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Aldehydes & Ketones

Subjective Problems
LEVEL – I

1. a) O OH

2,4cyclohexadiene-1-one Phenol (enol form)


(keto form)

Phenol is aromatic, so equiulibrium is shifted to the right hand side.


b) O O

Base
H
This ketone is more acidic because the resulting enolate ion obey's Huckel's rule
and is thus more stable.

2. a) i) ClCH2CH2CHO   ClCH2CH2CH(OEt)2
EtOH
HCl
KOH
EtOH

HOH2CCHOHCH(OEt)2  
 CH2 = CH – CH(OEt)2
KMnO 4

NaOH

H3O+

HOCH2CHOHCHO
This is called protection of carbonyl group.
ii) Proceed via same procedure
b) O OH OH

H= J= K=
O O
CH CH CHO
O O
3. a) +
OH
fast
CH3 – C – CH3 + H3O+ CH3 – C – CH2 – H
||
O slow

H3O+ + CH3 – C = CH2 + Br – Br


O–H
H2O

H3C C– – CH2Br + Br– + H3O


||
O

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In the r.d.s. bromine molecule is not used np. Hence the rate law does not
contain the concentration of Br2 i.e. the rate law is zero order with respect to
bromine.
b) i) Only double (C = C) bond is affected
O
A=

ii) Carbonyl group as well as double bond is reduced


OH
B=

iii) OH
C=

iv) OH

D = CH3 – C – CH2 – CH3

D
v) OD

E = CH3 – C – CH2 – CH3


a) PhCHO 3   PhCH(OH)CH3   Ph C – CH3
1. CH MgI H
4.
2. H3 O  K Cr O || 2 2 7

O
Ph – C – CH3   Ph C – CH2Br
Br 2

|| AlCl
|| 3

O O
Ph C – CH2Br + Ph3P  Ph3P+CH2COPh   Ph3P = CHCOPh
Na CO 2 3

||
O
PhCHO

PhCH = CHCOPh + Ph3PO

b) A: C6H5CHO B: PhCH(OH)COPh
C: C6H5CH = CHCOOH D: C6H5CHBr – CHBr – COOH
Cinnamic acid

5. This reaction is carried out in a solution of NaOH containing deuterium oxide (D2O).
If the solvent supplies the hydrogen benzyl alcohol produced will contain some
deuterium. If no deuterium is present the hydrogen must have come from a molecule
of benzaldehyde.

6. a) A contains one side chain only, now


C8H6O2 = C6H5 + C2HO2

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Also the D.B.E. of A is 8 + 1 – 6/2 = 6


Three double bonds and one ring account for benzene. Hence the side chain
contains two double bonds
 C8H6O2 = C6H5 – C – CHO
||
O
A on treatment with NaOH and then acid gives B, C8H8O3. The side chain is now
C2H3O3. Since acidification was necessary, this suggests that a Na salt was
formed first i.e. side chain now contain a carboxyl group. Also the D.B.E. of B is 8
+ 1 – 8/2 = 5.
Hence the side chain now contains one double bond (4 accounted for by
benzene). A structure of B which fits the fact is
C8H8O3 = C6H5 – CHOHCO2H
Since keto-group has been reduced and aldehyde group oxidises then is a case
of internal cannizaro reaction.

OH O– OH
OH– 
PH – C – CHO Ph – C – C – O– 
 Ph – C – C = O
H
shift
Proton exchange
O O H H

H2O + PhCO2H + CO2  PhCHOH – CO2H 
[ O]
 Ph – CHOH – C – O
H3O

O
b) The salt of the ketone is resonance stabilized
+
O OH  OH
+
H
etc.

7. a) O–

MeO C – Me  MeO+ C – Me


|| – OMe having + R

O
O O–
+
N+ C – Me  N+ C – Me 
|| ||
O 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

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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.

8. a) PhCO2H   PhCOCl 
SoCl

 PhCONMe2 
Me NH
2
 PhCHO
Li ( OEt ) AlH
2 2 2

9. a) I does not undergo haloform reaction whereas II does.


b) A: CH3CHO > CH3COCH3 > CH3COC6H5 > C6H5COC6H5
B: CF3CHO > CH3CHO > CH2 = CHCHO
10. a) Ph COPh Ph OH
C C
 PhCONHCOPh

|| 
H
 ||
N NCOPh
HO
Syn phenyl

Ph C – Ph HO COPh
C || C
O  Ph C – C –NHPh

|| 
H
 ||
N PhN || ||
O O
OH
antiphenyl

Here anti migration takes place


b) i) The  bond in >C=NOH prevents free rotation and threfore geometric
isomerism exists if the groups on the carbonyl carbon are different
ii) The order of electropositivity is Mg  Zn  Cd. The order of ionic character is
 s
Mg – C  Zn - C Cd – C in M R . The order of nucleophilicity of R is MgR 
ZnR CdR. Therefore, BrMgCH2COOEt reacts with  C = O of the ester
BrCH2COOEt. BrZnCH2COOEt can only react with RRC = O to be the
Reformatsky reaction .
v) In presence of Lewis acid, due to formation of anilinium ion, unexpected
m.substituted derivatives are formed.

11. MeCH = CH – CHO + HCN   MeCH = CHCH(OH)CN


OH

1, 2 addition is favoured because of high reactivity of aldehyde group.


12. CH2 = CH – C – H  C H2 – CH = CH – O–
||
O

CH3CH2 – C – H  H3C – CH2 – C H – O–
||
O
Because of conjugation in acraldehyde the charges and the distances between them
are both greater than the corresponding values in propionadehyde. Hence the former
has greater .

13. O
CH2 = CH –C – Me   CH2 ––– CHC–
1. H2O 2
– Me
|| 2. OH ||
O O
Mechanism H2O2 + O–H  H2O + HO – O–

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C = C – C = O  C – C = C – O–  C – C – C = O + OH
O –– OH O
O –– OH

14. Since ozonolysis involves fission at double or triple bonds, the formation of 3
products indicates the presence of two sites of attack. Hence an alkyne is excluded.
The positions of the two double bonds may be deduced as follows.
MeCO2H  MeCH = therefore occurs at end of chain.
Me2CO  Me2C = therefore occurs at end of chain
MeCOCO2H  CMeCH = therefore occurs in the chain

15. i) NaBH4, NaBH4 can reduce – C – Me but not – CO2Et


||
O
ii) LiBH4, NaBH4 same reason

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LEVEL – II

1. O CHOCH3
+ CH3OCH = P(Ph)3

+
+H –H
+

+
OH2
CH – OCH3 H
+H2O
+
–H2O CH = OCH3
+ +
–H +H

CH – OCH3 C–H
–CH3OH
OH O
+CH3OH

2. a)
 C H2  C – (CH2)3 – C – H
CH3 – C – (CH2)3 – C – H 
OH

|| || || ||
O O O O
O–
C–H
OH (CH2)3 CH2
CH
C


H O 2 ||
O
O
–H2O

O

b) (i) PhCH2OH + PhCOO (ii) Me3CCH2OH + Me3CCOO

(c) CH2OH+ COO
O O
3. H H

 
Base
+ BH
+
(B )

+ PhCH = CH – C
|| – Ph PhCH – CH –– C – Ph
O

+ +
+H –H

PhCH – CHC
||2 – – Ph
O

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4. a) 2-methyl 1,3-cyclohexane dione is more acidic because its enolate ion is


stabilised by an additional resonance structure.
O O O– O
CH3 CH3 CH3 CH3


H 
H

O O O O–
C.B. of A

b) In the case of the acid the double bond is activated due to the presence of a –
COOH group
O O O–
||  | 
 H CN
H2C  CH  C OH  H C  CH  C OH   CN—CH2—HC=C—OH
2
O O
||  ||
H
 CN  CH 2  C H  C OH  CN  CH 2  CH 2  C OH

5. a) (A) PhCH(OH)CH2OH
(B) PhCO2H
b) Analogous to Pinacol - Pinacolone rearrangement. Here in first step
diazotisation occurs.

6. It is an example of Knoevenagel reaction. This type condensation is favoured when


CH2(CO2Et)2 is present in excess and pipesidine is base.

N
|
H
EtCHO + 2CH2(CO2Et)2  EtCH[CH(CO2Et)2]2

7. Me(C  C)3 – C – CH = CH2   Me(C  C)3CHOHCH = CH2


NaBH 4

|| 1. H +

O 2. – H O 2

+
Me(C  C)3CH – CH = CH2

+
Me(C  C)3CH = CH – CH2OH   Me(C  C)3 – CH = CH – CH2
1. H O 2

2. H

NaBH4 reduces – C – group and the resulting alcohol undergoes the allylic
||
O
rearrangement to give more stable alcohol (in which there is increased conjugation).

8. a) We are given that


reduction
A  B
B   C
H2 SO4

C forms mono-ozonide, D
D   CH3CHO
H2 O / Zn

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The compound A gives a haloform reaction; it must contain CH3CO group. The
compound C contains a double bond as it forms mono-ozonide D. Since, the
compound D on hydrolysis gives only CH3CHO, the structure of C would be

CH3CH = CHCHO 2-butenal


(C)

The compound C is obtained by dehydration of B, thus the latter should be

CH3 –– CH –– CH2 –– CH3


|
OH 2-butanol
(B)

Finally, B is obtained by the reduction of A. Hence, the compound A should be


CH3 –– C –– CH2 –– CH3
||
O 2-butanone
(A)

The equations involved are as follows:


CH3 –– C –– CH2 –– CH3   CH3 –– CH –– CH2 –– CH3
[H ]

|| | H2SO4
O OH –H2O
(A) O (B)


O3

CH3 –– CH CH –– CH3 CH3 – CH = CH –– CH3
Zn/H2O | | (C)
O O
2CH3CHO

9.  keto acids undergo decarboxylation through the keto form via a cyclic transition
state which results in the formation of enol form of ketone product. The enol then
changes to more stable keto form. If decarboxylation of the given  keto acids could
follow this route then
CO2H
O OH O

 CO 2


(I) (II)
Structure (I) is very unstable because bridgehead carbon cannot chance its
hybridization from sp3 to sp2.

10. a) Me – C – Me Me2 – C –– CMe2


||
O
OH OH
(A)
(B)
Mechanism:
Mg  Mg2+ + 2e

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2Me – C – Me + 2e  Me – C – Me + Me – C – Me
||
O O–
O–

Me Me

Me2C –– CMe2 
H
Me – C –– C – Me

OH OH O– O–
+
H , –H2O

Me Me +
C+ –– C  
 Me3C – CMe
1, 2 Me
Me Me shift

OH O
+
–H
–H

Pinacolone Me3C – C – Me
||
O
b) Me2C=O Me2C O
 O
+ Mg  Mg Me2C +
H /H2O
Me2C O Mg
Me2C=O Me2C O

Me2C–OH H Me–C = O
Me2C–OH -H2O Me–C – Me
Me
(Pinacol – pinacolone rearr.)
11. a) The corresponding hydrate is very stable due to intra molecular hydrogen
bonding
O
||
C O O H
H
HO
Ph – C C – Ph C 2

|| || O
O O C C O

Ph Ph
b) A: HCOOH B: CO
B: COOH
|
COOH
12. A is ketone, as it forms oxime but does not reduce Tollen’s reagent.
D is aldehyde but if has no CH3 – C group
||
O
E is ketone containing CH3 – C – fragment
||
O

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Let consider D & E are RCH2CHO & RCOR respectively.


R R
RCH2CHO + O = C  RCH2CH = C
[O ] 3

R R
H2O

R R
RCH2 – C – CH 
 RCH2CH – CH
[H]

||
O R OH R
As A is C6H12O so R = R  = R = CH3
CH3 CH3
 A is CH3CH2 – C – CH C is CH3CH2CH = C
|| CH3 CH3
O
CH3
D is CH3CH2CHO
B is EtCH– CH
CH3 E is CH3COCH3
OH

13. CHO CN CN
 +
CN ,H H OH HO H
H OH +
H OH H OH
CH2OH CH2OH CH2OH
H , +
H2O H+,H2O

CHO COOH CHO


COOH
H OH Br2H2O H OH HO H Br2,H2O HO H
H OH H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH
()Threose
() Erythrose

Note: The erythro isomer is the one that is convertible (in principle at least) into a
meso structure, whereas the threo isomer is convertible into a racemic modification.
The names of these compounds are the basis for designations erythro and threo acid
to specify certain configurations of compounds containing two chiral carbons.
O O O
O
14. a) aqKOH CH (H2O)
+ H OH

CH3
b) aq KOH (H2O)
2CH3CH2CHO CH3CH2CHCHCHO CH3CH2CH=CCHO

OH CH3

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c) CH3 CH3

aq. OH
2CH3CHCHO CH3CHCHCCHO
(Self aldol)
CH3 OH CH3
Sodium dimethyl amide or
d) CH3CH2CCH2CH3 Lithium diisopropyl amide

OH
CH3CH2CHO
CH3CH2CCHCH3 CH3CH2CCHCHCH2CH3
O O CH3
(only one product)

Totally convert any of the aldehydes to the carbanion by using strong base,
followed by reaction with the other aldehyde. This is done to avoid multiple
products.

15. A: CH3OH B: CH3COOCH3


C: HCHO D: HCOOH
E: H.CONH2

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LEVEL – III

1. i) O

(A)
ii) O

(A)

2. Erythrose is an aldehyde and contains three - OH's cleavage by 3HIO4 show that it
has the following structure, containing two chiral carbons:
H H H H H H H
* *
H—C—C—C—C =O
H—C = O + C + C
O OH O OH OH OH OH
Erythrose
Oxidation of () erythrose yield a dicarboxylic acid, HO2C *CH(OH)*CH(OH) CO2H.
Since the acid is optically inactive, it must have the meso configuration, showing that
() erythrose is structure (I) or (II)
CHO CHO COOH
CO2H
H OH HNO3 H OH or HO H HNO3 HO H
H OH H OH HO H HO H
CH2OH CO2H CO2H COOH
Same meso
(I) meso-acid (II) acid
() Threose must be a diastereomer of erythrose, either structure (III) or (IV)
CHO CHO COOH
COOH
HO H HNO3 HO H H OH HNO3 H HO
H OH H OH HO H HO H
CH2OH COOH CH2OH COOH
Active acid
(III) Active acid (IV)

3. CH3 O CO2H
CO2H
—C—CH3
Vigorous Can form anhydride
oxidation
MeO MeO
(X) (Y)
Br2/NaOH

CH3
CH3
CO2H NaOH/CaO

OMe
MeO
(Z) 3-Metyl anisole

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4. HC  CCH2CH2–CH2OH

5. a) O
H5C6—C——CH—COOC2H5

CH3
b) CH=CH—COOH

NO2
c) O
CH3
C = CH3—C—OH
CH3
d) O O

e) O

7. A) CH3CH2CH2COOCH2CH3
B) CH3CH2OH
C) CH3CH2CH2CH2OH
D) CH3CHO
E) CH3CH–CH2CHO

OH
F) CH3CO2H

8. i) O
O

ii) CH3

Me
Me O

iii) CO2Et

CH—Cl CH – CO2Et
SN2 reaction

O O

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9. i) C6H5CH(OH)C  CH   C6H5CH – C  CH
H3O

OH2 –H2O
+

 
C6H5CH = CHCHO C6H5CH = C = CH  C6H5CH = C = C H
OH

Tautomerisation

OH

ii) +
 CH3


H

OH OH
–H+

O CH3

10. Since ozonolysis of A gives two aldehydes, the compound A contains the carbon-
carbon double bond. In fact, the molecule of A contains two double bonds as it is
successively oznolyzed products will remain same as in the compound A. Hence, it
may be concluded that the ozonolysis products include two molecules of
D(CH3CHO) and one molecule of E(OHC –– CHO). From this, we derive the
structure of A as shown in the following.
CH3CHO + OHC - CHO + OHCCH3 
 CH3CH = CH – CH = CHCH3
O3

(D) (E) (D) 2, 4-hexadiene


(A)

The structures of B and C are as follows.


H2
CH3CH = CHCH = CHCH3 
 CH3CH2CH2CH = CHCH3
2-hexadiene
(B)

H2

CH3CH2CH2CH2CH2CH3
hexane
(C)

The structure of F is as follows.


O O
|| ||
KMnO 4
CH3CH2CH2CH = CHCH3  CH3CH2CH2C –– OH + CH3C – OH
Butanoic acid
(F)

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11. a) OH CN

b)
S
S

c) CH3CH2C = NHC6H5 + H2O

CH3
d) OCH3
CH
OCH3

NO2

12. In large quantities AlCl3 complexes with C = O group to give m -


bromoacetophenone. In small amounts,. However it acts as a catalyst to form
phenacyl bromide.

+
O–AlCl3–
+
O–AlCl3–
O Br +
C + C CH3
—C—CH3
AlCl3 CH3 Br ---BrAlCl3
H

O
Br +
C CH3 + HBr

13. i) 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
O–
C
CN
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.
ii) In alkenes the double bond joins two carbon atoms and there is not 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.
iii) 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.

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This reduces the attraction of the atom for nucleophilic reagents. Hence ketones
are less electrophilic.
iv) 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.
v) HBr is strongly polar and is hence readily added to the polarised > C = O group.
The
OH
>C
addition product Br is however unstable and decomposes to give the
original carbonyl compound and HBr.

14. (a) CH3COCH2CH3


(b) CH3CHOHCH2CH3
(c) CH3CH = CHCH3

15. A: CH3 – CH – CH = CH2 B: CH3 – CH – CH – CH3


| | |
CH3 CH3 Br

C: CH3 – CH – CH – CH3 D: CH3 – CH – C – CH3


| | | ||
CH3 OH CH3 O

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