HALOALKANES

HALDARENES
CLASS XII

BOARD ExAM
Theae mots
au bwn w d
apfaulhes 2
Cese Sume

Toppes
Target LoD

Poreviouo YeAY s
Intyrakd

ALhnarSkukla
 FlouChart
Mehods o araton Cla Stifrcatin

From Aleokols
Nomen ladaa|
from Hy droCarbona
Nature
C-X bond
Halogen Exchange|
R-OH HX R-X H,o

ysital Propintus| R-OH Naltr H,S0,

SR-OH+ PX.
R - r ' NaHso, * H,O

3R-X * HPO,
R-CI + P0CI,
(XCL Br)
HCT

0- R-ON

R-OH
red P
X

SOCI,
,
R-X

R-CT S0, HCT

M-P Haloalkah and

Salubilid Halo arenus
Reaction o Haloarenu
CHIRALITY

Rauhions of Nuclophilic
Holoalkan ngermpe
**
Subatituim

ELetrophilic
Nuclophilic subhikhon Subahtuhon
SN and Sn2
Reachon wrh matal
FELmi natiom RuActin

H,
Reackon witk mtal HC-C CHCH-0
H,

Elimination D Substitution
O 0Haloak anu ad
Apiatc hydoo conhom
Pranc hydcaub
Haloareu0eceooc
aldi L {odaalkan1
AIKy
Rahiacamt o_ A ld Choloaran]
ydvogen bhaloan
tom

H MaHyl ckloich
xamph- CH4 CH
H
afas
cahn on ba &iA o numben o Kalogen
Cars
Monoalo
nd Ralogen aton ig URnt in struthrt of alkau anans alka

If two halogen atons are rrsent Didoslka Bifalsqzan. Momsalo

aTus

, Similak. res. halogen atums att pst sent ; Tiialoalka

TiKalo art

CaH Monohdoalka (x Haloge»)

xomle
Monodoare

Monohalo cCombaunda

Compounds Coteining. sp3 -x bod Cmbaunda Containing sP*c-x bod

to
O Vihydc Haddh x ia bodsd
:-

O Atky Koalds : CR-x)

rbnCaybm daubla Lnd
Prinany AAl halcds. &-¢*
ram CH
cH-CH-8r
CH CH=c8r-¬,
Sacnday * ) : *-
Kadkda,- xAdogen etm) i4
xampa AyA
amdod to Carho oqvomatic. iry (b

exmp-
Taxhio29) R--X
xamplu cH--u"
Aly&c Haloks: X M bodee Sp3 Rybmcices Carbon
Cuttm xt to Carbon -

Carbm dlalk bad

Allye Carm
xamble CHCHC*

AIlyL Carbn

All bromide
CHr
in skich tka halogen atam
Renzyke halide Compounda
o gh sp3 Ayb»id tacd Carbon am hext to benzae
A banded

Banzyhe arbn

Ngnendetvra |
ution of hain clain oand humbaning- o
kydvoa rbm,Jaha
As w khok about
Tuls is fare alho C Conaiduning-halgen adgma P,0, 0v, I) a ibatituzrj

lotann >ABabui
Rulk No oabon Max. no of ubaituext> Lowt at d

rample- c--H-a
IUPAC 1-Cramopopa 1- ckloro - kd pwbas.
CH3
cOs 3
CH-CH-CH- tH,

- chlo-3-thyl
1-cdoro - aa- dieyl posan 3- loro -2,a-NttylbutanL

ostho hoRhion
ND De
Comhm hahe m- ibromo b21zgha. 2011
PaTo pohhm
TUPA L.3 Bib1m behza NO
Brsmo beza
btnzak.

1.4Dickloro -a-y lbenzdu

C cars 20133
 - [c8sk 2011] cH-CHH-EH-0 cBsk 201
3 9romo propen
4-Brmo -a- eh

CH 201 o]0
1-rom o bluf-2- et
3-Avem--mtyAmpe
Dra R stauuky c Gulaaing Componda1
sc-0dyltyl eklode CH- -eM ( a- cklro bura IuPpc)
b:1Nao- Pentyl bsawid. 1 -Bomo - .2-dkmuthykpa
LuPac)

cL-Bromo -
4+- chloro.buut -a- en
CH-H=CH-
cMa
d3-Brom- - htyl pp--e
3
D 2011]
PRamyl ame- eklormyl banzu[x]3
NOTE Benz ad ubtihe
chloroiany@mkano1is co

- ( - bromo phnyl)
utana Dek hahL o
2011

s -(a-cklewpinpl) -1-iodo octan

C D i 2011 c]

Natoe oC-x bo
>x
Da to aurokagadivi otura o alage, - x bnd s pokar

ung h
 and Lung - x d i- bad enkalpizs

Ordun o d la momet|:

R-I +H0 +H0

Ofrm alekols|
(HBZhdd ) ,

HT
R-Br NaBr t H, 804-)
Her R-oH H ZnUda) R-a +H

Alskel
P u a

(P8r

HP+ R-& Rad P

R- + SoT+ HT

R-Br
R-8

C Al India 20141

breparatjom o a Aalid
Abova thod n hot abtlle for
kinal Aa H
Csthon oxxan bond
becaus t in

ohiod doub bond ckaraten

bond in y h
21 from Hydeanbm CuC1quivalat)

Radicol Halogenation CHa CH-CL+H

CH-CH CH-CH-a

CH CH,-CH Ovly mghockloro tuhral isamens

MUno, d
Po
CH H- O2
toloalko
 # Ay doarbam C H Na only Ont mono chlo natm prod4
D 2013
Idaf e ydocarbam
I4gma
C2/ 3 Podu ( Prusuna o 3 tyb
CsH12 Rydogth )
Produt (4 Ty odgeh

Find os bh monoclm trutura isomen4 o ,) CH-c"-CH

H--cH-cR3 TAre ore 4 d{arut ydvogam q7u beset So,

cH
c-C H- H-CM3
-cHCH

CH
e Elchofle Subhithim :--
-3
cH

porq cAlho toluen

a t fetta O-vho- chl
tolue
CH3 Ractuin
FetB - Br

Raatns wih z ave 7eVArgble in nadhre

AlGg
This veadion mquita pmsend ooxidh'sigett Add nidis*

Oxidise HI fored4 duung iodohtion

get(HN03

Hro

D to igh nacivity flai (am i rolabit «f exslos)

fluoo Carmpand ar ho pruand bytus dkod
 c]Sardhneyr4 aachiom inam, o rOmic HU
diq2ohium salt
ami h
NaNO,
NaNO
Hu Benzen ciazanjum hakdu

kI

Addihon cf kydvon kalldi (HU, H6«, HI,H¬)

d7 Frm alknu

CHCH
H

CH-C CH H CHH CH CH- CH

H

Minor d u d
Pdd to t t Cabon Major roduc
Pnhi Mmkovaikov
whach Ka m no' of *ydrogeh. Mar kovi koN

Her

8
(ej) H
Two Hydn

H
famion

Her Ahi' markovi kov«

O
addihn of

CHAH=CH H Ha02
PevoId

Addihom oalo a 4) CH 8&

Cd4 cH-Br
Suart. kaa thion
Pinkdtin Rnthim
Halogen Exchanga.
CH-CH-L + NaU, Metallic Hgn CH
CHa-CH-u N CH-Br
Acuhm

CH3-CHa-r NoT_ CH-CMaI * Na@7l

ALtan
Nau |NaBr
In Aeetn Nal is Aolubl bd hod
oke actva eom paund *.

wtich Con TaTata a pake palan sed l t

T Compaund Ratprion in riglt dasto
:
discin reta
A
PPL
ight PriAm Sobuhion ooyhital Rocnim in t t loavo
acthte Compauad diTeam staty
Polanimehr
No Rotm °pfol
xpin
inactve
Comp h d 4
dahro- Totadton Com pound and Jaavo- Totojon

atfacd uwh +
Carben
e aqbom iral Carbom- : sp3 bsdisad
Aayhm Mdle-2
a cird tarbm Maletals-
Aubatitawta is known
diffaren CHa
CH3
c i r a Carbm
on
H n
HO

L
Non-Supinposabl.

cro- objuti wki art Nm- 4nvimotoll tmisrer nagad

on tui mior mage art Aaid do be chira
cirad mole t u
"bole cule aving a

e r a Carbon is aloa Obh'ca ahve

ott achive"
Compou

nanhomusa Steroisonu4 wih hon auuinposablk" earactun

nier ina

hod o r mege c each otar.

ehahiomer o eachotky
In above rample tmole ctul- hou cash-a ae

Amiure lofajhin dwe haiomarA in ua

Kacamc mi-
knosn a Taa mic mixmre
pochimA A
T t i a «rustel b dl o )

T A ouss es frxming- aLic ixture iA khoun os 3acmdah'm

and qchiral moleculh -

ciroal
Gurtm Idahti f* On Chiro
Casbon
CH-CHCH 'a
HC
B ohl Achv

Acir
chira
Acki
as

CH

H
CH

Ch

Colled Teteno

iA Callad inVarhm

Rt8 Kacamic mixure

Pd hixT
xaamidotNon
Conterotim s oally inacjiu
Aand wih so -501
Mix ure
in i diredhoM oppotite to anatr
AA ÀAomir wil votadte lir
 PRcal ropertias
Malculs o ovgaie Aalogen tom pouda aT r a l l y þoloar due etr
o l a r i t a wdl as ighur mole tada) mars a Com patnd to a1ant 4ydwarban, t

attrachom tsonger kalogen dtívodva

di pol di bole ahd yah dn Hoalsfova o ave in

So. 8.P Holeyen Duivshive com poxd Parnt ydoca rbom

7
fom .P.
For q ven alogen
Por a ven ky rap P R-I > R-9« >R- U >R-¬

Bvanchina

Mukho poin fita in cryfal

btha-
iAgT tRo
Cc@E 20193 bater od oho
jatu ia low
Kalo alkahus n
Soluik T 4odubita d Ås qTutur than
hoaloalkanus -
wat
atathn b ctuen faloalhau
TB4cAuPe frca of
iterathm

ChemicaR Reach Haloalkaua

Raa chion with ndtls

Elimi nasm Raauhion
Nuhoplic subaitukim Reachon

N +CHX Nu-CH +*
Nutlobh:lie kbtthm Raathron N

Alkyl o l d Pvrodu luving

Nuchophil
In a T2aion, 4ubatituhrn «zathion
Nuca Jovi g

paua (+ ekorgr oving-)

ealled NSR
SN2
Tlachon
machaiama can explain abev
Two dffere SN
ealar Nuckostike Subtihtiom -
SN2
Bimoe
N S
Ho-CH +uO
Cmiidun a TRachom H-
 MeckoAm -
Transition
Stat
It foll o ARCOnd ovdun kinuhid

Racte EN 1 Subetrotu]
HO-
I t is a ainga atet (Con taid) r2adion -

Ovd o raativity- fiman alid Stonday holda. Tartary áalxa

CH-Xx CH- CH-X CH--x CH -x

.
3

Mot tactive : ka« hindranc arathiYa beau

bul grups indar hi aphmackng

Ovdn oTtaivita huthophlut adh Cavdom

wit ffurxt Ralhgen
WAk ad Atreh SAmg Bond,So tauh
So, Ray baak brak

CH3-OH
0-CH

Ho
CH-T Nar Autoa Na

CH-Br CHO

CH-N
NH3
h-C--oT
CHa-NH
AgcN
RCN

K
Mathy symida
NCHC2N

Ag-CaNO CHNC
Mddyt iascyanid
CH-NHCH3 KN0
K*3--N=0 CH-oN=0
Muthy Nuhitt

CH---m-CHg A N0
*CR-No2
Nitro naha
CH

CH-CHa
 Subarate having luss cvawodin g is mor4 4fec Thah more Crowdinq, Aubatu-
For Sn2 Tnchm
xampk Rate o Tthion
[cese 2oJ:]

CH-T CH-
D 204
c e r aolt
H-C-u

Unimolecwlar Subehi huhon hudu l t reathom

CH 8 NaoHo Ha- oH
NatH C1)

+Br
Mackanm

cH- CH -o

Abova Teathon folma rordun kihu8

Rotre Ayd Aalida J|
T4tion intaTmi diah ia fod
Iin a tw tep yla thion ad Carbe Caion

07deyTuchit CH-c r

Ma
7 eM
3tabslkt
Combscom
d aOdn otaeivity R - I K-Gr K-4 R--F

f i d th ordi o sathity for i l rrachn ?

0 CM-CHr

MCH Stabikt
Caduotetion

Dut 2013

Stabl Cavbo o n ordun aa thvity: O >

Cavboteon h
3

NTeaeim
gNA inVrtad oduc

racemiahim)
xaml CHa +
HO
HO

rbm- braminu b0ndSo À r jon

OH

S
CH- 3
A

planar molttudu

ixhrt
0Tds o sattivih for tN tt Hald ac Hal > 1* Halkdu tuaReui

SN2 CH,)c Br CHC«)- HCMg<ng-CMM, -8r

 Etminadhion Raathim Hodoalkake with p - 4ydrojon aton oH
Cadthda
Deydrskalogehation Ruechion H
OH eH-cH= CHa.
+Ho 8
CH-CH H-CHHa
H Liminadiom o CH-CH CH= CHtH (Major )
H
Stobe Alkane
ninahon eHL
CH-CH CHCH= CH
Mine)
Raathion wt mchal R-r R-Mg-X CGzhard KangetJ

+R-gX H R-H
RxNa +* K-
t

Rench Rloarea |
uss stadtve tound
A alidas qrt Rxtremly.
Nchopkc Sutihin
pdkiao13]
NSR due *o elosine vatons -
a
abod acquiuA
5 achial dast bad cterauhr
Dubi o ]
bad braking- in kalooveu is dftult
CHaCAway glu bond
Han 4odb alkau. TRrafre alo avans
cRarathr

Jase vtaNe Han aloalka douwar do NsR

Hadoarenu Can hatlN pat% b2thyA.

hich n nat xtablu

approac edac ich amna

 TR barsenta o an ekchron urhdruing
NaoH /622k 3ao -NO -CN) a orto od þavy

otioincr t t rachvityhado
arthul
Ht

oH
NaoH4
H NO
No
oM
ONaof, 2a, NO
NO () H N
N2

Slkeohke subatituin kaehm

Halogen are ortho -

paqra okrecing-
Dui 212]
in nur for SK
dAnnty ine) a at ofho and sarq
o&ihi
Halogentjon
-fcose zo5)

i ) Nitadiom-
Conc HNO3, NO
hiobenzaL NOMajo
Conc HO4 1- ckleo- 3-

(Min)

Sl.omatien-
ConHa T Mejm)

Mi nr
 Fiedd eraft4 Raachon CDe -
olo

AAKyloi Atylatin
L
Pdditm o ay gra n benzau
benzAhL
Pddhn o alkyt rap on

CHa-

Ch Min)
C Ddti
2014t 3
Rachen wr mutol
urt2 fittia Reaeh'm
Fitti Aachm
N a t+ *-R (
N g t+

Nax

+ N a +CH-B
intie-
hirogTo«p aoro -pav o i joa
Qun - T ruRn of
duandn NS R, WAy?
casEoL)
talorena
raachiit o
wthdraw lutrm
Noa at orho ond bara poitima
PAk-: ecau - 9Tu
n

ing and t s faetktatas t huduose ciack

dermt rm benza
Raloam
HO
hecdaniam-
Ho TA ahim ia teba
duu to inducive ad retonanu (musomMic.)

O
Mfet -No
 CHIRALITY
An object that cannot be superimposed
on its mirror image is called chiral
Marre

SN2 Reaton

OO HO HO H
Chiral objects Nonchiral objects H
Nonsuperimposable Superimposable
mirror images mirror imoges

P
Some common examples of chiral and
0 0 o
achiral objects
Red dot represents the tncoming hydroxide ion and green dot represents the
OLuilgotng halide ion

Nu: Nu: Nu: Nu: HH

Methyl Ethyl 1 Isopropyl 2°

H) tert-butyl3
(30) (1) (0)
(0.02)
Steric efects in S^2 reaction. The relative rate of S,2 reaction is given in parenthesis

Eimination versus substitution

A chemical reaction is the result of competition: it is a race that is won by the fastest
runner. A collection of molecules tend to do. by and large. what is easiest for them. An
alkyl halide with a-hydrogen atoms when reacted with a base or a nucleophlle has two
competing routes: substitution (S1 and S2) and elimination. Which route will be taken
up depends upo the nature of alkyl halide. strength and size of base/nucleophile and
reaction conditlons. Thus, a bulkier nucleophile will prefer to act as a base and abstracts
a proton rather than approach a tetravalent carbon atom (steric reasons) and vice versa.
Similarly. a primary alkyl halide will prefer a S,2 reaction, a secondary halide- S,2 or
elimination depending upon the strength of base/nucleophile and a tertiary halide- Sl or
elimination depending upon the stability of carbocation or the more substituted alkene.

CH,
H.C-- CH,CH-O
CH,

Elimination US Substitution
 Polyhalogen Compounds
Carbon compounds containing more than one halogen atom are usually referred to as
polyhalogen compounds. Many of these compounds are useful in industry and agriculture.

Dichloro- methane (Methylene chloride) CHC

Dichloromethane is widely used as a solvent as a paint re ver, as a propellant in a osols,
and as a process solvent in the manufacture of drugs. It is also used as a metal cleaning and
finishing solvent. Methylene chloride harms the human central nervous system.
In humans, direct skin contact with methylene chloride causes intense burning and mild
redness of the skin. Direct contact with the eyes can burn the conea.

Trichloro- methane (Chloroformn)

CHCl
Chemically, chloroform is employed as a solvent for fats, alkaloids, iodine and other
substances. The major use of chloroform today is in the production of the freon refrigerant
R-22. It was once used as a general anaesthetic in surgery but has been replaced by less toxic,
safer anacsthetics, such as ether.
Chloroform is slowly oxidised by air in the presence of light to an extremely poisonous gas,
carbonyl chloride, also known as phosgene. It is therefore stored in closed da coloured
bottles completely filled so that air is kept out.

2CHCl + O2 2COCl2 + 2HCI

Triiodo- methane (lodoform) CHI3

It was used earlier as an antiseptic but the antiseptic properties are due to the liberation of
free iodine and not due to iodoform itself. Due to its objectionable smell, it has been
replaced by other formulations containing iodine.

Tetrachloro-methane (Carbon tetrachloride) CCl4

It is produced in large quantities for use in the manufacture of refrigerants and propellants for
aerosol cans. It is also used as feedstock in the synthesis of chlorofluorocarbons and other
chemicals.

When carbon tetrachloride is released into the air, it rises to the atmosphere and depletes the
ozone layer. Depletion of the ozone layer is believed to increase human exposure to ultraviolet
rays, leading to increased skin cancer, eye diseases and disorders, and possible disruption of the
immune system.
 Freons
The chlorofluorocarbon compounds of methane and ethane are collectively known as freons.
They are extremely stable, unreactive, non-toxic, non-corrosive and easily liquefiable gases.
Freon 12 (CCI2F2) is one ofthe most common freons in industrial use. It is manufactured
from tetrachloromethane by Swarts reaction. These are usually produced for aerosol
propellants, refrigeration and air conditioning purposes.

Most freon, even that used in refrigeration, eventually makes its way into the atmosphere
where it diffuses unchanged into the stratosphere. In stratosphere, freon is able to initiate
radical chain reactions that can upset the natural ozone balance.

P.p'-Dichlo- rodiphenyl-trichloro- ethane (DDT)

DDT, the first chlorinated organic insecticides, was

originally prepared by Paul Muller.
Paul Muller was awarded the Nobel Prize in Medicine
and Physiology in 1948 for this discovery. The use of CIH
DDT increased enormously on a worldwide basis after
DDT
World War II, primarily because of its effectiveness
against the mosquito that spreads malaria and lice that
carry typhus.

ABhinar Shukla