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TOPIC PAGE NO.

1. INTRODUCTION 2
2. METHOD OF PREPARATION OFALDEHYDES AND KETONES 2
3. PHYSICAL PROPERTIES OF ALDEHYDES AND KETONES 5
4. CHEMICAL PROPERTIES OFALDEHYDES AND KETONES 6
5. ALDOL CONDENSATION 12
6. CANNIZAROS REACTION 14
7. REFORMATSKY REACTION 15
8. PINACOLE REDUCTIONS (BIMOLECULAR REDUCTION) 16
9. KNOVENGEAL REACTION 17
10. CLAISEN SCHMIDT CONDENSATION 18
11. USES OFALDEHYDES & KETONES 18
CONTENTS
S.NO. TOPIC PAGE NO
1
Carbonyl Compound
CARBONYLCOMPOUND
1. INTRODUCTION :
Introduction
Aldehydes and ketones are the compounds containing the same functional groups.
C = 0
i.e.
In aldehydes, the carbonyl group always is attached with one H atom where as in ketones the carbonyl
group does not have a H atom at all. e.g.
R- C - H R- C - R'
0
Aldehyde
0
Ketone
In ketones if the two alkyl groups are same then it is called a simple ketone. When the two alkyl groups are
different then the ketone is called a mixed ketone.
Structure : The carbon atomof the carbonyl group consists of one o and one t bond between the carbon and
the oxygen atom. The carbon atom of the carbonyl group is sp
2
hydridized.
C-atom ground state electronic configuration = 1s
2
2s
2
2p
x
2p
y
C-atom exited state electronic configuration = 1s
2
2s
1
2p
x
2p
y
2p
z
The C-atom in carbonyl group is sp
2
hybridized
Hence the carbonyl group is plane trigonal shaped.
1 1
1 1 1
i.e.
2. METHOD OF PREPARATION OFALDEHYDES AND KETONES :
(i) By oxidation of alcohols
Aldehydes and ketones are generally prepared byoxidation of primaryand secondary alcohols,
respectively
H
|
R - C - O+ [O] R - C = O
| H
aldehyde
Cr
2
0
7
I Pyridine
|
H
|
H
primaryalcohol
R
|
R - C - O+ [O]
R
|
R - C = O
Cr
2
0
7
I Pyridine
|
H
|
H ketone
2
Carbonyl Compound
(ii) By dehydrogenation of alcohols
Aldehydes may be prepared by passing the vapours of p-alcohols over copper as catalyst at
573 K.
Cu
R - C = 0 + H
2
H
Aldehyde
R- CH
2
- 0 - H
p-alcohol
573 K
Cu
CH
3
- C = 0 + H
2
H
acetaldehyde
CH
3
- CH
2
- 0 - H
Ethanol
573 K
R
R
CH
3
R
R
CH
3
Cu
CH - 0H
s-alcohol
C = 0 + H
2
Ketone
573 K
Cu
CH - 0H C = 0 + H
2
Butane -2-one
573 K
C
2
H
5
C
2
H
5
2-Butanol
2. Fromhydrocarbons
(i) By ozonolysis of alkenes: As we know, ozonolysis of alkenes followed by reaction with zinc dust
and water gives aldehydes, ketones or a mixture of both depending on the substitution pattern of
the
alkene.
ZnI H
2
0
H
2
0
2
R - CH = CH - R R - CH0 + RCH0
0
3
ZnI H
2
0
H
2
0
2
0
3
(ii) By hydrationof alkynes: Addition of water to ethyne in the presence of HS0 and HgS0 gives
2 4 4
acetaldehyde. All other alkynes give ketones inthis reaction.
CH CH + H0H
HgS0
4
I dil.H
2
S0
4 rearrangement
CH
2
= CH - 0H CH
3
- CH0
rearrangement
R - C C - H + H0H
HgS0
4
I dil.H
2
S0
4
(iii) By Gatterman reaction
3. (i) Fromacyl chloride (acid chloride)
Acyl chloride (acid chloride) is hydrogenated over catalyst, palladium on barium sulphate.
This reaction is called Rosenmundreduction.
3
Carbonyl Compound
(ii) Fromnitriles and esters
Nitriles are reduced to corresponding imine withstannous chloride in the presence of hydrochloric acid
or diisobutylaluminiumhydride, (DIBAL-H) which onhydrolysis give corresponding aldehyde.
(Stephen reaction)
4. From Grignards Reagent
Grignard reagents react with HCN followed by hydrolysis to form aldehydes while with alkyl cyanide
they form ketones.
H
R - C = N Mg x
Isolable
H - C N + RMg X
H
R - C= N Mg X
H
2
0
R - C = 0 + NH Mg X
2
H
C
2
H
5
H - C = N MgBr HCN + C
2
H
5
MgBr
C
2
H
5
H - C = 0 + NH
2
Mg Br
Propanol
R'
R - C = N Mg Br
C
2
H
5
H - C= N Mg Br
H
2
0
R - C N + R' MgBr
Alkyl cyanide
R'
R'
R - C= 0 + NH
2
Mg Br
Ketone
CH
3
- C = N Mg Br
H
2
0
R - C = N Mg Br
H
2
0
CH
3
C N + C
2
H
5
MgBr
CH
3
- C - C
2
H
5
+ NH
2
MgBr
C
2
H
5
0
5. Fromacyl chlorides : Reaction of acyl chlorides with dialkylcadmium, prepared by the reaction of
cadmiumchloride withGrignard reagent, gives ketones.
4
Carbonyl Compound
(ii) Fromnitriles and esters
Nitriles are reduced to corresponding imine withstannous chloride in the presence of hydrochloric acid
or diisobutylaluminiumhydride, (DIBAL-H) which onhydrolysis give corresponding aldehyde.
(Stephen reaction)
4. From Grignards Reagent
Grignards reagents react with HCN followed by hydrolysis to form aldehydes while with alkyl cyanide
they form ketones.
H
R - C = N Mg x
Isolable
H - C N + RMg X
H
R - C= N Mg X
H
2
0
R - C = 0 + NH Mg X
2
H
C
2
H
5
H - C = N MgBr HCN + C
2
H
5
MgBr
C
2
H
5
H - C = 0 + NH
2
Mg Br
Propanol
R'
R - C = N Mg Br
C
2
H
5
H - C= N Mg Br
H
2
0
R - C N + R' MgBr
Alkyl cyanide
R'
R'
R - C= 0 + NH
2
Mg Br
Ketone
CH
3
- C = N Mg Br
H
2
0
R - C = N Mg Br
H
2
0
CH
3
C N + C
2
H
5
MgBr
CH
3
- C - C
2
H
5
+ NH
2
MgBr
C
2
H
5
0
5. Fromacyl chlorides : Reaction of acyl chlorides with dialkylcadmium, prepared by the reaction of
cadmiumchloride withGrignard reagent, gives ketones.
5
Carbonyl Compound
6. Friedel-Crafts acylationreaction
7. From Fatty Acids
By dry distillation of calciumsalt of Fatty acids.
Pyrolysis of calcium salts of fatty acids or mixture of fatty acids reacts to the formation of aldehydes/
ketones depending upon the nature of carboxylic acids.
(a) Dry distillation of calcium formate forms formaldehyde.
HC00
2 2HCH0 + 2CaC0
3
. Ca
A
HC00
(b) Dry distillation of a mixture of calcium formate and the calcium salt of another carboxylic
acid reacts to the formation of aldehyde of the corresponding carboxylic acid.
0
(RC00)
2
Ca + (HC00)
2
Ca respectively. RCH0 + HCH0 + R - C - R
A
NOTE: In this reaction the yields are generally poor due to side reactions viz formal dehyde
andacetone fromcalciumformate andcalciumacetate respectively.
(c) Distillation of calcium salt of fatty acid other than calcium salt of formic acid gives symmetrical
ketones.
0
(RC00)
2
Ca R - C - R + CaC0
3
A
(CH
3
C00)
2
Ca
Calcium acetate
CH
3
- C - CH
3
+ CaC0
3
A
0
acetone
3. PHYSICALPROPERTIES OFALDEHYDES AND KETONES :
(i) Aldehydes are colourless with pungent smell liquid while ketones are pleasant smell liquids but
formaldehyde is gaseous innature.
(ii) Lower carbonyl compounds are soluble in water. It is due to polarity in carbonyl group.
(iii) Higher carbonyl compounds are insoluble in water due to more covalent character.
(iv) Melting point & Boiling point Molecular mass
6
Carbonyl Compound
1
Melting point & Boiling point
No. of branches
(v) Melting point and boiling point of carbonyl compounds are more than to corresponding alkanes
due to dipole-dipole attraction present between molecules in carbonyl compounds.
(vi) Reactivity of carbonyl compound is dependent on alkyl group which is linked with carbonyl
group.
(vii) 40% solution of formaldehyde is known as FORMALIN (40% HCH0, 54-56% H
2
0,
4-6% methanol)
(viii)Mixture of formaldehyde and lactose sugar is called FORMAMINT which is used in
medicine of throat infection.
Boiling point of carbonyl compounds are as under -
Compound
Formaldehyde
Acetaldehyde
Acetone
Boiling Point
- 21C
+ 21C
56C
1.
2.
3.
4. CHEMICAL PROPERTIES OFALDEHYDES AND KETONES :
Since aldehydes and ketones both possess the carbonyl functional group, theyundergo similar chemical
reactions.
(i) Nucleophilic additionreactions
Contrary to electrophilic addition reactions observed in alkenes , the aldehydes and ketones
undergo nucleophilic addition reactions.
(a) Mechanismof nucleophilic additionreactions
Anucleophile attacks the electrophilic carbon atomof the polar carbonyl group froma direction
approximately perpendicular to the plane of sp
2
hybridised orbitals of carbonyl carbon.
The hybridisation of carbon changes from sp
2
to sp
3
in this process, and a tetrahedral alkoxide
intermediate is produced. This intermediate captures a proton from the reaction medium to give
the electrically neutral product. The net result is addition of Nu
-
and H
+
across the carbon
oxygen double bond as shown in Fig.
Slow
Step 1
(b) Relative reactivity of carbonyl compounds. Aldehydes are more reactive than ketones due to following
two factors.
Inductive effect : Since the rate determining step is the attack of nucleophilic reagent at the positively
charged carbon atom of the carbonyl group, the reactivity of the carbonyl group towards the addition
reactions depends upon the magnitude of the positive charge on the carbonyl carbon atom. Thus any
1.
7
Carbonyl Compound
substituent or factor in the carbonyl compound that increases the positive charge on the carbonyl carbon
atom (i.e. electronegative group) must increase its reactivity towards addition reactions and vice versa. In
practice also it is found to be so, e.g. the introduction of alkyl group or any other electron-donatingfactor on
the carbonyl group decreases its reactivity and thus formaldehyde is more reactive than other aldehydes
(having one alkyl group) which in turn are more reactive than the ketones (having two alkyl group).
0
0 0
> >
R C R
Ketones
R C - H
Aldehydes
H - C - H
Formaldehyde
0n theother hand, introduction of electronegative group (e.g. chlorine) makes carbonyl carbon more positive
and hence increases its tendencyfor acceptingnucleophile. This explains why trichloroacetaldehydeundergoes
nucleohilic addition more readily than acetaldehyde. Thus we can explain following order of reactivity
among aldehydes and ketones.
N0
2
CH
2
CH0 >
Nitroacetaldehyde
ClCH
2
CH0 > CH
3
CH0
Acetaldehyde
> CH
3
CH
2
CH0
Propionaldehyde Chloroacetaldehyde
CH
3
.C0CH(CH
3
)
2 CH
3
.C0.CH
3
(2)
> > CH
3
.C0.C(CH
3
)
3
Steric factor : The nucleophile attacks the positively charged carbon atomof the carbonyl
group. If carbon atom of the carbonyl group carries bulky groups. the approach of the nucleophile to the
carbon atomis hindered and the compound thus will be less reactive. In short, bulkier the group attached to
the carbonyl carbon atom, lesser will be the reactivity of the compound towards nucleophilic addition
reactions. Thus formaldehyde having no alkyl group will be most reactive, and ketones having two alkyl
groups will be least reactive while aldehydes will be in between the two.
H
H
H
3
C - C = 0
CH
3
> H
3
C - C = 0
>
H - C = 0
Further among ketones, larger the size of the alkyl group lesser will be its reactivity. Thus
(CH
3
)
2
CH
(CH
3
)
3
C
(CH
3
)
3
C
Di-tert-butyl ketone
CH
3
C
2
H
5
Ethymethyl ketone
> >
C = 0 C = 0 C = 0
(CH
3
)
2
CH
Di-isopropyl ketone
Effect of aryl group on the reactivity of the carbonyl group. Aryl group exerts two opposing effects on the
reactivity of the carbonyl group. The -I effect of the aryl group increases the electron deficiency at
carbonyl carbon and thereby facilitates the electron deficiency at carbonyl group. 0n the contrary since
aromatic aldehydes and ketones have > C = 0group in conjugation with the benzene ring, resonance due to
benzene nucleus decreases the electron deficiency at carbonyl carbon (+ R effect) and consequently
deactivates the carbonyl group towards nucleophilic attack.
o+ o
R - C = 0
Phenyl group withdraws electrons by
-I effect and hence activates > C = 0
group to nucleophilic attack
8
Carbonyl Compound
..
R - C - 0
..
:
..
R - C = 0
..
:
..
R - C = 0
..
:
R - C = 0
..
:
+
+
+
Benzene ring releases electron by +R effect and hence deactivates > C = 0 to nucleophilic attack.
However, resonance effect outweights the inductive effect and thus on the whole aromatic aldehydes and
ketones are less reactive than their aliphatic counterparts towards nucleophilic attack.
Like aliphatic counterparts, aromatic aldehydes are more reactive than ketones due to steric hinderance in
ketones and electronic factors. Thus
C
6
H
5
C0CH
3
Acetophenone
C
6
H
5
C0C
6
H
5
Benzophenone
C
6
H
5
CH0
Benzaldehyde
> >
(B) Acidity of o-hydrogen : A carbon atom present on the adjacent position (i.e. C
1
) of the functional
group is known as o-carbon atomand the hydrogen atom(s) present on such carbon atomis (are) known
as o-hydrogen atoms, e.g.
0
1 3 2 1 1 4 2
CH
3
- CH
2
- CH
2
- CH
2
- CH0 CH
3
- CH
2
- C - CH
3
| o o o o
The hydrogen atoms present on C
1
i.e. on o-carbon atom in the above structures are known an
o-hydrogen atoms.
The o-hydrogen atoms of aldehydes and ketones are acidic in nature because the removal of such atom
results in a resonance stabilized anion ; i.e. once the anion is formed it is stabilized by resonance. The
resonance stabilised anion is called enolate ion.
: B
0
-
0 H 0
.-.
: B
CH
3
- C - C - H CH
3
- CH - C - H
enolate ion
CH
3
- C = C - H
H
(- BH)
H
Thus owing to the presence of a negative charge, the enolate ion acts as a nucleophile and can add easily
on the carbonyl group. This process of formation of enolate ion followed by its addition to a carbonyl
group is involved in all the condensation reactions of aldehydes and ketones.
Since both aldehydes (except formaldehyde) and ketones have an alkyl radical and a carbonyl group, the
properties due to these two group must be common in aldehydes and ketones. But further, the presence
of a hydrogen atom on the carbonyl group in aldehydes results some additional properties in which they
differ from ketones. Hence, in short, the chemical properties of aldehydes and ketones may be studied
under the following main heads.
1. nucleophilic additionandnucleophilic addition-elimination reactions:
(i)Addition of hydrogen cyanide (HCN): Aldehydes andketones react withhydrogen cyanide (HCN)
to yield cyanohydrins.
0H
C = 0+ HCN C
CN
9
Carbonyl Compound
(ii) Additionof sodiumhydrogensulphite: This reaction is useful for separation andpurification of
aldehydes.
(iii) Addition of Grignard reagents: Alochols are produced bythe carbonyl compound with Grignard
reagents. The first stepof the reaction is the nucleophilic addition of Grignard reagent to the
carbonyl group to forman adduct. Hydrolysis of the adduct yields analcohol.

2
0

The overall reactions using different aldehydes and ketones are as follows:
HCH0 + RMgX RCH
2
0H0Mgx
2
RCH
2
0H+ Mg(0H)X
1 Alcohol
H 0
Note : Aprimary alcohol with methanal, a secondaryalcohol with other aldehydes and tertiaryalcohol
with ketones.
(iv) Addition of alcohols:
Mechanism
10
Carbonyl Compound
(v) Addition of ammonia andits derivatives: Nucleophiles, such as ammonia andits derivatives
H N-Z add to the carbonyl group of aldehydes and ketones. The reaction is reversible and
2
catalysed byacid. The equilibriumfavours the product formationdue to rapiddehydration of the
intermediate to form
Mechanism. These reactions are acid catalysed.
+
H
+ C = 0H
C = 0 +
+
C = 0H
+
C - 0H
0
+
C = 0H NH
2
- Z C
NH
2
- Z
+
0 0H
C C
NH
2
- Z
+
0H
NH - Z
-H
2
0
C = N - Z C
NH- Z
Reaction with Ammonia derivatives
R
H
H
R
H
C = 0+
(a)
N R
C = N R
H
alkyl amine aldemine
(b)
(c)
H
(d)
H
phenyl
hydrazone
phenyl
hydrazine
11
Carbonyl Compound
H
|
N N
N0
2
N0
2
R H
R
H
(e)
C = 0 +
H
No
2
C = N N N0
2
H
2,4-dinitrophenyl hydrazone or DNP
(f)
(vi) Wittig Reaction
The interaction of aldehydes and ketones (aliphatic or aromatic) with triphenyl phosphine alkylidenes to
form olefins is called wittig reaction.
0
C
C
6
H
5
C
6
H
5
C
6
H
5
+ R - CH = P
C = CH - R
+ (C
6
H
5
)
3
P = 0
Mechanics
Ph
+
CH - P (C
6
H
5
)
3
C = 0
Ph
R
Ph
Ph C 0 :
CH P (C
6
H
5
)
3
R
Ph
C = CH - R + 0= P (C
6
H
5
)
3
Alkene
Ph
(vii) Reduction
Aldehyde onreduction formprimary alcohol while ketone onreductionformsecondaryalcohol.
- H + 2H R - CH
2
- 0H primary alchohol R
C
||
0
R - - R + 2H R - - R secondary alcohol
C
||
0
CH
|
0H
12
Carbonyl Compound
Note:
(i) In the above reaction if reducing agent is Na + C
2
H
5
0H then reaction is called Bouveault
Blanc Reaction.
(ii) If reducing agent is NaH reaction is called Darzens Reaction. We can also use LiAlH
4
in
this reaction.
(iii) If reducing agent is (red P / HI) then product will be alkane.
(iv) If reducing agent is Zn-Hg/conc. HCl then product will be alkane. Reaction is called
Clemmenson-Reduction.
(v) If reducing agent is alkaline solution of hydrazine, product will be alkane. Reaction is called
Wolf-kishner Reduction.
(viii) Oxidation
Aldehydes differ fromketones in their oxidation reactions. Aldehydes are easily oxidised to carboxylic
acids on treatment with common oxidising agents like nitric acid, potassiumpermanganate, potassium
dichromate, etc. Even mild oxidising agents, mainly Tollens reagent and Fehlings reagent also oxidise
aldehydes.
Ketones are generally oxidised under vigorous conditions, i.e., strong oxidising agents and at elevated
temperatures. Their oxidation involves carbon-carbon bond cleavage to afford a mixture of
carboxylic acids having lesser number of carbon atoms than the parent ketone.
The mild oxidising agents given beloware used to distinguishaldehydes fromketones:
(i) Tollens test: 0n warming an aldehyde with freshly prepared ammoniacal silver nitrate solution
(Tollens reagent), a bright silver mirror is produced due to the formation of silver metal.
The aldehydes are oxidised to corresponding carboxylate anion. The reaction occurs in alkaline
medium.
(ii) Fehlings test: Fehling reagent comprises of two solutions, Fehling solutionAandFehling solution
B. FehlingsolutionAis aqueous copper sulphate and FehlingsolutionBis alkaline sodiumpotassium
tartarate (Rochelle salt). These two solutions are mixed in equal amounts before test. 0n heating an
aldehyde with Fehlings reagent, a reddish brown precipitate is obtained. Aldehydes are oxidised to
corresponding carboxylate anion. Aromatic aldehydes do not respond to this test. (4)
5. ALDOLCONDENSATION :
This reaction involves the condensation of carbonyl compounds (aldehydes or ketones) with at least one o-
hydrogen in the presence of aqueous alkali to formaldols i.e. |-hydroxy carbonyl compounds.
R'
aq Na0H
2 R - CH - C - R' R - CH - C - CH - C - R'
2 2
0 0 0H R
|-Hydroxy carbonyl
compounds
13
Carbonyl Compound
All aldols on heating in the presence of alkali formo,|-unsaturated carbonyl compounds.
R'
R' H
alkali or base
A
R - CH - C = C - C - R' R - CH - C - C - C - R'
2 2
0 R 0
0H R
e.g. condensation between acetaldehyde molecules
2 Na0H
2 CH
3
CH0 CH
3
- CH - CH
2
- CH0
0H
0H
A
CH
3
- CH = CH - CH0
Crotonaldehyde
CH
3
- CH - CH
2
- CH0
0H
Mechanism of Aldol condensation.
The carbonyl compound form the carbanion due to the hyperconjugating H-atoms.
0H
R - CH - C - R' + H

(H
+
+ 0H
-
H
2
0) R - CH
2
- C - R'
0 0
Carbanion
R
R'
+ R - CH - C - R' R - CH
2
- C - R' R - CH
2
- C - CH - C - R'
0
0 0 0
R'
R
R' R
R - CH
2
- C - CH - C - R'
+ H
R - CH
2
- C - CH - C - R'
0 0 0
0H
0ther examples of aldol condensations
(i) Propanaldehyde
0H
CH
3
- CH
2
- CH - CH - CH0
2CH
3
- CH
2
- CH0
CH
3
0H
A
0H
CH
3
- CH
2
- CH = C - CH0
CH
3
14
Carbonyl Compound
(ii) Acetone
CH
3
0H
2CH
3
- C - CH
3
CH
3
- C = CH - C - CH
3
0 0H
0H
A
0
CH
3
CH
3
- C = CH - C - CH
3
0
Mesitylene oxide
The condensation of acetone can be achieved in HCl
CH
3
CH
3
- C = CH - C - CH = C
CH
3
Dry HCl gas
(-2H
2
0)
(iii) 3 CH
3
C - CH
3
CH
3
0 0
Phorone
6. CANNIZAROS REACTION :
Aldehydes and Ketones not containing o-H atoms disproportionate in the presence of cold,
concentrated alkali to form carboxylate and alcohol.
Na0H
2 HCH0 CH
3
0H + HC00Na
A
CH0 CH
2
- 0H
C00Na
Na0H
+
2
CH
3
CH
3
- C - CH0
CH
3
Na0H
(CH
3
)
3
CC00Na + (CH
3
)
3
CCH
2
- 0H
Mechanism
(a) Nucleophille attack
0H
H - C - H
0
H - C - H + 0H
0
(b) Release of H
0H
H - C - H
0
H - C - 0H + H
0
(c) Attack of H on carbonyl compound
H
H - C - H + H H - C - H
0
0
15
Carbonyl Compound
Proton Exchange
H - C - 0- H H - C - 0 + CH
3
0H
+ CH
3
- 0
0 0
7. REFORMATSKY REACTION :
It is the condensation of a carbonyl compound with o-Bromo esters to form |-hydroxy esters
0ZnBr
R - C - CH - C - 0R'
R''
0H
Zn/ether
Reflux
H
2
0
R - C - H + R'' - CH - C00R' R - C- CH - C00R'
H R'' 0 0
Mechanism
Br
R'' - CH - C00R' +
Br
H
ether
R'' - CH - C00R'
Zn
Br
Zn
0ZnBr
R - C - H
+ R'' - CH - C00R'
Zn
Br
R - C - CH - C00R'
H 0
R''
0ZnBr
0H
R - C- CH - C00R'
H
2
0
R - C - CH - C00R'
H R'' H R''
B-Hydroxy ester
Example:
0ZnBr
CH
3
- C - CH
2
- C00C
2
H
5
H
Zn
ether
CH
3
- C - H + CH
2
- C00 C
2
H
5
0 Br
0ZnBr
CH - C - CH - C00C H
0H
H
2
0
CH - C - CH - C00C H 3 2 2 5
3
2
2 5
H
H
0ZnBr
CH0
CH - CH
2
- C00C
2
H
5
0
-
+ CH
2
- C00 C
2
H
5
Zn
ether
0ZnBr
0H
CH - CH
2
- C00C
2
H
5
CH - CH
2
- C00C
2
H
5
H
2
0
16
Carbonyl Compound
8. PINACOLE REDUCTIONS (BIMOLECULAR REDUCTION) :
Ketones are reduced in neutral or alkaline medium to pinacoles..
This conversion is not observed in aldehydes.
0H 0H
Mg - Hg /H
2
0
A
CH
3
- C - CH
3
CH
3
- C - C - CH
3
CH
3
CH
3
PINAC0LE
Ph Ph
0
0
C
Mg - Hg /H
2
0
Ph- C - C - Ph
0H 0H
PINAC0LE
Pinacole Pinacolone Rearrangement
When Pinacoles are treated with dilute acids they undergo dehydration via rearrangement
to form
CH
3
CH
3
Pinacolene. CH
3
- C - C - CH
3
0H 0H
CH
3
CH
3
CH
3
- C - C - CH
3
CH
3
CH
3
- C - C - CH
3
H
2
S0
4
0
CH
3
CH
3
CH
3
CH
3
- C - C - CH
3
0H
2
0H
H
+
/H
2
0
0H 0H

CH
3
CH
3
- C - C - CH
3
CH
3
CH
3
CH
3
C C CH
3
0 - H
0H
2
CH
3
0
+ HS0
4
Benzilic Acid Rearrangement
The reaction in which benzil is converted to benzilic acid by treatment with K0H is called Benzil-Benzilic
acid rearrangement
0H
0 0H 0
H
+
/H
2
0
C C00H
C C C C00 K0H
A
Benzillic acid
Mechanism
0 0
0 0
C C
0H
C - C - 0H
17
Carbonyl Compound
0H
C - C - 0
0
C - C - 0H
0
0
0H
C - C - 0H
0H
C - C - 0
H
+
/H
2
0
0
0
Benzilic acid
9. KNOVENGEAL REACTION :
It is the condensation of any carbonyl compound with compounds containing active methylene compound
in the presence of pyridine.
CH0 CH = CH - C00H
C00H
Pyridine
- H
2
0, - C0
2
2
+ CH
2
C00H
C00H CN
CN
Instead of CH
2
we can also use CH
2
or
CH
2
C00H C00H
CN
Mechanism
C00H
C00H

CH + H
CH
2
C00H
C00H
0H
H - C - CH
0
H - C
C00H C00H
CH
C00H C00H
0H
H- C - CH
C00H
C00H
CH = CH - CH - C00H
(- H
2
0)
(- C0
2
)
0H
CN
Pyridine
CH
3
- C - CH - CN
CH
3
- C - H + CH
2
C00H
H
0 C00H
18
Carbonyl Compound
0H
- H
2
0
- C0
CH - C - CH - CN
CH - CH = CH - CN
3
3
2
H C00H
10. CLAISEN SCHMIDT CONDENSATION :
It is the condensation between benzaldehyde and another carbonyl compound containing o-hydrogen
atom in the presence of a base like Na0CH
3
or Na0C
2
H
5
.
0H
CH0 CH - CH
2
- CH0
Na 0C
2
H
5
+ CH CH0
3
Mechanism : - In the presence of alkoxide or base the carbanion is formed.
CH
2
- CH0 + H
.
CH
3
- CH0
0
0
C - CH
2
- CH0
H
C - H CH
2
- CH0
0
0H
H - C - CH
2
- CH0
CH - CH
2
- CH0
H

0H
CH = CH- CH0
CH - CH - CH0
2
Base
A
Cinnamaldehyde
(ii) Electrophilic substitution reaction: Aromatic aldehydes and ketones undergo electrophilic
substitutionat the ring inwhich the carbonyl group acts as a deactivating and meta-directing group.
11. USES OFALDEHYDES & KETONES :
In chemical industryaldehydes and ketones are used as solvents, starting materials and reagents for the
synthesis of other products. Formaldehyde is well known as formalin (40%) solution used to preserve
biological specimens and to prepare bakelite (a phenol-formaldehyde resin), urea-formaldehyde
glues and other polymeric products. Acetaldehyde is used primarily as a starting material in the
manufacture of acetic acid, ethyl acetate, vinyl acetate, polymers and drugs. Benzaldehyde is used in
perfumery and in dye industries. Acetone and ethyl methyl ketone are common industrial solvents.
Many aldehydes and ketones, e.g., butyraldehyde, vanillin, acetophenone, camphor, etc. are well
known for their odoursand flavours.
19
Carbonyl Compound
Q.1 Name the following compounds according to IUPACsystemof nomenclature.
(i) CH CH(CH )CH CH CH0 (ii)
(iv)
CH CH C0CH(C H )CH CH Cl
3 3 2 2 3 2 2 5 2 2
(iii) CH CH = CHCH0 CH CH(CH ) CH C (CH ) C0CH
3
(v) (CH ) CCH C00H
3 3 2 3 2 3
(vii) 0HCC H CH0-p
3 3 2 6 4
6-Chloro-4-ethylhexan-3-one
Pentane-2, 4-dione
Sol. (i) 4-Methylpentanal
(iii) But-2-en-1-al
(v) 3,3-Dimethylbutanoic acid
(ii)
(iv)
(vii) Benzene-1, 4-dicarbaldehyde
Q.2 Drawthe structure of the following compounds
(i) 3-Methylbutanal
(iii) p-Methylbenzaldehyde
(v) 4-Chloropentan-2-one
(vii) p,p-Dihydroxybenzophenone
(ii) p-Nitropropiophenoen
(iv) 4-Methylpent-3-en-2-one
(vi) 3-Bromo-4-phenylpentanoic acid
(viii) Hex-2-en-4-ynoic acid
Sol. (i) (ii)
(iii) (iv)
(v) (vi)
(vii) (viii)
Q.3 Predict the product formed when cyclohexanecarbaldehyde reacts withfollowing reagents:
(i) PhMgBr and then H 0
+
(ii) Tollens reagent
(iv) Excess ethanol and acid
3
(iii) Semicarbazide and weak acid
(v) Zince amalgamand dilute bydrochloric acid.
Sol. (i)
SOLVEDEXAMPLE
20
Carbonyl Compound
(ii)
(iii)
(iv)
(v)
Q.4 Which of the following compounds will undergo aldol condensation, whichthe cannizzaro reaction and
which neither ? Write the structures of the expected product of aldol condensation and Cannizzaro
reaction.
(i) Metahanol
(iii) Benzaldehyde
(v) Cyclohexanone
(vii) Phenylacetaldehyde
(ix) 2,2-Dimethylbutanal.
(ii) 2-Methylpentanal
(iv) Benzophenone
(vi) 1-Phenylpropanone
(viii) Butan-1-ol
Sol. (a) 2-Methylpentanal, cyclohexanone, 1-phenylpropanone, and penylacetaldehyde contain one or
more
o- hydrogens and hence undergo aldol condensation. The reactions and the structures of the expected
products are give below:
(ii)
21
Carbonyl Compound
(v)
(vi)
(vii)
(b) Methanal, benzaldehyde and 2,2-dimethylbutanal do not containo-hydrogen and hence undergo
Cannizzaro reaction. The reaction and the structures of the expected products are give as follows ;
2HCN0
C

onc

.Na0

H
CH 0H+ HC00Na
3
Methanol
Conc. NaoH
(i)
Methanal Sod.methanoate
(iii)
(ix)
(c) (iv) Benzophenone is a ketone having no o-hydrogen whereas (viii) butan-1-ol is an alcohol both of
these neither undergo aldo condensation nor Cannizzaro reaction.
Howwill you convert ethanal into the following compounds ?
(i) Butane-1, 3-diol
(ii) But-2-enal
(iii) But-2-enoic acid.
Q.5
22
Carbonyl Compound
Sol. (i)
(ii)
(iii)
Q.6 Write structural formulas and names of the four possible aldol condensation products frompropanal and
butanal. In each case indicate served as electrophile and whichas nucleophile.
(i) Propanal serves as nucleophile and also as elecstrophile. Sol.
(ii) Butanal serves both as nuclephile and anelectrophile.
(iii) Butanal serves as electrophile andpropanal as nucleophile.
(iv) Propanal serves as electrophile and butanal as nucleophile.
Ex.7 An organic compound (A) which has a characteristic odour, on treatment with Na0H forms two
compounds (B) and (C). Compound (B) has the molecular formula C H 0which on oxidation gives
7 8
back compound (A). Compound (C) is the sodiumsalt of an acid (C) when heated with sodalime yields
an aromatic hydrocarbon (D). Deduce the structures of (A), (B), (C) and (D).
23
Carbonyl Compound
Sol. (C) is the sodiumsalt of acid and (B) maybe alcohol because onoxidation it give aldehyde (A). (A) on
treatment with Na0H gives the alcohol and an acid of same carbon atoms. This reaction also indicates
that aldehyde (A) does not have o-carbon atom. (because it gives cannizarro's reaction). The molecular
formula of (B), C H 0suggests that it should be benzyl alcohol, C H CH 0H. Hence, (C) should be
7 8 6 5 2
C H C00Na and (A) should be C H CH0 (same carbon atoms). The sequence of reactions can be
6 5
shown as :
CH0
6 5
CH
2
0H C00Na
Na0H
2 +
Benzaldehyde
(A)
Benzyl alcohol
(B)
Sodium benzoate
(C)
Na0H
+
Ca0
heat
0xidation
[0]
Benzene
(D)
Ex.8
Sol.
What do you mean byK and pK values of the carboxylic acids.
a a
All the carboxylic acids release H
+
ions in aqueous medium. Theyare generallyweak acids, therefore, a
dynamic equilibrium is set up between the unionized acid molecules and their corresponding ions
(carboxylate ions and hydroniumions).
0n applying the lawof mass action,
- +
Equilibrium constant, K=
[RC00
][H
3
0 ]
[RC00H][H
2
0]
Because water is present in large excess, hence its concentration will remain constant i.e.,
[H 0] =constant. Thus
2
[RC00
-
][H
3
0
+
]
= K[H 0] = K
[RC00H]
2 a
Where K is the newequilibrium constant and is called the dissociation constant of acid. Its value varies
a
with temperature for a given acid. It is clear fromthe above expression that the value of K is directly
a
proportional to the concentration of H 0
+
or H
+
ions, therefore, the strength of an acid can be measured
3
in terms of K . Higher the value of K, greater will be the tendency of an acid to ionize, thus stronger will
a
a
be the acid.
The K values for formic, acetic and chloroacetic acid are 17.7 10
-5
, 1.75 10
-5
and 136 10
-5
a
respectively. Thus the increasing order of acidic strength will be
Acetic acid < formic acid <chloroacetic acid
The negative logarithm of the dissociation constant of acid i.e., K is known as pK value
a a
[pK = -log K ]. The acidic strengths of different acids can be compared with the help of their pK
a a a
values. Lower the numerical value of pK, stronger will be the acid. The pK values for chloroacetic
a a
acid, acetic acid and formic acid are 2.87, 4.76 and 3.75 respectively hence the chloroacetic acid is the
strongest acid among these three.
24
Carbonyl Compound
Ex.9 Write the IUPACnames for the following :
0
0 C C
2
H
5
CH
3
(i) (ii)
CH
3
CH CH
2
CH C00H
Cl
3-Chlorophenyl propanoate.
2, 4-Dimethyl-5-oxopentanoic acid
CH0
Sol. (i)
(ii)
Ex.10 Predict the major product in each of the following reactions :
0
C H
C
(i) HgS0
4
.H
3
0
+
(i) Br
2
(I equivalent)
CH
3 (a) (b)
(ii) NH
2
0H (ii) NaBH
4
(iii) Base
0 0
C C
(ii) NaBH
4
(i) Br
2
(I equi.)
CH
3
CH
3
Br
Sol. (a)
(Reduction)
- HBr
Acetophenone
H0
0
CH CH
(iii) Base
CH
2
CH
2
- HBr
1-Phenyloxirane 1-Phenyl-2-bromoethanol
0
C H
C
+
(i) HgS0
4
.H
3
0 (ii) NH
2
0H
CH
3
(b)
Phenylacetylene Acetophenone
N0H
C
CH
3
Acetophenone oxime
-H
2
0
25
Carbonyl Compound
Q.1
Q.2
Explain Knovengeal Reactionwith mechanism?
Which of the following compounds would undergo aldol condensation, which the Cannizzaro reaction
and whichneither?Write the structures of the expected products of aldol condensation and Cannizzaro
reaction.
(i) Methanal
(iv) Benzophenone
(vii) Phenylacetaldehyde
(ii) 2-Methylpentanal
(v) Cyclohexanone
(viii) Butan-1-ol
(iii) Benzaldehyde
(vi) 1-Phenylpropanone
(ix) 2,2-Dimethylbutanal
Q.3 Howwill you convert ethanal into the following compounds?
(i) Butane-1,3-diol (ii) But-2-enal (iii) But-2-enoic acid
Q.4 Write structural formulas and names of four possible aldol condensation products frompropanal and
butanal. In each case, indicate which aldehyde acts as nucleophile and which as electrophile.
Anorganic compound withthe molecular formula C H 0forms 2,4-DNPderivative, reduces Tollens Q.5
9 10
reagent and undergoes Cannizzaro reaction. 0n vigorous oxidation, it gives 1,2-benzenedicarboxylic
acid. Identifythe compound.
Describe the following reactions
Q.6
(i) Cannizzaro's reaction (ii) Cross aldol reaction
Q.7 Give chemical tests to distinguish between
(i)Acetaldehyde and Benzaldehyde (ii) Propanone andpropanol.
Q.8 Write the names of the reagents and equations in the conversion of
(i) phenol to salicylaldehyde. (ii) anisole to p-methoxyacetophenone.
Q.9 Write one chemical reaction each to exemplifythe following
(i) Rosenmund reduction (ii) Tollens' reagent
Q.10
Q.11
Explain Pinacole Pinacolone Rearrangement ?
Write reactions for obtaining
(i)Acetone fromacetic acid. (ii) Benzene fromtoluene.
Q.12 (a) Howwill you obtain an aldehyde byusing following process
(i) Dehydrogenation (ii) Catalytic hydrogenation ?
(b) (i) whydo aldehydes behave like polar compounds ?
(ii) Whydo aldehydes have lower boiling point than corresponding alcohols ?
Explain witting reactionwithmechanism?
Convert
Q.13
Q.14
(i)Acetaldehyde toAcetone (ii)Acetylene toAcetone
Q.15 Anorganic compound (A) (molecular formula C H 0) was hydrolysed with dilute sulphuric acid to
8 16 2
give a carboxylic acid (B) and analcohol (C). 0xidation of (C) withchromic acid produced (B). (C) on
dehydration gives but-1-ene. Write equations for the reactions involved.
Give simple chemical tests to distinguish between the following pairs of compounds. Q.16
(i) Propanal and Propanone
(iii) Phenol and Benzoic acid
(ii)Acetophenone and Benzophenone
EXERCISE-I
26
Carbonyl Compound
Q.17 Howwill you bring about the following conversions innot more thantwo steps?
(i) Propanone to Propene
(iii) Ethanol to 3-Hydroxybutanal
(v) Benzaldehyde to Benzophenone
Give posible explanation for each of the following:
(i) Cyclohexanone forms cyanohydrin ingood yield but 2,2,6-trimethylcyclohexanone does not.
(ii) There are two -NH groups in semicarbazide. However, onlyone is involved inthe formation of
Q.18
2
semicarbazones.
(iii) During the preparation of esters froma carboxylic acid and analcohol in the presence of an acid
catalyst, the water or the ester should be removed as soon as it is formed.
An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The molecular mass
of the compound is 86. It does not reduce Tollensreagent but forms an addition compound with sodium
hydrogensulphite and give positive iodoform test. 0n vigorous oxidation it gives ethanoic and propanoic
acid. Write the possible structure of the compound.
Write the difference between aldol condensation and cannizzaro reaction.
Acompound with molecular formula C
8
H
18
0
4
does not give litmus test and does not give colour with
2,4-DNP. It reacts with excess MeC0Cl to give a compound whose vapour densityis 131. Compound
Acontains howmanyhydroxy groups ?
Which of the following compounds will give Fehling's test positive?
Q.19
Q.20
Q.21
Q.22
(4) HC00H (5) CH
3
C C CH
3
(6)
CH
3
CH C CH
3
|| ||
0 0
| ||
0H 0
0
0Me
0
(7) (8)
Write compounds (number given to them) in increasing order in 0MRsheet.
[Hint: If compound 1,2,3 and4 is your answer, then write 1234 in OMRsheet.]
Which of the amino group in semi carbazide will react with Ph-CH= 0carbonyl group ?
0
||
H
2
N C NH NH
2
Q.23
(1) (2) (3)
Q.24 Howmanyorganic products are formed in good amount inabove reaction ?
Q.25
Howmany molecules of MeMgCl will be consumed for per molecule of phosgene Cl
||
Cl ?
C
0
27
Carbonyl Compound
(1) Ac 0, Ac0Na, A

(2)H
3
0

, A
Q.26 Reaction 1 (A)
0
||
Ph - CH = CH - C CH
3
Al(0CHMe )
Reaction 2 (B)
CH CH0H
2 3
3
|
CH
3
0H
|
Ph - CH = CH CH CH
3
(1)Na0I
Reaction 3 (C)
(2)H

Degree of unsaturation present in compound (A+ B+C) is ?


Among cycloalkanones onlycyclopropanone forms stable hydrate. Explain why?
Ahydrocarbon (A), C= 90.56%and vapour density 53 was subjected to vigorous oxidation to give a
dibasic acid (B). 0.10 g of (B) required 24.1 ml 0.05 NNa0Hfor complete neutralisation. Nitration of
(B) gave a single mononitro derivative. When (B) was heated strongly with soda lime, it gave benzene.
Identify (A) and (B) withproper reasoning and also give their structures.
Compound(A), C
6
H
12
0, forms anoxime but gives a negative Fehlings test. When (A) is reduced with
H
2
over a Pt catalyst, compound (B), C
6
H
14
0, is formed. Compound (B) is heated with conc.H
2
S0
4
to form (C), upon ozonolysis followed by hydrolysis, gives two compounds (D) and (E). Compound
(D) gives a negative Tollens test but a positive iodoformtest. Compound (E) gives a positive Tollens
test and a negative iodoformtest. Fromthis information, deduce the structures ofA, B, C, Dand E.
An organic compound A, C
6
H
10
0, on reaction with CH
3
MgBr followed by acid treatment gives
compound B. The compound Bon ozonolysis gives compound C, which in presence of a base gives
1-Acetylclopentene D. The compound Bon reaction with HBr gives compound E. Write the structures
ofA, B, C and E. ShowhowDis formed fromC.
Q.27
Q.28.
Q.29
Q.30
28
Carbonyl Compound
Complete the following equations and identifythe productsA, B, C, D, E, F, G, Hetc. inthe following
reactions
Anhydrous
AlCl
Zn-Hg
HCl
S0Cl
2
Q.1 o-H00C-C
6
H
4
-CH
2
-C
6
H
5
H I
G
3
CH
3
HBr
Peroxide
Q.2
[E]
H
2
Cr0
4
H
2
0
Cr0
3
(Pyridine)
[I]
Q.3
[J] CH
3
CH0.
NaHS0
4
0H
Q.4 Acetone (2 mol.)
[K] [L]
0
(i) Br
2
(1equivalent)
(ii) NaBH
4
CH
3 Q.5
C CH
(i) HgS0
4
, H
3
0
+
(ii) NH
2
0H
Q.6 ?
0
(i) MeMgBr
(ii) aq HCl
Q.7 ?
0Me
CH
3
CH
3
- C-CH
2
Br
CH
3
C
2
H
5
0H
A
Q.8
H
2
Lindlar Catalyst
Q.9
CH
3
F
Na0CH
3
A
Q.10
N0
2
0
Br
2
/Fe(aq)
Q.11
N
EXERCISE-II
29
Carbonyl Compound
0
1. dil. alkali
2. Heat
Q.12
0
Boil, alkali
Q.13 H
3
C-CH
2
-CHCl
2
?
K0H
Q.14 H
3
C0 CH0 + HCH0 ?
Br
2
/CCl
4
NaNH
2
HgS0
4
/H
2
S0
4
Q.15
B A C
NH
2
NHC0NH
2
C D
Na0D/D
2
0 (excess)
C E
HN0
3
/H
2
S0
4
(mononitration)
C00
Q.16 ?
0H
(CH
3
C0)
2
0
CH
3
C00Na
Q.17 ?
CH0
Na0H
CH = CH.CH0
Q.18 A' + B' ?
heat
C
Q.19 CH
3
C00H + NH
3
(0)
CH
3
NH
2 A B
Cl
2 dil. Na0H
Q.20 CH
3
CH
2
0H CHCl
3 A B
(i) alc. K0H (excess)
P and Br
2
Q.21 CH
3
CH
2
C00H
B
A
H
2
S0
4
C
2
H
5
0H
140C
moist
Ag
2
0
Q.22 C
2
H
5
I A B C
excess
NH
3
X
Q.23 CH
3
C00H ClCH
2
C00H Y
HgS0
4
H
2
S0
4
Na0I
Q.24 [A] or [B] + H
2
0 CH
3
CH
2
C0CH
3
[C] + [D]
CHCl
2
[C]
H
2
0, H
+
[A] C
6
H
6
AlCl
3
(anhy.)
Sod. acetate (anhyd.)
acetic anhydride
Q.25
[E]
CH
3
Br [B] CH
4
[D]
[F]
CH = N0H
30
Carbonyl Compound
Q.26
(1)
(2)
(3)
(4)
Explain giving reasons
Solubilityof carbonyl compounds decreases withthe increase in their molecular masses.
Sodiumbisulphite is used for the purification of aldehydes and ketones.
0xidation of toluene withchromiumtrioxide to benzaldehyde is carriedout inpresene of acetic anhydride.
Although aldehydes are easily oxidisable yet propanal can conveniently be prepared by the oxidation
of propanol byacidic dichromate.
0
0
(5)
Q.27
(1)
(2)
(3)
part of the - C - 0H group does not react withhydroxylamine hydrochloride. - C -
Give Reason
Me
3
CCH
2
C00His more acidic than Me
3
SiCH
2
C00H.
The K
2
for fumaric acid is greater than for maleic acid.
Carbon oxygen bond lengths in formic acid are 1.23 and 1.36 and both the carbon oxygen bonds
in sodiumformate have the same value i.e. 1.27 .
The reactioin CH
3
C00C
2
H
5
+ H
2
0 CH
3
C00H + C
2
H
5
0H is slow in the begining but fast
subsequently.
Although both > C = 0and > C = C < groupings have double bond, they exhibit different types of
addition reaction.
Arrange the following as directed
Decreasing order of acidity
(4)
(5)
Q.28
(1)
(i)
(ii)
(iii)
(iv)
CH
2
BrC00H, CH
2
ClC00H, CH
2
FC00H. CH
2
IC00H
o-Hydroxybenzoic acid, p-Hydroxybenzoic acid, 2, 6-Dihydroxybenzoic acid.
RC00H, R0H, RH, NH
3
, H0H, CH CH
C
6
H
5
C00H, p- 0H. C
6
H
4
. C00H, p- CH
3
. C
6
H
4
. C00H,
p-Br.C
6
H
4
.C00H,
p- Cl. C
6
H
4
C00H,
(2) Decreasing order of nucleophilic additions
(i)
(ii)
HCH0, CH
3
CH0, CH
3
C0CH
3
, Cl
3
CCH0
CH
3
C0CH
3
, C
6
H
5
C0CH
3
, C
6
H
5
C0C
6
H
5
, C
6
H
5
CH
2
C0CH
3
(3) Arrange the following inincreasing ease of hydrolysis.
CH
3
C00C
2
H
5
, CH
3
C0Cl, (CH
3
C0)
2
0, CH
3
C0NH
2
C00H
C00H
CH
3
C00H
CH
3 H
3
C
(4) (i)
CH
3
CH
3
(ii) CH
3
CH
2
C00H, (CH
3
)
2
CHC00H, (CH
3
)
3
CC00H
(5) Arrange the following esters inthe decreasing ease of alkaline hydrolysis.
C00CH
3
C00CH
3
C00CH
3
C00CH
3
(i)
N0
2
Cl
0CH
3
31
Carbonyl Compound
Q.29 An organic compound (A) C
9
H
12
0 was subjected to a series of tests in the laboratory. It was found that
this compound.
(a)
(b)
(c)
(d)
(e)
Rotates the plane of polarised light.
Evolves hydrogen withsodium.
Reacts with I
2
and Na0Hto produce a pale yellow solid compound.
Does not react with Br
2
/CCl
4
.
Reacts with hot KMn0
4
to formcompound (B) C
7
H
6
0
2
whichalso be synthesised by the
reaction of benzene and carbonyl chloride followed by hydrolysis.
Loss optical activityas a result of formation of compound (C) on being heated with HI and P.
Reacts Lucas reagent inabout 5 min. Give structure ofAand Cwith proper reasoning and draw
Fischer projections for (A). Give reactions for the steps wherever possible.
(f)
(g)
Q.30 When 0.0088 g of a compound (A) was dissolved in 0.5 g of camphor, the melting point of camphor
was lowered by 8C. Analysis of (A) gave 68.18% C and 13.63% H. Compound (A) showed the
following reactions :
(a)
(b)
It reacted withacetyl chloride and evolved hydrogen with sodium.
When reacted withHCl + ZnCl
2
, a dense oilylayer separated out immediately. Compound (A)
was passed overAl
2
0
3
at 350Cto give compound (B) which onozonolysis gives (C) and (D)
whichgave positive test withcarbonyl reagents but only(C) gave a positive test with Fehling
solutionand resinoussubstance withNa0H. Identify(A), (B), (C) and(D) withproper reasoning.
K
f
for camphor = 40 Kkg mol
-1
.
32
Carbonyl Compound
N

a0

A
Q.1 (A)
Reactant (A) is
0 0 0 0
|| || || ||
(A) (B) CH C(CH ) C H CH
3
C (CH
2
)
5
C CH
3 3 2 4
0 0
0
||
(D) CH
3
C (CH
2
)
4
CH
2
0H
|| ||
(C)
H C (CH
2
)
5
C H
0
||
CH
3
C CH
2
CH
3
Product Bis:
0
CH
3
C0
3
H CH
2
N
2
Q.2 A(Major) B(Major)
0
||
(B)
CH
3
C 0 CH
2
CH
2
CH
3
0
||
(D) CH
3
C 0 CH
2
CH
3
||
(A) CH
3
0 C CH
2
CH
2
CH
3
0
||
(C)
CH
3
CH
2
C 0 CH
2
CH
3
Q.3 The product 0ctalone is obtained by Michael addition followed by aldol condensation of reactants R
and Sin presence of a base. S gives positive iodoformtest.

,A

0ctalone
R + S
Rand S are respectively:
(A) + CH
3
-CH=0 (B) + CH
2
= CH C H
||
0
CH
2
= CH C CH
3
(C) + (D) + CH
3
CH
2
C CH
3
||
0
||
0
Q.4
The conversion is carried out byusing whichof the following
(A) NaBH
4
(B) LiAlH
4
(C) Pd/H
2
(D) Na-Et0H
EXERCISE-III
33
Carbonyl Compound

a0

Q.5 Me
2
CH - CH0
A
Major product of this reaction is :
0H Me Me
|
(B) Me
2
C = CH C CH0
|
Me
(D) Me
2
CH - C00H
| |
(A) Me
2
CH CH C CH0
|
Me
(C) Me
2
CH - CH
2
- 0H
Q.6 Which of the following compounds canundergo aldol condensation.
(A) Me
3
C-CH0 (B) PhCH0 (C) MeCH0 (D) HCH0
0
||

H
(Z)

3
P

Li
(Y)
A
Q.7 (X)
End-product (Z) in above reaction.
(A) (B) (C) (D)
B

a (0

)
2

A
Q.8 (X)
Major product (X) is:
(A) (B) (C) (D)
0
||
Q.9
NH CH
(X) Major.
CH
3
C CH
3

A
Major Product (X) is
NH= CH
2 NH N CH
3
||
(C) CH
3
C CH
3
NHCH
3
|
(D) CH
3
CH CH
3
|| |
(A) CH
3
CH CH
3
(B) CH
3
C CH
3
0
||
CH
3
C CH
3
(A) Iodoform
0
||
and CH
3
C H Q.10 is differentiated by
(B) NaHS0
3
(C) 2,4-DNP (D) None
Q.11 Conversioncan be achieved by
(A) Clemmenson reduction (B) Wolf-Kishner reduction
34
(C) CH
3
CH
2
- CH0 (D) CH
3
- CH
2
- CH0
O
Carbonyl Compound
Q.12 If 3-hexanone is reacted with NaBH
4
followed by hydrolysis with D
2
0, the product will be
(A) CH
3
CH
2
CH(0D)CH
2
CH
2
CH
3
(C) CH
3
CH
2
CH(0H)CH
2
CH
2
CH
3
Z

n H

(B) CH
3
CH
2
D(0H)CH
2
CH
2
CH
3
(D) CH
3
CH
2
CD(0D)CH
2
CH
2
CH
3
Q.13 A
HCl
Final major product of this reaction is
14
(A) CH
3
CH
2
CH
3
14
CH
3
CH
2
CH
3
14 14
(B)
||
Which of the amino group in semi carbazide will react with carbonyl group H
2
N C NH NH
2
Q.14
(1)
(D) 1 & 3
(2) (3)
(A) 1 (B) 2 (C) 3
Q.15 + Me
2
C = 0
d

ry H

Cl

Ais ?
(A) (B) (C) (D)
Q.16 CompoundA(molecular formula C
3
H
8
0) is treated with acidified potassiumdichromate to forma
product B(molecular formula C
3
H
6
0). Bforms a shining silver mirror on warming with ammoniacal
silver nitrate, Bwhen treated with an aqueous solution of NH
2
NHC0NH
2
and sodiumacetae gives a
product C. Identifythe structure of C.
(A) CH
3
CH
2
CH = NNHC0NH
2
(B) CH
3
C = NHHC0NH
2
|
CH
3
(D) CH
3
CH
2
CH = NC0NHNH
2
(C) CH
3
C = NC0NHNH
2
|
CH
3
Q.17 When cyclohexanone is treated with Na
2
C0
3
solution, we get
(A) (B) (C) (D)
K

A
Q.18 + CH
3
CH0 P is ?
(A) CH
3
CH
2
-C0CH
2
CH0 (B)
(C) (D)
35
Carbonyl Compound
Bu-CCH
L

iN

H
2

A

M

n0

2
C

i) P

hCH

B
Q.19 D
(ii ) H
2
0
Compound Dof the above reaction is
(A) (B) (C) (D)
Et0Na
+ HC0
2
Et (X), Identify unknown (X) in reaction Q.20
(A) (B) (C) (D)
0H 0
| ||
(B)
(82%)

a
2

0
40C
CH
3
CH CH
2
C H
3
Q.21 (A), 3HCH0 +A
(Retro aldol)
Product (B) of above reaction is
CH
2
0H
|
CH0
|
H0 CH
2
C CH0
|
CH
2
0H
(A) (B) H0 CH
2
C CH
2
0H
|
CH
2
0H
CH
2
0H
|
H0 CH
2
C CH
2
0H
|
CH0
CH0
|
(D) H0 CH
2
C CH
2
CH
2
0H
|
CH
2
0H
(C)
Q.22 Principal product of following reaction is isolated in formof CH
2
= C= 0+ H
2
S ?
SH
|
CH
2
= C
|
SH
0
||
(B) CH
3
CSH
0H
|
(D) CH
2
= C SH
(A) (C) CH
3
C 0H
||
S

2
H

Q.23 (X) (Y) + N . the structures of (X) and (Y) are


2
(A) and (B) and
(C) and (D) and
36
Carbonyl Compound
H
3
0

Q.24 (A) + (B) formed can be distinguished by

(B) Fehling (A) Iodoform (C) NaHS0


3
(D) 2,4-DNP

aB

H
3
C

Q.25 (X) + (Y) C


6
H
5
CH
2
NHCH
2
CH
3
methanol
(X) and (Y) are
(A) C
6
H
5
CH
2
0H + C
2
H
5
NH
2
(C) C
6
H
5
CH0 + CH
3
NHCH
2
CH
3
(B) C
6
H
6
+ CH
3
NHCH
2
CH
3
(D) C
6
H
5
CH0 + C
2
H
5
NH
2
H
+
H
+
(C) (major). Product C is
A

aB

(B)
Q.26 (A)

(A) (B) (C) (D)


Q.27
Above compound is hydrated maximumat whichposition?
(A) 1 (B) 2 (C) 3 (D) equal
Q.28 Et C Me is prepared as one of the products by dry distillation of calcium salt of which of the
||
0
following acids:
(A) ethanoic acid and methanoic acid (B) Propanoic acid and methanoic acid
(C) Propanoic acid and ethanoic acid (D) None of these
Similar as Q.30 in Carboxylic acids Q.29
Reagents A&Bare
(A) H
2
/Pd and LiAlH
4
(C) NaBH
4
& LiAlH
4
The end product of the reaction is
(B) LiAlH
4
&NaBH
4
(D) LiAlH
4
&H
2
/Pd
Q.30

l
2
(

1e

q.)

(A)
hv

aB

H
4

(B)

0H
(A) (B) (C) (D) None
37
Carbonyl Compound
Q.31 The reagent used to distinguish ethanol &acetone is
(A) Schiff's reagent
(C) Ceric ammoniumnitrate
(B) Fehling's solution
(D) iodine with Na0H
Q.32 Which one of the following compounds is the best candidate for being prepared by an efficient mixed
aldol addition reaction?
0
||
CCHCH
3
|
CH
2
0H
0H
0
| ||
CCH
2
CH
|
CH
3
(A) (B)
0 0
0
||
CH
2
CCHCH
3
|
H0 C CH
3
|
CH
3
|| ||
CCH
2
CCH
3
(C) (D)

2
0

A Q.33 PhMgBr + 2PhCH0


(A) Ph
2
CH-0H
B, B is ?
(C) PhCH
2
-0H
A
(B) Ph
3
C-0H (D) Ph-0H
- -

,A

A
0

,A

Q.34 CH
3
CH0 B, B is ?
aldol aldol
(A) CH
3
(CH=CH)
3
CH0
(C) CH
3
(CH=CH)
2
-CH0
(B) CH
3
CH=CHCH0
(D) none is correct
Q.35 PhCH0&HCH0 will behave differentlywith whichof the following reagents
(A) Tollen's Reagent (B) Fehling Solution (C)Schiff's reagent (D) NaBH
4

e0

Me0H
Q.36 Major product of this reaction is
(A) (B) (C) (D)
38
Carbonyl Compound
Q.37 In the given reaction
Product will be:
(A) 1 mole HC00Hand 1 mole HCH0
(C) 2 mole HCH0 and 1 mole HC00H
In the given reaction
(B) 2 mole HC00Hand 1 mole HCH0
(D) 2 mole HCH0 and 4 mole HC00H
Q.38
Br 0
| ||

2
N

H
2

/ alc

.K0

A
CH
3
CH
2
CH C CH
3
0
X, [X] will be:
Br
|
(B) CH
3
CH CH
2
CH
2
CH
3
(D) CH
3
-CH
2
-CH
2
-CH
2
-CH
3
||
(A) CH
3
CH = CH C CH
3
(C) CH
3
-CH=CH-CH
2
-CH
3
Q.39 Compound (X) C H 0, which gives 2,4-Dinitrophenyl hydrazine derivative (orange or red or yellow
4 8
colour) and negative haloform
test.
0
||
(A) CH
3
C CH
2
CH
3
(B) CH
3
CH CH0
|
CH
3
(D) CH - CH - CH - CH0 (C)
3 2 2
Q.40 Which of the following reaction is not representing major product.
0
||
C NHCH
H
+
CH (A)
3 3
A
14
CC (B)
P

Li
CH
3
0
||
Ph C NH
2
Br
(C)

2
Ph-NH
2
K0H
H

H
2
S0
4
(D)
39
Carbonyl Compound
0 0
|| ||
K0H
Q.41 Possible products are: CH
3
C CH
2
CH
2
CH
2
CH
2
C CH
3
A
(A) (B) (C) (D)
Q.42 The given reaction can be performed bythe use of which of the following reagents?

(A) KMn0
4
/ H
2
S0
4
(C) Ag
2
0 / Na0H
(B) K
2
Cr
2
0
7
/ H
2
S0
4
(D) LiAlH
4
Q.43 Citral can be converted into geraniol bythe use of
whichreagent :
(A) H
2
/Pd-C
(C) H
2
/Pd-BaS0
4
-CaC0
3
(B) LiAlH
4
(D) NaBH
4
H
3
0

Q.44 (A) + (B) formed cannot be differentiated by

(B) Fehling (A) Iodoform


Comprehension 1 :
0
||
(CH
3
)
3
C C CH
3
(C) NaHS0
3
(D) 2,4-DNP
0
||
58%
(CH
3
)
3
C C CH
2

Br
(a)
0H
|

8%
(CH ) C C CH
Br
3 3 2
|
H
Q.45 Suggest a reagent appropriate step (a) the synthesis:
(A) H0
Q
/Br
2
(1mole) (B) H
+
/Br
2
(1mole) (C) both (D) None
Q.46 Yield of each step as actuallycarried out in laboratory is given above each arrow. What is overallyield
of the reaction?
(A) 60% (B) 21% (C) 40% (D) 68%
40
Carbonyl Compound
Comprehension 2 :
0
||
(CH
3
)
3
C C CH
3
0
||
58%
(CH
3
)
3
C C CH
2

Br
(a)
0H
|

8%
(CH ) C C CH
Br
3 3 2
|
H
Q.47 Suggest a reagent appropriate step(a) the synthesis:
(A) H0
Q
/Br
2
(1mole) (B) H
+
/Br
2
(1mole) (C) both (D) None
Q.48 Yield of each step as actuallycarried out in laboratory is given above each arrow. What is overallyield
of the reaction?
(A) 60%
Match the Column:
(B) 21% (C) 40% (D) 68%
Q.49 ColumnI ColumnII

aN

0
2
(C)
HCl

tracesof K0H

L

iA

H
4
(B)
(A) (A) (P) Formation of six member ring takes place
H
+
(B)

N

H
2

(A)

(B)
A

L

(C) (Q) Final product is Ketone


0 0
|| ||
H0

A
(C) CH
3
C CH
2
CH
2
CH
2
C H (A) (R) Final product formed will give
positive Tollen's test
H

A
(D) (A) (S) Final product formed will react
with 2,4-DNP. (2,4-Di-nitrophenyl hydrazine)
ColumnII Q.50 ColumnI
Me
C = N c

onc

.H
2

S0

Product (A) (P) Carbene formation is involved


A
Et
0
0H

PB

A
Product
A
(B) (Q) Nitrene formation is involved
(C) CH
2
= CH
2
+ HN
3

Product (R) Carbocationformation is involved

HC

l
3

K0H/ excess
(D)
Product
(S) Final product is a cyclic compound
(T)Azoniumionformationis involved
41
Carbonyl Compound
EXERCISE - I
Q.5
Q.15
2-Ethylbenzaldehyde
(A) CH CH CH C00CH CH CH CH , butyl butanoate
3 2 2
(B) CH CH CH C00H
2 2 2 3
3 2 2
(C) CH CH CH CH 0H
3 2 2 2
methyl ketone (CH C0CH CH CH ) Q.19
Q.23
Q.27
Q.21 0002
Q.25 3
Q.22 1346
Q.26 17
3 2 2 3
Q.24 2 3
Hydrates have two 0Hon same carbon therefore theyare unstable but in cyclopropanone
formation of hydrates will releive theoretical angle strain therefore it is stable.

2
0

Theoritical angle strain


Me
60
C00H
49.28"
C00H
N0
2
Q.28 A= B = C =
Me C00H C00H
0
Me
CH - C - Et
Q.29 A= B = (Me)
2
CH - CH - Et
C = (Me) C = CH - Et
2
Me
0H
E = Propanaldehyde D=Acetone
Me
0 Me - C = 0
Q.30 A= B = D =
EXERCISE - II
0
0
Me
C - Cl
Q.1 G = H = I =
Q.2
Br
CH
2
J = CH
3
C00H I = CH
3
CH-0H
Q.3
0H
0
0
Me
Q.4 K = Me - C - CH
2
- C - Me L =
C = C - C - Me
Me
Me
0 0H
C - CH
2
- Br CH - CH
2
Br
Q.5
ANSWERKEY
42
Carbonyl Compound
N - 0H 0H
Me
C - CH
3 Me
Me
Q.6 Q.7 Q.8 C = CH
2
- Me
Me
0CH
3
Me
0
H
Q.9 Q.10 Q.11 Br
N
H
CH
2
0H
HC00K
Me0
Q.12 Q.13 CH
3
CH
2
CH0 Q.14
Br Br
0
Q.15 A = B = C =
0
0
NH-NH-C D
D D = E =
NH
2
D
0H
0
CH = CH - C - 0- H
Q.16 H = N0
2
Q.17 G = C 0
0
CH0
Q.18 A' =
B' = CH
3
CH0
Q.19
Q.20
A = CH
3
C00NH
4
A = CH
3
CH0
B = CH
3
C00NH
2
B = CCl
3
CH0
C = Br
2
/K0H
Q.21 A= CH
3
CH - C00H
Br
B = CH
2
=CH-C00H
Q.22 A = C
2
H
5
0H B = CH
2
= CH
2
Q.23 X = Cl
2
+ Red P Y =
CH
2
C00H
NH
2
A = CH
3
-CC-CH
3
B = CH
3
-CH
2
-CCH
CH
3
Q.24 C = CH
3
CH
2
C00Na D = CHI
3
CH0
B =
Q.25 A= Br
2
/ hv C = Cl
2
/hv D =
CH = CH - C00H
E = F = NH
2
-0H
43
Carbonyl Compound
Q.28 (1)
(iii)
(2)
(3)
(4)
(5)
(i) c > b > a > d (ii)
(iv)
(ii)
c > a > b
f > d > e > a > c > b
d > a > b > c
a > b > e > f > d > c
(i)
(i)
(i)
a > d > b > c
b > c > a > d
a > b > c (ii) a > b > c
c > d > a > b
0H
C00H
CH
2
CH
2
CH
3
CH
2
- CH - Me
Q.29 A = B = C =
Q.30 A= 2-Methyl butan-2-ol. B = 2-Methyl but-2-one C = Ethanol D = Propanone
EXERCISE - III
Q.1
Q.8
Q.15
Q.22
Q.29
Q.36
Q.43
Q.49
B
A
B
C
C
B
B,D
Q.2
Q.9
Q.16
Q.23
Q.30
Q.37
Q.44
B
C
A
B
C
D
B,C,D
Q.3
Q.10
Q.17
Q.24
Q.31
Q.38
Q.45
C
D
C
A
C
C
C
Q.4
Q.11
Q.18
Q.25
Q.32
Q.39
Q.46
A
B
A
D
B
B,D
B
Q.5
Q.12
Q.19
Q.26
Q.33
Q.40
Q.47
Q.50
C
A
D
C
C
A,B,D
C
Q.6
Q.13
Q.20
Q.27
Q.34
Q.41
Q.48
C
B
C
B
A
B,C
B
Q.7
Q.14
Q.21
Q.28
Q.35
Q.42
B
C
C
C
B
A,B,C
(A) P, Q, S; (B) P; (C) P, Q, S; (D) P, Q, S (A) R, (B) R,S (C) Q,S (D) P
44