HaloalkanegHaloarent

NTRODUCTION The halogen detivative» of alufhabic

Ond aomotic hudrocarbons ane
u halude
houde CHaloalanes and any! adCHaloaxènes)
CHaloanènea)
Contain halbgen atom attathed to Jhe
TloalRanes
Sp hybudised c-alom 0 alkyt goub
whekeashalbanenes Contaun
nalogen atom attached. to s hybnidibed C atom o
an 0yaoup
HALDARENES
CLASSIPICATION OFHALOALKNES $
On the basisof n )On the basis of
halogen atbms hybridisation 'slates

) CaHs-X (mono holoa|kane -C r- Pu'mary)

H taloalknes
CH-X (Dihaloalkanes)
H-X -C-X -8cond.auy)
ha loalkan
H
i) CH- X
CH -x uholoalkany)
R-C-X(3Teriary
CHX
R
Halbalkanes
X mmahalbarene X-Fhcl,BaT
(ohaloannu)
ACTuhaloarenes)
ALLYLIC tHLIDES
he halogen ts bonded to an
s
C-atom next t the C=C
R - R- CH=CH-CH-X Allylic
Carbon
Allyic Carbon
CC-C-X
BENZYLIC HALIDE:
The halogen alom i bonded do an
SPC- atom next to an aHomaiut oung
H-X
e
PROPAGYL HAUDE
The halogen atom s
SPC-ato m, nelt to a CEc bondbonded to
0 an

e-9 - H R- CEC- CHa- X

Vinyl HAuDE Aryl HAUDE
The hal gen atom 1s bonded The halogen atom 1s
o an
sp c-ato m bonded do SP
C-atom o anatomatic
e R-CH,=CHX, {Y*

NOMENCLATURE OF HALDALkANES :
Common Name LUPAC Name
CHg- CL Methyl chlonude Chlo no muhant
CHCH,CH,B n-PMobyl BHomide BADm propane
CH3-CH- CH2-CL thobutyl chlontde 1- thlono à-mekhl
propant
 3 heopentyl chlontde I-chloro-3, 2
Ch CH,-C oluimet hylL þropane

a) when bolh haloen atoms ) when two halo1en

ane adtathed do the 8ame dems ane bae Be nt
C atom , these aHe called at adjacent'C- then
they oane called
em-d hal des cqlso V'a'nal dihau de
calle d alkydent_dahalde alo Calle d. alkylene
C
duhadet
X CHa-CH c
hyldn -C G- CH CH2
X
gem-dihalde duchloride
Vlawnal
dahalrdeL ethylene
oluh lortde
NOMENCLATURE OF HALOARE NES-
CA

Chlono ,2- Dichlorobenzene 3-Dichloro

Benzn Co.-Dr'chlbenzene)
oro ben ze he

C (m Dichloro
benzen)

t' Cu-Dichloro ben2en,) 0atho 6 0atho

P- Dichloro ben 2ene) uda
4
Para
O m,
 ommon name
TUPAC name
CH =
CH CL Vinl Chlonde Ch loroethene
CH CH CH,B*| Alyl bronu de 3-Bromo probene

0-Chlorotoluene 1-ehlono-) -mdhy

C oenlene
- Chloro tolu ent

8enzyl chlonde Chloropheny!methant

Dichloromethane
CHC2 Mtthylene Chloride
CHcH,CH,F n-Proby Pluoride -Pluonopropone
CHC Chloroform Tuhloro aethane
CH BM Tou bromo methane
Bromoporm

Ccky Carbon tetrachlovid Tetrachloromethane

NATURE OF C-x Bond is Covalent

he C-Xbond
but the electroneg atuivty of halogen dtom 1
MORe han C due 0 to hich c-x bond 1
olan

-C-X xbolar bond

Carbon-tHalogen Cc-x) Bond Lenaths, bond ethalpioa
and Dipole moments

Bond hengtblpm C- Bond Diole Moment/

Bond. Debye
mel"
CH3-F 139 452 1841
CH-C 18 351 1860
193 293 1:830
CH3-B
214 234 636
CHa-I

Moleuler srudure
orbilal
CRO
 METHODS OF PREPARATION OF HALDAUkANES
From Alcohol
(a)By the ackion of balogenatid t
R-OH + HX R-Xt H,0
'8 altohols 0um chloroalkanesy when hydrocblo
aud ga 6 paase d theough dluhol i the
e &ence anhydrous Zncl Thi's Anown as

Grooves Procass"
Zhclh helh n the cleavage 0f C-o bond.
3al tohols aHe Vi Heauve, thu atact
With Come Hcl a Voom em wthout
Zn c
CH-CH,-0H Hcl hCH CH,-CL+ H,0
znt
H
CH CH -OH+Hc CH CH-cl +Ho
znC
CH-C-OH+ HC oo CH- Ccl +H, o

(Nodt b 3 bromides and iodsdes cannot berepared

rom 1he heshttue altohols betause d'6 3"
aluohals on headung wt'th eme H, sO+ undergo
dehydrabion and onm alkene
H P Ts east utoc ive 8oluo noalkane I ' no
Hmed.

Ordex o peacavnly of altwhal-33a'>1

Reacuinfy ol halogénsHI>HB1> Hc
( By the action of_Phogpborous tialides
R-OH 4 PCls R-c+ Pocl + Hel
R-OH+ PC R-cl + HPOg
Note PBn& PI, aHe hot Atable, So they ak
OHepared on the sit Haction. CSITU)
By the ation of thionyl chloride
R-OH +Soc "Vudin R-cl+ Sot t Hc!A
This mdhod i&Phoeied than olhew method
bAu both the 1de produtts tSo. bHCI)
Cae ga^eovi and Aam eAsly tscape
From Hydrocarbons:
0) From AIRaNE
B, teacis nNith alkanes 1o
C
uht paesen ce ef Uv Aught dooHm a loalkanes
subukitution seaction
hA eartion" i' Pre aadical
"

CH,CHa CH Ch CH,cL t (H(H CH

CHg
45.) (554)
Nole hein suearbity of dlneni tyhe o ya
holo tonipouhd a
Ben2ylic allylic)> Alkyl>a Vin
Alhe and benzyic habdes can be tosily
DAepaned.0
CH,CH-CH, tCl Ch,=CH- CH,cl4 Hel
Ch H
+He
Both ane hugh!y neaciive and dhts con be explaine
0 8 a bilibalion by nt bonante
.

In tenms

CHa CHCH CH,-CH =CH

CH (Ha CH

From Alkenes
CtHx
3t 1 PoAsible an 8ymrne t a l 'alkenes (-CH=CH)

Markonikov's Rule:
In unsymmetnutal alkenea, the -Ve
pant of ihe addendum gos to that Carbon hawing
Lowen no- drogen
Negaiuve C)
owun Ch-CH-CH, t Hx Ch-CH- CH

Edltydregen
ANTI -MarkoniKov RuLE *
Apbheoble to HBr -0-
TaRes blate in the pAESence of ORganic ptxoxide
the
in unsymmetucal olkene, the negdive þant of
additivL goe to that corbon havhg dujhe
no h qduoqen
CH3-CH - CH t HBt Peroxide CHa-CH-CH
Are monRowniky Rule i also Rnovon as eroxide effet
09 kharash 2ed
i Nigahive)
T OHighet
Addution 0 Halgen
when Ba, & t added Ho alkene
dhe addiion occux a Ahe doude bond.oming
VUAnal dhalude
Bx
C B, Ccl (viunal da halide
 TThis dest ib uied do check,unsatur avion beta
d When uealts
duso þpeaHe
Heddash coloun ef B4
wlh aVkene

6Y Halogen exchange
t Nal
Acetone R-T + NdA
{- l, Bo
R-X Heat
Pinkelskrin Reacdion
duaeclly dhrve
dilliull do pepane and "bromid
FluDs oalk anes ane alkyl chlonide
O DAepare d by dtaing CH4,f., Agf, Cofs» Sbt-
ith inougánic udrude sulh os"as warts Heaction
and dh sueaition is drmed

CHg B& + AF CH-F tAgBa

From Silver Salt of AudsacycooAgt1 CH,CooCH
CHgCDoA9+ B CHB« t C0,
+AgB btaed
Birnbaum Simonini
Borodine Huns diecken
Reachon Reachon

Methods of Prebaration of Haloarenes

Substiution of Arenes oR Dirett
Gleutrophilic aromatic aun1
Halogenation o
X

tX Halog enCaritr
310-3b(o+Hx Cr: cd, Bt)

Hene Halogen caxAier Pecla/feBMa/Alcl,

Lww Aad

Mechan ism
8teb-1-Generation electrophile
C,tFecl
formotion b tarbo cation
intermeda at
Be-d

the intermedu ate

uom
e 3 Los ef proton
+Hel+ Fecls
Fatle
3exces oHalogen fh Utd,ihe second halogen
attached Ao olho,6 bara posrHon,
fe cdg
excs.

Nole The Heaction with {luoune is violent oa vígrou4

and tan not be entk olled
The Meacbion vwith 12 is not pa'ble becaus. when
AOdurt 18 DHmed, HI Hedutdt back. t

J+ HI

8 0 th1 ntaction is caured dut in ihe puesence of

Oxidiblhg agent (H1o »Hgo) Jo Oxidise HI
 Sldechaint tlalogenation
+Cunliyht Hel
C , i in exes than all H"ane aeplatud by"tl
When Ahe 8ide chain t's lauge han Ehyl grouy
a me
halogenation dccun at (-atom nertLo benZene9t1ng
0
CH,09 e,3 CH -CH

From Diazonium Salt

Oia2otigation, Reacbion
NaN +Hc Nacl+ HoND
NA NC
+ HONO +HC-5 4 H,0

Sandmeyer keaction:
N CUX X
+Na
CX-Cl,Bx
Hx

Gattermonn Keaction
Na
Cu + N
HX
Nc
tkTorm DtNt kcl
 Balz-Schieman Reaction
-N'C+HBF NBFy +8, N

From Silver Sat of Aromatic Aud

.coo B B

+Ct AgBr
butbaned uom phenol because
ole haloanenes,Cont be Thi's I du
i dlicult do aeplace-bH gp
Hesonance in phenol

Proberties o Halbalkanes-
Physical
colnuss (when þune)
n genera haloalk anes aHe
Sneet 8melling uqu'ds
soluble in watn becaust o Aow
They aneAlgbtly
erdenty o tOHm Hydrogen Bond
Dunsity f<cl<Bn<I
mone no oH atom, less 1& densty.
CHa Cl, <CHC3
Boilinq_point 8-t Mol Mass
Bt
Brancht
PhysicalPropertiesof Haloarenes
1These aHe generally ColourlessJiquid o Crystallin ingolud
9.The ay haudei8olubleane,heavy than wate, &0ld
in waten but in "on9onic 8ovent
3Them-bl bbbt e anyl hau'des aue nean ly ihe same
alkyl halude toitauning he Aame ho. o
Carbon aioms
meta
B-t3 0ntho> Para>
Para > Ortho > meta
M-pt
Hemical þroperibies o HaloalRanes-
Nucleotbilic Substitution Reaction
--x + N -C-Nu4
R-B«>R-Cd>R-f
Reacuvity 0den R-I>
V
Nurleophilic Sub Rex
SN' (Un.malecudon
Types- CBimoleulan
Sub
Nutleophr1le Rer"
SN,

SN RK-x + Nu R-Nu +X Rate xCR-x]

Mech anisbm CH3 8Lon
Ch
CH- C-x +x
Ste-4
oomaion of C
CH3

8te- CHs
tNu dost
C NW
Attack ofl Nucleophile
CH3 Chs CM3

Retenb'on 0s nell Inversion uratuen

as
o
Aakes l ace
DHdes o SN' Aer"- Ct),C-x > CCH) CH-x >CH CH
CH-
 Ahow hugher pteacu vnty
Aybie and benzylii haludes
Uy OWards t h S N ' Meatuon.
slabilishd
he Carbo cahdn
he
dhus /onned get
thnougb Aesonance

Nulophuie subsutution Rex

N
SN Bimoleaulax
- X +NuP R-Nu +x
Rate[R-XJ [NJ
H
Mechanism
H6+-cl > HO c HO- +C
H

SN Aeaction. CH3X> i'>'>3'|

Otden
In vendion 0 Cenyg uration takes pl ace

lan- bolari'Zed,
u'ght hormal bolani2ing
OSourte
ght ught
filte
Ondin ary ght tonsist of
eleetromagnetvic-
Abeam DVibratingtnall laneswhen as
Waves
Nitol þusm, Vtbrates in one plane
dhroug
Called PPL CPlane Polariedght)
Rotatory which Aolate PPL tonards sughi
Dexo
hich Motate PPL donardslet
Levo-Rotafory:
 C

-
T

O
&Ubstituion by
Ub&titution Hmino 9roup
R-X 4 NH R-NH, t Hx
When halo alkanes is in exceM amount dhen al thnc
NH 1 aeplated oy oub R)
R-X +NH RaNKgN+ Hx
HoFfman Amanayu'i Reachon"
R-X+ knNO1 A R-0-N=0t kx

R-X tAg NG AR-N tAx

Subshtution by -OH group
A
R-x tkoH R-H + kx or
Agx
Ag0H

Substitutjon by alkoxy_rou
R-X tNa 0R AR-0-RA Nax
This neachien is Rno a Willhanson Synthesis
Substtution by Cyano grou
R-x+ kcCN R-CN tkxene Hd CHa CONH2Aide Acd
CaMs-L+ kcN CaHsCN Dil-H orNO CHa COOH
NO,CHs0 CHCH NH
'ACHy N/H amine
Mendius Reactjon
Theomation t omine amines by
by
educhon with nasScent "tydrogen
aduen
obtaned bs'ihe
dium 8m alehal
Substitutionby_1socyanide qroup.
ubsttviion
R-x 4 AgeN R-NTt Agx
Note A acvale Na 8acduvate C
Substitution by_azide gp
R-x+ NaN3 R-Na t Nax
Substitution by Carbory hs,
R- -oM1tX-R3Hc0H, R- -0R Agx
+

Elimination Reaction LDebydrogenation)

when a haloalkane with B-H alor heated with
alcohetk oH thee ls an 'minabon H H atomom
B-C and a halogen om d-C, ue'sultiyan U
alRene Oh med

8 7 C CtBH + Xxe

(hene B base
X- leaving at)
3thext ds a bossibility of Onmatu on emoHe
dhan ne olkene due availabMty o
emoxe than One -H wually eme alkehe T
OHmed as mayon produet
CH3-CH, -CH = CH-CH

CHa-CH,- CH,-CH - CH (e1)

8Y CH-CH,-CH-CH=CH
C19)
 Ac. to 6aytzeff's Aule, dhe alRene wrth gneadee
no U alkylgoup 1 Detned

LRC=CR, > R2C CHR> RsC =CH2 >RCH=(H

Note A umany alkyl halude þuelen a SN

Aeact on
A 8won dony halude puyen SN 8SN'
depending upon the 8lnength obose/Nu and
te hali de paeyen SN
Reoucdaivnty-> 3 >CHaX 0s Carbocahon
Aluoholuc koH Causes elmin ation, whie
aqueous 8oldien ebaieeadi to subsbitution

Keactubrl nilh aruive metals

Rea ttaon with Magnesium
OH
R-x+ M9 H R-Mg-X Cx-Cl,8t )
thn
UGrianard Reag em
Aeacuve
7The se nard neagentb aHe MeHY
Cempement They nt'act t h any ouxte
hoton to 0m hydro carbons. 90 t veny
'necessay o avou'
"
Anaets moirtuxeHon
ugnandd neagent
X
> R - H + M1
R- Max t HaD oH
CHoH)
Hydrocarbon
Reaction t h Na ( Wurtz Rx")
-X3Nat x-R ihi,DH R- R . Nax,
thu Used to DAe paze Summetrlc
alRartes.
Reattionwth Zn (Frank land Reacton):-
G Hs-B h t zn CHs Zn- C, Hs t zn8#
duethal Zinc ( frank land,

Reduction Reackion-
-x &tHJ-
+ R-H t Hx
Ca Hscl t 2th- (aH + HCl
Medutuon
Following dtajent ane Used on
ZnHC Na l HsOH, , LiÄIHy Red P/HI,
Kearrangement ReactionTso Reacthen

CH CH, CH,c ACl3

573 k
CH- CH- CH
CH, CALCle
2, CH3- C- CH-CH3
CH3 -C
573
CH c
Chemical properities oHaloarenes
Haloauenes ant ess ne acuve than Haloalkanes
due to

ResonaceEllect
Delg caliatio ef T e
.C

2.
2 Differena in hybridi'sation o C-x bond
R- CH-X Sp
m o e S- charadex m oHe electronegative, h0 hold
aiH moHe ughtly, so ess Meatlive

Polarnty o_(-x Bond 3n haude

anyl halde
bond of ayl
C-x
's es 80 Kears
lesi, 80 Heactuv1ky t les
Pelarity
Nucleophilic Subshtution Reaction
Dow Process
ONa DH
CL
(o)+ NaoH 623k
30 0 atm o) Drl Hd
- Nact

phens
Effect o subsutuent in Haloarenes on Reathivdy=
The puese nCe o ewithdra lki ing 9 Houpi such as
-N Da CN9 CooH ede a or-hs and ara postion
-NOa
to Lhe halogen odom gueatly aelirates the halosa
dowands Nuleophdiz zubiututon
pH
r)NaoH 693 0
i ) dal Hel 300 atm phunor
pH
) 157NaOH,V13
i ) dal Ht
NO2 NO
OH
NOANaoh,368t NO

) dh. H cL
NOz
NO
 Note7 N qutu Nt,) t 1n 1 n t

Exbl anetion uty at hora oon

GA
lor

n coit e 0 ho and bona iuuciurn, tne c t h

Lnath iutiures beaA h:3ave ov trth
aom bearing the NO u
Thest Carbtoniun 0 labrL zrd by th u
O eO henzene uf 9
Howevew in cae m- structunr,
none hr mesotia ting ,i HurBurt bio h-ve charga
OmcTben aom Aotori 1he NtN 9
The NN 9P doa nt ublut ih
Cotbe0nion and hu hoi noeifctd owarde eartuvty
0)out othlorobendene and eyclehuyl chloride Wbich
One more reattive tona rds nucleophilic
Substitubon taction and why?
 towa
chlou de is moHe Heatuve
ins Cyclohevyl subsutution, C-cl bond
ueoton be(aue than
Chlorobenien
Cyrtohe yyl Chlouudr
huil
les n
8LAength Chlonde, Cl-odom is bonded
9n Cytlohtiyl chlono benZent c i
- atom whi le in
to Sp? hybud C- atom
bonded o sp hybid n chlono
bon d IA mos 1rong Bub-
C-C donards nucleophilit
and lesI Meatbve
ben ene
molecale in the flowing þairu:
ldunily 1be Chiral
andct

Ans is chiral mele cule as it tontain an

a symmetric C-atom Which is

denoted by*
C H OH
c

N at ortho position co 0

8l on C OH
9te

Ng at weta Position
C
DH

OH 0

76
OH

das NO
ste
Substitulion of Amino 9
4 d NH+ C4,0 o)t Cu cl, tH, o
Anu'line

Subsltutien by_yone_j"
fN
O+Cu
tNy d r
A15 k o + CuB
yunoben Zehe or BenZonitrile.
fONHO
Con-HL
alk.4,0 8enzumide CPartial Hydrolys)
Od NabH

ATH Beoc, Comlete hydrolys,

Cyano Na /Hs0OH CH,NH
benzene Ben7lonine CReduction)
Reatbon lrth metal:
95x Grznard keou
 Reacubn with 6odium
Wurtz FiHi Rex" Pithi' Reachon

the n

D
FHy Re
cl
c t SNa t Cl-CHsethen Ct3

Rea ction With Copper

wurtz-Prtti
Cullmama Reaction)
o-I+u + I-K o o + Cu,I2

Reduction-
o H NFA +HCl
NaOH

Benzen

electrohilic Substit uti on Reaction

Netez 0) Halbdrenes undergo electrophuc 8ubstituhior-
eat ton slowy a mpared to benzene
(i) Hologennou 'b Dxtho and bara directly
Halogenation

+C
anby
pecls O
HCL
Cmayos) (mina)
Ntretion Cemc NO2
o]tHNG CConc) H,5Oy
m in o) NO2
Cmaj0dD

SulbbonaHon
A
+ HsOy
soH
Alkylation-y
Priedal craft
tCHc!
!Ank Anh t (o] +Hcl
Alc
CHs
Priedal cralt Acylahion

+CHclA
tats+ (o)+Mtk
AIcl
CocH

Reimer Tiemom Rea ttion:-

0H PH
koH
CHOH),
ot CHk l - o KoH

Phenol unstable -Ho

H
HO
Salicy aldehyde
Carbyl amioe readion
N=C
NH2
3koH- o t3Kcl +3 H, o
o t CHc t
Anil'ne Phmy
Isocyonide

Finkelstein aeadlion
CH-I t Nacl
CHg-CH-cl +NaTI Aceton CH
Chlondet hant

Hunsdiecker heaction
CH3
CH3 C- OAg +BM, -CC CH -B + AgBx + lo,1
Biwen Acetate 350k
Methyl
Bromide

) Why Vingl chlonide is less raacbve than methyl

Ant In
chloride?
Vinyl chloude, the electron pau on the thloride
0tam Lonjugates with the n- electron pai'n of double
con d
CH =CH,cl: :CH-CH= c:
Vinyl chloride
The stuength df Carbon chlorine bond
in creases and
tTts Cleavngebeomts
Cleavage moe dulliult o
Combarnd to
C-cl bond "In methyl ch lou'de. Thi's all hoppens
due
Meenante. So Vinl Chlouiud! Js ess eattuve
Ahan mdhyl Chloude
Wilionson Syntbesis When haloalkanes neacts with
Aodium kox1de, edherk areormed.
N
R-+ RoNa R-0-R+Nax
R-alayl) ethe

Haloalkones reacl with kCN to 2ive alkylL

yanide but
gie alkyl isorynide nrBh Azn
Ans Due to Jenue Chanacten ekcN, Cy
antde
en CCN), on ambident
nucleophile wilLU atiack
hrough Carbon due o0Tmauon o astronger C- C
bend than C-N bond But siWen- yantd'e s,
a CovaLent Charactet and acis as a riuel wphile
which ct tacks throush nin ogen ao m yield'ng
alkl DCyammde a the mao roduct

GHRtKCN GHCN++K'B
9HPA+AgCn sNC t Ag
ovale soanide
CN
ambdetate
CN-