CHAPTER1 5

FJ / Chemistry Unit, KMPk / Mac 2006

HALOALKANES
1

15.1 : Introduction
Haloalkanes or alkyl halides

- compounds that contains halo en atom !onded to an sp" hy!ridi#ed car!on atom.

$eneral %ormula :

or or

R-& CnH'n(1 & )acyclic* CnH'n-1 & )cyclic*

+here & : halo en atom ),- Cl- .r or I*

2

15.1.1 : Classi%ication o% Haloalkanes

Haloalkanes are classi%ied accordin

to the nature o% car!on atom !onded to the halo en. $eneral ,ormula Classi%ication methyl halide - halo en is !onded to methyl roup Primary )1/* halide - halo en is !onded to 1/ car!on atom 0econdary )'/* halide - halo en is !onded to 3 '/ car!on atom

CH "&

R CH ' & R R CH &

$eneral ,ormula R R C & R &

Classi%ication Tertiary )"/* halide - halo en is !onded to "/ car!on atom Aryl halide - halo en is !onded to aromatic rin 11 2ot a aryl halide

CH '&

E3ample :
Classi%y the %ollo+in

haloalkanes : Classi%ication 1/ '/ "/ "/

5

2o. i. ii. iii. i4.

Haloalkanes CH "CH '.r CH "CH)Cl*CH " )CH "*"C).r* H "C Cl

15.1.' : I5PAC 2omenclature

Haloalkanes are named as alkanes +ith

halo en as su!stituents.
6ocate and num!er the parent chain %rom

the direction that i4es the su!stituent encountered %irst the lo+er num!er.
0ho+

halo en su!stituents !y the pre%i3es flouro-- chloro-- bromo- and iodo-- and list them in alpha!etical order alon +ith other su!stituents.
6

E3ample :
i. CH "CHCH 'CH " .r '!romo!utan e ii.
Cl .rCH 'CH 'CHCHCH 'CH " CH "

1-!romo-"-chloro-7methylhe3ane

E3ample :
iii. CH 'CH ', CH "CH 'CH 'CHCH 'CH 'CH " 7-)'%louroethyl*heptane i4. H "C CH " Cl

'-chloro-1-1dimethylcyclopentane

E3ample :
4. .r

7!romocyclohe3e ne 4i. CH 'Cl 4ii. CH " Cl 'chlorotoluen

)chloromethyl*!en #ene

15.1." : 0tructure o% Haloalkane

The car!on 8 halo en !ond in haloalkene is polar

!ecause car!on.

halo ens

is

more

electrone ati4e

than

9( 9C &

electrophi lic site

the

The polar C 8 & !ond causes the car!on !earin

halo en is suscepti!le to nucleophilic attack.

Haloalkanes are reacti4e and under o nucleophilic

su!stitution and elimination reaction.

10

15.' : Chemical Properties

15.'.1 : Reaction 2ucleophilic 0u!stitution
Haloalkanes under o nucleophilic su!stitution

reactions in +hich the replaced !y a nucleophile.

halo en

atom

is

In this reaction- the nucleophile attacks the

partially positi4e char e )9(* car!on atom !onded to the halo en )9-*.

$eneral reaction :

R: &

: 2u:

R : 2u

: &:
11

)a* : Hydrolysis o% Haloalkane +ith A;ueous 0olution o% 2a<H )H'<=2a<H*

Alkaline

!oilin

hydrolysis is carried out !y R-& +ith 2a<H)a;* to %orm alcohol.

R: & ( 2a<H
E3ample :

H '<

R: <H ( 2a&

CH " H '< : : CH " C .r ( 2a<H CH "

CH " CH ": C :<H ( 2a.r CH "

12

)!* : Reaction o% Haloalkane +ith Potassium Cyanide )>C2*

?hen R-& is re%lu3ed +ith >C2 in alcohol-

the halo en atom is su!stituted !y the C2- to produce a nitrile compound.

: : R & ( C2

alcohol re%lu3

: : R C2 ( &

E3ample :

CH "CH '.r ( >C2

alcohol re%lu3

CH "CH 'C2 ( >.r

13

)c* :Reaction o% Haloalkane +ith Ammonia )2H"*

?hen

R-& is heated +ith e3cess concentrated 2H"- the halo en atom is replaced !y the amino roup- 2H'-.
R: & 2H" : ( R2H" & 2H" : : ( R 2H' ( 2H7 &
)amin e*

E3ample :
CH "CH 'Cl ( e3cess 2H " : ( CH "CH '2H ' ( 2H 7 Cl
14

15.'.'

: @echanisms o% 2ucleophilic 0u!stitution Reaction

They are ' important mechanisms %or the

su!stitution reaction: )A*. 5nimolecular 0u!stitution Reaction )021* ).*. .imolecular 0u!stitution Reaction )02'* 2ucleophilic

2ucleophilic

15

)A* : 5nimolecular 2ucleophilic 0u!stitution Reaction )021*

The term unimolecular means there is only one

molecule in4ol4ed in the transition state o% the rate-limitin step.

021 reactions are

o4erned mainly !y the relati4e sta!ilities o% car!ocations.

Relati4e reacti4ities o% haloalkanes in an 021

reaction : R-& 1o A R-& A 'o R-& "o

increasin

reacti4ity
16

 The rate o% 021 reaction does not depend

on the concentration o% nucleophile.

The

rate depends concentration o% the halide.

only on the su!strate- alkyl

rate B k CR"C-&D

1 021 is a %irst order reaction

17

 The mechanism o% 021 reaction in4ol4es ' steps.

0tep 1 : ,ormation determinin step*

o%

car!ocation

)rate

R R: C : & R "o alkyl halide

slo+

R : : R C( ( &
halide ion

R car!ocation

0tep ' : 2ucleophilic attack on the car!ocation

R : : R C ( ( 2u: R

%ast

R R: C : 2u R
18

 E3ample 1 :

Reaction o% H'<.

'-!romo-'-methylpropane +ith
CH " CH ": C : <H ( H.r CH "

CH " CH ": C : .r ( H '< CH "

021 mechanism :

0tep 1 : ,ormation o% a car!ocation

CH " CH ": C : .r CH "

slo+

CH " : : CH " C ( ( .r CH "

19

 0tep

' : 2ucleophilic car!ocation

attack

on

the

CH " %ast : ( CH " C ( H '< CH "

CH " H : : CH " C < ( H CH "

6oss o% proton- H( to sol4ent

CH " H : : CH " C < ( H CH "

( H '<

CH " CH ": C : <H ( H "<( CH "

20

 E3ample ' :

?rite the reaction.

mechanism

%or

the

%ollo+in

CH " CH ": C :CH '.r ( 2a<H)a;* CH "

CH " CH ": C :CH 'CH " ( 2a.r <H

021 @echanism :

0tep 1 : ,ormation o% car!ocation

CH " CH ": C : CH ': .r CH "

slo+

CH " : : : CH " C CH ' ( .r ( CH "

21

Rearran ement :
CH " CH ": C : CH ' ( CH " CH " CH ": C : CH ' ( CH "

1-'-methyl shi%t

0tep ' : 2ucleophilic car!ocation

CH " CH ": C : CH' ( CH " ( <H : %ast

attack

on

the

CH " CH ": C : CH 'CH " <H

22

E3ercise 1 : ),e! '//"* ?rite a reasona!le structures o% products %ormed +hen 1-iodo!utane reacts +ith i. ii. iii. >C2 2a<H=H'< e3cess 2H"

?rite the mechanism %or the reaction in )ii*.

23

E3ercise ' : )@ac '//'* The structure o% compound A is as %ollo+s:

CH3 CH3 C Br
i. $i4e I5PAC name %or A

CH3

ii.Compound A react +ith <H- %ormin an alcohol. ?rite the mechanism %or the %ormation o% this alcohol and name the reaction.

24

).* : .imolecular 2ucleophilic 0u!stitution Reaction )02'*

The

term !imolecular means that the transition state o% the rate limitin step in4ol4es the collision o% t+o molecules. reactions are o4erned mainly !y steric %actors )steric e%%ect*.

02'

0teric e%%ect

- is an e%%ect on relati4e rates caused !y the space-%illin properties o% those parts o% a molecule attached at or near to the reactin site.
25

 The reacti4ity on 02' reaction depends on the si#e o%

atoms or

roups attached to a C 8 &.

The presence o% !ulky alkyl

roups +ill pre4ent the nucleophilic attack and slo+ the reaction rate.

Relati4e reacti4ities o% haloalkanes in an 02' reaction :

R-& 'o

A 1o

R-&

CH"-&

increasin

reacti4ity

26

 The

rate o% reaction depends on the concentration o% the haloalkane and the concentration o% nucleophile.
rate B k CR-&D C2u:-D

1 02' is a second order reaction.

The mechanism o% 02' occurs in a sin le

step.

$eneral @echanism :
R Nu:H C X H slow

Nu C X H H

fast Nu C

R
H

+ X27

transition

 In 02' reaction- the nucleophile attacks %rom the !ack

side o% the electrophilic car!on- that is- %rom the side directly opposite !onded to the halo en. !et+een

The transition state in4ol4es partial !ondin

the attackin

nucleophile and the haloalkane.

.ack-side

attack causes the product %ormed has in4erse con%i uration %rom the ori inal con%i uration. 1 turns the tetrahedron o% the car!on atom inside out- like um!rella cau ht !y the +ind.

28

 E3ample " :

Reaction o% ethyl !romide +ith a;ueous sodium hydro3ide.

CH "CH '.r ( 2a<H )a;*

CH "CH '<H ( 2a.r

02' @echanism :
CH3 H C Br H CH3 OH C Br H H CH3 OH C H H

:OH-

slow

fast

+ Br-

transition state

29

Comparison o% 021 and 02' Reactions 02 1 02 ' A t+o-step mechanism A one-step mechanism A unimolecular rate-determinin A !imolecular step rate-determinin

step

0econd order : rate B k CR&D C2uD 0tron nucleophile

,irst order : rate B k CR&D ?eak nucleophile 2o car!ocation rearran ement Reacti4ity order : 30 methyl E 1o E 'o

Car!ocation rearran ement Reacti4ity order : "o E 'o E 1o

15.'." : Elimination Reaction )dehydrohalo enation o% haloalkanes*

Halo en can !e remo4ed %rom one car!on

o% a haloalkane and hydro en %rom an adFacent car!on to %orm a car!on-car!on dou!le !ond in the presence o% a stron !ase.
$eneral reaction :

H : C : C : ( :.: &
haloalka ne

: C C
alken e

( &

!ase

31

 E3ample :

.r

i.

CH "CHCHCH " CH "

CH "CH '<2a CH "CH '<H

CH "C CHCH " CH "

maFor
( CH "CHC CH '

ii.

mino r
.r CH "
CH "CH '<2a CH "CH '<H

CH "

CH " (

CH '

maFor

mino

32

15.'.7 : 0ynthesis o% <r anoma nesium Compound ) $ri nard Rea ent *
Prepared !y the reaction o% haloalkanes +ith

ma nesium metal in anhydrous ether as a sol4ent.

R-&

ether R-@ & $ri nard Rea ent

E3ample :

) alkylma nesium halide* i. CH "CH 'CH '.r ( @ ether CH "CH 'CH '@ .r
ii.

Cl ( @

ether

@ Cl
33

15.'.7.1 : 0ynthesis o% AlkanesAlcohols and Car!o3ylic Acids %rom $ri nard Rea ents.
The

$ri nard rea ents under o many reactions that make them use%ul as a startin materials in the synthesis o% other or anic compounds. 0ynthesis o% alkane

)i*.

The $ri nard rea ent is hydroly#ed to an alkane +hen +armed +ith H'<. H( R@ & ( H '< R-H ( @ )<H*&
34

E3ample : i.

( H CH "CH '@ .r ( H '< CH "CH " ( @ )<H*.r

ii.

CH "CH-@ .r ( H '< CH "

iii.

H(

CH "CH 'CH " ( @ )<H*.r

CH '@ Cl

H '<=H (

CH " ( @ )<H*Cl
35

)ii*.

0ynthesis o% 1o alcohol

@ethanal reacts +ith the $ri nard rea ent%ollo+ed !y the hydrolysis produces primary alcohol.
< R-@ & ( H-C-H H R-C-<@ & H H '<-H ( H R-C-<H ( @ )<H*& H
36

 E3ample :

i.

<

CH "@ .r ( H-C-H

H "<(

H CH "-C-<H ( @ )<H*.r H

ii.
@ .r < ( H-C-H H "<( CH '<H ( @ )<H*.r

37

)iii*. 0ynthesis o% 'o alcohol $ri nard rea ent reacts +ith aldehydes to produce secondary alcohol.
< R-@ & ( H-C-RG RG R-C-<@ & H H '<-H ( RG R-C-<H ( @ )<H*& H
38

 E3ample :

i.

< CH "CH '@ .r ( CH "CH '-C-H H '<=H ( H CH "CH '-C-CH 'CH " ( @ )<H*.r

ii.

<H
CH " H '<=H ( C-<H ( @ )<H*Cl H
39

@ Cl

< ( CH "-C-H

)i4*. 0ynthesis o% "o alcohol $ri nard rea ent reacts +ith ketons to produce the tertiary alcohol.
< R-@ & ( RG-C-RH RG R-C-<@ & RH H '<-H ( RG R-C-<H ( @ )<H*& RH
40

 E3ample :

i.

< CH "CH '@ .r ( CH "-C-CH " H '<=H ( CH " CH "CH '-C-CH " ( @ )<H*.r <H
CH " H "<( C-<H CH " ( @ )<H*Cl
41

ii.

@ Cl

< ( CH "-C-CH "

)4*.

0ynthesis o% car!o3ylic acid

$ri nard rea ent reacts +ith car!on dio3ide )C<'* %ollo+ed !y hydrolysis to %orm car!o3ylic acid.

< R@ & ( < C <

< R-C-<-@ & ( H '< < R-C-<H ( @ )<H*&
42

R-C-<-@ &

H(

 E3ample : < CH "CH '@ I ( C<' CH "CH '-C-<-@ I

< CH "CH '-C-<-@ I ( H '<

H(

< CH "CH 'C<H ( @ )<H*I

43

15.'.5 : ?urt# Reaction

Reaction o% haloalkane )R&* +ith an alkali metal

)usually 2a* to synthesise lon er alkane. i. To prepare an e4en num!er o% car!on atoms alkane 'R& ( '2a E3ample: RR ( '2a&

dry ether

'CH"CH'.r ( '2a CH"CH'CH'CH" ( '2a.r

44

ii.To prepare a odd num!er o% car!on atoms

alkane

R& ( RI& ( J2a RR ( RRI ( RIRI ( J2a& E3ample: CH"CH'.r ( CH".r ( J2a CH"CH'CH'CH" ( CH"CH'CH" ( CH"CH" ( J2a.r

45

15.'.J : Importance o% Haloalkanes as Inert 0u!stance

Haloalkanes CCl7 )car!on tetrachloride* CHCl" )chloro%orm* C,'Cl' - ,reon-1' )dichlorodi%luoromethane* C,C )chloro%lourocar!ons* KKT )KichloroKiphenylTrichloroet 5ses sol4ent %or dry cleanin - spot remo4in sol4ent %or cleanin and de reasin +ork propellants in aerosol sprays re%ri erant as
46

insecticide protects