Pneponcuton of Haloneneg

(a) Halogenatton;
ci elecho phi u'c anomatic substiuhion reotHion
Nutlean chouin ha 'genalisn
C 2 Onhyd.

Aic +HCI

NOTE anhud AICa Pecla, Fe used to genenote

elec o phile
Mechanism
U) Cienenahion Of elec rophile
CIc+AICl > ct+ AICa
(2) fomatia of canbcahan intenmediate a
C H
CH
(3) DeprdtonaHon
C * C

+AICA +HCI+ A ICl

CM3 CH3
+Cl2 anhyd
AIclg +
Fecl3 0-chlovotoluene c
(mi non) P-Chloundtzluen e
(major)
 uFree nadical substituhon Leactian
Side chouin halgeahon
Occuns in_presnce aj Av/suniight
C3 GH
2
9f ex tecs Cl2, iS USed
SH2C CHCl2
Cl2
Beuza
dichloride BenzotnchlcoTE
SM2Cn3 CMCM3
HCHa3
anhud
ATC
Ctz H-Cl2
+1HC

NOTE Stability of fnee nadicols

Ca CMa
CHCHECH,S CH° C >cncn
CH
Benzyic alylic 3
ree ree saval
odicat
 Diazotisation; Process of convension of
aniline into diazonium salt
NH2
HNO20NONOt HX
O-5C/213-278 K
B e u z e n e d i a z o n i u m n a l i c ) e

Oniline

(b) Sond meyen's reactiovn3

Nx
HxCuX2 +N2
X=CI,BT
Benzeve HalocNPne
dia2oniumhalide

(diazohiumsalt)

C) Gattezmann Reaction

CuHX +N2
X=CI,8r
Niazoniym Haloanene
Salt

G) Balz- Schie Mann Keachon

_Hefy
(fluDadbonc +N,t
+NtBF
ocid) een uM
X=CI,Gs Benzene FTuosdbeu zene
dia2onium
tetrafluordboaate

Le)
Le) By heakng diazonium salt uoith oq; KI

CLaK1
+ N2 +Kx
X=C,6n
 Physical pno penies
uSolubi lty Hlbal kanes and holo anen e
ane alcan molecules StYt hey ane insouuble
Lsligh tly so wble in wa On becase n w
kore_of in teNaChon Set up bJw holoolkone
O halpanene_gnd u atN molCler n e
not so skong_Os H-bonds aloeody eKicHin
blw Hlo 0 mo'lecules ON wec a n so s u
tnat k-X and CgHs-X can neithen toam
H-bmding with H,O nor can bredk
H-bond alneady preent in HOmelewa
1hey aNe qu'te solwhle in Onanic solvent
liKe ehen benzene _CHCls, Ce4 etc,
( 2 Dipole mo menti = A,xd
G distance
Changee
R-CI RE>RBrR-I ( beccuuse qxd forci is
gneaten than axd for F

CH2 Fa CHCl2 > CHBs, > Cn1 Dipole momen t Vs

with i n eN)
CHF CHCl32 CHB CHI2 (Dipole mome1ts
with v inEN)
CX4 hag zeno dipole momen t

U= O
(SAARTH
X X
 (Dipole momen t
c
(L=D)
loUuen
O y dipole moment of chombenaene is
than that of cuclohexy) cnlonide
CI
S p
(Dipole momen)

n chlorobenzene dipole due to -I et°t pantiay

Cancetled out by dipole due to +R-effect
3) Boiing point

Boiuna point Vandenwaalstorce

d mo lCn mas

suntaceonea

branching
R-FCR-cI (R-Br (R-I (Bp 1 with inmos&
X)
ChaCnC1 CH3CH,CH CH3CH2CHCWC
LBp 1swih insize of R )
C3
CHaCHC HaCH,C | >CHar H-Cn,CI CH3
CH3
nbutyl chlonde iso-butylchloide tent-bLuty
BPs with i n bonching) chleide
 CBp14with T in moss of-X

C
met Pana

neonly saMe
he bps isomenic dihalbbenzenel ane
bu thei me have vania biliky. Mp -iome
fs aluiayc highen than that d o and m- some2
because p isomen 9 mor Symmemca arnd
ts into crystal veny ehecbvel
Densit4 Densiy inneoses with increase in mass
-X and K_gnoup
R-F R-cI R-6Y R- (Deusity 1& with
Tinmasc h-X)

(Dencity ^ with i n
mos s
o Iky gcup
Chenucad pnopenties Of Haloolkones 6
(1) Ntcleophu ue Substituhon neachon 6

In thic type o nea chon, anucleophile

reacts with maloalkane(called substrote).
Substituhm noaction ckes plteond halogen
o s haude
atom (cal led leauin group) clepant
on
+Nu C-NU +X

Wucteophi le Main produE

Keagent
ROH (Olcohol)
NaOHKOH R-H (hydnotanbn
H
Li'AIH4
H2O ROH(alctho1)
H2O
CN ReNtYonde
KCNDCN
On nitnle)
R-NC ISOLpnile
AgCN g-cNS On iso nitm le)

KNNO2 NtaNO, ONO RoN=FO

Ca'kyi nitote)

HA-0-=O R-NO2
Cniboolkane)

N aOR R-O RoRlethen)

KI (ayliodib
Ataf
R-NH (omire)
ntH
ROoRletter)
ecoo Rcoo
KR (aIkane )
R-mt
 anuCloophilO
Nuclooghilicitya Tendency C
to douafe"epn
tn ahkyhrg nuleDpiuuty

Neucleophi u'tity o Size

C Bs<I
Nuclophui x_
élechonegafviy

CH NH DH > F
Nuc leophilu ctty basiity
-

CH30 Cs H50
Halllde im (keaving
qrouP
That halogen witt be a b e t e n Leavin9

oUp uluch ha a ange sizé o s

Lt Can e m v e eas hy due to low
bnd dissott ahon en holpy

Solue n ' The Sube tance in u o l n C

somethung iuo( Ues

 Solve nt

Non-polay so vent Polan solvent

(2end dipole moment) (non-zenodipole
MOMent)
ef. cela, CH6, CS2 ete H20, acetone
CH3OH ett.

Polan solve nt

Folanprtic solvent Polanc moticcolvent

In thi H not
Solven tin usthich
H is bomded to highly bonded to highy
eleconegahve
elechnegahve

elements ( E,
0,NJand e lemeMf (FON)
Can sol vate cation1s
and onions
HC Ocetone,
H20, oHs OH
CHCOOH ett
ionuyleulphoxile
CDMSO)

oimerSDMF
OimemyhoomonuNe
 ****************
. . Date...
Topic

Substituhiornneorhcn
Cate OiEs Nucleophel

aSN Gimole culan ANuc teophiuc suhrtituhn reorto

2 hd padea)
H
Pola
OH + a p t i HO--C - Ci
Nucleohi le) H H
solvent
OIkyi halide) ansitiMtote
H
HO-
TIHCLegu7

Rate= KICHa-CI|[OH Csecomd onden)

9t olloS Si gle-step mechonikm
Nucleo pwle dtlocks om back sde
opnotC
SA tokes ploce in pre4 ence Of polcun
Solvent
9t S a luoys accompanied bY invos i n c
conHGwrouticm[walden invensin)

Rea chivity towands SNneochionsX 1

Steanic nindronce
Merhyl PrimonyC) > Secondary ) 1etny
halideg holides halida naluses
 uthuch ic mone neachve towandr SNreachonb
(a) CHC and CH3-HCI

(b) and
Br Br

CC) CH3CHBr a n d CH3CH2

TOns la) CHa-CI asit is i° so 1essen steanit hindone

(b as it is s o less en steanic hindrone

CC) riom s a b e t e n 1auin?

CtaCH,I a
becauseC
gnoup lange size .
Ambldeunt alucleophile
Nucleophile utuch ha ve tuo attoc kins
Centres orcite
e CN CN- feoyonide
Cyanide
hitnle) COnihmle )

NO NO
nitnte
 HaloalKaney malky auO nde
neaCt with KCA fO
wih AgCN fpmms isoyonude as chisg brrdut
but
Erplain
CNin
m 9n coseo KCN/NOCN, it provtdes
c n atfoc k eihen hnough C o n N but
ustuich
Ottock hnougn C tokee ploce as C-C> CAJ
bond
and covaent
AgCNiSa coUOle nt com pouMd
changcter con be seen HhooughN (bydorathvg

O:9dentity A and Bin pllowing neochon

HeECAA

CHaCH2OH*SOCI2 >A-

A cHgCH c!, HCEC-CHC

UnimoleculaN Nucleoprillc Substituhan

Cb)S7
eachM

9t takes in res en cl Ck Polc pnot iC

place
s o luent wohuch
stabiuke c a b o Cater
int mediatesteP
SO foom ed i

Rate o neachodependr upom concenahcr

AARTH
 Cny cme reat tant 1. P, alkyl halihe Ibrstundenkinant.e)

(CHa)2C-6r + OH (Ca)-OH + Br
-hutylbvnide L butyloleio|
Kate =K CHa)a C-B
Mechanism 0f Salneociom o
Step Fomatron of canbotation
Cl
C - 8 ola > +Br
potiesolvent
Slouw
Plonan
CarboCatonn

Step2 Atack o nueleopthileter)

ast
D
OH CM
HO
CY\ +

H OH
CH
gwensiUY Retenhom
50) L507.)

KacemiC m1Xtune
NOTE Stepi i's slowes1 step so it ig val
detenmi nun Sep
 Keac hvity touandc SNheathon x stabiuty d

Canho Cohorn

ClCtECH 1étian(3) Secmdortl:hi7

Conbocoahon Canhtohcn ( )
Cahucahon
Sy CanhoCahn
Cnbo (ah m
stabilsed by
Kesomance
t i s o teenupanted bY NacemisatGN
Cmounatn

(2Eliminahon
eocthn
veoc7d7 Oeydrohalegeratin
when halvakan e- with B-H atmri i heated
witn ale SoI" KOM, Hhene is elminatieri
Hatum mS Canbm and a haleger
om - Cabon aum

Takes plote in presen ce o 8foo71a base

ike alC NaoH|KDH C2Hs ONa, otls OK
NaN, tent-butoxide kHa)a C-0 etc
sodamde)
Main poducd alkene frmed
 C=Ct e-H tX

B- bas e, X= leauing Croup

Ease o dehydhohalogenahom Soylzth'4rule)

tehany (3") 7 Secondanyl2)>paimanyl1)
haide hatide halide
ytaenkrule n dehydrohals genahon (elinination)
neachoms, he poekenned tma br)pDdvCt S
that alkene wwtuich has preaten numben e
olky groupsor ess number oh hydnogenc) m
double bnded canbO1 atoms.

Ease e de rydho halogenahbn

R-T R-Br R-cI>R-F (Due to decneas e2
in size of halegerns
ease okdehydh0-
halogenaim As)
alc Ko
CHaCH,-c/ OlCKOH
CHaCH t HC

C H - H - H -NaNI A H=CH,
7
HC
CH
c

CH-CH-CH2-CH2 alcNoOris cH,= CH-CHC3

(minor)

CH3-H=CH-CH3
(major)
Saytzehh rule)
 ******* ***

Complete the veothion

CHs
CH-CH-CH-(Ha tentianu
tdoxide
butoxide
BA
cHa Ch3
n CHg-H-(H-CH Henhiany
butoxido HCH-Ct1= (H
Br minor)

CH-é = C-CM
H
Cmajor)

The reatment o alkyl chlyides wim a

KO
ives alcohol but in presence ch alcKOH, olkeney
ane Maj0 product

An 9n _caseh aq KoH laoH M is a shon2 nucle

phsle So nucteepillC Substifuhn neohbm
Phile
tokesplace

gncasehalc KOn|Nao n, C2M50 isa tong base

wuch
wuch lim/nates B-H so elimi'natin
NeaLthon takes place.

(3) Reathon wih metal

Lowith AM2 |dy ethen.
Mxf oungo niC chlondee, brmide/ and iodides eatt
SAARTH
 wih cen tain meta ls to atve com d
po un
Containin
CaDbom- met al bomds. SUCh COm pound ane

Calle Ongano- me tallit eompounds. An imp0ttont

class o ongano-metallic compouns d'rcovenel
by victor Gignand (1990) catted akyl magresium

habide (R-MgN) nefennedag Ciiond Keonout

-Mgx ic oblained by reacion of P-xwith
Mg in dry ehe
R-X +M dy
eme R-gx
Cngnand negeut
CHTghlyneschve)
NOTE CriMand neogent! anehighly reo ctive
and eact with any sounce oh proton to
give hydrocanbom 9ti theneore
nececs any to avod even
ta ceg o moisture
om ANgNnd neogent
& 9denh by A. B,C in {ollowing neachon,
CHg-Ct=tH2 HBr A M2
M dreheB-
H2 O

on A CHa-H-CH3
Bx
CHC H-CH3

C
CHa-CH-Ct
 & 9 d e t i py &, Y 2 n otlowt ng nearhon

C2 X Mg H2 O
anhd nic dnhehe

MgC
Y

CE RealHn uwith Na |dyeme' Wulz

Reochom
AIKyl hali de ic treatd usith
Na| dny emen
Mafor product alkane
haz double numben
canbOm atoms wft
non b m afms
precent (n k-X

RX+2Na+ XR
2then R-R+
alkan2 2NaX
CHacH cl +2 Na d
eHuyl chloside efhor CHaCHH2 CH,CUat2NacI
Bultane
CH3-(H-B +Na dry
SAARTHI CH Ohen CH(H-(HCH + AloB3r
 the neacion
' Com ple e
Na
Neopentyl chlode dryethe
CH
Na -HtH -(na
CH3
CH -t-c2 druether
CH3 CH

chemical propertiee ch Haloan eni

(1 Nucleophiut Subetrtuhion Rea

chon
let
Asyl heludes [ haloanend)ane exem ely
subctituhon
neachve towan df nucleophiit
neeChons due to ko/ow ing Keasonu

L)Resmance Chhect 9n hal0aneney, C-CI bond

Lq uirespantal double bomd chanac ton

due to nesoman ce asareguUt bond
clewage beemes ditticult than halcalkone

() ithenenci in hybiditation ek Catom inexbond

sps
R
333 X S). S-chanae
S-chanatlen
he sp? huybrdised C wigneaton S-chanac te z
1S more elecho negahve and car Pold e
 12a h X band m0re tigva tluy than sps
yhndised Canben in hatootkane wilh lesc
ChaNocten2

Gecause cpOsible nepuleim

t i s le cs liktly for Nuctesphile to appnooch
c h anenes which ia hizh e-ençity
due fo esrnance

Dow's pOOces For the manukachue

phenol

NaOH, 623K,
30patm, H
Chlowbenven e Pheno
C

NaOH,423BK
H+
N

Na0H, 368 K I N0
1
N0
O
 OH

wanm ,NU2
H O

NOTE Kesence Of NO, noup at 0-ondp-positiom

incneases Neactivi t of haloaenegtouwaMs

hucteophilic substituhion neoctiom O!

is £wG it witmdhouws e
-NO an so

desiy krom benzene sinA and hug

atilittar tthe erttock ok nucleophile
On haloanene2

(2) etecbophilit Substi tuhiorm neachomso

Hoaloanenes undengo elechophiut subshtuhom
neahons such a holo gemahon, nifratn,
sulphon ahom and Fnedel -Cnollt neachMS
HOlogen atom besideC Sughy dleacthvahng
is o, p-dire chg becauue due to
nescnonce
e density is more at o and
p-posihons so
e lechophule a tlock ot and 0 and p postieng.
o
O
X
6
 Halogeuahm Odd"o halogen
Jn preence chonhyd AK'h|Far
(Lewirorid)

+C anyc
AICl3
2-Dichloobenzene
C minon) 1,u-Dehlortben 2ena
CtMDOr)

(iNitaion a of -NO(nito gnoup

9n pres ence, a Cgm HN0 a r d c H2S4
C
Conc HNO3
NO
Conc H2 SO4
IChloro-2nitoben2ene
Cminon) -Chlo rD-4niobenzen
cmejon)
Sulphonahons add" o S0aH8ulkonicattdgneuP
9n poeLence oh Conc: Ha S4
CLL
Lonc: H2
S04>0 +
2-(hlbsDben2ene sutmicotid
CAMinDn) SOH

4-chlovobenrenesultomi
aid
Ma j03
AARTHI
(iv) Fsredel- Cxah1s neathon
(a) AIKylation addhok alky qoup(K)
Im presence o antuti AKI,(Lewit oticl)
C

+CHa-C| On ud ,cH3
AIC3
1-Chloro-memylberzene CHa
mino
I-Chlb0-4-mehyl
benzenMe
Major)
b) Aylathon; add" of au roup (R--)
n presence ok anyd A iCl3 or
Ocetc (ehonoic)anhydride
CCHaco),0)
O CI
+CH--c|nyd: ud COH3 +
AIC
2-Chlooore tophenonë oCHa
(minon
4-chlorvacetd-
phenone
cmajor)
 AMough cl i ane wittndnwing Z0up, e t
P-t ic otho,_pana-diecing inelecopri
anematit suhrt it thi) Neo h n t : Uhy ?

0ng cwimdnaus es thneugh I -etbhect avd

Meleaies es tuouJh sesonance
Through Rebbeet_tralLoge ng tend to stabile
Carbolahom and ehéA ° m one PuniuniY
a to and_pposihon s . I-ehhect is
shon fOL han R - ethe ct in halogens so
eult ine wimdnawl and caue n e
deothuaion
Kea Lhvi ty is_eontolle by sfrongenI-etett
and orentahiom Con tolled by R-ehtect

(3) Keo chon_with metals

(o wurtz- Fit# ig neachiom

A mixtne of o n alkyl balde and anl halide

2odueL alKylanene wshen treate wiHn
N a i n dny ethen

2Na + R-x dA
ehen + NX
AlkyaMene
b) Fitt ig neacom

Aryl halideg uwhen trealed wih aNaladyetmen

pound in umich two an oupr
ives
Aves c om

joined togetheN

2 2No dny
ther +2NOX
Dipheny