+ Reverse Sulphonation

eadily eal wi, eehanism

sulfrtioide uokey

J is veersible eattion h
by addlnq bea
prdue
ulferf ad and heal,There fo
ad in diluted ouebas
sa)fie
Fdie aid
to benaene ulfonik
ic

tion is everted .
Hs0-heat + Has0y
Sulfurte aid
Hasoy

Benzene

Secmpoe Hhese

Applications of RSulfonalion, (an

is Yevergible teaton it be wed in

furthure klon Yeahon She

SubsH
Ezanple:
blockîng
belauteIt tan be eatdly
reali'[Link] the benzene
tarqeted sh,W'dahion
L

Saenk al ce
othey
Sa foniEblocls the tarban tor forhuye atau bg

after the Ye athion i's (an bo

Sabstitue and conpleled
DEmONed by everse Salfonálion.

2- Benzene sulfopic ad is alto unit used the .1°primo

alfur drugs,
Sgn hesis
3-'Benzene salbniylchlovde to sulforamde, 9° Sec
precurter
Cali
wbeh are used in
chenoteray
Larg

Frieda! cret Alkylalion

french dhermist + Amerikan mine eae0x imit
enincer Cor-
2t.
Lewte aid Ue as (A\CI3) we eyed is to
be ma
oukfale allelqroup
Converl in to calion and hen
and these
benzene atlak. BE-is alto a

Cosban

shift
AlCt,
 Broton Hydvger
no e
pretad
H

Mechonism>

#ol.
Step 8ol kCt
#[Link] steps
helidey
AlClsRCn-
t All, -All3J (arbo olion)
d Otep

+X- ALCL,

are intermediale (Yesoane stabilized state)

Sep o3: Depye tonal en.

CH-R -HX
+ A43+HX
Ezanple:
AC3
CHa- CHa-Bx
Pne
HC- CH- CH

A|Cl3
(Ho)
be ben2ene
irto benzere
24 carbotalion
duge
Carboalion,
primo

Carbo caliohe most stable carboalion

Calions to male it stade.
Teamange
hemsehes
chan ike
-lage
Senous drawbaul

.Limitatios;
certain benzene
4. Corbocalon Reaangemead. Coy
bequse
be made due to d tendeny of eation

of when
Hhese is he carbocal'on Tentargemad
posibi4 Jhan
OYe to add Carban Chain
ard
due to shift mehy
Coxban. Rearangemaud

(so
shift. from 1°to2°)
Cchange
 foils to procede
fiecal corakt
J Comyound
whe
Simitalion
jed
Pesull

Auy
vmitobenaene
NO
He sing
groups deaulivale
Deautivaling eneval
no allowed
itto
and

even Yno
fiedal allylalon are
Broctud of
Goaft
in
When
Ye autive sariog malerial.
hon
aYe e donalinq Cuhstftted
fredal eaft allylalion'
haroduul OYe to eledrophile stable
Supictabl
mening wh
attak than whal beyn
Realien of friedal CraftAlibytoaon
hen
Erample
Gieys of

Ala,
(Mestyle)

-nedal subchtueud will be add bul Qufde

here Hhere Subef fule a Jine (done due to exces of har

AIUs)
-Melhy is itsell Stab
2-dondlin4 qup So it
to ortho bl
ard
no stese htndrane ) so hals
torm Com
(dYauw baue)

•Alkl is isa drang alka e donang

activate tbe ben gene
gresp and t wáll
le Fledol caft Aalalion -02-2o25
Ledl nff leones formaion.

benzene

LGenoal Readlon
o.o0eer
uethollde
idoufldionbia
onbyde
tshe
Wen (ue e
he
forned ky
which eave bohind
shong
stable

CI

Yesonane.
aidatyhite

Enpbnalian
te be ahieved aupdhalde
Alakon can
odad)
oddonhy diid he podui otone. Aig halldes ave more Teacive

sl holdes

búl leisatd cda lyst

of e
Honadonby i esoan
h pronote he cuton The ollaukinq speie
lon Ihe complex bause produt of
hat con
Anedal cot aation easllon(ontains
L
wh o AlCIs mut be (anied oul othmone than

ale) 60e when he Yeation Over

dded Youhon rontue to hberate(veleae) he prndul

wil Hhe oluinurn [Link]
from the Comples bq hyenly sing
btler han' alkaon (Ato)
Moe ihde produ t somed. auyl group is
ond
deadiung
fomet (prclued)
 Then eNess

.Gereral Reacion + HCI he bond

GmitaHans:

Aeylfun

Mechan ism; 4- Becaute

1 step
Upeible
to
+A CI:
Applfcatr
1-There
3-Dyes
|-ACI p-c (aylaium ion
fomtion)
3-yme
4- Natura

(more stable) tesstabe)

ion
(e-O: R-c=O aulium
nalural nalure) formglat
(not beyorn) the
Pesorance stobiliaed going
ion
atauk o bersane ving
9nd Step

qenead R
R

(anniarnfon fomlion)

.3rd Mechar
Sep (bepnbandin)
e
(a) Al

)
(ketone

Yn0ye .This pocu vol forned iome datel

in and tecalionpoeec) further Whe
Jmportant
ng aer to Hhe
Srom

product,

(b)The oM4gou pleleud on ovu uith e deiieid BICI,and

Salt
ermed he sat he nel s
procluu is

(Galt)
Then exces. okwaer is odeda the water iL netral and brealudown
he
bond
s Owygen and aluminlum ondd pue produ? is obanet.
.Umiahons:
fon
Acqltan is tabiliaed Yesona nte no amonge mea
ocCUYPlas poi nt)

QUS
4- Becauke

pe chible to
Ckacthation

elecophtlte
produc
at ark cnd
it have. no
no longe,

to fusther
lonq qoe
Yeadion.(Uim itahon)

Applicationsi
1-Theie aulated proces is used for frognorveprodudin

3-Dyes produdlon

3- Folymex syolhei
4- Nalyal (calentoe)
Aromatie
ldayproduued

Gatlemann koch Realon -

formalation of benzene done. is n this Yealion.

C-H cttached witth beaene.

Geneal Pealion
A{Cl3

Culs

Mechanism
reautive ith e help
with spaie
ormahio

f autd
HCI and qenerale veatlve speie.
wih
C=o Yeal
+
[H-ceo? H-C=
Step 2i.
is added it would Ye move he chl orine

When Seuis cicd

Arom
he speuie. Aas

H-C=0: H-C=0

H_0 H-ceo] +ALCly.

 Reiton H•w l
qatemann HcL innol
he diretly
lo he meoli involved
toslyt otoud
and
atfva
-Mechanisnm

-H

ACls
H-C

,Ihis Te aution wi)

ail nol oppliabdle to
is used
pherol
as
and

st traes Step
H incchlortde
phero clher substrale.
s cfkn needed to at
Ceppe chlaide

•Orientahon and
Reaitvihy
on
of
oyfentafion
(Benaene)
and
Efect of subsituton

of Ben2ane Aromalic

stself s he e tch peú ba debalized e pesel.

Benzene
Step 3:
SublikeatiA a
OH
deaiuating
Haloq ent
Holoqens are kself dendivahinggups
directed the Subshin at
bu conanical

OHho ond
pon positors

attetmonn Reation" 1-Electrod

chemial where an
Teaulion proceas bengene
he Gaternmann
arp mic pheno)
Ovomclic ts formed by .Subctit
haldehyde CHCN) and
oanide ficc
Compound hydngn Lewis auid
in he presence of rate
chlonde (HCU)

aluminjum chlovde(AiCia). predue uliulaldehyde 4-

Electron d
The mechonism invobesthe genetion of Yeoulive
EShe
which Hhen attaeke the
"formimino calion 4pe
produe
he adege. to
tollowed by he
Geneal Peattbn Th
CHO

HCL
subit?tu
HCN

henadehyde
an
utivte
CHNH

CMO NH
-Mechanism

A\C
HC NH + Al Cs

H-C=NA ttA-c: CH =NH

traes

ott
CH =NH CH =NH

(iohormediate podul)

eH=NH -Al-Ci: + AlClzt

eseul H

3- Jna
Step

OH
te presente H0 hlg CHO tNH3

H,o
CHENH
t NH
Ht
torkebydioxq bengaldlye)
Efed ot Subrteution
oienlation Doalt
Orientation and Realiy
e to
1-Elecro'dorahng qro They dotity
bengene to enhanteit cledw nuleopenakute
enol) .Subyitoion
ficst SubgtiueuJ shich at auk ait benzene Contol he
rate
e reationand turthersubeifuti
on.

direL
pora
he YOJ0nan/e the conbined efel
o focuu'ge cHei atates he yings
sng
to heJPuajugolisn
elee subihhon

hee qToyps enhontey

enhontes he
he bu thare
huythuye eletro
philie
A1
SubiPhion and nuzleophii
lihyof ning increaies.
 OH,
e OR
ond lta atatk
huwing
and drei)he
th
.Thene Yesonane
auates he
posilons
or U pora
Saecton to the orlh
also
are he
Alhen ctket
t](indutiveefed),

Albo catecmeta cehrg yeupS2

omahe ring
which Seacivatethe stable bea
Mote The qro? eafive
Qen Canban alom
Ses nudeophile ond
Ymale the inq tho
eleatrophi Scbstikuhion and
toward he fur thuy
incutlv
diyect he touords the
the mota poson
Example. G e -NO,- NR:-CaN,
tase
ete.
adjatent"
Styette
Cas hocaor
moje Sta

3
Halagens- hongy elelrneqtie
qoups.
b QURecon
0 A
Are dea dired dhe ne
and ph
to the artho
+M (meso
enhone Turther dedrophlksahsitution.
tat
Subii
"Bedrondanaling
qroupsi Gie posíhe inoldve fed (1) bxonple
Ovtho atatl
R

Ext
(orthoatoa) (Stoble
Cananfgil
foro)
eMei'
Mee attaulaz R
ava alla
and Mta atalk

Alhe atetkeOTt
•Altkgl are ockvaFing
qoups and otho pova cdhekinq
nhen the attak
hups urs al outho poihHon,
3 canonial tom he chucture 1 is speuolly
bz
sable n his styautore )dhorge i planed on
carban alom
innedialely ned to he alkyl paup altyl
tobilizas henihboning
on indusive efed (t) rchonge

EN, one of he cangnical fom t'a' in the

(ase atlae 0 ha choge Caiban alon

etc. to the no Such
od'arent alyl qryp. There is
Be equivalen
Shukur e tomed by otlaik al the ma posilon Theje fore
Cas hocaHon yam otho and pora porifens
moje stable than Cenboaion Losmed by nmeta 12osl'on
2Recon ane efectLoH,
-0RHCOR LNee qogs
Ph They Can alto otivate he benzene bo through is
which

+M Cmeomertc e(fed) and theie roup divel he

Subgttaion al the ordho ard para Porihn
b Oge
the thduie ege pacued
Gomple oHkesonone clomiiever
OH OH

tonjugaled

due to
e occuY due to
Extented delocalizdhonof Peronante
efea
OH ond called he mesomen
qrep OH
eRed. OH

ava atlakH
 ond niqen nudeo pbili and can Share dorepi,
oygen
hew 7 bond o he neiqhbouring.
h om
Yesult onae
Yes

shuchone ukere Ihe t)change s n holeroalom in . ths

tate he Yes qnante eled íc moTe

inporton than the
odache efect o he olecrgneq
de ahe helorgtom
Ihus ztion
celocali Stoblizes he
intemediade torbotation.
None of he Canonical truchre

$Yom meta atale

nuk so only subsHfafion cuoul
orsing
ov tho a poro posHn

chargedencihy
delo caiaatve

cs benzene deide ned gubslikuhion:

4) Anium m
ionStobliy
2) StabiUty of charqe denity tocaltazalion.
Totensig he t charge f desabil2odthe inermediale
CavhocaTon.
"Electronawithdvauirgqoup
Sappete fale nito or Sabshifection
4hew
1-NO, oeided by charge ensiy)
6-N0

As hee is
charqe on ortho cunol

positon ond posikaih sgieid densily

Ymla hals ah is mela

auadirg
dhorgp dnsity
 Jnepa
Hding h Afnham Ion
Stabi:ty(otrele
eted).

he

NO

Me ctauk..
NO2

and pona
ions Oe toble bez
Cosbon attask ith dehan

is rlsuitoble obsiutn.
are he
[Link] he
dereghe
oe deadintg Hhef ont.
beostvote Hhe brgene ing
nedue ede].bd dire

orho ard ora positions,

detroregahe hon casbon

hey
withdrow the e rom
(unghored)
hove
Powever halogen Lnpaitede
ruleepksbie
hich be debocolized to by extendbd

when
atle
poisible
beding
Grd pora psiio Yesonene

Auanding to Charge bensiy

 Aropum fon De
Orthog
(3)
(1)

Pava attaki
Sterf

when

atla
É H E H

ron

Can

pora

The eaybon he bergene vi substitden ir called

Spso
ipso Carb on. Jrn Some ases add on he
pso canbon.

Beporture of the Substitilionwhich alyeady

Preseut Eut to he ipsosubstitutio
n prcluu.

ample ipso substithulion.

(1) c(CHs)s cteMs,cre

-0-01
Such Subs h'tutfion huo case

4 Already prerel subs Ht hial is

2- 9f leave in stable Gliovie4om.
bromple. Haso4.

H
 AceO
aLelic

CH

Ne

HCI MeSi -Me

Orho eRect
ole Fuion
substi
Sterfe hindhane pys a yniftcail
when Subsituer benzane iog is he bulky ,ovtho
preiel
Con inclue stefe hidrante the
atak by ekdophile
tronsiton shale bowever when Subsituteril ha aom
hohern which

with moe is
Can Coodinale ortho predut
incoming rop
The inyease in the ortho prcluilal the espente
formed,
called ortho

(dtrelal orthoand pore

d e dorehiey qrap

HND/Hs0y

(bire al para than ortho).

foraposiHkon
NO
Phencl Yealions are
Erample- Apléinumaln ) than benaene
Lotho Precui OH
oH
CooH ACo
NaOH Hso
fon )
tPheno-Ha
Shrong s stable

esterormaion
Esglaration Nat Nat
formhation)
Na

qe
velelrneahe
invde
he ortho
(Boon dep ofonatlon) Cubchtution
 Racteal No 2

trom eHhang) and

Acclale
of
Aelie
Ca Hç OH+ H3ccooH
ehanol Acelicad hyl aukile.
aulieaid
Chenialst
etano)

lo m o Hasoy

2S me distiledl H0

Na HlO3 (suraled schion)

Na, Soythnberos) deatluesgt