Question21(6marks)

Compound(A) undergoesmethylation
selectivelyatoneofthetwophenoxyl groupsto
give(B) asamajorisolatedproduct.Providean
explanationfortheaboveobservation.

(b)
C

(a)
O

1. WhenoneequivalentofNaOH isused,itwilldeprotonatetherelativelymore
acidicproton,either(a)or(b),toformphenoxide anionsC orD,respectively.
2. InA,thenegativechargecouldbepartiallydelocalizedintotheelectron
withdrawingNO2 groupbyresonance,asindicatedinC1 C2.
3. SoOHin(a)isrelativelymoreacidic,andselectivelybeingdeprotonatedwhen
NaOH isaddedtoformonlyanionC.
4. ThenanionC reactswithMeI viaaSN2reactiontogivetheproductB.

OH

C1

O
N

OH

C2

Question22(8marks)
Provideasyntheticschemeforthesynthesisoftransstilbene(C)frombenzene.Youmayuse
anyorganicreagentwithtwoorlesscarbonatoms.Youmayalsouseanyinorganicreagent.

CH2OH

NOTE:Thereareotheracceptablesyntheticroutes.

DessMartin
oxidation

2. H3O+

1.
H

OH
catalyst

H3O+

MgBr
OHC

conc H2SO4

Mg
Br2
FeBr3

Br

Question23(8marks)
Illustratehowyoucouldconvertcompound(D) tocompound
(E).Youmayuseanyorganicandinorganicreagents.

Br

NOTES: 1. Thebulkytbutylgroupstrongly
discouragesorthosubstitution.
Onlyparanitrationispreferred.

Br

2. NH2 isaverystrongactivating
group.Dibromination will
predominate.

NH2
(see NOTE 2)

conc HNO3
conc H2SO4

SnCl2

(see NOTE 1)

H3O+

Br2

CH3COCl

Br
(see NOTE 4)

NHCOCH3

NH2

NO2
conc HNO3
conc H2SO4

3. NH2 isabasicgroup.Additionof
strongacidsprotonateittoform
NH3+ thatisstronglydeactivating,
metadirectingandthereactionis
veryslow.

Br2
FeBr3

NHCOCH3

(see NOTE 3)

conc HNO3
conc H2SO4

H2O/OH
Br
Br
NH3

NO2
NH2

NO2
NHCOCH3

4. ConvertingtheNH2 toNHCOCH3
reducesitsNbasicityandthusits
activity.Monobromination and
nitrationarenowpossible.

Question24(6marks)
WhichofthefollowingspeciesshouldbearomaticbytheHckels rule?

CH2CH3

Boronhasanempty
orbitalinconjugation.
Monocyclic,planar,
conjugated,4:anti
aromatic.

C
H2

ThemoleculeisNOTconjugated.
ThereisasaturatedCH2 unitas
indicated:nonaromatic.

Oxygenatomisrehybridizedtosp2.
Onelonepairelectronsinaporbital
areinconjugation.Monocyclic,
planar,conjugated,6:aromatic.

Lookatthemolecular
periphery.
Monocyclicconjugated
systeminred,planar,10
(4n+2,n=2):aromatic.

Lookatthestructurecarefully.There
arethreepossiblemonocyclic,planar,
6,conjugatedsystems.Thesewill
exhibitaromatic character.

Nitrogenatomisrehybridizedtosp2.
Onelonepairelectronsinaporbital
areinconjugation.Monocyclic,planar,
conjugated,6:aromatic.

Question25(8marks)
Illustratehowyoucouldconvertcompound(L) tocompound
(M).Youmayuseanyorganicandinorganicreagents.

Question26(6marks)
Showallthepossibleproductswhencompound(N) istreatedwithHBr.

Br

Br

1,2-addition
Br

Br
HBr

HBr
Br

Br

HBr

HBr
1,4-addition

1,2-addition

1,4-addition

Br

Br

Question26(6marks)
Showallthepossibleproductswhencompound(N) istreatedwithHBr.

HO

NOTES:
H

OH

HO

1. UsingLiAlH4 mayrisksomereductionoftheCOOHgroup.NaBH4 ismilderand

willreduceonlytheCHOgroup.
2. Thekeyaspectiswhereprotonationoccursforreactiontoproceed.
ProtonationisasindicatedtomaketheC=OmoreelectrophilicforaweakOH
nucleophiletoattack.ThiswillformthesixmemberedringinQ asgiveninthe
question.

NaBH2
O

H
H2O
O

OH
OH
OH

H+

HO
OH
OH

OH
OH

OH2
O

O
O

Question27(12marks)
Compound(O)isconvertedtocompound(Q) viacompound(P).
a. Whatcouldbetheappropriatestructuresforreagent(X) andcompound(P),respectively.
b. Provideamechanismfortheconversionofcompound(P) tocompound(Q).
O

HO

NOTES:
1. UsingLiAlH4 mayrisksomereductionoftheCOOHgroup.NaBH4 ismilderand
willreduceonlytheCHOgroup.

H
H
NaBH4
O

OH

HO

2. Thekeyaspectiswhereprotonationoccursforthereactiontoproceed.
ProtonationisasindicatedtomaketheC=OmoreelectrophilicforaweakOH
nucleophiletoattack.ThiswillformthesixmemberedringinQ asgiveninthe
question.

H2O
O

OH
OH
OH

H+

HO
OH
OH

OH
OH

OH2
O

O
O

Question28(6marks)
Oneormoreproductscouldbeobtainedinthefollowingreaction.Giveallpossible
productsandindicatethemajorproduct.Explainwhythemajorproductispreferred.

1. ItisanexampleofHofmannelimination.
2. Thecontrollingfactorisstericfactorduetothe
bulkyleavinggroup,(CH3)3N.
3. Thepreferredrouteistheabstractionofthe
stericallylesshinderedproton,inthiscasethe
2o H.

4. Eliminationgivesboththetransandcis
isomers.
5. Transisomeristhemajorproductbecause
transisomerisrelativelymorestablebasedon
stericfactor.