ALKYL HALIDES

aka Halogenoalkanes
si
functional
group is the carbonhalogenbond C
reactivesite
PREPARATION
i Fromalkaner
FreeRadical Substitution of alkanesresults in alkylhalides

ie Chu tch CHsCl t HCl

ie CH3CH3 t Br z CHzCHzBr t HBR
aV C
ie t Cla t HCl

2 From alkenes
by electrophilic addition
hexane
ie CHz CHz t Bre l
Rep
s Br Cha Cha Br
Rep
ie CHz CHz t HBR CH3CHzBr
RIP
ie CH CH CHz HI s CHz CH CHS
f iodopropane

3 Fromalcohols substitution
by nucleophilicZinckcatalyst
a CH3CHz0H t HCl s CHzCHzC1 t H2O
conc heat
liquid liquid
b Pcb Pds Sociz
Byusing a chlorinatingagent ie
solid
CH3912011 t PCls warms CHsCHzC1 t HCl g t POCI3
while
firmer
RTP
c CHZCHOH t Soda cH3CHz t HCl t 502cg
thionylchloride whileg
fumes
conc H2SOutNaBr
d CHzCHzOH t ftp.r s CHzCHzBr t H2O
heat
 Pt 12
e 3413912011 t PI 3 3CHzCHz I t H3PO3
Solid

REACTIONS OF ALKYL HALIDES

Mechanism Nucleophilic Substitution SN
l
C 7
SN SN 2
Nucleophilic substitution Nucleophilic substitution
unimolecular bimolecular

For organicreactions experiments are done by heatingunder reflux

f Nagas
inertenvironment
REFLUX
CONDENSER f 11,7
H2Oout Reasons for reflux
i Ensure that reactiongoes
to completion
2 Increases the rate of
1 k reactant reaction
H2Oin
y f condensate
Ifallbackintoflask 3 Ensuresthat the volatile
T reactants or products are
notlostby evaporation
reactantvapour when
boiling
L
r
Note organiccompounds are
reactants flammable sothey are never
ooo heated over a nakedflame
oilbath possiblealternatives
tank o water1 steam bath
bumpinggranules o oil bath
electrichealingmantle
 REACTIVITY OF ALKYL HALIDES
Determined primarily
by bondenergy and secondarilyby bondpolarity
i Bondpolarity
gt g
C X where X is a halogen
hence this bond is polar

Stc F S MostPolar
Stc CtS
si C Br s I
5 Is Least Polar

Based on
onlypolarity we would predict that C E is the most
reactive and CL is the least reactive

2 BondEnergy
KJ1m01
C F 467 strongestbond
C d 346
C Br 290
C I 288 weakestbond
Based on the bond data c 1 is mostreactive as it's bond
energy
energy is the lowest
But since bondenergy is the PRIMARY determinant of reactivity
C I would be considered more reactive than C F
However bond polarity is also important as it'sused to predict
the typeof reaction and the nature of the reagent that will
attack the alkylhalide
 REACTION OF ALKYL HALIDES WITH Ad NaOH
Hydrolysis
SN
heatunder
Overall Reaction CH CH z Br t NaOH aq s CHs CHIH t Na Br
bromoethane reagent
reflux ethanol
Mechanism KJ1m01
C H 413
C Br 290
slow step
nucleophile
highEa
CHz OH CHz
Is alive
H H
1st
C H
H
heterolysis
C
1 attractsnucleophiles C
Br s Br OH faststep
primaryalkylhalide pentavalent transition cannotbe isolated
stale
c Br bond is breaking
C OH is forming these
arepartialbonds

CH3
I
H ti Nat Br 3
f
OH
finalproducts

Thenucleophile OH ion is attracted to the Cst carbon of the

C Halogen bond

It approachesthemolecule from the oppositeside to the halogen to

minimise repulsion from the partiallynegativelycharged bromine

Soit'sattack is notimpeded by the Brs

 A pentavalenttransitionstate is formed simultaneously
It is a charged activated complex
Brosbondbreaks
The C heterolytically to form the productEthan
and the bromide ion is released
The reaction is called nucleophilic as the first step involves an
attackby a nucleophile

EnergyProfileof this reaction

a
is thebottleneck of thereaction
energy a
KJ1m01
Ea

r
Ect
NaOH
DH

V 2011 NaBr
CHSCH

RIN

SI
Overallreaction
CH s
CH3 1
heatunder
113C d Br t NaOH aq
reflux tbc C OH t Na Br
l reagent 1
CHz CHs
2 bromo 2 methylpropane 2 methylpropan 2 ol

Mechanism slowstep tertiarycarbocation intermediate

CH3 CH3
I 1
H3C CSI B S 43C Ct eyDative Br
I Heterolysis 1 fast
CH3 Ctb H step
tertiaryalkylhalide
 CH3
I
HIC OH t Nat Br
f
CH3
finalproducts

Thereactionstartsout by the heterolytic fission of the E BEbond

dueto collisions to form a 3 carbocation
The carbocation is readilyattacked
form the productalcohol by the nucleophile Cote to

Rate CLCH3 s C Br

ratedepends on the concentration of

only one species
alkylhalides as only the alkyl halide is involved in forming
the carbocation intermediate
Hence the reaction is uni molecular

Energyprofile of this reaction exothermic reaction

energy
Kflmol a
Ea fast
slow
3ocarbo
I
e cation
cabbc.BR
NaOH
DH

V
cats econ naBr

Exn
 I S S

Primary
H
Secondary
H Tertiary CH3
I I 1
HzC C X 113C C X 113C C X
l I 1
H CH CH z
SN z SNz o SN SN

X Halogen atom

whyis this the case SN vs SN z depends on

type of alkyl halide
H
ie a primary
alkyl halide I
R C H
if it forms a carbocation 1
it will be a 10 one GBR
not stable
very
Hence I haliderprefer to gothrough
alkyl
the SN z mechanism forming a
pentavalent transition state

A 30 alkyl halide R R more stable due

1 1 topositive
R C Br R C inductive
I 1 effect
R R
Too bulky
In
This doesn't happenbecause
HO I Cst is s hindered
C
l Br b ie there is not enough
CH3 space for the pentavalen
transition state to form
so it
goes through the
carbocation intermediate
REACTION OF ALKYLHALIDES WITH WATER
Hydrolysis
H2O is a weak nucleophile so the reaction with water and
alkyl halide is veryslow
in ethanol
CH3CHz Br t Hao s CHIH20H t HB r
heat under
reflux for
several
hours

Because this reaction is so slow hydrolysis is

usually carried out by
using NaOH aq

REACTION OF ALKYLHALIDES WITH AMMONIA

NHS is a nucleophilebecause it has a lone pair ofelectrons so it can
attack the partially positivelycharged carbon
Product is an anime
Te R NH 2

Types of Anurnes
I amine 2 amine 3 amine
H R R
l I i
R N R N R N
I 1
H H R

ethanol 10 am he
overallReaction CHSCHz Br t 2MHz heat in a
CH3442NHz t NHyB
limiting excess sealed tube ethylamine
reagent

To stop the reaction at the taurine stage excess NH 3 should be

used
If NHz g is limiting and CHSCHz Br is in excess
The primary amine product CHsCHzin Hz Ca nucleophile will
attack the unreacted CH sCH z Br to form a 20 amine
 H
I gt A
CH3 C Bres cHzCHz I CHIH HB
I l
ti y o H diethylamne
ti N CHIH 3
I ethylamine The 20 amine is still a
H nucleophile and again attacks
the alkyl halide
H
1st A
Cl13 C Bres
It cuzcuz in CHIH
I triethylamine
cHzCHz in CHIH z CHIH z
1
H

H
I gt Nu ti
CH3 C Bres
CHIH 3
t

f
t
CHzCHz N CHIH z Br
CHzCHz I CHIH z I
i CH CHz
CH CHz
tetraethyl ammonium bromide
N
finally uses up its lone ionic salt
because it has
pairHs no more
togiveup

If we
ammonia
want to make the primary anime
only use a
large excess of

SN 2 primaryalkylhalide
H CH3 H H
I N I
Hsc Cst Brs HN C Br HzC C H t Br
l l l
H H N E H
H N E1
pentavalent ft
transitionstate NHS
 ft
HzC C H t NHuffBr

H N H
ee

SN i 130alkylhalide

413 CHz Gt3

I l l
H3C Ct CH3 HzC C CH z 43C C CH3 t Br
t 1
GB're a
H n't H
HzN
tertiary H
carbocation HyN I

413
I
H3C CH 3 t NH4TBR
g
H N H

NaCN
REACTION OF ALKYLHALIDES WITH SODIUM CYANIDE IN ETHANOL
Produces a nitrile note Differencebw cyanideand

OverallReaction
I c Nyt nitri e
cyanide inorganiccompounds
ie sodiumcyanide Naan
ethanol propanenitrile
bromo
ethane n
yr
nitrite organiccompounds
CH3CHzBr t NaCN
healand CH3CHzCN t Na Br nitrile CHICHEN
ie propane
reflux
cThis is an importantreaction in organicsynthesis as it can be used
to elongate1lengthen the carbon chain
always
In the above example the
a SN z reaction
alkyl halide is a 10 one hence it undergoes
 Below is an example where a 20alkylhalideundergoes a SN reaction
SNz or SN1
CH3 CH3
I ethanol
H3C CH Ct
W
t NaCN heat under
s 113C d1 CN 1 NaCl
substituted reflux
H

o 30alkylhalide Sns only

CHIH3 CHzCHz
I I
HN C CI t NaCN Hsc C CN t Nad
l I
CHs CH3

Moreexamples

ethanol
Br CHz CHIH Br t 2 NaCN CH2 z CN t 2 Na Br
heat NC
z
under
reflux

nitriles can be converted to other functional groups easily

Possibleconversions

Hydrolysis HzCN
CH3C Reduction
a
corresponding corresponding
carboxylic Amine
Acid
CH3CHzCHz NH z
CHsCHzCOOH

HYDROLYSIS of nitrites

the RCN under reflux with dilute aqueous acid ie HCl

Byheating
Ht aq
CH3CHEN
heatunder CHICHzCOOH
reflux
 REDUCTION ofnitriles
a Na metal in ethanol as solvent Hz is evolved which acts as
gas
the required reducingagent

CHz CHIN t 4EH CH3CHzCHzNHz

T t.at atomichydrogenreduction
2h signifies
Reagent Nals
condition ethanol rtp
OR
b NaBHu in water as a solvent
NaBHu
CHIH z CN t 4 H water cHzCHzCH2NH2

reagent NaBHu
condition water
rtp

SUMMARYofNucleophilicSubstitution Rains

Nucleophile Productformed when it isreacted with CHsCHzBr

water H2O Hydrolysis CH3CHz0H t HBR
NaOH
Caq H
hydroxide Hydrolysis CHsatzOH t Na Br

ammonia NH3 CtbCHzNHz t NHuBr

t
cyanide ion C C N ctbctta.CN t Na Br

10 amine R N Hz CHCHEN R t H Br
Ll
20 amine
 COMPARING THERATEOF HYDROLYSIS Of R X where Cl us Br us 1

Based on the identification test for halide ion test Agnos

Ratesofhydrolysis can be studied by dissolving the alkylhalide in
ethanol and water and adding Agnos aq to the reactionmixture
As the alkylhalide slowly hydrolyses the halide ion X is
released and forms
appt with Agnos aq
R X t Hao Agt R OH Ht
t t
Agxppts
Example

CH3 CH3
I 1
HsC C X t H2O HsC OH HX
I o q f
CH3 CH3

SUMMARY
compound observation colorof ppt
CHS C a slightcloudiness while Agds s
after 1 how
CHS C Br Cloudeners after pale cream AgBr s
a fewminutes
6th C 1 Thick precipitatewithin paleyellow Agt s
a minute
pquolevalues in answer
Q Explain this observation with ref theDaaBooke
odoalkanes are the mostreactive as the C I bond is the
Towest energy
240631moi whereas the chloroalkane is the least reachme
withthe highest bond energy 340551moi
Therefore thereaction 1 hydrolysis is fastest for iodoalkanes

C d C Br C I bondenergy1 and rateofhydrolysist

 ELIMINATION REACTIONSOFALKYLHALIDES
whether the halide undergoes nucleophilicsubstitution or
alkyl
elimination depends on the reaction conditions or the solvent being
used
in ethanol
Reagent ethanolic NaOH or ethanolic KOH
condition
Twhy KOH
KOH isbetterfor this reaction
because it is more soluble in
Q How is eliminationdifferent ethanolthan NaOH
from substitution
In elimination we are removing a smallmoleculefromthe startingmaterial
OH ion behaves as a base and net as a nucleophile
A base is a proton Ht acceptor ie OH Ht H2O
An acid is a proton Ht donor Gproton

In ethanol NaOH behaves as a base

OverallReaction
NaOH
CH3CHz Br ethanol CH z CHz t H Br
bromoethane heatunder ethene
reflux

Mechanism Notreally in our syllabus but predicting the

µ st Hstfyneterolysis
organicproduct is
H H
si CIst Br
est e i 1
g C C H Br 1120
H H C t t

gt est
H H
aline
Ho

TheHetfromthe carbon adjacent to where the halogen is attached is

removed

The EN halogen creates a St charge on all thehydrogens so the test

are acidic in nature

The OH ion behaves as a base in ethanol and deprotonates the

 ay
As a result the test andthe Br are eliminated and an alkene is
produced

Example
butane
2 bromo
CHz CHz CH CH
I
z
4 3 12
t
It can
Br
I
be removed
from here here
If we remove test from C
but 1 ene
CH3 CH2CH CH z t HBr
If we remove Hest from Crs
cis but 2 ene and transbut 2 ene
CHS CH CH CH3

d How alkenesformed as a result of this reaction

Am many
3
1 But I ene
2 cis but 2 ene 3 differentalkenes
3 trans but 2 ene

Example

NaOH
Br CHz CHz CHz Br heatunder Br Hz CH cuz
1 t reflux
test removed
removed

2 3 4 5
NaOH fromCz
CHs CHz CH CHz CH3 S CHz CH CH CH z CH3
1 heatunder
reflux fromCu
Ct CHz CH z CH CH CHz

same product
d How alkenes produced pent 2 ene
many
Aun 1 Cis pent 2 ene
2 transpent 2 ene 2 differentalkenes
 REVISION OF NUCLEOPHILIC SUBSTITUTION
NaOHLag
Br CH2 z B r S HO
heatunder Hz OH
reflux i 3 propanedid

NaCN l S pentanedinihile
ethanol heat NC LCH2 s CN
0 0
HtLaq il 11
Hydrolysis heatunderreflux HO C LCH273 C OH

8CH
Reduction HzNz CH2 s Nz Hz
Na s ethanol
excessNH
3cg
ethanol heal H2N CH2 z NH z
in sealedtube 1,3 propanediamine

USES OF ALKYLHALIDES
1 Used as CFCs chlorofluorocarbons
Properties of CFCs that made them useful
theywere inert andnontoxic
they are volatile and have lowboilingpoints
can becompressedeasily
Becauseof theseproperties could be used as aerosol propellants
they
refrigerants andcoolants

Buttheyhavebeenphased out as theygeneratethe chlorinefree radical

whichhas destroyed the ozone COD layer in the stratosphere upper
atmosphere
F H Homolysis F H
l in Uv light 1 I
H C c Cl H C C t Cl
1 I Suh l
F H F H

2 Anesthetics Chloroform CHCb notused anymore

Generally known as a clan of compounds called Halothanes
ie CF CH Brd
3 fire retardants extinguishers known as Halons
ie CBRCtFa

u Used to make polymers ie Teflon PVC etc

s Solvents ie CH202 paint remover

can non polar solvent

6 Insecticides DDT highlytoxic

7 Herbicides

Ozonedepletion in the stratosphere

naturalEquilibrium
ur light
2m01s of
Production of atoms
oxygen
oxygen atom 02
250mm
3 20

Natural ozone formation 02 to 03 Equilibrium

occurs naturally
Natural Ozonedepletion Oz o o

The Cl freeradical disrupts theequilibrium by actingas a catalyst for

breaking up ozone
removed
r
CL t.TT CLO t Oz
CLO t CC t 02

Docile depletioneffect it is removingatomic oxygen and

as
0 from the natural equilibrium process