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Chapter16

ChemistryofBenzene:Electrophilic
Aroma9cSubs9tu9ons

ElectrophilicAroma9cSubs9tu9on
Fluorina9on(16.2)
Reactants:
1.
2.

Products:
1.

ElectrophilicAroma9cSubs9tu9on
Fluorina9on(16.2)
Reactants:
1.Benzene
2.FTEDABF4

Products:
1.Fluorobenzene

ElectrophilicAroma9cSubs9tu9on
Bromina9on(16.1)
Reactants:
1.
2.
3.

Products:
1.
2.

ElectrophilicAroma9cSubs9tu9on
Bromina9on(16.1)
Reactants:
1.Benzene
2.Br2
3.FeBr3

Products:
1.Bromobenzene
2.HBr

ElectrophilicAroma9cSubs9tu9on
Chlorina9on(16.2)
Reactants:
1.
2.
3.

Products:
1.
2.

ElectrophilicAroma9cSubs9tu9on
Chlorina9on(16.2)
Reactants:
1.Benzene
2.Cl2
3.FeCl3

Products:
1.Chlorobenzene
2.HCl

ElectrophilicAroma9cSubs9tu9on
Iodina9on(16.2)
Step1

Reactants:
1.
2.
Products:
1.
2.

Step2

Reactants
1.
2.
3.
Intermediate
1.
Products
1.

ElectrophilicAroma9cSubs9tu9on
Iodina9on(16.2)
Step1

Reactants:
1.I2
2.2Cu2+
Products:
1.2I+
2.2Cu+

Step2

Reactants
1.Benzene
2.I+
3.I2,CuCl2
Intermediate
1.Carboca9on,aLackedbybase
Products
1.Iodobenzene

ElectrophilicAroma9cSubs9tu9on
Nitra9on(16.2)
Step1

Reactants:
1.
2.
Products:
1.
2.

Step2

Reactants
1.
2.
Intermediate
1.
Products
1.
2.

ElectrophilicAroma9cSubs9tu9on
Nitra9on(16.2)
Step1

Reactants:
1.HNO3(Nitricacid)
2.H2SO4
Products:
1.H2O
2.NO2+(Nitroniumion)

Step2

Reactants
1.Benzene
2.NO2+
Intermediate
1.Carboca9on,aLackedbyH2O
Products
1.Nitrobenzene
2.H3O

ElectrophilicAroma9cSubs9tu9on
Sulfona9on(16.2)
Step1

Reactants:
1.
2.
Products:
1.
2.

Step2

Reactants
1.
2.
Intermediate
1.
Products
1.
Note
1.
2.
3.

ElectrophilicAroma9cSubs9tu9on
Sulfona9on(16.2)
Step1

Reactants:
1.SO3(Sulfurtrioxide)
2.H2SO4
Products:
1.HSO4
2.HSO3+orSO3

Step2

Reactants
1.Benzene
2.HSO3+orSO3
Intermediate
1.Carboca9on,aLackedbybase
Products
1.Benzenesulfonicacid
Note
1.Thereac9oniseasilyreversible
2.Sulfona9onisfavoredinstrongacid
3.Desulfona9onisfavoredinhot,diluteaqueousacid

ElectrophilicAroma9cSubs9tu9on
FriedelCraTsReac9on:Alkyla9on(16.2)
Step1

Reactants:
1.
2.
Products:
1.
2.

Step2

Reactants
1.
2.
3.
Intermediate
1.
Products
1.
2.
3.
Note:Severallimita9ons
1.
2.Cantoccuronaroma9cthatisalreadysubs9tutedbyeither:
A.
B.
3.
4.

ElectrophilicAroma9cSubs9tu9on

FriedelCraTsReac9on:Alkyla9on(16.2)
Step1

Reactants:
1.RCl(Alkylchloride;primary,secondaryorter9ary)
2.AlCl3
Products:
1.Carboca9on
2.AlCl4

Step2

Reactants
1.Benzene
2.Carboca9on(mayundergorearrangement)
3.AlCl4
Intermediate
1.Carboca9on,aLackedbyAlCl4
Products
1.Alkylbenzene
2.HCl
3.AlCl3
Note:Severallimita9ons
1.Onlyalkylhalidescanbeused;aroma9c(aryl)andvinylic(alkenyl)cannot;youCANuseallylic
2.Cantoccuronaroma9cthatisalreadysubs9tutedbyeither:
A.Stronglyelectronwithdrawinggroup(N+R3,NO2,CN,SO3H,CHO,COCH3,CO2H)
B.Basicaminogroupthatcanbeprotonated(NH2,NHR,NR2)(NONITROGENCONTAINING
GROUPS)
3.Polyalkyla9on
4.Skeletalrearrangement(canbeslowedinlowtemperatures,butneverstopped)

ElectrophilicAroma9cSubs9tu9on
FriedelCraTsReac9on:Acyla9on(16.2)
Step1

Reactants:
1.
2.
Products:
1.
2.

Step2

Reactants
1.
2.
3.
Intermediate
1.
Products
1.
2.
3.
Note:Severallimita9ons
1.
2.Likealkyl,cantoccuronaroma9cthatisalreadysubs9tutedbyeither:
A.
B.
C.
3.
4.

ElectrophilicAroma9cSubs9tu9on
FriedelCraTsReac9on:Acyla9on(16.2)
Step1

Reactants:
1.RCOCl(Carboxylicacidchloride)
2.AlCl3
Products:
1.Acylca9on(doubleortriplebonded)
2.AlCl4

Step2

Reactants
1.Acylca9on
2.AlCl4
3.Benzene
Intermediate
1.Carboca9on,aLackedbyAlCl4
Products
1.Acetophenone
2.HCl
3.AlCl3
Note:Severallimita9ons
1.Unlikealkyls,acyla9oncanusephenylandalkenyl
2.Likealkyl,cantoccuronaroma9cthatisalreadysubs9tutedbyeither:
A.Stronglyelectronwithdrawinggroup(carbonyl)
B.Basicaminogroupthatcanbeprotonated
C.N+R3,NO2,CN,SO3H,CHO,COCH3,CO2H,NH2,NHR,NR2(NONITROGENCONTAININGGROUPS)
3.Unlikealkyls,nopolyalkyla9on
4.Unlikealkyls,noskeletalrearragementbecausetheacylca9onisstabilizedbyresonance

ElectrophilicAroma9cSubs9tu9on
Reduc9onofaroma9cnitrogroups(16.2)
Reactants:
1.
2.

Products:
1.

ElectrophilicAroma9cSubs9tu9on
Reduc9onofaroma9cnitrogroups(16.2)
Reactants:
1.Nitrobenzene
2.1.Fe,H3O+/2.OH

Products:
1.Aniline

ElectrophilicAroma9cSubs9tu9on
Reduc9onofaroma9cnitrogroups(16.2)
Reactants:
1.
2.

Products:
1.

ElectrophilicAroma9cSubs9tu9on
Reduc9onofaroma9cnitrogroups(16.2)
Reactants:
1.Nitrobenzene
2.1.SnCl2,H3O+/2.OH

Products:
1.Aniline

ElectrophilicAroma9cSubs9tu9on
Reduc9onofaroma9cnitrogroups(16.2)
Reactants:
1.
2.

Products:
1.

ElectrophilicAroma9cSubs9tu9on
Reduc9onofaroma9cnitrogroups(16.2)
Reactants:
1.Nitrobenzene
2.H2/Pd/C

Products:
1.Aniline

ElectrophilicAroma9cSubs9tu9on
ClemmensonReduc9on
Reactants:
1.
2.
3.and

Products:
1.
2.

Note:
1.
2.
3.

ElectrophilicAroma9cSubs9tu9on
ClemmensonReduc9on
Reactants:
1.Acetophenone
2.Zn(Hg)
3.HClandHeat

Products:
1.AlkylBenzyl
2.H2O

Note:
1.Substratemustbestableinstronglyacidiccondi9ons
2.Doesntreducealkenes
3.Ketonedoesnthavetobebenzylic

ElectrophilicAroma9cSubs9tu9on
WolKischerReduc9on
Reactants:
1.
2.
3.

Products:
1.
2.

Note:
1.
2.
3.

ElectrophilicAroma9cSubs9tu9on
WolKischerReduc9on
Reactants:
1.Acetophenone
2.H2NNH2
3.KOH

Products:
1.Alkylbenzyl
2.H2O

Note:
1.Goodforacidsensi9vecompounds
2.Doesntreducealkenes
3.Ketonedoesnthavetobebenzylic

ElectrophilicAroma9cSubs9tu9on
GaLermanKochFormyla9on
Reactants:
1.
2.
3.

Products:
1.

Note:
1.

ElectrophilicAroma9cSubs9tu9on
GaLermanKochFormyla9on
Reactants:
1.Benzene
2.CO,HCl
3.AlCl3

Products:
1.Benzaldehyde

Note:
1.Intermediateelectrophile(chloroaldehyde)formedinsitu

ElectrophilicAroma9cSubs9tu9on
Metadirec9ngdeac9vators(16.4)
1.
2.
3.
4.
5.
6.
7.
8.

ElectrophilicAroma9cSubs9tu9on
Metadirec9ngdeac9vators(16.4)
1.N+R3
2.NO2
3.CN
4.CO2H
5.CO2CH3
6.COCH3
7.CHO
8.SO3H

ElectrophilicAroma9cSubs9tu9on
OrthoandParadirec9ngdeac9vators(16.4)
1.
2.
3.
4.

ElectrophilicAroma9cSubs9tu9on
OrthoandParadirec9ngdeac9vators(16.4)
1.F
2.Cl
3.Br
4.I

ElectrophilicAroma9cSubs9tu9on
OrthoandParadirec9ngac9vators(16.4)
1.
2.
3.
4.
5.

ElectrophilicAroma9cSubs9tu9on
OrthoandParadirec9ngac9vators(16.4)
1.CH3
2.OH
3.NHCOCH3(amide)
4.OCH3(Methoxy[ether])
5.NH2(Nocatalyst;Anilineishighlyac9va9ng)

ElectrophilicAroma9cSubs9tu9on
Trisubs9tutedBenzenes:Addi9vityofEects
1.
2.
3.

ElectrophilicAroma9cSubs9tu9on
Trisubs9tutedBenzenes:Addi9vityofEects
1.Ifthedirec9ngeectsofthetwogroupsreinforceeach
other,thentheanswerisobvious
2.Ifthedirec9ngeectsofthetwogroupsopposeeach
other,themorepowerfulac9va9nggrouphasthe
dominantinuence,butmixturesofproductareoTen
formed
3.Furthersubs9tu9onbetweentwogroupsmetatoeach
otherrarelyoccursbecauseofstericinterac9ons,butthree
subs9tuentsinarowcans9llbeformedbyothermeans
(orthosubs9tu9onofanorthocompound)

ElectrophilicAroma9cSubs9tu9on
Nucleophilicaroma9csubs9tu9on:A)Byaddi9onto
ac9vatedarylhalides(16.7)
Reactants:
1.
2.
1.
2.

Intermediates
1.
2.

Products:
1.
2.

Note

1.
2.
3.

ElectrophilicAroma9cSubs9tu9on
Nucleophilicaroma9csubs9tu9on:A)Byaddi9ontoac9vatedarylhalides
(16.7)
Reactants:

1.2,4,6trinitrochlorobenzene
2.
1.NaOH
2.H3O+

Intermediates

1.Thehydroxideaddstotheelectrondecienthalogen,crea9ngaresonancestabilized
carbanion,calledaMeisenheimercomplex
2.Dissocia9onofhalogengivesthesubs9tu9onproduct

Products:

1.2,4,6trinitrohydroxylbenzene
2.NaCl

Note

1.Nucleophilicaroma9csubs9tu9onsoccursonlyifthearoma9cringhasanelectron
withdrawingsubs9tuentinaposi9onorthoorparatotheleavinggrouptostabilizetheanion
intermediatethroughresonance.
2.Groupsthatdeac9vateringinelectrophilicsubs9tu9onactuallyac9vateringsfornucleophilic
subs9tu9on
3.Groupsthataremetadirectorsinelectrophilicsubs9tu9onareorthoandparadirectorsfor
nucleophilicsubs9tu9on

ElectrophilicAroma9cSubs9tu9on
AlkaliFusionReac9on
Reactants:
1.
2.
1.
2.

Products:
1.

ElectrophilicAroma9cSubs9tu9on
AlkaliFusionReac9on
Reactants:
1.Sulfonicacid
2.
1.NaOH,300C
2.H3O+

Products:
1.Phenol

ElectrophilicAroma9cSubs9tu9on
Prepara9onofPhenol
Reactants:
1.
2.

Intermediates:
1.

Products:
1.
2.

ElectrophilicAroma9cSubs9tu9on
Prepara9onofPhenol
Reactants:
1.Isopropylphenol
2.O2,heat

Intermediates:
1.Hydrogenperoxidephenol,addH3O+

Products:
1.Phenol
2.Acetone

ElectrophilicAroma9cSubs9tu9on
Benzyne
Reactants:
1.
2.
1.
2.

Products:
1.
2.

ElectrophilicAroma9cSubs9tu9on
Benzyne
Reactants:
1.Chlorobenzene
2.
1.NaOH,H2O,Heat,2500PSI
2.H3O+

Products:
1.Phenol
2.SodiumChloride

ElectrophilicAroma9cSubs9tu9on
Oxida9onofalkylsidechains(16.9)
Reactants:
1.

Solvent
1.

Products:
1.

Note
1.

ElectrophilicAroma9cSubs9tu9on
Oxida9onofalkylsidechains(16.9)
Reactants:
1.AlkylBenzene

Solvent
1.KMnO4inH2O

Products:
1.Carboxylgroupsubs9tutedaroma9cring

Note
1.Onlyoccursonbenzylichydrogensandthusnomixtureof
productsisgiven

ElectrophilicAroma9cSubs9tu9on
Oxida9onofalkylsidechains(16.9)
Reactants:
1.

Solvent
1.

Products:
1.

Note
1.

ElectrophilicAroma9cSubs9tu9on
Oxida9onofalkylsidechains(16.9)
Reactants:
1.AlkylBenzene

Solvent
1.O2inCo(III)catalyst

Products:
1.Carboxylgroupsubs9tutedaroma9cring

Note
1.Onlyoccursonbenzylichydrogensandthusnomixtureof
productsisgiven

ElectrophilicAroma9cSubs9tu9on
Bromina9onofAlkylbenzenesidechains
Reactants:
1.

Solvent
1.
2.

Products:
1.

Note
1.
2.

ElectrophilicAroma9cSubs9tu9on
Bromina9onofAlkylbenzenesidechains
Reactants:
1.Toluene

Solvent
1.NBS
2.(PhCO2)2,CCl4

Products:
1.Bromoalkylbenzene

Note
1.Onlyoccursatthebenzylicposi9onandthusnomixtureof
productsisgiven
2.AddingNaOHwillreplacethebrominewithahydroxylgroup

ElectrophilicAroma9cSubs9tu9on
Cataly9cHydrogena9onofAroma9cRings:Using
Pla9numandextremetemperatures
Reactants:
1.
2.

Solvent
1.

Environment
1.
2.

Products:
1.

ElectrophilicAroma9cSubs9tu9on
Cataly9cHydrogena9onofAroma9cRings:Using
Pla9numandextremepressure
Reactants:
1.Benzene
2.H2/Pt/EtOH

Solvent
1.Ethanol

Environment
1.2000psi
2.25C

Products:
1.Cyclohexane

ElectrophilicAroma9cSubs9tu9on
Cataly9cHydrogena9onofAroma9cRings:Usingmore
ecientcatalysts(i.e.Rhodium)
Reactants:
1.
2.
3.

Solvent
1.

Environment
1.
2.

Products:
1.

ElectrophilicAroma9cSubs9tu9on
Cataly9cHydrogena9onofAroma9cRings:Usingmore
ecientcatalysts(i.e.Rhodium)
Reactants:
1.Benzene
2.H2
3.Rh/EtOH

Solvent
1.Ethanol

Environment
1.1atm
2.25C

Products:
1.Cyclohexane

ElectrophilicAroma9cSubs9tu9on
Reduc9onofArylAlkylKetones
Reactants:
1.
2.

Solvent
1.

Products:
1.

Note
1.
2.
3.
4.

ElectrophilicAroma9cSubs9tu9on
Reduc9onofArylAlkylKetones
Reactants:
1.Phenone(Ketoneonabenzene)
2.H2/Pd/C

Solvent

1.Ethanol

Products:
1.Alkylbenzene

Note
1.BypassestherearrangementprobleminherenttoFriedelCraTs
2.Arylalkylketonescannotbereducedwiththepresenceofanitro
grouponthearoma9cringbecausethenitrogroupisreducedtoan
aminogroupsunderthereac9oncondi9ons
3.Dialkylketonesarenotreducedunderanycondi9ons
4.MUSTbebenzylic