R a n ke rs S tudy Ma terial-45-P I V-A&

3'l

K-CH

SOLVED PROBLEMS

Subjective:
Problem

1.

Solution:

An organic compound (A), C6H1yO, on reaction with CftMgBr foilowed by acid

treatment gives compound (B). The campound (B) on ozonolysis gives
compound (C) which in presence of a base gives 1 -acetylcyclopentene (D).
Write the structures ot (A), (B), (C) and (D).
The reactions suggest that (A) is
o
ll

tt
\.,-

U''X*,

A
(-)*(-l
(A)

CH,
HOH

cocH3
OH,

intEmolEulrr
aldol con&nsaton

CH.

L)o
.ro

t\_.-) --:--'L\_.J
r\

&ono,Ets

/'

(B)

.\
\-/
(D)

Problem 2.

ldentify A, B, C and D, in the following schernes and write their structures.

,ts\

etlccr"
rbH,

r14;

Na^rH,

,F)--Is:9LtflLr(C)

NH2NHCONH'

(c)

Solution:

G^";:-

Gr'''u*'"'

/\/

h,*

el"o'"n'

,CH.

r-\/

.N

HN

H,N

r=

.\\i$t\S\\d\i\\\\\\N\\\$\\
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R a n ke

rs Study

Ma teria/-45- P I V-A

&

32
NN\\.\\\

K-C H

s$\\\\\N\\\\\\\\\\\

Problem 3.

Cyclobutylbromide on treatment magnesium in dry ether forms an organometallic

compound (A). The organometallic compound reacts with ethanol to give an
alcohol(B) after mild acidification. Prolonged treatment of alcohol (B) with an
equivalent amount of HBr gives 14romo-+nethylcyclopentane (C). Write the
sfrucfures of (A), (B) and explain how C is obtained by (B).

Solution:

.,8,

ff

u"**

' il

/MsBr
"tB"'

HoXcH' (d1"''

'' --"-fIj"

--"u-

&", ,-eL6n3 &,oc;.

Problem 4.

ozonolysis gives only one product (B) CaHaO.

Compound (B) on reaction with NaOH/lz yields sodium benzoate. Compound (B)
reacts with KOH/NHz-NHz yielding a hydrocarbon (C) CaHro. Write the structure
of (B) and (C). Based on this information give two isomeric structures of (,A)

An alkene (A)

(CrcH16)

on

Solution:

il

oznoFs,rO^"*.

"'-L/"'

(A) has two isomeric structures

H,C.o

,CoHu

H.c

cH.

'\-J"''

HrCo

-cH,

H.c

boHu

and

/
5/
\/

Problem

An organic compound (A) CyH4O3 in dry benzene in the presence of anhydrous

AtCft gives compound (B), the compound (B) on treatment with PCts foltowed by
reaction with Hy'Pd (BaSOq) gives compound (C) which on reaction with
hdyrazine gives a cyclized compound (D) CqH$NI. ldentify (A), (B), (C) and (D).
Explain the formation of (D) from (C).

Solution:

T.H"

rcL
(B)

H2Pd/BSO4 .

oH

rrs"

-Wo

NH.-M"

(c)

N\\\$R\\\\\\\\$\\$q\R\\\\\$$
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Rankers Study

K-CH

33

N'N
Problem 6.

compound (A) (caHso) on treatment with NH2)HHC]gives (B)

and (c). (B) and
(c) rearrange to give (D) and (E) respectivery, on treatment
with acid. (B), (c),

(D) and (E) are all isomers of molecular formula

csHsNo. r,uhen (D) is boited with
alcoholic KoH an oily liquid (F) (c6u?N) separfes out. F
reacts rapidry with
cHscocl to give back (D). on the other hand (E) on boiting with atkafi fottowed
by acidification gives white sotid (G) C7H6O2. tdentify (A)
to (G).

Solution:

i)

il

*,rF,.''"(.-./o'

[iY^t'.

HuC.

NH2oHHcr

\)

H.C

ii) Oxime undergo Beckmann

syn
(oxime)

rearrangement as follows

HuCo pH

H"C^
-\
\ /
and
FN
F*.
H.c
H.i

OH

anti

-----'----'> Huc.

bn

//

{\

//

+ H^c-4
,\

/NH

/NH

H.c
(E)

HuCu

(D)

NH,

*o*

rclt

COOK +

NH^

t'

uov
I

,r\

s-cm,

(F)

r\t-*Vo
J".
(D)

^o'>CH3NH+cuHucooH
(G)-white sotid

Prob'em

7.

How would you bring about the foilowing conversion?

Ethanal to 24ydroxy-34utenoic acid

i)
ii)

2tnethyl propanalto
CH.

H.C
CH.

24utanone from ethyt atcohol

iv) 34exanon from n-propyt alcohol
iii)

Solution:

ot-l

-#-- 4c<

4c-cHo

--A-+

r-Lc1 *

CHO

to ,

FLC=1

FLC:r
)

CHO
NC

r-.*l

\_oFl

HOOC

ii)

cH.

cH"

/"
H"C--<

H-|]cHo -_---)

dil. NaOH

cHo

f.lfitc6 Ltd., ICES House, Sortapiya fAr",

Ofr"iA)",

cH3

fA)l
'1,

l,!:,

...r=#*#j
R a n kers S tudy Ma terial-45-F I V-A& K-CH
$\\\\\r$ii$ss\N$\\\\\$N\N\$N\N\\

iii)

H,C-

H
n'"X..-^,
cHscHo
> H.c--\ -;ffi-* H.c-l
>
-Mgcl
bt
Mgcr
H,J

socr'

9H.

//

-5o----)

H.c-.-AoH --!l--

H.C

cH.

butan-2-one

iv)

H.c*-,rAon

socl'

Mq

) H.c--,2\cl

-#-

,c"Ho

H.c\,,Augcl --qgg-- H,c5-(

CiMs

H,o*

Problem 8.

>

PzHa

H,c<

,CrHu

Iol

r H,Cr-(

Sy nthe si ze 2 -+nethyl cyclohexanone from cyclohexane

ct

Solutian:

-----'
"r,nu

-,^'I I

i)BFr"/rHF /-y'o'

lHplo*+
Problem 9.

\rf

H.C. pH

il

r)nrrox
_iixof_,

\-.,

?*'

' oo.,*,
oo /tu

H",sO"

--1-=_>

cH'

,)

ry'

Predict products of the following reactions

D,P

H,c{

crf

oFr

cooc2Hs

cH.

-------+

ii)
i),I NaOH
ii) Fr

CH,

iii)
NaOCI

iv)

-ffi"

>A+B

n.l

v)

c(c7H12o)

O-HOOC-CuHo -CH, -CuHu "o"L ,(Al=mal"**(B)-+;ls--+(C)

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Ra n kers Study Ma terial-45-P I V-Ae

Solution:

K-CH

35

i)

'."/\
H.C^

cooc2H5

aTr

ii)

)ro

iii)

/
H.c-d.
\
/

cH.

HOOC
o.

ll

iv)

ll

cn,o

aY(
(,

'",, ffi

.+r.

/'o-l-"oo*n

ar

(,

Br

Fe'.
Br

1'..
v

fl

.Y;",
\-,/

ll

cn"

a\L;
I
I

"r.

-coz

(Easy decarboxylation)

v)

=#'H-@o
Problem

10.

Predict the products in the following reaction

6

a)
+

b)

H'cy1,-cH'
cHa

c)

//
H3C--{
\cHs

bc.

Koc,

OH
I

IAs(NHs)'lNo3

,."-^\r-""

>

II

Solution:

a)

lll *' t'ase

Base+
-^ /i
+ l-i-l .- *'"-i\
\-/
\-,lJ

\_-/

,-l
()

-------)

_t

/"'.

o-c-cH3
uH3

jnoH
HO-

l-\
v/

H3C-C-CH3
OH

$\i$r\\SSRr\\tq\r\\tir\\r\\\\\'.\
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R a n ke rs

Study Ma terial-45-P I V-A

&

K-CH

,."YYO'

b) Haloform

reaction. So product is

CH"
c)

It is Tollen's Reagent. lt does not oxidise

ketone. But

if 2' OH group

is

present, that will be oxidised to ketone.

o
Problem 11.

ldentify A, B, C,

ln the following

a)

_URaney

Ni,

H2 . trr

b)
NaBH

4,

CH 3Ol

c)

CHsd)

CHse)

NaBD4 .

HZO .n

il

DcO
C- CHz- CHs NaBD,
--U
-...------------1-__---,1o

lt

CHso

C- CH2- CHs

I
I

I
I

il

C- CH2- CHe
o

equivatont

\cno

NaBt-t4

NaBH4
DZO
'-'-------------. ----------------.Et

>

cH3oH

s)

lt

II

II

exc6NaBH4

\cro

>H

CH:OH

- fl

h)

n
I

-!Er--+r

L
\crto JoIt, ,*

Naa&
cH3oH

,J

Hao*

>K

Solution: a) Carbonyl group as well as doubl+ bond is reduced

$, =

S\ili\\S$\\\\St[\$+i\
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Ra nkers Study Ma terial-45-Pl V-A&

!A\\\\\\$\\\\$U\\N\\\!U\N\\:N$$\$NSW$N

K-CH

Hc)

b)-

OH

i-

37

U-

D= CHs-9-Cnr-CHa

e)

OD

d)

?o
F= CHs-f-arr-CH,

E= CHs-C-CH2-CH3

H
OH

s)

-cH'oH

h)

AA
'=l [p(o\,

\cHroH

,9

oH

;J

;?

Which of the following ketones is more acidic. Give

_ lI

Solution:

OH

[- l"ro.

Prohlem 12.

=a)
tt

a reason

tJ--\[]-'
.ll

c+*

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

Problem 13.

Two moles of an ester A are condensed in the presence of sodium ethoxide to

give a P-keto esfe4 B, and ethanol. on heating in an acidic solution, B gives
ethanol and a p-keto acid, c. on decarboxylation c gives 3-pentanone. ldentify
A, B and C with proper reasoning.

Solution:

The reaction of 2 mol of an ester giving B-keto ester and alcohol in the presence
of sodium ethoxide is known as Claisen condensation.
Let the given reactions may be depicted as shown in the following.

RCHz-fr-OO,+RCHz-fi
o

(A)

(A)

R-

-oczH.

-eft,

CHz

CH

C-

lt- tiloRo
ester

OR, + R,OH

p-keto

ethanol

(B)

cHz-

-$, -

on
?r fi
OROOAOathanol
fi

- -

cHz-uc

F, -u"

oH + q,eg

p-keloacid

(c)

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R a n ke rs

38

Study Ma terial45- P I V-A E K-CH

N\\\\NI

R-CHz-C-CH-C-OH

R-CHz-C-CHz

haat

lllll
oRo

ill

------)

OR

From these reactions, it is obvious that

R'

R=-CHa

CH2CH3

Hence, the compounds A, B and C are

B:
A: CHsCHzfi
OCHzCHg

cHscHzfi-?H-3-oczHs

C: CHgCHzC
lt

Problem

cH
I

CHs

cooH

CH:

/
organic compound A (C6H12O) forms an oxime but does not reduce Tollen's
/An
\ jl reagent. A on reduction with sodium-amatgam forms an alcohol B which on
14.

dehydration forms chiefly a single alkene C. The ozonolysis of C produces D and

E. The compound D reduces Tollens reagent buf does not answer iodoform test.
What are the structures of fhe above compounds? Explain the reactions.

Solution:

The compound A must be a ketone as it forms oxime but does not reduce
Tollen's reagent.

The compound D must be an aldehyde. lts structure does not include the
fragment CH..Q as it does not answer iodoform test.

IU

The compound E must be a ketone containing cH. c _ fragment.

"8

Let the compounds D and E be RCH2CHO and R'COR", respectively, where R,

R' and R" are all alkyl groups. From these, we get

7R, ( 03
RCI-|zCHO*O=C(
.R,,
(D)
(E), p,
RCHzccH

7R,

RCHzCH=Cr
\R,,

(c)

./R,

(*,, --'*'*"*,:x- "*(*,,

(A)

(B)

Since the molecular formula of A is CoHrzO, it follows that R = R' = R" = CHe.
Hence, the structures of molecules (A) to (E) and the reactions are as follows.

/c{z

ii.I

ll
ooH

rl

:l

rHr

CHgCHzCCI-|\
\cn. --lll+
(A)

CHgCHzCHO + CHgCOCH3

Tollens
no
test

Reduce
reagent but
iodoform

\cn.

(B)

Forms oxime but does not reduce

Tollens reagent

(D)

TcHz

CHsCHzCHCHT

(E)

alcohol

o.
-!-+

CHgCHzCH =

//cH3

C,.

(c)

cHe

Does not reduce

Tollens reagent
but gives iodoform

test

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39

R a n ke rs Study Ma terial-45- P I V-A& K-C H

Problem 15.

A compound A reduces Fehling's solution and gives positive silver mirror fesf. On
warming with dilute alkali, followed by dehydration it gives a product B which also
responds to both the above fesfs. /n addition, it decolourises the colour of
bromine water. On treatment with hydrogen in the presence of nickel under
pressure the compound B is converted to C which does nof give any one of the
above fhree test Molar mass of the compound C is 74g mof1. Deduce the
structures of A and B giving the chemical equations involved.

Solution:

The compound A must be an aldehyde as it reduces Fehling's solution and gives

positive silver mirror test. The compound A also contains ct-hydrogen atom as it
undergoes aldol condensation, the dehydration of which gives B. The latter
contains unsaturation as bromine water is decolourised. Let the structure of A be
RCH2CHO. The reactions involved are

RCHzcHo + HzccHo

ttt

NaoH ,
RCHz cH

cH

OHR

cHo

t| -H2C
RCHzCH=C-CHO

(B)

The reduction of B with H2lNi under pressure would be

RCHzcH =

ccHo-H2/Ni > RCHzcHzcHCHzoH

tt

RR

(c)

Since the molar mass of C is 74 g mol-l, R in the compound C must be hydrogen

atom. Hence, the structures of A, B and C are.

A = CHgCHO
C = CHgCHzCH2CH2OH

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Ra n kers

4A

N.N

Study Material'45-Flv-Ae K-CH

N.\i\xss:Hr$.r\r\$s\i.r:*N\\"X.!u

Objective:
Problem

1.

tn the Cannizzaro reaction given below:

Ph*cHo

oH- >Ph-cH,
-oH+PhCOO-

fhe s/ouresf sfeP is

(A) the attack of Ol{ at the carbonyl group.
(B) the transfer of hydride to the carbonyl group
(C) the abstraction of proton from ca;rboxylic acid

(D) the deprotonation of of Ph - CAOH

Solution:

Transfer

of

is the slowest or the rate

hYdride ion to

determining steP.

pnl

,p

oH ,

on-!")
..*

G
onV
*ol,-*\-, l

srowesr

o-l

.onx*l
Hl

,n-4\o-

Pr

oH

Hence (B) is the correct answer.

Problem 2.

A mixture of benzaldehyde and formaldehyde on heating with

aqueous NaOH

solution gives
(A) Benzyl alcahol and sodium formate(B) Sodium benzoate and methylalcohol
(C) Sodium benzoate and sodium formate
(D) None

Solution:

C6H'CHO + CHrO

NaoH

,C6H.CH2OH + HCOONa

ln cross Cannizzaro reaction of formaldehyde, formaldehyde is always oxidised'

Hence (A) is the correct answer'
Problem 3.

Solution:

Hence (A) is the correct answer'

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Ra n kers Study Ma

teria!45-Plv-A& K-CH

Problem 4.

Aldolcondensation will not be obserued in

(A) Chloral

41

(B) Phenylaceialdehyde
(D) None of these

(C) Hexanal

Solution:

chlorral does not contain an o-hydrogen atom hence does not undergo aldol
condensation. lnstead it undergoes hydrolysis to give CHC|3.
Hence (A) is the conect answer.

Problem 5.

The product (s) obtained via oxymercuration (HgSOa

be

(A) *'tal-"t'

(B)

(c) n.cncHo

H.c

HzSOq) of butyne would

,/cHo

CH2O @) H.CACOOH + HCOOH

o

Solution:

H.c--,r-\cH

+ Hro

Hssoo+H,Soo

__1/
/\
H.C
CH.
butan-2-one

Hence (A) is the correct answer.

Problem

6.

Which one of the following reaction cannot be used for the reduction
R

F"

------->

(A) Clemmensen reaction

(C) Wurtz reaction
Solution:

Problem

(B) Wolf-Kishner reaction

(D) Hl and red phosphorus at 200"C

Wurtz reaction is not applicable for above reduction.

Hence (C) is the correct answer.
7.

Solution:

The most reactive compound towards formation of cyanohydric on treatment with

KCN followed by acidification is
(A) Benzaldehyde
(B) p-nitrobenzaldehyde
(C) Phenylacetaldehyde
(D) p Aydroxybenzaldehyde
Due to electron-withdrawing effect of No2 group, the partial +ve charge on c
atom of the c = o group increases hence it becomes more susceptible to
nucleophilic attack by CN-.
Hence (B) is the correct answer.

Problem 8.

The compound that will not form iodoform on treatment with alkali and
iodine is

(A) Acetone
(C) Diethylketone

(B) Ethanol
(D) lsopropyl alcohol

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Ra n kers S tudy Ma terial-45-Plv-A& Ki::a::ri:!ri:i\ili$$::ir\:i\i.+isiF\\\\\l\:.1

Solutian:

42

Cll

Diethyl ketone CHg - CHz - CO - CH2 - CH.. does not contain CH3CO group
linked to carbon and hence does not give iodoform test.
Hence (C) is the correct answer.

Problem 9.

The appropriate reagent for the transformation is

/1--{
cH.
\ I
ti

1^\--\
\/CH.

----------->

HO

HO

(E) NHz- NH2/ Of{

(D) None of these

iA) Zn iHs)/HCt
(C) Both (A)and (B)

Solution:

Both Zn(Hg)/HCl and NHz - NHz / OH- can reduce COCH3 group to
- CHa but HCI will aiso bring about replacement of OH group by Cl.

CHz

Therefore the most appropriate reagent is NHz

Hence (C) is the correct answer.

- NH2/OH-.

IJ

Problem 10.

li

u.c1\r-cuH'
il

HrCu_-,/

",-

,/

OH

'coo-

HrCu

o
The above reaction is known as

(A) Beckmann rearrangement

(C) benzoin condensation

(B) Benzilic acid rearrangement

(D) AIdol condensation

Solution:

Benzilic acid rearrangement.

Hence (B) is the correct answer.

Problem'11.

Oppenaur oxidatian is the reverse process of

iA) Wolt-Kishner reduction
(B) Rosenmund reduction
(C) Clemmensen reductian

(D) MeerweinPondort-Verley reduction

Solution:

Oppenauer oxidation is reverse of Meenrvein Pondorf Verley reduction.

Hence (D) is the correct answer.

Problem 12.

ldentlfy the product C in the serles

CfuCN

Na/ceHsoH

HNoz

,4

KMnoa,

,3

(A) CtuCOOH

CHs

CN +

4H

,g

(B) CfuCH2NHAH
(D) CruCHO

(c) crucoNH2
Solution:

H+

Na/czHsoH

, CH3CH2NH2
{A)

CH3CHzNH2 + HO
CH3CH3CH2

N=

O----+

CH3COO
---lE+
KMno4

CHu

CH2OH + Nz + HzO

(c)

Hence (A) is the correct answer.

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Rankers Study

Material-45-PtV-A&K-CH

4A

$\\r\\\\\\Ni$N\\rrd.\n$$\r\\\\r\rhsr\tN

Problem

N\N\\\\N

13. ln the reaction

C,H, - CH = CH - CHo .j:*r-,
'
agent

agent can be
(A) alkaline KMnOq

CH3CH =

CH

_ CH = CH _ CeoH,

Benedict (Cu**) solution

the oxidising

(B) acidified KzCrzOt

(D) all of the above

(C) Benedict's solution

Solution:

CH,

"rO

, ar. - CH = CH - COOF.|

Benedict solution (solution of CuSO+, sodium carbonate and sodium citrate)

is
specific for oxidation of aldehydes.

Problem 14.

ln a cannizaro reaction, the intermediate that will be best hydride donor is

(B)
NOz
H
I

(D) Both (A) and (B)

Problem 15.

(D)

Benaldehyde on reaction wrth CHz = CH CHppfu forms

ln a cannizaro reaction, the intermediate that witt be best hydride donor is
= CH

f-'--/CH
(A)('

= CH

Solution:

@1--",

(C)

CH =

CHz

-/\_-/CH
(A)lJ

CHg

(D)

U"H

(y-cH

= CH

CHg

= cH

cH -= cHz

Wittig reaction
PPh.

CoHu-C- H

CH

-CH

= CHz----+ C6Hs-CH =

itltt\{i\BN\NNtN\NSr\\\$r\N
Jttttcc Ltd., ICES House. sarrapriya Vihar (trear Hauz Khas Bus

CH-CH

= CH2+ pOpha

r"iitiiU,'iliit-iiii "t o, pn zos i iiiii,' )ial,iit oi'r*

t6st 3942