl compounds by hydrazine and KOH, the first intermediate formed is
(A) RC  N (B) RCONH2
(C) RCH = NH (D) RCH = NNH2

2. A substance C4H10O yields on oxidation and compound, C4H8O which gives an oxime and a
positive iodoform test. The original substance on treatment with conc. H 2SO4 gives C4H8. The
structure of the compound is
 (A) CH3CH2CH2CH2OH (B) CH3CHOHCH2CH3
(C) (CH3)3COH (D) CH3CH2 – O – CH2CH3


3. (CH3)2CO 
NaCN
( HCl )
 A 
H 3O

 B
In the above sequence of reactions A and B are
(A) (CH3)2C(OH)CN, (CH3)2C(OH)COOH (B) (CH3)2C(OH)CN, (CH3)2C(OH)2
(C) (CH3)2C(OH)CN, (CH3)2CHCOOH (D) (CH3)2C(OH)CN, (CH3)2C= O

4. The most reactive compound towards formation of cyanohydrin on treatment with KCN followed
by acidification is
(A) Benzaldehyde (B) p-nitrobenzaldehye
(C) Phenylacetaldehyde (D) p-hydroxybenzaldehyde

5. Which of the following statements regarding chemical properties of acetophenone are wrong ?
I. It is reduced to methyphenylcarbinol by sodium and ethanol
II. It is oxidized to benzoic acid with acidified KMnO 4.
III. It does not undergo aldol condensation.
IV. It does not undergo iodofrom reaction with iodine and alkali
(A) I and II (B) II and IV
(C) III and IV (D) I and II

6. If 3-hexanone is reacted with NaBH4 followed by hydrolysis with D2O, the product will be
(A) CH3CH2CH(OH)CH2CH2CH3 (B) CH3CH2CD(OH)CH2CH2CH3
(C) CH3CH2CH(OD)CH2CH2CH3 (D) CH3CH2CD(OD)CH2CH2CH3

7. Predict the product ‘B’ in the sequence of reaction

CH  CH 
30% H 2 SO4
HgSO4
 A 
NaOH
 B
(A) CH3COONa (B) CH3COOH
(C) CH3CHO (D) CH3  CH  CH 2  CHO
|
OH

8. An organic compound ‘A’ has the molecular formula C3H6O. It undergoes iodoform test. When
saturated with HCl it gives ‘B’ of molecular formula C9H14O. ‘A’ and ‘B’ respectively are

(A) propanal and mesitylene

(B) Propanone and mesityl oxide
(C) Propanone and 2, 6-dimethyl-2, 5-heptadien-4-one
(D) Propanone and mesitylene oxide

9. Which one of the following undergoes reaction with 50% sodium hydroxide solution to give the
corresponding alcohol and acid ?
(A) Phenol (B) Benzaldehyde
(C) Butanol (D) Benzoic acid

10. Reaction of cyclohexanone with dimethylamine in the presence of catalytic amount of an acid
forms a compound if water during the reaction is continuously removed. The compound formed
is generally known as
(A) A Schiff’s base (B) An enamine
(C) An imine (D) An amine
11. But-2-one can be converted to propanoic acid by which of the following
(A) NaOH, NaI/+ (B) Fehling solution
(C) NaOH, I2/H+ (D) Tollen’s reagent

12: Which one of the following pairs is not correctly matched

Wolf  Kishner reduction

(A) > C = O
Clemension ' s reduction
 > CH2 (B) > C = O   > CHOH
(C)  COCL   CHO (D)  C  N   CHO
Rosenmund ' s reduction Stephen reduction

13. Treatment of propionaldehyde with dilute NaOH solution gives.

(A) CH3CH2COOCH2CH2CH3 (B) CH3CH2CHOHCH(CH3)CHO
(C) CH3CH2CHOHCH2CH2CHO (D) CH3CH2COCH2CH2CHO

SECTION - II
LEVEL - I Subjective

1. Identify (A) to (E) as reactant, reagent, product as name of the reaction in following:
i) 3(CH3)2 C = O 
(A)
(B) Aldol condensation
ii) CH3COCl + H2  (D)
(C)
Rosenmund’s reaction
iii) (E)   CH3CH2CH3
NH2 NH2
C2 H5ONa

2. 0.535 g ethanol and acetaldehyde mixture when heated with Fehling solution gave 1.2 g of a red
precipitate. What is the percentage of acetaldehyde in the mixture? (At. wt. of
Cu = 63.8)

3. Which of the carbonyl groups in p-meo C6H4 come and P-NO2C6H4 come protonates more readily
in acid solution and why?

A) C8H6O2   C8H8O3   C6H5CO2H

1. aqueous [O]
4.
(A) NaOH (B) 
2. H

b) The following ketone is unusually basic. Explain

O

5. A) distinguish between phcoet and P-MEC6H4 come by a chemical method

b) Arrange the following in the order of increasing reactivity towards nucleophilic addition
reactions.
i) CH3CHO, C6H5COC6H5, CH3COC6H5, CH3COCH3
ii) CH3CHO, CF3CHO, CH2 = CHCHO

6. Compound X with molecular formula C9H10O forms a semicarbazone and give negative Tollen’s
and Iodoform tests. Upon reduction it gives n-propyl benzene. Deduce the structure of X.

7. Two different Grignard reagents, (X) and (Y) produce C6H5CH2C(CH3)2OH on reaction with (P)
and (Q) respectively. Give structures of (X), (Y) and (Q).
8. A) 2-methyl 1,3-cyclohexanedione is more acidic than cyclohexanone – explain with reason
b) Explain why HCN will add to the double bond in CH2 = CHCOOH but not in
RCH = CHR

9. Account for the following:

a) The double bond in aldehydes and ketones is reactive towards nucleophilic reagents like CN –
whereas that in an alkene is not.
b) Alkenes undergo electrophilic addition whereas aldehydes and ketones undergo nucleophilic
addition.

10. A compound C5H10O does not reduce Fehling’s solution, forms a phenyl hydrazone, shows the
haloform reaction, and can be converted into n-pentane by Zn – Hg and conc. HCl. What is this
compound?

LEVEL - II Subjective

1*. Complete the following equations giving the structures of the major organic product.
O
i)


SeO2


Cl
ii)
O  OEt  
base
?
O

2. A) CONVERT
PHCHO INTO PHCH = CHCOPH
b) Identify A, B, C and D in the following reaction.
C7H6O Alc.
 C14H12O2
KCN
[A] [B]
Na acetate
C9H8O2
Acetic anhydride
[C]
(an aromatic acid)

Br2

C9H8O2Br2
[D]

3. A ketone (A) which undergoes haloform reaction gives compound B on reduction. B on heating
with sulphuric acid gives compound C, which forms mono ozonide D. D on hydrolysis in presence
of Zn dust gives only acetaldehyde. Identify A, B and C. Write down the reactions involved.

4*. Complete the following equations:

a) O
H3C  HC CH 
i) NaNH 2
ii) H O 
?
3

CH3
 b) O Cl

H3C  O 
NaNH 2

CH3 O C 2 H5

5. Two organic compounds (A) and (B) have same empirical formula CH2O. Vapourdensity of (B) is
twice the vapour density of (A). (A) reduces Fehling solution but does not react with NaHCO 3.
Compound (B) neither reacts with NaHCO3 nor reduces Fehling solution. What are (A) and (B)?
Also report an isomer of (B) if it reacts with NaHCO3.

6*. Complete the following equations:

OH

Hg 2 / H  H H3C 
I2

HC CH 
NaNH 2
 ? 
CH3 Br
 ? 
H O
 ?  NaOH
2

CH3 O
H3C

7. A compound has two isomers (A) and (B) of formula C5H10O. Isomer (A) on treating with NaOH
(aq.) gives 2, 2-dimethylpropan-1-ol and 2, 2-dimethylpropanoic acid salt. The isomer (B) on
treating with NaOH (aq.) gives 3-hydroxy, 2-propylheptanal. What are A and B?
8. Complete the following reactions:
i) O
HC

(  H 2 O)
 Na
+

H3O
(A) 
dil. H 2SO4
Hg 2+
(B)  (C) 
i) OsO4

ii) HIO4
(D)

Give the IUPAC nomenclature of (D).

ii) O

CH3
H3C NaOH
H 2 O,100 C
(A)

9. Give reasons for the following

a) Ketones are less electrophilic than aldehydes.
b) Aldehydes are reducing agents and ketones are not.
c) HBr fails to give addition products with carbonyl compounds.

10. The sodium salt of a carboxylic acid, A, was produced by passing a gas, B, into an aqueous
solution of caustic alkali at an elevated temperature and pressure. A on heating in presence of
sodium hydroxide followed by treatment with sulphuric acid gave a dibasic acid C. A sample of
0.4 g of C on combustion gave 0.08 g of water and 0.39 g of carbondioxide. The silver salt of acid
weigh in 1g on ignition yielded 0.71 g of silver as residue. Identify A, B and C.

SECTION - III
A Matrix-Match Type

1. Match compound of List – I with pKa of List – II

Column – I (Compound) Column – II (pKa)
(A) O O (p) 17
C2 H5
H3C O
 (B) O O (q) 8.9

H3C CH3
(C) O (r) 10.6

O
CH3 – CHO (s). 5
(D)

2. Aldol dondensation proceeds by carbon-carbon bond formation between an enolate donor and a
carbonyl acceptor. For each of the following aldol products (1 through 4)
O O
CO2 C2 H5
OH
OH
CH
CO2 C2 H5
CHO
(1) (2) (3) (4)

match the donor and acceptor compound.

Column – I (Donor) Column – II (Acceptor)
(p) CH2 = O
(A)(a) CH2 CHO

(B)
(b) O (q) CHO

(C)
(c) O (r) O

(D CO2 C2 H5
(s) CH2 CHO
CH2
CO2 C2 H5

B Linked Comprehension Type

Comprehension - I
The reaction is self oxidation – reduction type and takes place in presence of 50% aqueous or
ethanolic alkali. One molecule of the aldehyde (missing of -hydrogen atom) oxidizes, the other
molecule to corresponding carboxylic acid and the self being reduced to the corresponding
alcohol.
R2 R2 OH R2 H
H
R1  R1
OH
Ethanol
+ R1
O R3 O R3 OH
R3
Mechanism: The mechanism involves two distinct steps Nucleophilic attack and hydride ion
transfer.
O
H H HO H O
OH  H H -
O 
 H OH  O + H O H C O + CH3OH
slow
-
H O H H
H2 O

O
H C OH + CH3OH
 O
1.


CH 2 O
OH(conc.)
 Product

O
H3C

OH
O OH

(A) (B)

O O
H3C
H3C
O O OH

(C) (D)

OH OH
CH2O / OH
2. C8H6O2 
 C8H10O2 
 C8H8Br2 . Identify A, B and C.
EtOH
PBr3

(A) (B) (C)

OH Br
CHO
OH Br CHO
, , OH Br
(A) CHO
(B) , ,
CHO
OH Br
OH Br
Br
OH
CHO CH3
Br
(C) , , (D) All of the above
CHO CH3
OH

3. O
H 

OH
EtOH
 A. The A is
O
Ph
(A) Lactic acid (B) Mandelic acid
(C) Salicylic acid (D) Malonic acid

Comprehension - II
Aldehyde, ketone, carboxylic acid and acid derivatives contain C = O group. Aldehyde and
ketones give nucleophilic addition reactions where as acid and acid derivatives give nucleophilic
addition followed by elimination reactions. Nucleophilic addition reactions followed by elimination
of acid derivatives is known as acyl substitution reaction. This substitution reaction takes place by
formation of tetrahedral intermediate.

4. For the given reaction

O O
L Nu 
 Nu  L
R R
 which of these is correct?
(A) L must be better leaving group than Nu
(B) Nu must be strong enough nucleophile to attack carbonyl carbon
(C) Carbonyl carbon must be enough electrophilic to react with Nu
(D) all of these

5. Which one of the following compounds has very poor leaving group?
O O
(A) R (B) R
H Cl
O O
(C) R (D) R
OH OR'
6. Which one of the following is least reactive compound for nulceophilic acyl substitution.
O
O
H3C
(A) H3C (B)
NH
Cl
H3C
O
O
H3C
H3C
NH
NH
(C) (D)

O2 N

Comprehension - III
Aldehydes and ketones are amphoteric. Thus they can react both as acids and bases. Under
acidic conditions, the carbon of the protonated carbonyl group is much more electrophilic,
reacting even with weak nucleophile. Carbonyl compound gives nucleophilic addition reaction. In
this reaction the nucleophilic attack precedes the electrophilic attack.
7. Which of these statements are correct?
(A) Carbonyl compound is amphoteric in character
(B) Acid catalyst makes the carbonyl carbon more electrophilic
(C) basic catalyst makes the nucleophile more nucleophilic
(D) All of these
8. Which of the statemetns are/is correct?
(A) The rate determining step of addition reaction is the addition of nucleophile
(B) The rate-determining step is addition of electrophile
(C) The reaction intermeidate of the reaction is alkoxide ion
(D) both (A) and (C)
9. Which one of the carbonyl compounds is more reactive towards NaCN/H +?
O H3C
(A) H5 C6 (B) O CHO
H
O O
(C) H3C (D) NC
H
10. Carbonyl compounds gives nucleophilic addition with
(A) carbon nucleophile (B) oxygen nucleophile
(C) Nitrogen nucleophile (D) All of these

C Assertion and Reasoning

CODE :
(A) Statement – 1 is True, Statement – 2 is True; Statement – 2 is a correct explanation for
Statement – 1.
(B) Statement – 1 is True, Statement – 2 is True; Statement – 2 is NOT a correct explanation for
Statement – 1.
(C) Statement – 1 is True, Statement – 2 is False.
(D) Statement – 1 is False, Statement – 2 is True.
1. STATEMENT – 1: Ph – CHO when treated with conc. OH– formation of PhCH2OH and
PhCOO– takes place.
STATEMENT – 2: It involves hydride transfer, hence one molecule is reduced and another is
oxidized.

2. STATEMENT – 1: HCHO is more reactive than CH3COCH3 towards nucleophilic addition

reaction
STATEMENT – 2: In CH3COCH3, –CH3 shows –I effect.

3. STATEMENT – 1
O

on reduction with NaBH4 in ethanol gives cyclopentanol

STATEMENT – 2: Conjugate addition first occurs followed by second direct addition.

4. STATEMENT – 1: A mixture of
O O

and Me H
Ph Ph
on treatment with dil. NaOH gives
H3C O

H
STATEMENT – 2 : The ketone is very hindered and very conjugated and so less reactive
than aldehyde.

5. STATEMENT-1: The addition of amines in aldehyde and ketone is carried out in weakly
acidic medium
because
STATEMENT-2: In strong acidic medium amines will be protonated hence the nucleophilic
character of amine decrease.

6. STATEMENT-1: An aldehyde is more reactive than ketone towards nucleophilic addition

reaction
because
 STATEMENT-2: An aldehyde contains an hydrogen at the carbonyl carbon whereas a
ketone contains two alkyl groups at the carbonyl carbon.

7. STATEMENT-1: Benzaldehyde give red precipitates of Cu2O with Fehling’s solution.

because
STATEMENT-2: Aldehydes are reducing agents.

8. STATEMENT-1: RCOCl fails to give ketone with RMgX

because
STATEMENT-2: RCOCl give ketone with R2Cd
Answers to Assignments
SECTION - I

LEVEL – I LEVEL – II LEVEL – III

1. (D) 1. (A, C) 1. (D)

2. (B)
2. (D) 2. (A, B)
3. (A)
3. (D) 3. (B, D)
4. (B)
4. (D) 4. (A, B, D)
5. (C)
5. (B) 5. (B, C, D)
6. (C)
6. (B) 6. (A, B, D)
7. (D)
7. (C) 7. (A, B)
8. (C)
8. (C) 8. (C, D)
9. (B)
9. (A) 9. (A, B, C)
10. (B)
10. (D) 10. (B, D)
11. (C)
12. (B)
13. (B)

SECTION - II

LEVEL – I

1. i) H3C H3C CH3

3 O dry HCl
CHCOCH
H3C H3C CH3
Phorone
CH3

or 3CH 3COCH 3 

conc. H 2SO 4


H3C CH3
mesitylene

ii) CH3COCl  H2 

Pd / BaSO4
quinolene
 CH3CHO  HCl
H3C
iii) CO 
NH 2 NH2
C2 H5ONa
 CH3CH 2CH3
H3C

2. C2H5OH + CH3CHO = 0.535 g

Let a g C2H5OH and b g CH3CHO be present in mixture
 a + b = 0.535
Now mixture reacts with Fehling solution to give a red precipitate, which suggests a characteristic
reaction for aldehyde., i.e.
CH3CHO  2CuO 
 CH3COOH  Cu 2O
Fehling red ppt.
solution
 143.6 g Cu2O is given by 44 g CH3CHO
44 1.2
 1.2 g Cu2O is given by  0.368 g CH3CHO
143.6
 b = 0.368 g
0.368
 % of CH3CHO   100  68.73%
0.535

3. O–

MeO C – Me  MeO+ C – Me

|| (– OMe having + R)
–
(I) O
O O–
N+ C – Me  N+ + C – Me 
|| ||
O (II) O O– O
(– NO2 having – R)
i will be more readily protonated than (ii). alternatively protonated (i) is more stabilised by
resonance than is protonated (II)
+
OH OH

MeO C – Me  MeO+ C – Me

+ +
OH (Ia) OH
O– O–
+
N+ C – Me  N+ C – Me 
(IIa) –
O O
in (ia) there is extended conjugation and only one charge is involved. in (iia) there is not this
extended conjugation and the relative close proximity of two positive charges is a destabilising
factor. hence (ia) is more stable than (iia).

4. A)  C8H6O2 = C6H5 – C – CHO

||
O
C8H8O3 = C6H5 – CHOHCO2H
b) The salt of the ketone is resonance stabilized
+
O OH  OH
+
H
etc.

5. a) i does not undergo haloform reaction whereas ii does.

b) A = C6H5COC6H5  CH3COC6H5  CH3COCH3  CH3CHO
B = CH2 = CHCHO  CH3CHO  CF3CHO

6. i) X forms semicarbazone and thus possesses carbonyl group.

 C  O  H2N.NHCONH2 
  C  N.NHCONH2
ii) It does not give Tollen’s reagent test and thus it is ketone.
iii) It does not give iodoform test and thus it is not methyl ketone.
iv) Keeping in view of the above facts and molecular formula; X is
 H5C6 C.CH2.CH3
O
v) This on reduction will give n-propyl benzene.

O
||
7. If X is Ph – CH2Mg X, then P is CH3 – C –CH3 and if Y is CH3 – MgX, then Q is
O

Ph
CH3

8. a) 2-methyl 1,3-cyclohexane dione is more acidic because its enolate ion is stabilized by an
additional resonance structure.
O O O– O
CH3 CH3 CH3 CH3

H 
H 
 
O O O O–

resonance stabilized conjugate base.

b) In the case of the acid the double bond is activated due to the presence of a –COOH group
O O O–
||  | 

H2C  CH  C OH  H C  CH  C OH 
 H CN
 CN—CH2—HC=C—OH
2
O O
||  ||
H
 CN  CH 2  C H  C OH  CN  CH 2  CH 2  C OH

9. a) The carbonyl group in aldehydes and ketones add on CN – resulting in the formation of an
anion where the negative charge resides on oxygen. However if a nucleophile adds on to an
alkene the negative charge resides on carbon. Since carbon is much less strongly electron
attracting than oxygen this species is less stable and hence not readily formed.
O–
C
CN
b) In alkenes the double bond joins two carbon atoms and there is no resultant polarity. In
carbonyl compounds, the carbonyl group is highly polar and the high partial positive charge
on the C atom makes it subsceptible to nucleophilic attack.

10. i) Since C5H10O forms a phenyl hydrazone, hence it is an aldehyde or ketone.

ii) As it does not reduce Fehling’s solution, hence it is not an aldehyde but a ketone.
O
||
iii) Since it undergoes haloform reaction, therefore it is CH3  C  R type of ketone. The value of
R – can be derived as follows:
R= C5H10O – C2H3O = C3H7
O
O CH3

Hence this ketone is H3C CH3 or

H3C CH3
 iv) Ketone on Clemmensen reduction yields n-pentane; hence R is n-propyl and not isopropyl.
O

4[H]
Zn  Hg  HCl
 H3C CH3
H3C CH3
pentane
pentan-2-one
C 6H5


2CuO
 No reaction NH
N

C6 H5 NHNH 2
H O

2

H3C CH3
O

3I2  4NaOH /  +
  CHI3 + H3C O Na + 3NaI + 3H 2 O

LEVEL – II

1. i) O ii) O
O OEt

2. A) PHCOCH3, OH–, 
B) A = C6H5CHO B = PHCH(OH)COPH
C = C6H5CH = CHCOOH D = C6H5CHBR – CHBR – COOH
3. H3C H3C
CH3 CH3
A= B=
O OH
O
H3C
H3C
C= CH3 D= CH3
O
O

4. a) H3C OH b) O
H3C O
H3C C 2 H5
H3C
HC O
5. A = HCHO (Formaldehyde)
B = HCOOCH3 (Methyl methanoate)
O
6. +
HC C Na ,
H3C , H3C
CH CH3
OH O
H3C  CHI3

CH3 O
Na
7. CH3

A= H3C CH3 B= H3C CHO

CHO
OH OH CH3
8. i)
CH
A= B=
O
 O
O
CH3
OHC
C= CH3 D=
O
6,7-dioxooctanal

ii) O

CH3
9. a) The positive inductive effect of the second alkyl radical reinforces that of the first one
decreasing still further the partial positive charge on the carbonyl carbon atom.
This reduces the attraction of the atom for nucleophilic reagents. Hence ketones are less
electrophilic.
b) The > C = O group in aldehydes activates the H atom attached to the carbonyl group. This is
due to the relaying of the –I effect of the oxygen atom to the C – H bond so that partial
positive charge is created on the H atom. The result of this activation is that the H atom of the
–CHO group can be oxidised readily to a (OH) group. Thus aldehydes are reducers.
c) HBr is strongly polar and is hence readily added to the polarized > C = O group. The addition
OH
H3C

Br
product H3C is however unstable and decomposes to give the original carbonyl
compound and HBr.
10. A = HCOOH
B = CO
COOH
C =
COOH

SECTION - III
A B C
Match the following Write-up Assertion and Reasoning
1. (A) – (r) 1. (A) 1. (A)
(B) – (q) 2. (A) 2. (C)
(C) – (s) 3. (B) 3. (A)
(D) – (p) 4. (D) 4. (A)
2. (A) – (s) 5. (A) 5. (A)
(B) – (p) 6. (B) 6. (B)
(C) – (q) 7. (D) 7. (D)
(D) – (r) 8. (D) 8. (B)
9. (D)
10. (D)