ALDEHYDES AND KETONES

1.

Introduction
These have general formula CnH2nO and contains >C = O group which is present in aldehyde

and

ketone . Thus aldehydes and ketones are collectively called as carbonyl compounds which are
constituents of fabrics, flavourings plastics and drugs. These are also used as reagents and solvents.
Note : Aldehyde is always at terminal position while ketone is never at terminal position.

2.

Structure of carbonyl compounds

In carbonyl group both the carbon and oxygen atoms are in sp2 hybridised state i.e. both contain three sp2
hybrid orbitals. One of the sp2 hybrid orbital of one carbon atom overlaps with one of the sp2 hybrid orbital of
oxygen atom forming CO -bond. Remaining two sp2 hybrid orbitals of C atom overlap with either sp3 orbital
of C-atoms (as in ketone) or one with sp3 orbital carbon and other with s orbital of hydrogen (as in aldehyde)
forming 2 more -bonds. On other hand each of two sp2 hybrid orbitals of 'oxygen' atom contains a lone pair
of electrons. Unhybrid orbitals present at carbon and oxygen atom forms -bond by sideway overlaping. The
structrue can be represented as :

Thus C = O group contains one -bond and one -bond as :

3.

Strucutre and bonding in aldehydes and ketones

The carbonyl carbon atom is sp2 hybridized. The unhybridized p-orbital overlaps with a p-orbital of oxygen to
form a pi bond. The double bond between carbon and oxygen is shorter, stronger, and polarized.

R
120

120

RESONANCE

Aldehydes, Ketones - 1

Ketone C = O bond

Length
1.23

Alkene C = C bond

1.34

Energy
178 kcal / mol
(745 kJ / mol)
146 kcal/mol
(611 kJ / mol)

The double bond of the carbonyl group has a large dipole moment because oxygen is more electronegative
than carbon.
R
R

..
C=O
..

major

4.

..C O:
..

minor

Comparision of C=O with C=C bond

1. Both atoms in both the cases are in sp2 hybridised state.
2. Both the cases contain one -bond and one -bond.
The difference between C = O and C = C is because of O-atom in carbonyl group is more electronegative
than carbon as a result polarity is developed as

Thus double bond of carbonyl group has a large dipole moment. This polarity confirms that there is nucleophilic
addition reaction in carbonyl compound on other hand in alkene (C=C) there is electrophilic addition reaction.

5.

General methods of preparation of Aldehyde and Ketones

(I)

Hydration of Alkyne :
It is addition of water in the presence of heavy metal ion. Acetylene on hydration gives aldehyde while any
higher alkyne gives ketone.
Hg / H SO

4
CH3 CH = O
H C CH 2
H2 O

Hg / H SO

R C CH 2
H2 O

The preparation of carbonyl compounds from alkyne depends upon R part of (A) and also presence of
inductive effect group attached to R.
Ex.1

R C CH

Hg / H2SO 4

(A)

(B)
R

(i)

(ii)

CH3

(iii)

ClCH2

ClCH2 CH2CH = O

Note : Here carbonyl group will be at that C-atom at which H2O will attack as a nucleophile.
(II)

Hydroboration of alkyne :
It is used to get aldehyde from terminal alkyne. Here reagent is (i) diborane (B2H6) (ii) H2O2 (OH)
(i) B H

2 6
R C C H

R CH 2 CH O

( ii ) H2 O 2 / OH

In this reaction Borane (BH3) is electrophile.

RESONANCE

Aldehydes, Ketones - 2

Higher alkyne except terminal alkyne will give ketone during hydroboration.

CH3CH2CCCH2CH3

( i ) BH3 , THF

( ii ) H2O 2 ( OH )

Note : For unsymmetrical alkyne ketone will be corresponding to that carbon atom over which electrophile BH3 will
attack. It depends upon inductive effect and finally polarization of -electrons of C C bond.
Hydroboration occurs on antimarkovnikoff position.
( i ) BH3 , THF

(+ I of ethyl is more than CH3)

(III)

( ii ) H2O 2 ( OH )

Ozonolysis of alkene :
It is used to get carbonyl compounds from alkene. The reaction is

Zn H2 O

Zn H2 O

CH3 CH = O +

Ex.2

+ ZnO

Note : (i) During the cleavage of ozonide Zn is used to check further oxidation of aldehyde into acid.
(ii) By this method we can locate double bond in olefin or exact structrue of hydrocarbon can be determined
by knowing ozonolysis product i.e. by placing double bond at the place of two carbonyl oxygen atoms of two
carbonyl compounds.
(iii) Among the three molecules of carbonyl compounds
(a) If one molecule contains two carbonyl groups, then hydrocarbon will be alkadiene.
(b) If all the three molecules contain two carbonyl group then hydrocarbon will be cycloalkatriene.
Ex.3

Which hydrocarbon on ozonolysis gives a mixture of acetone, acetaldehyde and methyl glyoxal.

+ CH3CH = O

2,3-dimethylhex-2,4-diene

RESONANCE

Aldehydes, Ketones - 3

CH3CH = O +

2,4-dimethylhex-2,4-diene
Answer will be both isomeric structures (A) and (B)
Ex.4

Which hydrocarbon on ozonolysis gives 3 moles of glyoxal

ozone
Benzene
Benzenetriozonide

(IV)

Oxidation of Alcohol :
1 alcohol on oxidation using PCC gives aldehyde. 2 alcohol gives ketone on oxidation by Na2Cr2O7.
[O]
RCH2OH
R CH = O
If acidified K2Cr2O7 or KMnO4 is used then aldehyde further oxidise to give acid

Ex.5

CH3CH2OH + Cr2O72 (orange) + H+ CH3COOH + Cr3+ (green)

Note : (i) Aldehyde is very susceptible to further oxidation to give acid.

(ii) PCC (Pyridinium chloro-chromate in CH2Cl2) and collin's reagent (CrO3 Pyridine) are used to get aldehyde
from 1 alcohol. These reagents do not attack at double bond.
(iii) 2 alcohol on oxidation gives ketone
[O]
R2CHOH
R2 C = O

Ex.6

(V)

PCC

Dehydrogenation of Alcohol :
Dehydrogenation means removal of hydrogen and reagent used is heated copper.
o

1 alcohol (RCH2OH)

Cu / 300 C

Aldehyde (RCH = O)

2 alcohol (R2CHOH)

Cu / 300 C

Ketone (R2C = O)

H2

H2

3 alcohol

Cu / 300 C

Alkene
H2 O

Cu / 300 C

Ex.7

H2 O

Note : 2 alcohol can also be oxidised to ketone by aluminium t-butoxide. During reaction 2 alcohol is first refluxed
with reagent [(CH3)3CO]3 Al, followed by adding acetone.
3R2CHOH + [(CH3)3CO]3Al (R2CHO)3 Al + 3 (CH3)3COH
2 alcohol

(R2CHO)3Al + 3

RESONANCE

Al

Aldehydes, Ketones - 4

(VI)

Dry distillation of Calcium salt of acid :

(RCOO)2Ca

+ CaCO3

On dry distillation of calcium salt of acid with calcium salt of formic acid we get a mixture of aldehyde, ketone
and formaldehyde.

(RCOO)2Ca + (HCOO)2Ca

Ex.8

(CH3COO)2Ca
calcium acetate

(VII)

On passing vapours of fatty acids over Mangnous oxide at 300C.

On passing mixture of vapours of fatty acid with formic acid we get a mixture of aldehyde, ketone and
formaldehyde.

(VIII)

On aqueous alkali hydrolysis of gem-dihalides :

Terminal gemdihalides will give aldehyde while non-terminal will give ketones as follows

(IX)

Wacker Process :
Alkenes can directly be oxidised to corresponding aldehydes or ketones by treating them with a solution of
PdCl2 containing a catalytic amount of CuCl2 in presence of air or O2 . Except ethene any higher alkene will
give ketone.
CH2 = CH2 + H2O + PdCl2

CuCl 2

CH3 CH = O + Pd + 2HCl

R CH = CH2 + H2O + PdCl2

air or O 2

CuCl 2

+ Pd + 2HCl

air or O 2

Note : During the reaction PdCl2 is reduced to Pd and CuCl2 is reduced to Cu(1)

RESONANCE

Aldehydes, Ketones - 5

(X)

Preparation of Carbonyl compounds using Grignard's Reagent :

(a) Hydrogen cyanide on treating with Grignard reagent followed by double decomposition with water gives
aldehyde via aldimine.

H2 O / H

H2 O / H

Alkylcyanide by using above process gives ketone via ketimine

H2 O / H

H2 O / H

(b) Alkylformate with Grignard reagent gives 2 alcohol via aldehyde while alkyl alkanoate under similar
condition gives 3 alcohol via ketone

+ R MgBr

+ RMgBr

Ex.9

1. CH MgBr ( excess )

C6H5CH2CO2CH3 3 A
H2 O

H SO 4
2
B

Sol.

CH3
|
C6H5 CH2 C CH3
|
OH

(A)

Methods used for the preparation of Aldehydes only.

and

CH3
|
C6H5 CH C CH3

(i) Rosenmund's reaction :

Here acid chlorides are reduced to aldehyde with H2 in boiling xylene using palladium as a catalyst supported
on barium sulphate.

PdBaSO 4

+ HCl

Boiling Xylene

Note : (a) Pd Catalyst is poisoned by BaSO4 to check further reduction of aldehyde to alcohol
(b) Formaldehyde cannot be obtained by this method because HCOCl is unstable at common temperature.
(c) Reaction with acid chloride and dialkyl cadmium we can obtain ketone.
(ii) Stephen's reduction :
SnCl 2 / HCl
RCN

H2 O

RCH = O + NH4Cl

(iii) Oxo-process :
It is also called as carbonylation here alkene reacts with water gas at high temperature and pressure in the
presence of cobalt carbonyl catalyst to give aldehyde.
CO H / , Pr essure

2
RCH=CH2

[CO( CO )4 ]2

RESONANCE

Aldehydes, Ketones - 6

(iv) Reimer-Teimann Reaction :

By this method phenolic aldehyde is prepared

CHCl3 / KOH

(B)

Methods used for the preparation of Ketones only

(i) Using alkanoyl chloride and Grignard reagent

+ R' MgCl
(ii) Using alkanoic anhydride and Grignard reagent

+ R'MgBr

(iii) Using alkanoylchloride and dialkyl cadmium

+ R'2Cd

+ R'2 Cd

(iv) By acylation or benzoylation of aromatic hydrocarbon (Friedel-Craft Reaction)

Dry
C6H6 + CH3COCl C6H5 COCH3 HCl
AlCl 3
Acetophenone
Dry
C6H6 + C6H5COCl C 6H5 COC 6H5 HCl
AlCl 3 Benzopheno ne

(v) By Acid hydrolysis followed by heating of -Ketoester.

H2 O / H

Note : It is -ketoacid which decarboxylate more readily as it proceeds via six membered cyclic transition-state.

CO
2

RESONANCE

Aldehydes, Ketones - 7

(C)

Pinacol-Pinacolone rearrangement :
Pinacole is obtained when 2 moles of acetone are heated with divalent active metal magnesium followed by
treating with water.

Mg /

H2 O

Pinacole
Pinacole undergoes rearrangement in acidic media to give pinacolone
H

H2O

6. Chemical Reactions of Carbonyl Compounds :

Carbonyl compounds undergo nucleophilic addition reaction and reactivity order will be :

6.1

Nucleophilic Addition Reactions :

Addition of a nuceophile and a proton across the (C = O) double bond. The reactivity of the carbonyl group
arises from the electronegativity of the oxygen atom and the resulting polarization of the carbon-oxygen
double bond. The electrophilic carbonyl carbon atom is sp2 hybridized and flat, leaving it relatively unhindered
and open to attack from either face of the double bond.
R

>

C=O >
H

Ex.10
Ans.

Why aldehyde are more reactive than ketones ?

There are two factors which influence the reactivity of ketone and aldehyde.
(i) Inductive effect

(ii) steric factor

(i) + I effect of alkyl group decrease the amount of charge on C+ (C+ O). in ketones.
(ii) Steric effect also causes the less reactivity of carbonyl group.

(i)

Reaction with alcohol :

Carbonyl compounds react with alcohols in the presence of dry HCl gas to give acetal (if aldehyde) and
ketal if ketone via formation of unstable hemiacetal and hemiketal respectively.

Note : (i) Acetal is formed to protect aldehyde for a long time.

(ii) Acetal has functional groups ether.
(iii) Acetal formed can be decomposed to orignal aldehyde by dilute acid.
(iv) On treating with ethyleneglycol we get cyclic acetal or ketal (1,3-dioxolans)

RESONANCE

Aldehydes, Ketones - 8

Mechanism :

H2 O

(v) Acetal formation is found to be more favourable than ketal formation if both the carbonyl groups are
present within the molecule.
(ii) Additon of HCN :
It is base catalysed addition

BH

Note : (i) Addition of HCN over aldehyde gives cyanohydrin.

(ii) Cynohydrin on acid hydrolysis gives -hydroxy acid.
(iii) Cyanohydrin on treating with NH3(l) followed by acid hydrolysis gives -amino acid.
(iv) In case of ketone cyanohydrin formation is reversible due to bulky group of ketone which hinder the
formation.
(iii) Addition of sodiumbisulphite (NaHSO3) :
This addition is used to isolate carbonyl compounds from the mixture as we get salt.
+ NaHSO3

(salt)

salt on acidification gives carbonyl compounds again.

H2 O

H O
2

(iv) Addition of water : Aldehyde or ketone reacts with water to form gem-diols. Water is a poor nucelophile and
therefore adds relatively slowly to the carbonyl group, but the rate of reaction can be increased by an acid
catalyst.
Mechanism:

RESONANCE

Aldehydes, Ketones - 9

6.2

Addition elimination reactions :

Certain compounds related to ammonia add to the carbonyl group to form derivatives that are important
chiefly for the characterization and identification of aldehydes and Ketones, the product contain a carbonnitrogen double bond resulting from elimination of a molecule of water from the initial addition products.

+ : NH2OH

+ : NH2NHC6H5

+ : NH2NHCONH2

(i)

|
C NHOH
|
OH

|
C NHNHC6H5
|
OH

|
C NHNHCONH2
|
OH

Reaction with ammonia derivatives

This reaction is nucleophilic addition followed by water elimination.

H2 O

This reaction is carried out in slightly acidic media which will generate a nucleophilic centre for weak base
ammonia derivatives.

On using strong acidic media lone pair of electrons present at N-atom of ammonia derivatives will accept
proton forming protonated ammonia derivatives which can not act as nucleophile for carbonyl carbon.
>C = O + H2NZ >C = N Z

RESONANCE

Aldehydes, Ketones - 10

6.3

Beckmann Rearrangement in Oxime:

(If R' is bulkier than R)

Mechanism :

H2 O

Note : (i) Brady's reagent is used to distinguish carbonyl compounds from the mixture.
(ii) Oxime undergoes Beckmann rearrangement to give its isomer amide.
(iii) In this reaction the group which is anti to OH group migrates.
Re arrangemen t

Re arrangemen t

(CH3 is anti to OH)

Re arrangemen t

(C6H5 is anti to OH)

6.4

Aldol Condensation :
It is condensation between two moles of carbonyl compounds among which at least one must have hydrogen atom in dilute basic media to get , -unsaturated aldehyde / ketone via the formation of -hydroxy
aldehyde / ketone.
Base
2CH3CH = O

H2 O

Mechanism :

RESONANCE

Aldehydes, Ketones - 11

from -hydroxy aldehyde / ketone, water is eliminated on using either acidic or basic media as :

Now try to get carbonyl compounds from , -unsaturated carbonyl compounds as :

keep 'H' at -position and OH at -position of unsaturated carbonyl compound to get -hydroxy carbonyl
compound.

Now break and carbon as shown below to get carbonyl compound.

These two carbonyl compounds can be obtained on ozonolysis of hydrocarbon

Ex.11

if it is asked.

Which hydrocarbon on ozonolysis followed by heating with alkali gives 2-methylpent-2-en-1-al

Go through above sequence as

In given reaction both the carbonyl compounds are same hence reaction is intermolecular aldol-condensation
and hydrocarbon will be hex-3-ene.

Cross-Aldol condensation :
On using two types of carbonyl compounds both having -hydrogen atoms we get a mixture of four condensed
product because two types of carbonyl compounds will give two type of carbanions which will be nucleophile
for it self and other molecule.
On using formaldehyde and acetaldehyde during crossed aldol all the -hydrogen atom of acetaldehyde are
replaced one by one by hydroxymethyl group because of smaller size of formaldehyde to give
trihydroxymethylacetaldehyde which undergoes crossed cannizaro's reaction with formaldehyde to give
tetrahydroxymethyl methane and formate ion as a final product.

(CH2OH)2CHCH=O

(CH2OH)4C + HCOONa+

RESONANCE

Aldehydes, Ketones - 12

Ex.12

Show how cinnamaldehyde is prepared by crossed aldol condensation ?

Sol.

C6H5CHO + CH3CHO

C6H5CH = CH CHO + H2O

Cinnamaldehyde

Intramolecular aldol condensation :

If two carbonyl groups with -hydrogen atoms are present within the same molecule, then we get cyclic unsaturated aldehyde / ketones via the formation of cyclic--hydroxy aldehyde / ketone in presence of basic
media.

By knowing product we can get reactant as in case of intermolecular aldol condensation :

Note : Aldol condensation also takes place in acidic media too as

6.5

Cannizzaro reaction :
Carbonyl compounds not having -hydrogen atom undergo disproportionation or redox reaction in strong
basic media.
(i)

(ii) 2 C6H5CH = O

(iii)

These reactions are intermolecular cannizzaro reaction.

RESONANCE

Aldehydes, Ketones - 13

Mechanism :

By this mechanism it clear that acid is corresponding to that carbonyl compound over which
easily as nucleophile.

is going

Note : It is observed that hydride ion transfer from (I) to Carbonyl compound (B) is rate determining step.

Crossed Cannizzaro reaction :

On using two types of carbonyl compounds not having -hydrogen atom, acid will be corresponding to that
aldehyde over which
will approach without any hindrence.

(i)

(ii)

in case (i)
cases.

will easily go to (A) and in case (ii) it will go to (B) hence acid will be formate ion in both the

Intramolecular Cannizzaro reacion :

Here two carbonyl groups (without -hydrogen atom) are present within the same molecule.

Mechanism :

Ex.13.

(mendalic acid ion)

RESONANCE

Aldehydes, Ketones - 14

Benzil-benzilic acid rearrangement:

other examples is

Mechanism :

6.6

Perkin reaction :
When aromatic aldehyde like benzaldehyde is treated with anhydride in the presence of sodium salt of
acid from which anhydride is derived we get -unsaturated acid.

e.g.

Mechanism :

RESONANCE

Aldehydes, Ketones - 15

Note : By knowing -unsaturated acid we can get idea about the anhydride used in perkin reaction. This can
be done by keeping 'H' at and OH at -carbon atom followed by breaking carbon as given below.
By this we can know about acid and it will be anhydride of this acid only.
NaOC H in absolute

Ex.14

2 5
(D)
C6H5 CHO + CH3 COOC2H5

Sol.

(D) C6H5CH = CHCOOC2H5

6.7

Knoevenagel reaction :

C2H5OH and heat

It is preparation of -unsaturated acid with carbonyl compound using malonic ester in the presence of
pyridine base.

Mechanism :

6.8

Reformatsky reaction :
When carbonyl compound and -halogenated ester are heated with zinc followed by treating with water we
get -hydroxyester.

This reaction can be represented as

RESONANCE

Aldehydes, Ketones - 16

6.9

Wittig reaction :
It is used to get alkene from carbonyl compound using phosphorus ylide via the formation of cyclic structure
betaine.

Note : Phosphorus ylides are prepared from alkylhalide and triphenylphosphine in the presence of base like
sodium ethoxide as

Ex.15

6.10

+ Ph3P = CH2

Benzoin Condensation :
During this reaction benzoin is obtained when an ethanolic solution of benzaldehyde is heated with strong
alkali potassium cyanide or sodium cyanide.

Reaction Mechanism :

6.11

Baeyer-Villiger oxidation :
It is preparation of ester from ketone using peracid.

peracid

RESONANCE

Aldehydes, Ketones - 17

Mechanism :

6.12

Haloform reaction :
Acetaldehyde and methylalkyl ketones react rapidly with halogen (Cl2, Br2 or I2) in the presence of alkali to
give haloform and acid salt.
O
O
||
||
Br / NaOH
R C CH3 2 R C ONa CHBr3 (Bromoform)

O
||
In this reaction CH3 of CH3 C group is converted into haloform as it contains acidic hydrogen atom and
rest-part of alkyl methyl ketone give acid salt having carbon atom corresponding to alkyl ketone.
Preparation of haloform from methylketone involves two steps.
(a) Halogenation
(b) Alkalihydrolysis
O
||
R C CH3

O
||
R C CBr3 (Halogenation)
Br2

O
O
||
||
NaOH
R C CBr3 CHBr3 + R C ONa (Alkalihydrolysis)
O
||
Note : This reaction is used to distinguish the presence of CH3 C group.

6.13

Clemmensen reduction :
Used to get alkane from carbonyl compounds.

Mechanism

RESONANCE

Aldehydes, Ketones - 18

6.14

Wolf-Kishner reduction :
Used to get alkane from carbonyl compounds

Mechanism

6.15 Addition of Grignard reagent over Carbonyl compound :

It gives alcohol
+ MgBr OH
(i) When formaldehyde is treated with Grignard reagent followed by acid hydrolysis primary alcohol is
obtained.
H
|
H C O + R MgBr

H
|
H C OMgBr
|
R

H
|
H C OH
|
R
1 alcohol

(ii) When aldehyde except formaldehyde is treated with grignard reagent followed by hydrolysis we get 2
alcohol

This 2 alcohol is also obtained as :

H
|
RC O

(iii) When ketone is treated with grignard reagent followed by acid hydrolysis gives 3 alcohol.

This 3 alcohol is also obtained by using following two method

RESONANCE

Aldehydes, Ketones - 19

Note : 2 alcohol on oxidation gives ketone.

6.16 Reduction of Carbonyl Compounds :

(i)

Reduction to alcohols
H / Ni or Pt or Pd

2
LiAlH4 or NaBH4

e.g.

O
||
C
H

O
||
C

Ni H
2

H (
Raney nickel )

OH
|
H
C
H
H

Ni H

(90%)

O
||
CH3CH2CH2CCH3

(ii)

(1) NaBH 4

( 2) H , H2O

OH
|
CH3CH2CH2CHCH3

Reduction to pinacols
CH3CH3
|
|
CH3 C C CH3
||
||
O O

e.g.

(i) Mg

(ii) H2O

CH3 CH3
|
|
CH3 C ____ C CH3
|
|
OH
OH

C6H5
CH3
|
|
(i) Mg
C6H5 C
+ C CH3
(ii) H2O
||
||
O
O

C6H5 CH3
|
|
C6H5 C C CH3
|
|
OH OH

6.17 Reaction with PCl5 :

Carbonyl compounds give gemdihalides
>C = O + PCl5

+ POCl3

(i) CH3CH = O + PCl5 CH3CHCl2 + POCl3

(ii)

Other reactions :

(1)

RESONANCE

Aldehydes, Ketones - 20

(2)

(3)

(4)

(5)

(6)

RESONANCE

Aldehydes, Ketones - 21

Some important reagents used for identification of aldehyde.

(i)

Tollens reagent :
It is ammonical silver nitrate solution, prepared by adding ammonium hydroxide to AgNO3 solution. During
reaction, first Ag2O is formed which is dissolved in ammoniumhydroxide to give Tollens reagent.
2AgNO3 + 2NH4OH Ag2O + NH4NO3 + H2O
Ag2O + 4NH4OH 2 Ag(NH3 )2 OH 3H2 O
Tollen' s reagent

Tollens reagent is weak oxidising agent. It gives Ag mirror test with aldehyde.

R CH = O + 2Ag (NH3 )2 +
+ 2Ag + 2NH3 + 2H2O

R CH = O + Ag2O R COOH + 2Ag (Silver mirror)

(ii)

Fehlings solution :
It is an alkaline solution of cupric ion complexed with sodium potassium tartarate. Two solutions are kept by
naming Fehling solution (I) (CuSO4 solution) and Fehling solution (II) (Alkaline solution of sodium
potassiumtartarate). When these two solutions are mixed we get deep blue coloured solution.
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4
Cu(OH)2 +

Equal volume of both the solutions are heated with aldehyde to give red brown precipitate of cuprous oxide
(Cu2O) which confirms the presence of aldehyde.
R CHO + 2CuO RCOOH + Cu2O (Red ppt)
Blue

RCHO + 2Cu2+ +
(iii)

RCOO +

+ 2H2O

Benedict solution :
It is solution of CuSO4, sodium citrate and sodium carbonate. It also consists of two solutions. solution (I)
is alkaline solution of sodium citrate and solution (II) is CuSO4 solution.
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4

Cu(OH)2 +

Aldehyde gives positive test with Benedict solution.

RCH = O +

(iv)

Schiffs reagent :
It is dilute solution of rosaniline hydrochloride whose red colour has been discharged by passing SO2.
Aldehyde restores red colour when treated with schiffs reagent (Magenta solution in H2SO3).

RESONANCE

Aldehydes, Ketones - 22

MISCELLANEOUS SOLVED PROBLEMS

1.

What will be hydration and hydroboration product for Cyclohexylethyne.

Sol.

2.
Sol.

Which hydrocarbon on ozonolysis gives acetone only ?

Acetone only, means two moles of acetone.

(i) O3

( ii ) Zn / H2 O

3.

Predict the structure of (A) in the following sequence :

Sol.

Since (B) is alcohol and (C) is alkene hence (B) is 3 alcohol only according to question (It is known that
alkene can only be obtained from 3 alcohol when heated with copper). Thus structure of (B) is (CH3)3COH
and its corresponding. alkyl bromide will be (CH3)3CBr (tertiarybutylbromide)

4.

Find out unknown in following reactions.

Sol.

Since E is obtained on dry distillation of calcium salt of acetic acid hence E will be
unknowns are

A=

B = CH3 CH = CH2

C=

D = CH3 C C H

RESONANCE

. Thus other

Aldehydes, Ketones - 23

5.
Sol.

What will be structure of C8H8Cl2 (A), which on aqueous alkalihydrolysis gives product (B). (B) gives positive
iodoform test.
Since (B) is showing iodoform test hence it will be methylketone only as it is obtained on aqueous alkali
hydrolysis of (A) which will be non-terminal gem dihalides as

Now unknown 'R' can be known as :

= C8H8Cl2

R = C8H8Cl2 C2H3Cl2 = C6H5

6.

Hence 'A' is

Which one of the following will give 2 propanol

(a)

(b)

(c)

(d)

Sol.

(a)

+ CH3MgBr

(b)

(c)

(d)

RESONANCE

+ CH3MgBr

+ CH3MgBr

+ CH3MgBr

Aldehydes, Ketones - 24

7.

What will be structure of C4H8O2 which on treating with excess CH3MgBr followed by acidification gives sole
alcohol (A). (A) on treating with sodium hypolodide solution gives positive iodoform test.

Sol.

Since (A) gives positively iodoform test hence it will be alkanol-2. 2 alcohol can be obtained only when
alkylformate is treated with Grignard's reagent via aldehyde where alkyl part is alkyl part of Grignard's reagent.
As Grignard's reagent is CH3MgBr hence 2 alcohol will be
(propanol-2). Thus C4H8O2 is either

(i) or

(ii)

Reactions :
(i) CH MgBr

H2 O / H

3 CH3CH=O +
( ii) Acidificat ion

Here we get two alcohols propanol-2 and propanol-1. Alkyl part of formic acid ester which gives propanol-2

will be isopropyl only. Thus structure of C4H8O2 is (ii)

8.

SO2 + PCl5 A + B
CH3COOH + A C + SO2 + HCl
2C + CH3MgBr (1 mole) 2D + MgBrCl
Recognise A, B, C, and D

Sol.

A = SOCl2

B = POCl3,

C=

D = (CH3)2C = O

H O
1.PCl / Ether
5
A 3 B + C.

9.

2. H2 O

A , B , C are
(A) PhCONH-p - CH3C6H4
Sol.

(B) PhCOOH

(C) pCH3C6H4NH2

(D) PhCHO

(A,B,C)

1.PCl / Ether

2. H2 O

10.

Predict the unknown(s) for the following :

C H ONa

2 5
A
2CH3 CH2 COOC2H5

C 2H5 OH

Sol.

RESONANCE

H2 O / H

C + CO2

Aldehydes, Ketones - 25

11.

Predict the unknowns for the following :

Sol.

CH3COOC2H5 ; B =

C = CH3CH2I

D = CH3CCHCOOC2H5
CH2CH3

12.

Predict the product (P)

C6H5CH2Cl / C2H5ONa

(P)

C H ONa

5
2

Sol.

13.

C H CH Cl

5
6
2

Which carbonyl compound on heated with dilute alkali gives 1- acetylcyclopentene.

Sol.

14.

What will be unknown in the following :

(i) R CH = O

(ii) A

Sol.

Perkin reaction

(i)

A = (CH3CH2CO)2O , B = CH3CH2COONa

RESONANCE

(ii)

A=

Aldehydes, Ketones - 26

15.

What is product for the following reaction

Sol.

2
5 2
CH3 CH O
2

(P)
Knoevenagel reaction, P = CH3CH=CHCOOH

CH ( COOC H ) / Pyridine

16.

Sol.

Reformatsky reaction

A=

17.

B=

Predict the product for the followings :

(i)

(ii)

(iii)
Sol.

Witting reaction

(i)

18.

(iii)

Predict Product

(i)

Sol.

(ii)

Product

(ii)

Product

Benzoin condensation reaction

(i)

RESONANCE

(ii)

Aldehydes, Ketones - 27

19.

Predict product for the following

Sol.

Baeyer-villiger oxidation

20.

Which of the following is correct order of rate of halogenation of acetone ?

(a) Cl2 > Br2 > I2
(b) Br2 > I2 > Cl2
(c) I2 > Cl2 > Br2
(d*) Cl2 = Br2 = I2

Sol.

By the following reaction path it is clear that (d) is correct

O
||
CH3 C CH3

OH
|
CH3 C CH2

X
X
Fast

CH2 C CH3

21.

(1)

Sol.

(1)

(2)

(2)

(a) =

(b) =

(c) =

22.

(A) on treating with (B) in the presence of dry ether gives (C) which on acids hydrolysis gives (D). (D) on
oxidation gives 2,5-dimethylhexan-3-one.

Sol.

By knowning structure of given product (D) will be

hence (C) will be

and finaly A & B will have following two structures.

A=

B=

RESONANCE

or

or

A=

B=

Aldehydes, Ketones - 28