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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