1. ORGANIC CHEMISTRY
C O N T E N T S
EXERCISE - I
EXERCISE - II
EXERCISE-III
EXERCISE IV
ANSWER KEY

2. EXERCISE–I
(Choose the correct option. Only one is correct)
Q.1




H
A, the productAis:
(A) (B) (C) (D)
Q.2 Which carbocationis least likelyto formas intermediate?
(A)

C
)
H
C
( 5
5
6 (B) (C) (D) H
C
CH2


Q.3 2-chloropentane onhalogenationwithchlorine gives2,3, dichloropentane. What willbethe structureof
free radicalspecies forminthe reaction?
(A) Planar (B)Trigonalplanar (C) Square planar (D) Pyramidal
Q.4 What willbe major product, when2-methylbutane undergoes bromination inpresence oflight?
(A) 1-bromo-2-methylbutane (B) 2-bromo-2-methylbutane
(C) 2-bromo-3-methylbutane (D) 1-bromo-3-methylbutane
Q.5 The smallest compound, which onphotochlorinationproduces diastereomers is
(A) 3-methyl, 3-chloro hexane (B) 2-chloro butane
(C) 1-bromo propane (D) 1-bromo-3-methylbutane
Q.6 Whichofthefollowing willgive two isomeric monochloro derivatives?
(A) 2,3-dimethylbutane (B) n-hexane (C) Isopentane (D) Butane
Q.7 How manyisomers can be produced fromthe molecular formula C4H10O?
(A) 8 (B) 7 (C) 6 (D) 5
Q.8 
 


OEt
The major product is
(A) (B) (C) (D)
Q.9


 

O
H
RMgX
3
?
(A) (B) (C) (D) None ofthese

3. Q.10 


H P. The product P is:
(A) (B) (C) (D)
Q.11 Among the given compounds, the correct dehydration order is:
(I) (II) (III) (IV)
(A) I < II < III < IV (B) II < III < IV < I (C) I < III < IV < II (D) I < II < III = IV
Q.12 IdentifyZinthe following seriesofreaction:
C
170
SO
H
.
conc 4
2




 
 X
4
2
CCl
Br


 Y



 
 KOH
.
alc
Z
(A) (B) (C) (D)
Q.13 In thereaction sequence
3
2
5
6 CH
C
CH
CH
H
C
|
|
|
O
OH








 

)
iii
(
H
/
O
H
)
ii
(
NaOBr
)
i
(
2
product
product willbe
(A) COOH
CH
CH
H
C
|
OH
2
5
6 

 (B) C6H5–COOH, COOH–COOH and CHBr3
(C) 3
5
6 CH
C
H
C
|
|
O

 , CO2 and CHBr3 (D) OnlyCHBr3
Q.14 

 


OEt
.
eq
1 A(major product),Ais
(A) (B) (C) (D)
Q.15 


H major product is
(A) (B) (C) (D)

4. Q.16 HBr reactsfastest with
(A) 2-methylbutane-2-ol (B) 3-methylbutane-2-ol
(C) Butane-1-ol (D) 2-methylbutane-1-ol
Q.17 

 

NaOBr Product
The product is
(A) (B) (C) (D)
Q.18 
 


O
H3 A, Ais
(A) (B) (C) (D)
Q.19 Which one ofthe following alcoholwillundergo acid catalysed dehydration with greatest ease byE1
mechanism?
(A) CH2 = CH–OH (B) (C) (D) Me2CHOH
Q.20 (A) C3H6O
4
2SO
H
NaCN

 
 cyanohydrin of (A). If the cyanohydrin is optically active, then the possible
structure of(A) is
(A) (B) (C) (D)
Q.21 Whichofthe following has minimumreactivitytowards nucleophiles?
(A) CH2O (B) CH3CHO (C) 3
3 CH
C
CH
|
|
O

 (D) 3
2
3 CH
CH
C
CH
|
|
O



Q.22 

 


H
/
ROH
P (major org. product)
The product P is
(A) (B) (C) (D)

5. Q.23
)
I
(
CH
CH
C
Cl 2
3
1
2
3


In additionofHOBr to (I) and (II)
(A) Br is at C2 in both cases (B) Br is at C2 in II and at C1 in I
(C) Br is at C1 in II and C2 in I (D) Br is at C1 in both cases
Q.24 Greatest amount ofhydrationis in
(A) (B) (C) (D)Allare equal
Q.25
ether
Mg
equivalent
1




 
 X 
 

O
D2
Y; Y is
is
(A) (B) (C) (D) noneofthese
Q.26 How manynumber ofopticallyactive isomers are possible for 2,3-dibromo butane 1,4-dioic acid?
(A) 2 (B) 3 (C) 4 (D) 1
Q.27 and
Are whichtype ofisomers
(A) Chain (B) Position (C) Metamerism (D)functional
Q.28 Most stable conformationofethylene glycol
(A) Eclipsed form (B) Staggered form (C) Skew form (D) None ofthese
Q.29 Whichhas maximumB.P.?
(A) (B)
(C) (D)
Q.30 Whichofthe following carbocation ismost stable?
(A) (B)
(C) (D)

6. Q.31 Whichofthefollowing alcoholshows fastest reactionwithHI ?
(A) (B)
(C) (D)
Q.32 Whichofthefollowing is strongest base.
(A) (B) (C) (D)
Q.33 Inwhichofthe followingmoleculealltheeffect namelyinductive, mesomeric&hyperconjugationoperate
(A) (B) (C) (D)
Q.34 For the reactions
(I)  + Clr , o
1
H

(II)  + Clr , o
2
H

(III)  +

Cl , o
3
H

(IV)  + Cl , o
4
H

The correct decreasing order ofenthalpies ofreactionfor producing carbocation is
(A) o
1
H
 > o
2
H
 > o
3
H
 > o
4
H
 (B) o
4
H
 > o
1
H
 > o
2
H
 > o
3
H

(C) o
3
H
 > o
2
H
 > o
1
H
 > o
4
H
 (D) o
2
H
 > o
1
H
 > o
4
H
 > o
3
H

Q.35 Correct order ofbasicityofvarious nitrogeninLSD is
(A) 1>2>3 (B) 2>1>3 (C) 2>3>1 (D) 3>2>1

7. Q.36 One ofthe configurationofn-butane is drawnin the given figure.Anticlockwise rotation ofC2 around
C2–C3 bond by 120° will lead to
(A) gauche (B) staggerred (C) partiallyeclipsed (D) fullyeclipsed
Q.37 Whichoffollowingis correctlymatched.
(A)
3
3
3
CH
|
CH
C
CH
|
OH

 , E1 reaction (B) CH3–CH2–CH2OH, E1cb reaction
(C)
3
3
3
CH
|
CH
C
CH
|
OH

 , thermalreaction (D) , E1 cb reaction
Q.38 Arrange reactivityofgivenalcoholinincreasing orderofeliminationreaction
(I)
2
2
2
2
2
NO
|
OH
CH
CH
CH
CH 

 (II)
2
2
2
3
NO
|
OH
CH
CH
CH
CH 


(III)
2
2
2
3
NO
|
OH
CH
CH
CH
CH 

 (IV) CH3–CH2–CH2–CH2OH
Select answer fromcodes given below:
(A) I, II, IV, III (B) I, II, III, IV (C) II, III, I , IV (D) II, III, IV, I
Q.39 Arrange leaving power ofNur group in decreasing order
(I)
O
|
|
CH
H
C
S
O
|
|
O
3
4
6




(II)
O
|
|
H
C
S
O
|
|
O
5
6



(III)

3
N (IV)

Br
(A) II, I, III, IV (B) II, I, IV, III (C) I, II, IV, III (D) I, II, III, IV
Q.40 Arrange decreasingorder ofreactivityofthese compounds for nucleophilicsubstitutionreaction
(I)
O
|
|
CF
S
O
CH
CH
|
|
O
3
2
3



 (II) CH3–CH2–O–TsCl
(III)
OH
|
CH
CH
CH 3
3 
 (IV)
5
6
3
H
C
|
OH
CH
CH 

(A) III, IV, I, II (B) III, IV, II, I (C) I, II, III, IV (D) I, II, IV, III

8. Q.41 + OH 
 

2
SN
A, A is
(A) (B) (C) Bothare correct (D) None is correct
Q.42 

 
 KOH
.
alc
A, Ais
(A) (B) (C) (D) None is correct
Q.43 Major product obtained in reaction of 1-phenyl-2-bromo butane with NaOMe.
(A) (E)-1-phenylbut-1-ene (B) (E)-1-phenylbut-2-ene
(C) 1-phenyl-1-ethoxybutane (D) (Z)-1-phenylbut-2-ene
Q.44 2-Aminocyclohexane-1-olon treatment with HNO2 produces
(A) Cyclopentane carboxaldehyde (B) Cyclo hexane-1,2-diol
(C) 2-amino cyclohexene (D) Cyclohex-2-enol
Q.45 Arrange the following inorder ofC–Br bond strength inpolar solvent.
(I) (II) (III) (IV)
(A) I < II < III < IV (B) III < IV < I < II (C) IV < III < II < I (D) II < I < III < IV
Q.46 
 

EtOH Rate R1

 

EtOH Rate R2

 

EtOH Rate R3
Whichoffollowingis correct :
(A) R1 > R2 > R3 (B) R3 > R2 > R1 (C) R2 > R1 > R3 (D) R2 > R3 > R1
Q.47 Among the foloowingpairs inwhichcasethe second compound has higher heat ofhydrogenation.
(A) , (B) Cis-2-butene, trans-2-butene
(C) , (D) 1-butene, 2-butene

9. Q.48 (I) , which is not correct about (I)
(A) I ismore soluble than bromocyclopropane
(B) I gives pale yellow ppt. onaddition withAgNO3
(C) I is having lower dipole moment thanbromocyclo propane
(D) I have more ionic character than
Q.49 + CH3SNa 

 

OH
H
C 5
2 ?
The product formed is
(A)
OH
|
)
CH
(
C
CH
SCH
CH 3
3
2
3 
 (B)
3
2
3
3
SCH
|
OH
CH
CH
C
)
CH
( 

(C)
OH
|
)
CH
(
C
CH
SCH
CH 3
3
2
3  (D)
OH
|
SCH
CH
CH
C
)
CH
( 3
2
3
3 

Q.50
Correct order ofbasicityis
(A) 3>1>2>4 (B) 3<1<2<4 (C) 3<4<1<2 (D) 3>4>1>2
Q.51 Whichofthefollowingstatement about the reactivityof1-chloro apocamphane
towardAgNO3 is true.
(A) React bySN1 mechanism (B) React bySN2 mechanism
(C) React bySNimechanism (D) Does not react
Q.52 The resonance energyoffollowing heterocycles isinthe order
(A) pyrole > furan > pyridine (B) furan > pyrole > pyridine
(C) pyridine > pyrole > furan (D) pyridine >furan > pyrole
Q.53 Arrange the following halideindecreasing order ofSN1reactivity.
(I) CH3CH2CH2Cl (II)
Cl
|
CH
CH
CH
CH 3
2  (III)
Cl
|
CH
CH
CH
CH 3
2
3
(A) I > II > III (B) II > I > III (C) II > III > I (D) III > II > I

10. EXERCISE–II
(Choose the correct option. One or more than one are correct)
Q.1 whichis/are incorrect statements?
(A) P is cis– and Q is trans– (B) P is Z and Q is E
(C) P is R and Q is S (D) Pand Q are having same structuralformula
Q.2 CH3CH2NO2 willnot show...... isomerism:
(A) Chain (B)functional (C) tautomerism (D) geometrical
Q.3
CHCOOH
|
|
CHCOOH
(maleic acid) canform:
(A) stereoisomer (B)geometricalisomer (C) positionisomer (D) functionalisomer
Q.4 Which canshow tautomerism?
(A) (B) Ph–CH2–NO (C) 3
CH
C
|
|
O
 (D)
O
|
|
NH
C
CH 2
3 

Q.5
I and II are not
(A) achiral-identicalmirror images (B)chiral-enantiomers
(C) geometricalisomers ofeach other (D)racemic mixture
Q.6 Inwhichoffollowing compound chiralcenter is not affectedonheating.
(A)
OH
|
COOH
CH
CH3 
 (B)
(C)
OH
|
COOH
CH
CH
CH 2
3 

 (D)
COOH
CH
|
CHCOOH
CH
2
3

Q.7 Which are correct statements?
(A) methylmalonic acid is converted into propanoicacid onheating
(B) succinicacid forms succinic anhydrideonheating
(C) 3-hydroxypropanoic acid forms Lactideon heating
(D) COOH
CH
C
CH
|
|
O
2
3 
 forms acetone onheating
Q.8 Select incorrect statements:
(A) and both give colour withneutralFeCl3 solution
(B) 2-pentanone and 3-pentanone are metamers
(C) product formedwhenbenzaldehyde reacts withhydroxylamineshows opticalisomerism
(D) 1,2-dibromocyclohexane showsgeometricaland opticalisomerism.

11. Q.9 C5H8O4 (A) 

 C4H8O2 (B)



 
 lime
Soda
(C)
C is hydrocarbonoccupying 0.509 litre per g approximately. HenceAand B are:
(A) methylmalonicacid, propanoic acid (B) succinic acid, succinic anhydride
(C) Dimethylmalonicacid, 2-Methylpropanoic acid (D) EthylMalonicacid, Butanoic acid
Q.10 
 


O
H3
products canbe: (Both stable &unstable form)
(A) CH3CH(OH)2, CH3CH(OH)COOH (B) CH3CHO, CH3CH(OH)COOH
(C) CH3CH2COOH, CH3CH2OH (D) CH3CH(OH)COOH, CH3CH2OH
Q.11 Whichareincorrect statements:
(A) and are enantiomers
(B)
H
|
CH
CH
C
CH
|
Cl
3
2
3

 and
3
2
3
CH
CH
|
H
C
Cl
|
H
C

 are enantiomers
(C)Argol(sodiumpotassiumtartarate) willshow opticalisomerism.
(D) CH3CHO onreaction with HCN gives racemic mixture.
Q.12 Whichis/are less acidic than Benzoic acid?
(A) CH3COOH (B) (C) (D) H2O
Q.13 Whichhave active methylene group?
(A) 3
2
3 CH
C
CH
C
CH
|
|
|
|
O
O



 (B) CH3–CH2–NO2
(C) Et
O
C
CH
C
CH
||
|
|
O
O
2
3 



 (D) CN
CH
C
|
|
O
2 

Q.14 Whichofthefollowing are not resonating structuresofeachother:
(A) (B)
(C) (D)

12. Q.15 Theunshared electronontheoxygenatomofanether(basiccentre) account for allthe following except:
(A) Combination 
F
|
F
B
|
F

(B) Formationofoxoniumsalt withacids suchas












 Cl
H
H
C
O
H
C 5
2
5
2
(C) Formationofperoxides (explosive)
(D) Chemicalinactivityofether
Q.16 Which ofthefollowing compounds yield most stable carbanionafter rupture of(C1–C2)bond:
(A)
2
1
CCl
C
CH
||
O
3
3 
 (B)
2
1
CBr
C
CH
||
O
3
3 
 (C)
2
1
CI
C
CH
CH
||
O
3
2
3 

 (D) noneofthese
Q.17
pyrrole (I) pyridine (II) aniline (III)
which is/are correct statements ?
(A) I is more basic than II (B) II is more basic thanI and III
(C) III is more basic than II (D) allare aromatic bases
Q.18 Whichis/areuntrue statement(s)?
(A) Protonationincreases electrophilic nature ofcarbonylgroup
(B) 
3
3SO
CF is better leaving group than 
3
3SO
CH
(C) Benzylcarboniumionis stabilised byresonance
(D) CCl3CH is unstable.
Q.19 Which reacts withAgNO3 to give ppt.?
(A) (B) CH=CH–CH2Br
(C) (D)
Q.20 Identifythecorrect statment(s).
I II III IV
(A) I &III are antiaromatic (B) III &IV are non-aromatic
(C) II alone is aromatic (D) II &IV are non-aromatic
Q.21 Which haveacidic hydrogen?
(A) CH3COOH (B)
(C) CN
CH
C
CH
|
|
O
2
3 

 (D) NaNH2

13. Q.22 C–C and C=C bond lengths are unequal in:
(A) benzene (B) 1,3 buta-di-ene
(C) 1,3 cyclohexa-di-ene (D) None
Q.23 Products formed when HCladds to 2,4- hexadiene is:
(A) 4-chloro-2-hexene (B) 2-chloro-3-hexene
(C) 2-chloro-4-hexene (D) 1-chloro-2-hexene
Q.24 Which ofthe following maybe classed as an electrophilic reagent?
(A) BCl3 (B) 
4
NH (C) 3
H
C

(D) 
4
AlCl
Q.25 The acid strengthofsubstituted carboxylic acidsis knownto bedependent onthe natureand positionof
the substituent. Inthe following examples, anattempt has beenmade to arrange theacids inorder ofacid
strength, the strongest first. One ofthe series is incorrect–whichone?
(A) CH3.CH2CH(Cl).COOH > CH3.CH(Cl).CH2COOH > CH3.CH2.CH2.COOH
(B) NO2.CH2.COOH > HOCH2.COOH > CH3.COOH
(C) Cl3C.COOH > BrCH2.COOH > FCH2.COOH
(D) CH3.COOH > CH3.CH2.COOH > (CH3)3C.COOH
Q.26 Whichofthefollowing would not havea dipole moment?
(A) CCl4 (B) CH2Cl2 (C) trans-1,2-dichloroethene (D) ClCCCl
Q.27 Whichofthe following structures represent the lessstable tautomeric form?
(A) (B)
(C) (D)
Q.28 Whichofthe following compounds cannot exhibit keto-enoltautomerism?
(A) (B)
(C) C=O (D)
Q.29 Intautomerism
(A) a proton is moved around the molecule (B) electrons are moved around the molecule
(C) no actualmovement occurs (D) shift ofdouble bond occurs
Q.30 Which species is not aromatic?
(A) (B) (C) (D)
Q.31 Aromatic character is possible onlywhen
(A) sixelectrons are delocalized
(B) the molecule is cyclic and planar having delocalized (4n +2) electrons where n= 1,2,3....
(C) alternate sigma () &pie () bond are present.
(D) None is true

14. EXERCISE–III
Q.1 Arrange the following compounds indecreasing order ofKeq forhydrate formation.
C6H5COCH3
(1) (2)
(3) (4)
Q.2 Arrange thefollowing compounds inorder of:
Decreasing SN1 reactionrate :
Q.3(a)Decreasing SN2 reactionrate :
(b)Explainwhich ofthese reactions would have the faster rate?
(i)
3
3
2
2
3
3
CH
Cl
|
|
N
CH
CH
CH
CH
|
CH


 
 or (ii)
Cl
|
H
N
CH
CH
CH
CH 2
3
2
2
3 




Q.4 Which compound ismore stable explain
(a) 







N
N
CH
C
CH
|
|
O
3
(b) 






N
N
CH
CH3
Q.5 Arrange the isomers ofmolecular formula C4H9Clin order ofdecreasing rate ofreaction with sodium
iodide in acetone.
Q.6 Explain inwhichsolvents these reactionsare faster :
(a) + KOH in CH3OH or CH3CH2OH
(b) 2
2
2
3 CH
CH
CH
CH
|
I
+ H
O

in CH3OH or 50% CH3OH, 50% H2O
(c) 2
2
3 CH
CH
CH
|
Cl
+ 


  N
C

in CH3CH2OH or DMSO.

15. Q.7(i)Choose the member ofthe following pairs ofunsaturated hydrocarbons that is more reactive towards
acid-catalysed hydration and predict the regiochemistryofthe alcohols formed fromthis compound.
(a) or (b) or
(c) or
(ii) Predict onthe basis ofcabocationstability, whichmember ofeach ofthe following pairs hydrolysesat
the faster rate.
(a) or (b) or
(c) or
Q.8 Assuming that cation stability governs the barrier for protonation in H – X additions, predict which
compound ineachofthe pairsinparts (a) to (b) willbe morerapidlyhydrochlorinated inapolar solvent.
(I) (II)
(a) CH2 = CH2 or
(b) or
Q.9 Select the member ofeach pair that shows faster rate ofSN2 reactionwith KI in acetone.
(a)
3
2
3
2
2
2
3
CH
|
Cl
CH
CH
CH
or
Cl
CH
CH
CH
CH 






(I) (II)
(b) CH3 – CH2 – CH2 – Cl or CH3 – CH2 – CH2 – CH2 – Br
(I) (II)
(c)
3
3
2
3
2
2
3
3
CH
CH
|
|
Cl
CH
C
CH
or
Cl
CH
CH
CH
CH
|
CH






(I) (II)
(d)
3
3
3
3
2
2
3
CH
|
CH
CH
CH
CH
CH
or
CH
CH
CH
CH
CH
|
|
Br
Br








(I) (II)

16. Q.10 Select the member ofeach pair that undergoes SN1 solvoysis in aqueous ethanolmore rapidly.
(a) CH3– CH2 – CH2 – CH2 – Cl or
3
3
3
CH
|
Cl
C
CH
|
CH


(b) CH2 = CH – CH2 – Cl or CH3 – CH2 – CH2 – Cl
(c)
3
3
3
CH
|
Cl
C
CH
|
CH

 or
3
3
3
CH
|
Br
C
CH
|
CH


(d) or
Q.11 Ineachofthe following indicate whichreactionwilloccur faster. Explainyour reasoning.
(a) CH3CH2CH2CH2Br or CH3CH2CH2CH2I withsodiumcyanide indimethylsulfoxide.
(b) 1-chloro-2-methylbutane or 1-chloropentane with sodiumiodideinacetone.
(c) Hexylchloride orcyclohexylchloride with sodiumazide inDMF.
(d) Solvolysis of1-bromo-2,2-dimethylpropane or tert-butylbromideinethanol.
(e) Reaction of1-chlorobutanewithsodiumacetate inacetic acid or with sodiummethoxide inmethanol.
(f) Reactionof1-chlorobutane withsodiumazideor sodiump-toluenesulfonate inaqueous ethanol.
Q.12 Classifyeachofthe following species aselectrophile or nucleophile &explain your choice.
(a) CH3
CO2
–
(b) CH3
O–
(c) BF3
(d) Cl

(e) C

Me3
(f) :CCl2
(g) SiF4
(h) Br–
(i) :P(CH3
)3
(j) Me2 C

H (k) CH2
= CH2
(l) HCl
Q.13 Propene 

 


h
/
Cl2 H 
 


OH
I 

 

O
H
/
Cl 2
2
J



 
 2
)
OH
(
Ca
K 
 


O
H3
L (glycerol)
Q.14 Ofthe following statements, which are true for SN2reaction.
(a) Tertiaryalkylhalides reacts faster thansecondary.
(b) Theabsoluteconfigurationofproductisoppositetothatofthereactantwhenanopticallyactivesubstrateisused.
(c) The reaction shows first order kinetics.
(d) The rate ofthe reactiondepends markedlyonthe nucleophilicityofthe attacking reagent.
(e) The mechanismis one step.
(f) Carbocations are intermediate.
(g) Rate [Alkylhalides]
(h) The rate ofthe reactiondepends on the nature ofthe leaving group.
Q.15 Ofthe following statementswhich are true for SN1reaction.
(a) Tertiaryalkylhalides react faster thansecondary.
(b) The absolute configuration of the product is opposite to that of the reactant when an optical active
substrate is used.
(c) The reaction shows first order kinetics.
(d) The rateofreaction depends markedlyon the nucleophilicityofthe nucleophile.
(e) The mechanismis two step.
(f) Carbocations are intermediate.
(g) Rate  [Alkylhalides]
(h) The rate ofthe reactiondepends on the nature ofthe leaving group.

17. Q.16 Explain why Cl – CH2– O – CH2– CH3 is hydrolysed more rapidly than CH3– O – CH2– CH2– Cl
Q.17 Ifthetemperature is not kept below25°C during thereactionofprimaryalcoholswithp-toluenesulfonyl
chloride in pyridine, it is sometimes observed that the isolated product is not the desired alkyl
p-toluenesulfonatebut isinstead the correspondingalkylchloride. Suggest amechanistic explanationfor
thisobservation.
Q.18 Because the SN1 reaction goes though a flat carbocation, we might except anopticallyactive starting
materialto give a completelyracemized. Inmost cases, however, SN1 reactionsactuallygivemoreofthe
inversionproduct. Ingeneral, as the stabilityofthe carbocation increases, theexcess inversion product
decreases. Extremelystablecarbocations give completelyracemic products. Explainthese observation.
Q.19 cis-1-Bromo-2-tert-butylcyclohexaneandtrans-1-bromo-2-tert-butylcyclohexanebothreact withsodium
ethoxide in ethanolto give 1-tert-butylcyclohexene. The cis isomer reacts muchmore rapidlythan the
transisomer. Explain.
Q.20 The reactionofan amine withan alkylhalide gives anammoniumsalt.


N
R3
+ R'–X 

N
R3
– R' X–
amine alkyl halide ammoniumsalt
The rateofthis SN2 reactionis sensitive to the polarityofthe solvent. Draw an energydiagramfor this
reaction ina nonpolar solvent and anotherin a polar solvent. Consider the nature ofthe transitionstate,
and explainwhythis reaction should besensitive to the polarityofthe solvent. Predict whetheritwillbe
faster or slower ina morepolar solvent.
Q.21 There isanoverall29-folddifferenceinreactivityof1-chlorohexane,2-chlorohexanetowards potassium
iodide inacetone.
(a) Which one is the most reactive? Why?
(b) Two oftheisomers differ byonlya factor of2 inreactivity. Whichtwo are these?Whcihoneis themore
reactive? Why?
Q.22 The compound KSCN is a source of thiocyanate ion.
Write the two most stable Lewis structuresfor thiocyanate ionand identifythe atomin eachthat bears a
formalchargeof–1.
Q.23 Withthehelp offollowing datashow HBr exhibits the peroxide effect.
H1
0
H2
0
H–X X

+ CH2
= CH2
 X CH2
– C

H2
XCH2
–C

H2
+ H–X  XCH2
CH3
+ X


HCl –67 + 12.6
HBr –25.1 – 50.2
HI +46 –117.1
All are in kJ mole–1
.
Q.24 CHCl2
F is found to react more slowly than CHCl3
in alkaline hydrolysis with plausible mechanism.
Illustratethis phenomenon.
Q.25 Formulate the reactions between but–1–ene inpresence ofsmallamount ofbenzoylperoxide &
(i) CCl4
(ii) CBrCl3
Give your reasons.
Q.26 p-Amino benzaldehyde behaves like an amide as is evident bythe fact that it is not readily attackedby
the nucleophile at the carbonylcarbon. Explain.
Q.27 WhenCH3MgBr react with5-chloro-2-pentanone, cyclic etheris formed instead ofalocohol. Explain.
Q.28 The dichlorocarbenereactswithelectronrichspecies likephenolwhereas it doesn’t reactswithbenzene
explain.

18. Q.29 Explainthefollowing:
(a) 3-pentanol reacts with HBr to give a mixture of3 &2- bromopentane. The exact composition of the
mixture depends uponwhether gaseous or aqueousHBr is used.
(b) Hydration of 3-phenyl-1-butene in dil H2SO4 is not a satisfactory method for preparing
3-phenyl-2- butanol
Q.30 Whyiseliminationpreferredtohemiacetalformationintheacidcatalysedcyclisationofthisketone?




H
Q.31 CH2 = CH – CH2
3
2
NaHCO
Br
2 OH
C
CH
|
|
O





This type ofreactionis called “bromolactonistaion”. Suggest a mechanism.
Q.32 Draw mechanisms for these reactions, explaining whythese particular products are formed.

 

MeOH
Q.33 Write a reasonable and detailed mechanismforthe following transformation.
4
2SO
H
.
conc

 
 + H2
O
Q.34 The reactionofcyclopentylbromide withsodiumcyanide to givecyclopentylcyanide
water
ethanol
NaCN


 

Cyclopentyl bromide Cyclopentylcyanide
proceeds faster ifa smallamount ofsodiumiodide is added to the reaction mixture. Canyou suggesta
reasonable mechanismto explainthe catalytic functionofsodiumiodide?
Q.35 The reactionof2,2-dimethyl-1-propanolwith HBr is veryslow and gives 2-bromo-2-methyl-propane
as the major product.
3
C
65
HBr
2
3
3
CH
|
OH
CCH
CH
|
CH


 

Br
|
CH
CCH
CH
|
CH
3
2
3
3
Give a mechanisticexplanationfor these observations.
Q.36 1-Bromobicyclo[2.2.1]heptane(thestructureofwhichisshown)isexceedinglyunreactivetowardsnucleophilic
substitutionbyeithertheSN1orSN2mechanism.
1-Bromobicyclo [2.2.1] heptane

19. Q.37 Wesawthat acid-catalyzed dehydrationof2,2-dimethyl-cyclohexanolafforded 1,2-dimethylcyclohexene.
To explainthisproduct we must writea mechanismfor the reactioninwhich a methylshift transforms a
secondarycarbocationto atertiaryone.Another product ofthedehydrationof2,2-dimethylcyclohexanol
is isopropylidencyclopentane.Write a mechanismto rationalize its formation.
heat
H



+ C(CH3)2
2,2-Dimethylcyclohexanol 1,2-Dimethylcyclohexene Isopropylidenecyclopentane
Q.38 When2-bromo-2,3-dimethylbutanereacts witha baseunder E2 conditions, two alkenes (2,3-dimethyl-
1-butene and 2,3-dimethyl-2-butene) are formed.
(a) Which ofthefollowing bases would give the highest percentage ofthe 1-alkene ?
(b) Which would givethe highest percentage ofthe 2-alkene “
3
3
3
CH
|
CO
CH
|
CH

3
2
2
3
3
2
CH
CH
|
CO
CH
CH
|
CH
CH

CH3CH2O–
3
2
3
3
CH
|
CO
CH
CH
|
CH

Q.39 Dr. DonT. Doit wanted to synthesizethe anesthetic 2-ethoxy-2-methylpropane. Heused ethoxide ion
and 2-chloro-2-methylpropane for his synthesis and ended up with very little ether. What was the
predominant product ofhis synthesis ?What reagent should he have used ?
Q.40 The followingreactiontakes place undersecond-order conditions(strongnucleophile), yet the structure
oftheproduct shows rearrangement.Also, the rate ofthis reactionis severalthousandtimes fasterthan
therateofsubstitutionofhydroxideionon2-chlorobutaneundersimilarconditions.Proposeamechanism
to explaintheenhancedrateandrearragement observed inthisunusualreaction. (“Et”isthe abbreviation
for ethyl.)
Cl
|
CH
CH
CH
C
H
|
N
Et
3
2
2
2





 


OH
OH
|
Cl
CH
CH
CH
C
H
|
NEt
3
2
2
2






Q.41 When ethylbromide is added to potassiumt-butoxide, the product is ethylt-butylether.
CH3CH2 – Br + (CH3)3C – O– +K  (CH3)3C – O – CH2CH3
ethylbromide potassiumt-butoxide ethylt-butylether
(a) What happens to the reaction rate ifthe concentration ofethylbromide is doubled ?
(b) What happensto the rate ifthe concentrationofpotassiumt-butoxide id tripled andthe concentrationof
ethylbromide is doubled ?
(c) What happens to the rate if the temperature is raised ?
Q.42 Give amechanismto explainthetwo products formed inthe following reaction.


 


h
,
NBS +
3-methyl-1-butene not rearranged rearranged

20. Q.43 Give the structuresofallpossible productswhen2-chloro-2-methylbutane reacts bythe E1 mechanism.
Q.44 Solvolysis of1,2-dimethylpropylp-toluenesulfonate inaceticacid (75°C) yields fivedifferent products :
three arealkenesand two are substitutionproducts. Suggest reasonablestructures forthesefiveproducts.
Q.45 SolutionA was prepared by dissolving potassium acetate in methanol Solution B was prepared by
adding potassiummethoxide to acetic acid. Reaction of methyl iodide either with solutionAor with
solution B gave the same major product. Why? What was this product?
Q.46 Solvolysis of2-bromo-2-methylbutane inacetic acid containing potassiumacetate gavethree products.
Identifythem.
Q.47
(a) Write the structures or build molecular models ofallthe isomeric alkylbromides having the molecular
formula C5H11Br.
(b) Which one undergoes E1 eliminationat thefastest rate ?
(c) Which one is incapable ofreacting bythe E2 mechanism?
(d) Which one can yield onlya single alkene onE2 elimination ?
(e) For whichisomersdoes E2 eliminationgivetwo alkenes that are not constitutionalisomers ?
(f) Which one yields the most complexmixture ofalkenes onE2 elimination ?
Q.48 Evidence has beenreported in the chemicalliterature that the reaction
(CH3CH2)2CHCH2Br + KNH2  (CH3CH2)2C = CH2 + NH3 + KBr
proceeds bythe E2 mechanism. Use curved arrow notation to represent the flow ofelectrons for this
process.
Q.49 The givencompoundgive mixture ofsixproductsontreatment withCH3OH. Writestructures ofallfive
products and give mechanismofthe reaction.


 

OH
CH3 A + B + C + D + E+ F
Q.50 Comment on the selectivity, (that is, saywhat else might have happened & whyit didn’t)shown in this
grignard additionreactionused inthemanufacture ofanantihistamine drug,A.
Q.51 Outlineanefficient synthesisofeachofthe following compoundsfromthe indicatedstartingmaterialand
anynecessaryorganicor inorganic reagents :
(a) Cyclopentylcyanide fromcyclopentane.
(b) Cyclopentylcyanide fromcyclopentene.
(c) Cyclopentylcyanide fromcyclopentanol.
(d) Isobutyliodidefromisobutylchloride.
(e) Isobutyliodidefromtert-butylchloride.
(f) Isobutylazidefromisopropylalcohol
Q.52 Select thecombinationofalkylbromide and potassiumalkoxide that would be the most effective in the
synthesisofthefollowingethers :
(a) CH3OC(CH3)3 (b) OCH3 (c) (CH3)3CCH2OCH2CH3

21. Q.53 Indicate the major alkene produced byeachofthe following
(a)
3
/
K
O
CH
3
2
2
3
CH
|
CH
C
CH
CH
CH
|
Br
3



 




 



(b)
3
3
3
2
2
3
3
CH
|
H
O
)
CH
(
N
C
CH
CH
CH
|
CH









(c)
3
3
2
3
3
3
CH
|
H
O
CH
CH
C
N
)
CH
(
|
CH








(d) 



 







K
O
C
)
CH
(
3
2
2
3
3
3
CH
CH
CH
CH
CH
|
F
Q.54 Choose the compound of molecular formula C7H13Br that gives each alkene shownas the exclusive
product ofE2elimination.
(a) (b) (c)
(d) (e) CH = CH2 (f)
(g) C(CH3)3
Q.55 Select the alkylhalide and a nucleophile that willgive each ofthe following products.
(a) CH3 – CH2 – CH2 – NH2 (b) CH3 – CH2 – O – CH2– CH3
(c) CH  C – CH2 – CH2 – CH3 (d) (CH3)2CHS(CH3)2
(e) C6H5 – O – CH2 – CH3
Q.56 Identifythe product in eachofthefollowing reactions :
(a)
Cl
|
ClI
H
C
CH
CHCH
CH
ClCH 10
5
acetone
)
mole
1
(
NaI
3
2
2
2 


 

(b) BrCH2CH2Br + NaSCH2CH2SNa  C4H8S2
(c) ClCH2CH2CH2CH2Cl + Na2S  C4H8S
Q.57 Writethestructure ofthe principalorganic product to beexpected fromthe reactionof1-bromopropane
witheachofthe following :
(a) Sodiumiodide in acetone.
(b) Sodiumacetate ( CONa
CH
|
|
O
3
) inacetic acid.
(c) Sodiumethoxide in ethanol.
(d) Sodiumcyanideindimethylsulfoxide.
(e) Sodiumazidein aqueous ethanol
(f) Sodiumhydrogensulfideinethanol
(g) Sodiummethanethiolate (NaSCH3)inethanol.

22. Q.58 Predict the products ofthe following SN2reaction:
(a) C6H5 – CH2– CH2 –Br 
 

NaCN
(b) Cl 

 
 3
NaSCH
(c) CH3 – (CH2)8– CH2– Cl acetone
NaI


 (d) CH3I 
(e) HO – CH2 – CH2 – CH2 – CH2 – Cl 
 

NaOH
Q.59 Draw eachofthe following reactionina waythat clearlyshow the stereoisomerismofthe products.
(a)
3
2
2
S
methanol
3
3
CH
CH
|
ONa
CH
Br
C
CH
|
H
N



 



 (b)
7
3
1
S
3
2
3
3
H
C
|
OH
CH
Br
C
CH
CH
|
CH
N







(c) 1
SN
NaSH

 

Q.60 What willbe the products (A, B, C) in the folowing reaction?
Give a mechanismfor each ofthe reactions.
Q.61 Completethefollowingreactions. Giveallpossibleproductsineachcase. Givemechanismofthereactions.
(a) 


 

O
Ag
Moist 2 (b) CH2
– Cl 

 


/
HOH
Q.62 Identify(A)to (D) in thegiven reactionsequence.
CH3
– CH2
– CH3 

 

hv
/
Br2 (A)



 
 KOH
alc
(B)
Peroxide
HBr

 
 (C)
DMF
LiF


 (D)
Q.63 Identify(A) to (E) inthegivenreactionsequence
CH3
–CH2
–Br 

 
 CuX
/
Li
(A) 



 


 Br
CH
CH 2
3 (B) 

 
 hv
/
Cl2 (C)+(D)+(E) 


 



K
O
C
)
CH
( 3
3 (F)+(G)+(H).
Q.64 Completethefollowing reactions :
(a) )
B
(
)
A
(
CH
C
)
CH
(
C
CH
|
|
|
|
O
O
H
)
ii
(
/
NaOH
/
I
)
i
(
3
4
2
3
2





 







(b) )
D
(
)
C
(
CH
C
|
|
O
H
)
ii
(
NaOH
/
Br
)
i
(
3
2





 

 
(c) CHOH – CH3 





 

H
)
ii
(
HOH
/
CaOCl
)
i
( 2 (E) + (F)
(d)
Cl
|
CH
CH
CH
CH 2
F
/
NaOH
3
2
3 

 



 G + H

23. Q.65 Completethefollowing reactions
(a)
Br
|
HOH
NaCl
CH
CH
H
C is
Electrolys
3
5
6 


 




 Asweet smelling liquid
(b) C6H5 – 

 

NaOH
.
aq
Q.66(i)What are the products ofthe following reactions ?
(a) PhCH = CHCH3 + HBr A (b) + HI  B
(c) + HBr 

 

Peroxide
C (d) + HCl D
(ii) What are the products ofthefollowing reactions ?
(a) PhC  CH + Br2  (b) CH3CH2CH = CH2 O
H
Cl
2
2



(c) O
H
Br
2
2


 (d) O
H
Br
2
2



O
H
NaOH
2

 

Q.67 What products would be formed inthese reactions ?
(a) Ph – C  CH
Cl
NH
)
iii
(
CO
Ph
)
ii
(
EtMgBr
)
i
(
4
2



 
 A (b)
O
H
/
H
)
iii
(
,
CO
)
ii
(
PhLi
)
i
(
2
2







 
 B
Q.68 CH3CH2CH2Cl 

 

KOH
.
alc
A 

 
 2
2Cl
SO
B 

 

O
Et
/
Mg 2 C
Cl
NH
.
aq
)
ii
(
CH
C
CH
)
i
(
|
|
O
4
3
3




 
 

D 

 


/
SO
H 4
2
E.
Q.69 B
A
Na
OH
C
C
Cl
|
|
O
2
2 CH
CH
3



 





 . Find outA& B.
Q.70 Give product and suggest mechanismforthese reactions.
(i) ?
Cl
MeOCH
BuLi
2

 
 BuOK
CHBr
t
3

 
 ? (ii)
Zn


?
Ph – CH = CH2
Q.71 Propose a mechanismfor the following reaction



 


OH
CH
O
CH 3
3 /

24. Q.72 Propose a mechanismfor the following reaction
HO–CH2–CH2–CH2–CH2–OH 


H + HOH
Q.73 Compound (A) C6H14O is insoluble in water and gives negative Lucaus test. On treatment with
concentrated H2SO4 followed byhydrolysis it gives onlyonecompound (B), C3H8O. Compound(B) is
insolubleinwaterand gives red colourwithcerricammoniumnitrate. (B) gives yellowprecipitate (C)and
compound (D) ontreatment with I2/Na2CO3/ followed byacidification.
What are structures of(A), (B), (C) and (D) and give synthesis of(A)?
Q.74 Give theproduct ofreactionofeachofthefollowingwithexcess phenylmagnesiumbromidefollowedby
acidhydrolysis:
(a) (b) (c) (d)
(e) C6H5–CN
Q.75 Complete thereactiongiven below:
Pyridine
PBr

 
 3
(E) 
 
NaCN (F) 


 
 4
2
2 / SO
H
O
H (G)
Q.76 Whichamongthe following ismost reactive for aliphaticnucleophilic substitutionreaction?
(A) CH3–CH2–Br (B) C6H5–CH2–Br (C) (D) CH2=CH–Br
Q.77(a) Which compound willgive Walden Inversionin SN2 reaction?
(A) CH3–CH2–Br (B) Ch3–CHD–Br (C) CH3–Br (D) C6H5–CH2–CH2Cl
(b) Whichamongthe following willgiveSN1 reaction?
(A) (B) (C) CH3–CH2–I (D)
Q.78 Considerthefollowing statements:
(1) CH3 group is o, p–directing groupdue to hyperconjugation
(2) CCl3 ismeta directing group due to reverse hyperconjugation
(3) CCl3 group ismeta directing group due to mesomaric effect.
(4) –CH=CH2 is group is o, p–directing group.
ofthese statements:
(A) 1 and 2 are correct (B) 1 and 3 are correct
(C) 1, 2 and 4 are correct (D) 3 and 4 correct

25. Q.79 Considerthefollowingreaction
[X] as major product willbe
(A) (B) (C) (D)
Q.80 Indicate theproductswhichare expected fromthefollowing eliminationreactions. Ifseveralalkaneswill
be formed thenindicate which willbe the major product.
(a) 

(b) 

(c) 

(d) 

Q.81 Give majorproduct ineachofthe following reactions:
(a) 


 
 
/
. 4
2SO
H
conc
(b) 

 
 KOH
Alc.
(c) 





 
 
H
ii
H
C
NaNH
i
)
(
/
/
)
( 12
6
2

26. Q.82 IdentifyAto H in thegiven reactionsequence:
)
(
3
excess
I
CH

 
 (A) 
 
AgOH (B) 
 (C)
G + H Zn
O
H
ii
O
i
/
)
(
)
(
2
3

 
 (F) 
 (E) 
 
AgOH (D)
Q.83 AssignAto (D) inthegivenreactionsequence:
AgOH
ii
excess
I
CH
i
)
(
)
(
)
( 3



 
 (A) 
 (B)
(D) AgOH
ii
I
CH
i
)
(
)
( 3


 
 (C)
Q.84 In whichreactionformationtakes placebyHoffmannrule?
(1) 


 
 
/
)
( 3
3 COK
CH (2) 

(3) 
 (4) 

 
 
/
3ONa
CH
Select the correct answer fromthe codes given below:
(A) 1, 2 and 3 (B) 1, 2 and 4 (C) 2, 3 and 4 (D) 1, 3 and 4
Q.85 Considerthefollowing statements:
(1) Pyrolytic eliminationisalwayssynelemination
(2) Inpyrolytic elimination product formationtakes place bymost stable eclipsed.
(3) Inpyrolyticeliminationproduct formationtakes placebyHoffmannrule.
(4) Inpyrolytic elimination product formation takes placebySaytzeffrule.
Ofthese statements
(A) 1, 2 and 4 are correct (B) 1, 2 and 3 are correct
(C) 1 and 2 are correct (D) 2 and 3 are correct

27. EXERCISE–IV (A)
Q.1 Reaction of R–CO–NH2 with a mixture of Br2 and KOH gives R–NH2 as the main product. The
intemediates involvedinthis reactionare:
(A) R–CO–NHBr (B) RNHBr
(C) R–N=C=O (D) R.CO.NBr2
Q.2 Whichoneofthe following hasthe smallest heat ofhydrogenationper mole?
(A) 1-Butene (B) trans-2-Butene
(C) cis-2-Butene (D) 1,3-Butadiene
Q.3 Inthefollowing compounds:
The orderofacidityis:
(A) III > IV > I > II (B) I > IV > III > II (C) II > I > III > IV (D) IV > III > I > II
Q.4 The reaction ofCH3– CH=CH OH withHBr gives:
(A) CH3CHBrCH2 OH (B) CH3H2CHBr OH
(C) CH3CHBrCH2 Br (D) CH3CH2CHBr Br
Q.5 Asolutionof(+) 1-chloro-1-phenylethane in toluene racemizes slowlyinthe presence ofsmallamount
ofSbCl5 due to formationof:
(A) carbanion (B) carbene (C) free radical (D) carbocation
Q.6 Anaromaticmolecule will:
(A) have 4n  electrons (B) have (4n+2)  electrons
(C) be planar (D) be cyclic
Q.7 The enolformofacetone, after Prolonged treatment with D2O, gives:
(A) 2
3 CH
C
CH
|
OD

 (B) 3
3 CH
C
CH
|
|
O

 (C) D
CH
C
CH
|
OH
2
2 
 (D) 3
2 CD
C
CD
|
OD


Q.8 Amongst thefollowing, the most basiccompound is:
(A) C6H5NH2 (B) p-NO2–C6H4NH2 (C) m-NO2–C6H4NH2(D) C6H5CH2NH2
Q.9 An SN2 reaction at anassymetricalcarbon ofa compound always gives:
(A) enantiomerofthe substrate (B) a product with opposite opticalrotation
(C) a mixture ofdiastereomeres (D) a single stero isomers

28. Q.10 The correct orderofbasicities ofthefollowing compounds is:
CH3CH2NH2 (CH3)2NH
2
3CNH
CH
|
|
O
(1) (2) (3) (4)
(A) 2 > 1 > 3 > 4 (B) 1 > 3 > 2 > 4 (C) 3 > 1 > 2 > 4 (D) 1
Q.11 Identifythe correct orderofreactivityinelectrophilic substitutionreactionofthe following compounds:
(A) 1>2>3>4 (B) 4>3>2>1 (C) 2>1>3>4 (D) 2>3>1>4
Q.12 Left to right sp2, sp2, sp, sp hybridization is present in:
(A) H2C = CH–CN (B) H2C=C=CH–CH3 (C) HCC–CCH (D) HCC–CH=CH2
Q.13 Maximumdipole moment willbe of:
(A) CCl4 (B) CHCl3 (C) CH2Cl2 (D) CH3Cl
Q.14
when X is made to react with 2 eq. ofNaNH2 the product formed will be:
(A) (B)
(C) (D)

29. Q.15 Order ofrate ofreactionoffollowing compound with phenylmagnesiumbromide is:
)
I
(
O
|
|
Ph
C
Ph 

)
II
(
O
|
|
H
C
Me 

)
III
(
O
|
|
Me
C
Me 

(A) I > II > III (B) II > III > I (C) III > I > II (D) II > I > III
Q.16
Correct order ofacidic strengthis:
(A) x > y > z (B) z > y > x (C) y > z > x (D) x > z > y
Q.17 1-Bromo-3-chloro cyclobutene onreactionwith2-equivalent ofsodiumin ether gives
(A) (B) (C) (D)
Q.18 )
solution
.
aq
(
)
excess
(
COONa
CH3





 

(A) (B)
(C) + CH3COOH (D) + H2SO3
Q.19 Conversionofcyclohexanolinto cyclohexene ismost effective in
(A) concentrated H3PO4 (B) concentrated HCl
(C) concentrated HCl/ ZnCl2 (D) concentrated HBr
Q.20 Ph – MgBr + CH3
3
3
CH
|
OH
C
|
CH

  A
A
(A) (B)
3
3
3
CH
|
OPh
C
CH
|
CH

 (C) (D)
3
3
3
CH
|
Ph
C
CH
|
CH



30. Q.21 For 1-methoxy-1,3-butadiene, whichofthe following resonating structure is theleast stable?
(A) 3
2 CH
O
CH
CH
CH
C
H 






(B) 3
2 CH
O
CH
CH
CH
C
H 






(C) 3
2 CH
O
CH
CH
CH
C
H 






(D) 3
2 CH
O
CH
CH
CH
C
H 






Q.22
on hydrolysis inpresence ofacetone
(K) (L)
(M)
(A) K & L (B) only (C) M only (D) K & M
Q.23 Whenbenzenesulfonicacid andp-nitrophenolaretreated withNaHCO3, thegases released respectively
are
(A) SO2, NO2 (B) SO2, NO (C) SO2, CO2 (D) CO2, CO2
Q.24 CH3NH2 + CHCl3 + KOH  Nitrogen containing compound + KCl + H2O. Nitrogen containing
compound is
(A) CH3-CN (B) CH3-NH-CH3 (C)


 C
N
CH
—
3 (D)
—
3 C
N
CH 

Q.25 (I) 1,2-dihydroxybenzene (II) 1,3-dihydroxybenzene
(III) 1,4-dihydroxybenzene (IV) Hydroxybenzene
The increasing orderofboiling points ofabove mentioned alcohols is
(A) I < II < III < IV (B) I < II < IV < III (C) IV < I < II < III (D) IV < II < I < III

31. Question No. 26 to 28 ( 3 questions)
Comprehension I
RCONH2 is converted into RNH2 bymeans ofHofmannbromamide degradation.
In this reaction, RCONHBr is formed fromwhichthis reactionhas derived its name. Electron donating
group at phenylactivates the reaction. Hofmanndegradationreactionis anintramolecular reaction.
Q.26 How can theconversion of(i) to (ii) be brought about?
(A) KBr (B) KBr + CH3ONa (C) KBr + KOH (D) Br2 + KOH
Q.27 Whichis the rate determining step inHofmannbromamide degradation?
(A) Formationof(i) (B) Formationof(ii) (C) Formationof(iii) (D) Formationof(iv)
Q.28 What arethe constituent amines formedwhenthe mixture of(i) and (ii) undergoesHofmannbromamide
degradation?
(A)
(B) (C)
(D)

32. Q29. Whichofthefollowing reactants onreactionwith conc. NaOH followed byacidificationgives the
following lactone asthe onlyproduct?
(A) (B) (C) (D)
Q30. The smallest ketone and its next homologue are reacted withNH2OH to formoxime.
(A)Two different oximes are formed (B) Three different oximes are formed
(C)Two oximes are opticallyactive (D)Alloximes are opticallyactive
Q31. Matchthefollowing:
ColumnI ColumnII
(A) CH3–CHBr–CD3 on treatment with alc. KOH gives (P) E1 reaction
CH2=CH-CD3 as a major product.
(B) Ph – CHBr - CH3 reacts faster than Ph-CHBr-CD3. (Q) E2 reaction
(C) Ph-CH2-CH2Br ontreatment with C2H5OD/C2H5O. (R) E1cb reaction
gives Ph-CD=CH2 as the major product.
(D) PhCH2CH2Br and PhCD2CH2Br react with same rate. (S) First order reaction
EXERCISE–IV (B)
Q.1 CH3CH2CHCl2 

 

KOH
.
aq ?
Q.2 C6H6+ (CH3)2CHCH2Cl 
 
 3
AlCl ?
Q.3 COO
ion
mononitrat
SO
H
/
HNO 4
2
3




 
 ?
Q.4 Draw the stereochemicalstructure ofthe products inthe following reaction:
2
S
NaOH
N

 
 ?
Q.5 Completethe following,giving the structures oftheprincipalorganic products:
(a) + KNH2  A
A
(b) + CHBr3 + t – BuOK  B
(c) ClCH2CH2CH2COPh + KOH + MeOH  C
Q.6 Write the intermediatesteps for each ofthe following reaction.
(i) C6H5CH(OH) CCH 
 


O
H3
C6H5CH = CH–CHO

33. (ii) 



H
Q.7 Each ofthefollowing reactiongives two products. Write the structure ofthe products.
(a) C6H5CH2CHClC6H5 


 


,
KOH
.
Alc
(b) CH3CONHC6H5 
 

Fe
,
Br2
Q.8 Out ofanhydrousAlCl3 andhydrousAlCl3 whichis more soluble indiethylether?Explainwithreason.
Q.9 Match Ka values withsuitable acid:
Ka Acid
(i) 3.3 × 10–5 (a)
(ii) 4.2 × 10–5 (b)
(iii) 6.3 ×10–5 (c)
(iv) 6.4 × 10–5 (d)
(v) 30.6 × 10–5 (e)
Q.10 Give resonatingstructuresoffollowingcompound.
Q.11 Which ofthe following is more acidic and why?
Q.12 Predict whether the following molecules are iso structuralor not. Justifyyour answer.
(i) NMe3 (ii) N(SiMe3)3
Q.13 Give reasons:
(a) (i) 


 

.)
aq
(
OH
H
C 5
2 acidic solution
(ii) 


 

.)
aq
(
OH
H
C 5
2 neutral
(b) (i) 


 

.)
aq
(
NaOH
F (liberated)

34. (ii) 


 

.)
aq
(
NaOH Fis not liberated
(c) (i)
4
2
3
SO
H
.
Conc
HNO
.
Conc



 
 +
(ii)
4
2
3
SO
H
.
Conc
HNO
.
Conc



 

(d)
2
H
of
moles
3
C
/
Pd

 
 is formed but not
Q.14 





smell
pungent
and
fumes
Brown
B 


 

 2
MnO
NaBr
A 


 
 3
HNO
.
Conc
C(intermediate) D(Explosive product)
FindA, B, C and D.Also write equationsAto B andAto C.
Q.15 obs =  i
ix
where i is the dipole moment ofstable conformer and xi isthe fraction ofthat conformer.
(a) Write stable conformer for Z– CH2– CH2– Z in Newman's projection. If solution = 1.0 D and mole
fraction ofantiform= 0.82, find Gauche.
(b) Write most stablemeso conformer of
CHDY
|
CHDY
If (i) Y = CH3 about C2 – C3 rotation and (ii)Y = OH about C1 – C2 rotation.

35. ANSWER KEY
EXERCISE–I
Q.1 D Q.2 C Q.3 B Q.4 B Q.5 B Q.6 A Q.7 A
Q.8 D Q.9 A Q.10 B Q.11 A Q.12 C Q.13 C Q.14 C
Q.15 C Q.16 A Q.17 B Q.18 B Q.19 C Q.20 A Q.21 D
Q.22 A Q.23 C Q.24 C Q.25 D Q.26 A Q.27 D Q.28 C
Q.29 A Q.30 C Q.31 B Q.32 B Q.33 C Q.34 B Q.35 B
Q.36 A Q.37 A Q.38 C Q.39 B Q.40 D Q.41 B Q.42 A
Q.43 A Q.44 A Q.45 A Q.46 C Q.47 C Q.48 C Q.49 A
Q.50 D Q.51 D Q.52 C Q.53 C
EXERCISE–II
Q.1 C Q.2 A,D Q.3 A,B,C,D Q.4 A,B,C,D
Q.5 B,C,D Q.6 A,B,D Q.7 A,B,D Q.8 C
Q.9 C,D Q.10 A,B Q.11 A,B Q.12 A,D
Q.13 A,C,D Q.14 C,D Q.15 D Q.16 A
Q.17 B,D Q.18 D Q.19 B,D Q.20 A,C
Q.21 A,B,C Q.22 B,C Q.23 A,B Q.24 A,C
Q.25 C Q.26 A,C,D Q.27 A,B,C Q.28 D
Q.29 A,D Q.30 B Q.31 D
EXERCISE–III
Q.1 3 > 2 > 1 > 4 Q.2 IV > I > II > III Q.3 (a) II > I > III > IV ; (b) (ii)
Q.4 (a) Q.5 C–C–C–C–Cl >
C
|
Cl
C
C
C 

 >
C
|
Cl
C
C
C 

 >
C
|
Cl
C
C
|
C


Q.6 (a) II, (b) I, (c) II Q.7 (i) (a) II, (b) I, (c) II ; (ii) (a) II, (b) II, (c) I
Q.8 (a) II, (b) I Q.9 (a) I, (b) II, (c) I, (d) I Q.10 (a) II, (b) I, (c) II, (d) II
Q.11 (a) II ; (b) II ; (c) I ; (d) II ; (e) II Q.14 b, d, e, g, h Q.15 a, c, e, f, g, h
Q.27 Q.38 (a) Et3CO ; (b) EtO Q.45 MeCOOMe
Q.46
C
|
C
C
C
C 

 ,
C
|
C
C
C
C 

 ,
C
|
C
C
C
C
|
OAC



Q.47 (b)
C
|
Br
C
C
C
|
C


 ; (c)
C
|
C
C
C
Br
|
C


 ; (d) C–C–C–C–C–Br ; (e)
Br
|
C
C
C
C
C 



(f)
Br
|
C
C
C
C
C 




36. Q.50
Q.53 (a)
C
|
C
C
C
C
C 


 ; (b) C
C
C
C
C
|
C



 ; (c) C
C
C
C
|
C


 ; (d) C–C–C–C=C
Q.54 (a) ; (b) ; (c) ; (d) ; (e)
(f) , (g)
Q.55 (a) CH3CH2CH2Cl + NH3 ; (b) CH3CH2ONa + CH3CH2Cl ; (c) HCºCNa + CH3CH2CH2–Cl
(d) Me2CH–Cl + Me2S ; (e) C6H5ONa + CH3CH2–Cl
Q.56 (a)
Cl
|
CH
CH
CH
CH
ICH 3
2
2
2 
 ; (b) ; (c)
Q.57 (a) ; (b) ; (c) ; (d) ; (e) ; (f) ; (g)
Q.58 (a) C6H5–CH2–CH3–CN, (b) , (c) CH3–(CH2)9–I, (d) , (e)
Q.59 a)
3
2
3
3
CH
CH
|
CH
C
O
CH
|
H

 ; (b)
Pr
|
OMe
C
Et
|
Me

 +
Pr
|
Et
C
MeO
|
Me

 , (c) +
Q.60 (A) RCH2CH2SR (B) RCHBrCH2CCl3 (C) RCHClCH2CCl3
Q.62 CH3–CH2–CH2–F
Q.64 (a) CHI3+(CH2)4(COOH)2, (b) CHBr3+ , (c) CHCl3+ , (d) CHF3 + EtCOONa
Q.65 (a) CHCl3, (b) PhCHO

37. Q.66 (i) (a)
Br
|
Et
CH
Ph 
 , (b) Me2C(I)–Et, (c) , (d)
(ii) (a) , (b)
OH
|
Cl
CH
CH
Et 2


 , (c) , (df)
Q.67 (a)
Ph
|
Ph
C
C
C
Ph
|
Ph



 ; (b)
Q.68 Me2C=CH–CH=CH2
Q.69 A: 2
CCl

 B :
Q.70 (i) & ; (ii)
EXERCISE–IV (A)
Q.1 A, C Q.2 D Q.3 D Q.4 B Q.5 D
Q.6 B, C, D Q.7 D Q.8 D Q.9 D Q.10 B
Q.11 C Q.12 A Q.13 D Q.14 C Q.15 B
Q.16 D Q.17 C Q.18 C Q.19 A Q.20 A
Q.21 C Q.22 A Q.23 D Q.24 D Q.25 C
Q.26 D Q.27 D Q.28 B Q.29 C Q.30 B
Q.32 A – Q; B – Q; C – R,S; D – P,S
EXERCISE–IV (B)
Q.1 CH3CH2CHO Q.2 Q.3
Q.4
3
3
5
6
3
CH
|
CH
C
H
C
|
CH

 Q.5 (A) PhCCPh, (B) , (C)

38. Q.6
OH
OH
|
|
CH
C
CH
H
C
CH
C
CH
H
C
CH
C
CH
H
C 5
6
O
H
5
6
H
5
6
2







 











2
5
6
O
H
5
6
OH
|
H
C
C
CH
H
C
CH
C
CH
H
C 2






 




 –H+
2
5
6
OH
|
CH
C
CH
H
C 

 C6H5–CH=CH–CHO
(ii)
Q.7 (a) (b) +
Q.8 AnhydrousAlCl3 is morestable thenhydrousAlCl3 becauseit ishaving vacant 3porbitalofAlwhichcan
accept lone pair ofelectrons fromoxygenofdiethylether.
Q.9 (i)–(d), (ii)–(b), (iii)–(a), (iv)–(c), (v)–(e) Q.10
Q.11 ismore acidic as overalleffect of–Fiselectron withdrawing, so loss ofportionis easierfromthis
compound.
Q.12 Not. NMe3 is trigonalpyramidalwhile N(SiMe3)3 is trigonalplanar due to back bonding.
Q.13 (a) (i)
3
5
2
6
5
3
CH
|
)
acid
(
HBr
H
OC
C
C
H
|
CH


 ; (ii) no reaction due to partialdouble bond character
(b) (i) + F– is liberated ; (ii) Bimomecular mechanism is not possible in (ii) case

39. (c) (i) due to presence oflone pair ofnitrogen atomNO group is electron denating and ortho, para
directing
(ii) NO2 group is electron withdrawing and meta directing
(d) Due to reduction ofcentralring, three fourmembered antiaromatic rings become stable while on
recuction ofterminalring onlyone antiaromatic ring can be stabilized.
Q.14 (A) H2SO4, (B) Br2, (C) 
2
NO , (D)
Q.15 (a) Gauche= 5.55 D ; (b) (i) , (ii)