Anenes

BENZENE

qqf
aoab.istau.fm
qunhymidisedeo planar acloud
e aboveandbelow
I 88 benzene
ring
s sp2
hybrid 14
resonancestructures resonance guesextrastabilitytonng
structure
v j v
Physicalproperties preferentiallyundergoeselectrophilicsubstitutionto
Nonpolar onlyweakdispersion preservearomaticity stability
forces betweenmolecules
41 v
lowmeltingandboilingpoints its stabilityalsomakes it lesssusceptible to
volatileand flammable attack electrophiles than GC bonds in
solubleinnonpolarsolventslike alkenesby requiresstrongerelectrophiles form
ccl insolubleinH2O
Benzeneis a colourless liquid
at room temperature

REACTIONS INVOLVING BENZENE ELECTROPHILIC SUBSTITUTION

Aug FeltzCSI warm

or Generationofelectrophile
UzcgsFees warm
Obv decolonisationofgreenishyellow Cl
UscgandwhitefumesofHucg

concHNOs concHIOacatalyst55 C
N2
Obu paleyellow
oilyliquidformed
Friedel Wattsalkylation
Utsa Alllses warm Vtb
ObvwhitefumesofHeegformed
MECHANISMOFELECTROPHILICSUBSTITUTION
FeBrcs
6h12 l 1 Braces 2 ClothBr t HBr
warm

FeBr t BE Brt t FeBrq onlyoccurs in

Reaction
strong electrophilegenerated anhydrousconditions
H2OwillcompetewithBra
H Br forFeBrsas anacceptorof a
slow lonepairof electronsThis
Brt t preventstheformation of
v
strongelectrophileBrt
H Br T fast
Br

LFEB.iq HBR t FeBB

byprod Lewisacidcatalyst
regenerated

Notes
Has04is a strongerLenisacid than HMOsthus H2S04protonalesHNos to
generate NOI
Nosis electron withdrawing and deactivates thebenzenering Morerigorous
conditions are requiredfor further nitration

Nos is a 3 directingsubstituent furthergroupsaddedto benzene

ring
are added at Cs LkIV

Note Use Brzcaq as a distinguishingtest between alkenes and anenes

Eg Add Br capdropwisewith shakingto Lcm'sof 2methylcyclohexaneand
benzene

Bkcalls noreaction yelloworangeBracapnotdecolourised

Br OH
Bracaq Her YelloworangeBracageis decolourised

major
 METHYLBENZENE
AIZU
Aug UVlight
onlymajorproductsshown Freeradicalsubstitution

Alkylsidechain
reactions COOH

KMnO Caq di H2804heat

Oxidation

Utz
Otb
UtzCt AldsCs roomtemp ES Utz

Utz
Aug FedsCs rt absenceofUV Eg U

CH3
NosconcHI04catalyst30C
concH Es Noa

Note because Utsis electrondonating it 9 electrondensityofthebonzeringthus

it is an activatingsubstituent Thereforeconditionsfor electrophilic
substitution are milderthan forbenzene

EFFECTSOFSUBSTITUENTS ONBENZENERING

Inductiveeffect electron donatingsubstituentsincreaseelectrondensityofthe

benzeneringthrough the
Sigmabond leg Utz OH NHa
They are activating
conversely electronwithdrawingsubstituentsreduceelectrondensity
leg Br CHO NODThey are deactivating
Resonanceeffect substituents with a lonepairof electrons residingin the
orbital can donatetheminto the benzenering viaresonance
p
8 f throughthe TI bondCdelocalisationof e Leg I OH Nth
Electronegativesubstituents canwithdrawelectronsfrom the
N benzeneringvia resonance throughthe TI bond COOH CN
leg
st s Uto
 Activatinggroupsandhalogens are 2,4directing while deactivating groups are 3 directing

substituent Effectonbenzenering to Effectonpositionof

electrophilicattack electrophilicattack
R alkylgroup Activating 2,4 directing
OH OR NHz 2,4 directing
Mtr Nra strongly activating

Cl Br 2 Deactivating 2,4 directing

CHO UH WR
strongly deactivating 3 detecting
GR NHI NO
W
OH OH OH
I Et I E I
G 2 6 2 6 2
s s s s s 3
4 4 4
E
Nos Nos
G Pe Et s
G
I
z
s s s 3
4 E

SIDECHAINOXIDATION
AHalkylgroupsexcept 30sidechains ual getoxidised to WOH
KMnoacaq
Utz GEO
Utz dtheHaffo COOH t 21120 t CO2 Purple KMnogisdecolourised
whitepptofbenzoicacidisfarmed
Benzoicacid
Cuhaeppt
KMnoacaq
UtzUtz
Utz bto dthetaffo GOH t Hao t 41300011

µ3 KMnoacaql
daH2S04
c Ut noreaction
I heat
Utz
OH KMnoacaql
I daNaOH ONa131120 t
g Ctb 8Eo heat 202 PurplekMnOqis decolourised
BmmpptofMna isformed
3 sodiumbenzoate
solubleinH2O

0 KMnoacaql
c Utz t 46 dthetaffo Coot t H2O coz