Benzene

8 Planar osp hybridization

8 GHG

8 All
bondsaresamelength
bizthe_in Benzeneis delocalised
g Theanhybridizedporbitalofeachcartoonisttotheplaneso2
8 electron cloudsform above8belowtheplane Cbelectrons

it
Electrophilic 2Eremoved 1
the
substitution
O2 EKE O Ht
Et Intermediate
Electrophileattacks
delocalizedelectroncloud

1
Reactions 9reduction Arsene I KtHz Ni c c
fit
Benzene
O HzNithightene
highpressure
GHG cyclohexane
GHz
HalogenAddition 2 Additionwithhalogens
Alkene IIc tch Nolight dE
de di
Alberti e'c Brzcaq No
conditions
c
BrBr
il
Benzene 0 tch Electrophilic substitution 0 THU
Noting ALClzlfedzttl.BR
Nolight Br
Benzene O Br ALU O HBR
Noting
Nolight

BrztALBrz Brt ALBRI

no
1 Br Br ALBm Brt ALBRI
O
e'mptyorbital

2 HttALBI HBrtACBrz
whydoestheBrBr
breatshetetoitically FEIAL havehigh chargedensity socandrawelectrons to it
I rs 8 Mzt
Br Br Fe Br
Br
Nitration 3 Nitration
conc conc N
TANG Hrsa
550C O H2O

GHG 8HsN0z

Mechanism mechanism

1
htt HzN0zttHS0I
HN0tHzS0y
3 1
Nof H2O
it
2 2E removed
fNoa f NG
Oz 402 O Ht
Not Intermediate
Electrophileattacks
delocalizedelectroncloud

3 HttHSOI HzS0y

Furthernitration FurtherNitration If conditionpermit tens 87CANS

N2 NO
102 g Nq
4 2 4 2

Voz Voz
1 nitrobenzene 1,3dinitrobenzene 43,5 trinitrobenzene

Alkylation 4 FriedelCraftsAlkylation
Alkyl
t R x ALU's Rt HX
haligen Reflux

GHSA Ethylbenzene HA
GHsGHs

Mechanism

1 CzHgUtALUz CzHgttALAI
H il
a Oy2Etemoved Efe Effie O Ht
Celts Intermediate

3 HttALAI HCl takes

 Acyclation 5FriedelCraftsacylation
COR
t RCox ALU's
NOReflux 0 THX
COCH3 ketone
tutzcod ALU's t HCl
Ethanoyl
Chloride ColtsCOCHs

Mechanism

1 CHzcocltALClz CHICO TAKI

2 2Eremoved I
Q E EKE O'F At
CHICOT Intermediate

3 HttALAI ACLTALUS
CHz
Methyl benzene
i Methylbenzene ismorereactive6ozmethylgrouppusheselectrons
Reactions 0 intotheringIncreasingdensity of electroncloud

HzSqtANg NqtHsI
Nitration 1Nitration the
Utz CH3 CHS
conc conc No
TANG Hiu
30 C
O t
O 1 2h20

GHG N2
2nitromethylbenzene 4 nitromethylbenzene
GHSCNODCHz
2 Halogenation
Utz Utz Utz
a
20 t2U2gAlU3 O t O
CL
3 Reactionofsidechains
CHEL
CH3q
UV 1 HU
O 1Uz
freeradicalsubstitution 0
4 Oxidation ofsidechains
Albanestheiddumatant
NoReaction
Acid
Base
CH3 COOH
MnojinHthassame
MnailHt
O O tHz0 effect as Mnaiinott

GHgCHzt3C0 Benzoicacid H2O

CH COOH
21
Mnailott
O O
5 Haloatenes halogens bondedtoBenzene ringdirectly

Ost CE b
The c X bondinthehaloatenesisshorter strongerthaninthe
haloalkanes be oneoftheLone
pairsonthehalogenatomoverlaps
stronger withthepibondinginthering
As Haloalkanes
hydrolysis
R XtHz0 Reflux
VerySlow
R XtNaoH
tags
Reflux R OH
veryslow

0 bCEt NaOH Reflux NOhydrolysis

Stronger

BUT Haloaltsanes CHzolt

t NaOH Reflux Nad

O O t
 Phenol Alcohol
Phenol with
Hao
CHI
go
ftp.tpoimasrtt.B

0
Functionalgroupphenolgroup

Themeltingpointisrelativelyhighduetohydrogenbond
Thelarge nonpolarringmakesphenolonlyslightlysolubleas it distrapts hydrogen
bondswithH2omolecules
Interactions it is mostlydissolved in NaOH

C O hassomedoublebondcharactermaking it stronger thanC oin

Alcohol
Reactions
Reactions of phenol
Phenolhasacidic propertiesveryweakacid

OH o Oira
O Ht which is 0 THO
phenoxide in NaOH
conjugate base
astabledue
to telocalisation and8pisystemin
thering
other
I
Notsharedelectrons
wat alcohol aS
Na t R OH R ONa t 42Hz
Nat CzHgOH Na th Hz
CzHs0
aHasacidicproperties sodiumethoxide salt
with Vreactivemetals

NaOH alcohol Noreaction

Natphenol
A2
OH N
µ O t 42Hz

Molten sodiumphenoxide
GHgoNat orGHgoNa
Phenoxide H2O alcohol so

OH
NaOH t Colts qHgONatHzO
base acid

Butnot
Nazcoz Phenol Noreaction
Whyisalcohol Due toelectrondonating alkylgroup inductiveeffect
weakacid
Batin phenoxidethenegativecharge is spreadoverthewholeatomdueto
theoverlapof lone e Oto with thepisystemotthering

1 substitutionin benzene
ring
It
Theelectrontensit inthe benzeneringisgreaterduetooverlapingottonepairof electrons
thismakestheringdmoreopen toattackfromelectrophile

Nitration A Nitration
Utz CH3 CH3
Benzene conc conc N 2
TANG Hou
30 C
O t
O 1 2h20
GHG Noz

conc conc N
TANG Hrsa
550C O H2O

GHG 4HsN0z
Phenol OH OH OH
dilute Nor
20 t2HNg room
temp
O t O 12h20
GHG CfHsN0z Noz
4Nitrophenol

OH OH
Conc NO2 No
20 t2HNg room
temp
O t 3h20
Cotto
Naz
2 4,6 trinitrophenol

B Halogenation

Benzene Br
O Br ALU O HBr
NOT
lag
Nolight
 OH OH
phenol Br Br
Testforphenol
0 t3Brz Nocatalyst 0 t3HBr
Mustbecool
2,4 f tribromophenol
decolorises whiteppt
oxidation c oxidation
AS
primary alcohol aldehyde acid
secondary alcohol ketone

Tertiary alcohol Nooxidation

A2
phenol No oxidation

A.si 1 Hulton
R 0kt PUS R U
R 0kt SOUL R I
R OH 1 HBrtheat R Br
b Noreaction
Phenol 1 any

acids Acids
Generalformula foracidtester_CnHzn0z
Acidity ethanol phenolLethanoic

Ethanoic acid

Hz carbon is electrondeticent
o H
Due to c o whichweakenstheott bond

O o
N N t
CHz C Utz C TH
o H O
conjugatebase is stabilised
bydelocalisationotelectrons
around COO
 Acid oxidation noreaction

Except
coop FehlingIBenedict CoztHP
11031
Hollen's
Mn0IlHtKrz0EHt
Heat

EthanedioicHEzoy Strongoxidant 0211420

or Mnojayt
Cook
OOH

Acid derivatives

to no no
R C p C R C R C
Olt U o R NHz
Acid acylchloride ester amide

Acylchloride
CHzcocl CHzatzcod
FunctionalgroupMOU
Generalformula Cool EthanoylChloride propanogechloride

a ro
LH C 1 tussock Hz C Pod THA
o H Noteasy CC steamytunes
COOH cool
Pou THA
0 taels O t

Benzoylchloride
Phenolt PUS Nonaction

thanacids dueto thehighly stcarbonatom

Agechloridesaremuchmorereactive
joinedto 2 electronegative
atoms

Haloaltsanes
jog
R Xt Hyo Nonaction

R Xt NaOHHot ROH t Nak

0 At NaOH heat Nonaction

tunes
cazcoontacerwhite
Gt3COAT Hz0 rtemp
 no
CHz CE OH CHz c THA
CL OH
CH
CH UtNH3 CHz NHz THA
Amide

X Wrong utz E cltdtzNHzatz E NHztct.BA

Esters
esterification 1 condensation reactionCadditiont elimination
acid alcohol estertHzo
Hydrolysis
o
HtCHzOH CHIE H2O
Utz OCH

HzC U t CH3CHzCHzOH CH ocHzCHzCHz THU

chloride
acyl
NotCaq Nottevirsible fast
it can hydrolysis toacid
O N
N
C At Ho 41540
Hs
Notcash 0 0
Propanoyl inNaOH phenyl propanoatate

organic acid phenol No reaction

d tito
O 0
0 O to
a
0
Benzoylchloride phenyl Benzanoate

Amines NHz Nlt

NHz R Nlt R NH R y R
R R
Primaryamine secondargamine Tertiaryamine

HSNHz KHzzNH CHD N

Ethylamine trimethylamine trimethylamine

 Preparation ofamines

1 haloalkanetNH amine HX
Reflux
excessNHz inethanol
highpressure1sealedcontainer

HgBr t NHz CzHsNHz 1HBR

2 Reduction of NitrobenzenesitcomHa
Nitta Followed
by phenylamine
ColtsNoz Reflux
0 NaOH

salt
NOz NHz

O t 6CHI O t 2h20

3 Reduction of Nitrite
2h
R CH AztNiINatethanol RatzNHz
ZHI l LiAlHu
o
Il
4 Reduction of Otamide c Nlt amide
o
11
R C NHz LiAH
l u R CHIH
indryether

Bases
NH Ht NHI
NHztHU NHall
t
NHz NAza

O HU O
NHz

R NHL NHS 0
Strongestbase weakest base

Alkyl groupison
electron TheLonepairon Natom is delocalised
donating
groupitmakesthe loverlapswiththepisystemin thering
lone
pairof N monavailableto
 kept polo

e withdrawinggroupincreasesacidity
e releasinggroupincreases basicity

1 Reaction with bromine

NHz NHz
Br Bk
t 31382
Cag O t 3HBt

whiteppt Br
OH OH
Br Br
O t3Brz Nocatalyst 0 t3HBr
Mustbecaq Br
44,6 tribromophenol
decolorises whiteppt
2 Diazotisationi
tuzHuK
O ii rut
nine'IT Nicilcoasnici
O diazonium
NanoztHU NaUtHN0z ion

whymust I be
Nt Nit T Wc
lool
0 Water 0 OH 1Nz

whatdowedo Nt wit t i N
withdiazoniumion 0 4 O2 OH o
z
Ato dye yellowlorange
verystable

Amide
0 o
Il Y
R c NHz c yH
preparation
v
acylchloride NIB CH c THUG
conc NHz steamy tunes
why can't weuse Ethanamide
ethanoicacid

NHz CH E OH 1NHz CHzcodifHc

 5
Utz C HjNH2 415
q µ cHztHU
Nucleophilic substitution

cantata Amides are Neutral

alone pairfromNorton isnotavailabletoacceptproton
why
cliffy
1 Reduction ofamide
CO NH Reduction
CHz NH

CH CONAL LiAlH4 CHzCHzvHz

inether
2 Hydrolysis Hzotacidlcatalysttheat
ester Hao Ht OIF
19 OH artevirsible I
R ch it notnoirsible
HER r Ht HoR R 9 0Nag 1 HOR

Ht r EOH tNHy
Amide 1H2O
o
R C NHI 11
NaOH R C ONA 1 NHS