ELECTROPHILIC ARDMATIC SUBSTITUTION

24/a/22

Momatiu wpundb
A pmpoumd ma claied a aomatic t lils H
pllawing ibrite.
wmfoml honls ycli and plama
mt
Poubehak.
i)em adem
ni cloud as KE
should rame tbetratu un inimuptud jclic
4t
mouule [7 duord) .

aone Dmd
Md hulew thu plone q h»

i) 41 houd lu Complcely Legated

must lentim am
add mo: 7 pon
v) he Ae urnd

pPumambhun.
Benm napthale

Rptkul Rule
planar enpomd to
dhe u ptatu hat
o eyeb Lentain 4n +2) TE
tlouds murt
aomabie, lsunintenptd
whww n my uhol mmln.
womatit ompimd must hae
Auadig do am

2 (h 0
Cn D
n ehthen
14 (n3) t e
Aapmau hat C

BeCau Jhne Pai

compod mu rae 35,1,9 ete paiw
nemub o
a
nute mati cal wo gig th
ule
ug
t ome Cm odd
Cm anomaiu cowyomd
 Pule An +2

Benen

4+2 6

4t2 S n2

42+2=ID

4n+2 s n=3

4x3+2 1t/.

arematic bubaikuin
3oa edro plhilie
anemati pulati tukon, an slatro pal
a ltco picbi Cremaho Lompomd.
mn
Auusrti but fo ydrg

+Y

ultiuien
auwies
anomaic

tewnnon1 alecdo plile

asu

)HALDhENATION
chlrid o 9ocdide s u i buks a a yorg
A Bremede,
n) NITRATION
a ogn
A wbo o CNo)
o ) AULPnONATloN
be o agdagtn
acid ( sog) Aulsi
A 3ulhonme
FRIEDEL CRAFT
ACYLATION
i)

cy gnaup (
R -c=o)
Justwh ho a kdrog
V) FRIEDEL CRAPT ALKYLA11DN
An atk ro uyt udu ho a
ynogn
qenuad muhmmw o lunophilie anomak suhsti uien

+He

Carbocalion Irlermudiate

th 1st uaids uith an eedro pkil. ty

Btp, mgene
ong a Catbo taiuen nurmaiat
aproumated
u

JBuuu e miu mudia.

laukottin
cam

and
u ulatinuky Mew
Lonibutou. o ff
33 wsonamu
cenveltA mlo a

apmae
aubmatiec compound-i uim
endgoi ab wm

a o rdic imlu mudaate .

wen
a oan
hu uautio mitluu pulls
nd
Sn h 2 tu, lednons
tabDathen mumediat. Omd
ou
prolenmom
h aa

mone m th ing stablish

tabus1 aklb
aupal
hat ld e olens
egom e taue stup

arwmatiudg.
utou t e
tabi lidy tnhanng
1HALOMENATION F BENzENE
h leis oid in
B, c onby wm h ppusnu

wacton mintnw
i s r u s n , lnpne nacs
wwwn Revins aid

Onemo Lowene amol chloro Pumene

ond to hotm
ovomi nation amd eiiloinatian
kouis ud wost ommonly uxd elht
all mbydraus jom
uahons ane Feclg, Feb3, Al

#Brominatum
H
C +Ba
 Meehaa
Br + FeBra
82 B +FeBr Br Br- FeBr

Br
+ n B t

,.® slo fas+

+Br
Carbo cation intermediate.

CHLDRINATION

Reackion

Fecls +H.
+

chlorwbnaenu
Mechaism

ceei: -Fect
:c -

c +Fec

HB
B:

+C Past
slo

itAir
1ODATION
Reacion
oxidizing aget.
+2
Todo wnzene

Muuhomis (vo).
oluteind hum nidising
i2 uith an onidishg agent.
4ludopalie s
oxidisina gnt 21 2
2
B: +BH
slow fast

Car batio
ntu meoliatu,
ep 2NnRATIDN
RAin
MSO4 No
HN HND3 +H,O

Muchaw
Nibatim o Btmn wwbh mbuw aid ruauu H,so4 as a

Calatyst
H,so4rotonata wibu i d

hots w polonntd vitne wd toema mnem um

4 th ahucbo pl reyisud to h mmbulhon
Step 1
H

HO NO2 + H -D s0g-H uo +Ho.

H,o -ND,
iHonium

B NO2
+ NO NO2 +H8

nibobangen

3SULPHDNATLON

+H,so4 +Mo

Bewm
8ulphoiu aud.

M,SD). i uscd to
sO4 ulpluu uo nide m H,SO4 ol Lone
Fumin
ulphonatu onomatic amid- aings

Mechamm
azid.
8hp 1 Fownaon o ulpbonit
S - on
HO - o -H ..
+ HD --H
8ulthunic aid
So4Mao HD- H0

(sot)
 Step 2

+HB
B
Sast
+SQ 3low

FRIEDEL CRAFT ACYLATION ANH YD

DR IE
4). a m
ACID
A ip ANHY IDE

CHLORIDE

m
M AcYL byn
byn
oLads with
do em aam
Bmyne omjdnous
Aldz

h pun
Ruackha +H
Anh. Allg
R--c
Aayl bengpo

R--on
+R--o-U-R A1

acid aubydnide

R
R
Mckamiem rieolul tnalt avylalion
a aquinned shdrgAL

uacion. ou chlovide en
m
ruuties
Shw i omud t h u ALlls
a uwns ccid
ith
aid amhydride

8up4
R-B-i: + Ad, R-
Acylium 4on

B
R
 Al - +H C
CH-E-a
Autgt barp

Mrchamum
tup 1 Forman a <hdropkile

ALL3 =CM- tAu

hdopile

+CH CH3-
how o noton
Bap 3:

HC

ALKYLATIDN
5 FRIEDEL CRAFT
wilh alkyl kaliilu B pruwnu
Bem u n

aluminium chloride to 1hetn alkye Bennt

+R
Alds H

Huchaum

R- c : Al CR R +Al£
 R
r

9del ovayt alkylation

uaon, a

h u a cuen
anborai houmad

halde uuth ALCls dn c l

alhyl lromide
Lonomi d
alhyt chloidag,
dhyl 6tuoudu,
"e used.
alhyl 4dekidu cam

AlCl chs
CH,

Mechamim

CHce +ALda

cHs+ HB

Muthgt Bmgont.
o/22
n1D2
EFFELT OF SUBSTI1UENTS ON REACTIVITY

Lik nymu austLedd umms alo wongo ehdno phibe

avemai buhyti uon Madio

ownt 3 wuti ww mak ua tti mel

make ati hn
tow andb Aludnoptuili aemaiu >ulusü ion .

arematic u l i lian
e ctnopie
naen atlack a poitiely thanged sluuinoplil
on t mluotiilic anematnc aing

Snuasing the lerwn duniby lumgemu nmg

wn Uleae atratti wns d m dophil

Bules i tmins capule odlonang eleurm imo hw

wil m Uleas h nadu o lubo pailie
emume Known
anerabit Aulti tulien md u ubuti buunts anu
as Activatons.

Bulsti tnews apaule uh wth obnamg luhon om

she i n g uuill durear t rale lecbopi uc
aoomaki Julyi tulion omd th uletituuens hmown

as tacuvatou

RELATIVE RATE OF ELE CTRo PHLIC SUBSTITUTIDN

ulatilu Cam

dongde eluhon mto Juemgme

 mcmcu detnon Donalion
unom Danation y uoneme

Z denatw lunon Y wihdna elucton

Jn unt
Bmym i

an no was uy uhich ulrti tmnu uwith

1) mduuti urm uithdrawal and dunativon

2) Rnonamw ltron i t h drawal mel donatin

mdudie unen with dranal md Donalnn

utnon thnaugh a ond s cehed

Donaliin o
ncucbi e lutwm doutio
oonats suubren neuetiuly
rrap uuh as CH grou
Aht
Lombinnd mith ny dnoyn.

sulusti uns denats udren mduiwly.

uihdranwal luben twouglh a lumd i alled

ngluti n lednon wthduyal

8ulti uems uubhobnaw elnen gncudiel

NH
 Sus altive
8ulstitmamw mar touwwyda
elubropuut msi uua

8brangy aclivahng bulutiluumts ony duati vatiq 4uatil

OR CEN

Mgdunatly autivain bulsti lwn Moderatuly deactivamg zulstulu

HN--R -

Buleu un
Bulyti unts Weakl deacivalg
Wrakhy ocivating
8T
CH-CHR

DETERMINATIDN DF DRIENTATION IN ELECTRDPHILIC

3 ss 5

whun uluthaad unpn wndugeu mletho phili c

Bulctiiuo JuRtn, he mew Dulstihunk Cen ata ch

Pura

Pana omu .
ordho Mita
somu soma

sulyti bumt alauady authed

piuntaln mew Buleti uws

L uivalaig uulestitumts mme

huakly diailivali
oalogpn a iucos
 t

Prrarenotáiere
hlose bmy* be

A uuti kunt hat wow clnttivaMang than alogu a

HSO4
+HNO3
NO
i o auto phene
Aulapenew

+ Br Fe13
M-brrme nubhe birgva .
Nubo bun

dution mueng lucto pl can ie p a nad e

mtu med.ate
tablity tie cao at
Nore stable
duaanim
etho

faA

NDe $able
3 dilpu Calhotnluo a theumad tenpatng ih nulala w
prukerud puthhn
Anbilty the2 inul dabe i ne

Ahe naten. Lentu butou tunt

w n
met
Mot bnl.
n.),
Rumana Lenti bulou
alene aicated to A pest
pesut ul,
alune
he
uathud dunuhg lo
sulytiuent
Dazau hdutti u ulia
lu slailiud ey
tanben
chogd
denaim Lenbu bulwu wu ptnne
Mma
shese ulaliwly srulls otao

ey eh nulestiluun ditiud
otM
oC
para poistioo . orho

Mor
ots oc
Meta

Anisole cM
Par 3

Y
iho Coube Catin
coube Catur
dhe lstdunt dena ubn y usonamel,
otho ant
Owig cludropil o
foumed ay puting Aucau the
Lnti butou
hant a
ous mant

lehon huneheu au
zulti bunt Com donau auanana.
that donate ilvunen g wwmu a o-P duusto
ou

or lhs

Meta

Protonated
Ani

y
Least stable
kes ti nens th poutiw LAarge ot paekial posi i thatry
atom aMacud h Jumym ins unth cuuus

ultbw rem Jhe

m duti ey d
o u uesti uendu wth daw lbion

u i draw lbum
She a d i tatid Resonamu tonti butou a Deayt stal
aeljaend cutom4
JLaw hone poiw hargu a 2

bo he most taul caubocation isfotmed uh

Sn Lin cb lveted t t uuta pasttier
pmle

ACTIVATING Sv8STITUENs STRENGTH ol MIP DIRECTDRS

- NH2

-NHR
fongy actvalig tho pana
-NR
diuuelou
OR

- NH-8-e
-0-- Modualy actrakiy tha pua
darcting
R

CH: CR2 ot o paua

WLaky attiväig ouve tng
DEACTIVATIN S0&STITVEN TS STRENGTH oMIP DIRECT DRSs
c
Br I
WLakly deachvativ octho para divutig
-n,J-e,-i-a
-OR
Moduately Aualt vale Hta diveh ng
-

-d-oH
-CEN -SO3 H

- NM -NHR stvon' deacti vatiig

Heta divnuti
-NMR - NRs

NO2
 BENZ ENE
AROMATI 3VBSTITUTIDN 1N ALKY L
sulusi brunt wndusgo
Ualum uuth an alkyt
a lena Mn ane omud
2 produb
an eletho plhiluc aemai mulei uiin, t
1.e am rtho somu and paa omu a
The PpuCenknge
bn
nelustiluenks
ulhu he
%onfomed depnds on
eldno pes
he duua
auattm iuus tras
e follouig nitvaloo
natio uith an 4nuay im

alkyl ulsti bunt

cH
Ma504
+HNDg
NO uune ( 34.)
o nibwto luine P nibo to
Toluene
C6r').
CMcHs
CH-ts cHCH
HSoL NO
+HND
Na.
euthyl benme
O ethugl nibopumgme P etht mbw bengns
so) (so'1.)
Ccm),us
(cM)-CMs (cis
HD NO2
+HNDs NO2
0-tut bybyl nubro P but bubyl nabi
4-bu mge ben ana
benme (52 )

BENZENE
OF ALKYL
SDE CHAIN HALD&E NATIDN
Cam lee
pidethvinao on ulk henpue
alegn at All mleeting
- utuhamud). remne
ung enemo
i

oone NBSt m-

nulutiuuh o a Jumaylic kydnogen m a uaital sulusti latien

NAtuor. nte a has hem lacud on a lenyyle polien,
Can e nplaud Savavy u, mliopilu ey mnms
SN' d SN uacion
umyr tan
umyre can h tupaud
muide Nanl, o uhstiatzd
by thid w
-CH-CH3
+Her

+ NBS
4 pheng prepemt
a breme
aop Bn
RE SONANCE StABILIz ATIoN OF BEN2YL RA DICALS

tabilizud Raditul
Radital
i a sesnamte
aditat
Bemay usmam, jolmn
9u au 2 nally tule majia
lethon pn a Jenyylic carben
u nun puunud