SCHOLARSACADEMYforIITJEE(19052013)

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Topic
Reaction Mechanism
1.

SCHOLARS ACADEMY
for IIT/AIEEE/PMT

Batch:Target
ProblemSheet26

2. 3.

SN1 is a twostep reaction. For each step, there has to be a transition state. Which of the followingstructuresrepresentcorrectlythetransitionstateoffirststep: (a)[Rd+ Ld ] (b)[Rd Ld+ ] (c)[Rd+ Nud ] (d)[Rd Nud+ ] HowmanyintermediatesareinvolvedinSN2reactions: (a)1 (b)2 (c)3 (d)0 Keeping in mind that nucleophilic substitutions involve two thingscleavage of CL bond and formationofCNubond,whichofthefollowingpathwayscanbeproposed: (a)FirstCLbondiscleavedandthenCNubondisformed.Thiscanbeformulatesas CL C+L
r s

C+Nu

CNu

This is a two step pathway. First step is slower than the second step because former involves ionization of the substrate. Hence, first step is the ratedeterming step (rds). Therefore,ratelawwillbeRate [substrate] Consequently,Order=1andMolecularity=1. ThispathwayiscalledunimolecularnucleophilicsubstitutionSN1 (b)BothcleavageofCLbondandformationofCNubondoccursimultaneously.Thiscan beformulatedas CNu
s

NuC

+L

Thisisonesteppathway.Hence,ratelawwillbeRate [Substrate][Nus] Consequently,Order=1+1=2andMolecularity=2 ThispathwayiscalledbimolecularnucleophilicsubstitutionSN2 (c)FirstCNubondisformedandthenCLbondiscleaved.Thiscanbeformulatedas O (sp 2 ) RCL Nu

s
3 (sp ) (i) RCL

O
s RCNu+L (ii)

RCL Nu

Nu
(Tetrahedralintermediate)

4.

This is a two step pathway. First step is rds. Therefore, rate law is Rate [substrate] [Nucleophile] Consequently,Order=1+1=2andMolecularity=2 This pathway is called nucleophilic acyl substitution through tetrahedral intermediate. 3 Secondly,thispathwayisnotpossibleonsp Catomsbecausepentavalentcarbonisnot possible (d)allofthese s s RL+Nu RNu+L (ListheleavinggroupandNuisthenucleophile).Nucleophilic substitutionscan,ingeneral,bebestrepresentedasthis.Now,innucleophilicsubstitutions:
(a) Nu comesinwithapairofelectronstoformCNubond (b)leavinggroup(L)goesawaywithCLbondpairelectrons (c)both(a)and(b) (d)noneofthese Whichofthefollowingstructuresrepresentcorrectlythetransitionstateofsecondstep:

5.

SCHOLARSACADEMYforIITJEE(19052013)
d+ d d+ d+ d d

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6.

7.

(a)[R Ld ] (b)[R L ] (c)[R Nu ] (d)[R Nud+ ] WhichofthefollowingstatementsiscorrectaboutSN2reactions: (a)Firstnucleophileattacksandthenleavinggroupdeparts (b)Boththeattackofnucleophileanddepartureofleavinggroupoccursimultaneously (c)both(a)and(b) (d)noneofthese 3 InSN2reactionsonsp Catoms: (a)nucleophileattacksfromthebacksideoftheleavinggroup.Thisattackeventuallyoccurs 3 onthesmallerlobeoftheCLsp orbital.Thiscanbeshownas Nu
s

(b)Nucleophile attacks from the same side of the leaving group. This attacks eventually. 3 OccursonthebiggerlobeoftheCLsp orbital.Thiscanbeshownas C Nu (c)either(a)or(b)dependinguponsituation (d)noneofthese Which of the following diagrams represents correctly the reactionenergyprofile of themost idealSN1reactions:
TSI Energy TSII Energy TSII TSI Energy Energy Rr s RL+Nu RNu+L Progressofreaction s RNu+L Rr Rr

8.

(a)

Rr s RL+Nu RNu+L Progressofreaction

(b)

(c)

s RL+Nu

(d)

s RNu+L Progressofreaction

s RL+Nu Progressofreaction

9.

In SN2 reactions, attack of nucleophile from the backside of the leaving group is favoured becauseinfrontsideattacknucleophilesuffersfrom: (a)strongelectronicrepulsionwithCLbondpairelectrons (b)strongtorsionalstrain (c)stronganglestrain (d)allofthese 10. Which of the following figure represent correctly the structure of transition state in this reaction: Nu+
d s

C
d L

SN2

[TS]

Nu

C
d+

s +L

(a) Nu

(b) Nu

d+ L L

(c)either(a)or(b)dependinguponsituation

(d)noneofthese

11. Thesiteofreaction(theCatom)inthetransitionstateofSN2reactionsis: 3 2 (a)sp hybridized (b)sp hybridized (c)sphybridized (d)unhybridized

12. InSN2reactionsonasymmetriccentres: (a)inversionofconfigurationoccursbecausenucleophileattacksfromthebacksideofleaving group

SCHOLARSACADEMYforIITJEE(19052013)

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(b)retentionofconfigurationoccursbecausenucleophileattacksfromthefrontsideofleaving group (c)both retention and inversion occur in equal proportions. It means a racemic mixture is produced (d)thechiralcentrebecomesachiral 13. AnidealSN1reactiononchiralcentresleadsto: (a)almost100%retentionofconfiguration (b)almost100%inversionofconfiguration (c)almost100%racemization (d)retentionmorethaninversionleadingtopartialracemization 14. WhichofthefollowingstatementsiscorrectforSN1reactions: (a)Itoccursthroughionizationofthesubstrategivingflatcarbocationintermediateas L C C
r

+L

(Carbocation)

(b)Nucleophilecanattackoneitherlobe(eitherside)ofthecarbocationsemptyporbitalwith equalopportunityas
Fromthetop

Nu C + C Nu
(Retention) (Inversion)

+Nu
Fromthebottom

Thisattackleadstobothinversionandretentionofconfigurationinalmostequalamount (c)both(a)and(b) (d)noneofthese 15. Which of the following diagrams represent correctly the reactionenergyprofile of the most idealSN2reactions:
TS TS Energy TSI TSII Energy TSII TSI

Energy

Energy

(a)

(b)
s RL+Nu s RNu+L Progressofreaction

s RNu+L s RL+Nu Progressofreaction

(c)

Intermediate

(d)

Intermediate

s RL+Nu RNu+L Progressofreaction

s RL+Nu RNu+L Progressofreaction

3 16. Whichofthefollowingstatementsiscorrectaboutnucleophilicsubstitutionsonsp hybridized carbonatoms: (a)RatelawofSN2reactionis:rate [substrate][Nucleophile].Sincenucleophiletakespart inratedeterminingstep(theonlystep)ofSN2reactions,astrongernucleophilepromotes SN2reactionsmoreefficiently (b)RatelawofSN1reactionis:rate [substrate].Sincenucleophiledoesnottakepartinthe ratedeterminingstepoftheSN1reactions,aweaknucleophileprefersSN1pathway (c)both(a)and(b) (d)noneofthese

17. Thisreactionfollowswhichofthefollowingpathwayspredominantly: I OCH3

CH3OH D

SCHOLARSACADEMYforIITJEE(19052013)
(a)SN1 (b)SN2 (c)bothequally 18. Thisreactionfollowswhichofthefollowingpathwayspredominantly: Br OEt
NaOEt

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(d)noneofthese

+NaBr (d)noneofthese

(a)SN1 (b)SN2 (c)bothequally 19. Thisreactionfollowswhichofthefollowingpathwayspredominantly: Br CH3 CH2 CCH3 CH3

CH3COOH D

Br CH3 CH2 COCCH3 CH3 O (d)noneofthese

(a)SN1 (b)SN2 (c)bothequally 20. Thisreactionfollowswhichofthefollowingpathwayspredominantly: CH3 CHCH2 I CH3

NaOMe

CH3 CHCH2 OMe CH3

(a)SN1 (b)SN2 (c)bothequally (d)noneofthese 21. Solvolysis of this substrate would lead to maximum racemization in which of the following solventsystem: H Br CH3

(a)80%acetone+20%water (b)50%acetone+50%water (c)20%acetone+80%water (d)100%water 22. Under identical conditions, solvolysis of which of the following substrates would lead to maximumracemization: OCH3 NO2 CH3 (a) H D Cl (b) H (c) (d)

H Cl Cl H Cl CH3 CH3 CH3 23. SN2reactionwithwhichofthefollowinghalideswillbemosteffectiveinacetone: (a)LiF (b)LiCl (c)LiBr (d)LiI 24. Whichofthefollowingstatementsistrueaboutnucleophilicsubstitutionreactions: (a)SN1reactivityincreasesasthestabilityofresultingcarboniumionintermediateincreases (b)SN2reactivitydecreasesasstericcrowdinginthesubstrateincreases (c)SN2reactivityincreasesastheattractionbetweensubstrateandnucleophileincreases (d)allofthese 25. InSN1reactions,proportionofracemizationincreasesif: (a)carboniumionintermediateismoststable (b)Nucleophileisweaker (c)Leavinggroupisnotgood (d)both(a)and(b)

SCHOLARSACADEMYforIITJEE(19052013)

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21. 22. 23. 24. 25. d d d d d

AnswerKey
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. a d d c c b a a a a 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. b a c c a c a b b b