Topic 12.

4
HALOALKANES
Structure and bonding in haloalkanes
Nucleophilic substitution
Eliination
Mill Hill County High School
HALOALKANES
1. Structure
Halogenoalkanes are molecules containing a C-X bond, where X = F, Cl, Br or I.
X C
The molecules are generally saturated, and so cannot undergo addition reactions.
The C-X bond is olar, and the carbon is δ!"e. There#ore the molecule can react with
nucleohiles.
Thus halogenoalkanes tend to undergo nucleophilic substitution reactions.
The X can combine with an ad$acent H atom to #orm a stable HX molecule. Thus
halogenoalkanes can also undergo elimination reactions.
%lthough halogenolkanes are olar, there is no hydrogen bonding between them and
as a result they are not generally soluble in water.
Haloalkanes can be di"ided into three classes& rimary, secondary and tertiary.
2. Nucleophilic substitution reactions
The three nucleohiles most commonly used in nucleohilic substitution o#
halogenoalkanes are hydro'ide ions, (H
-
, cyanide ions, C)
-
and ammonia, )H
*
.
a) ith hy!ro"i!e ions
Halogenoalkanes react with hydro'ide ions when boiled under re#lu' with a+ueous
)a(H or a+ueous ,(H&
--X ! (H
-
 --(H ! X
-
The nucleohile .ie the hydro'ide ion/ attacks the δ!"e carbon atom #rom behind,
#orcing the X atom to lea"e as the halide ion. It is a one-ste mechanism&
X C
CH
3
H
H
HO:
-
OH C
CH
3
H
H
+ X
-
)ote that the hydro'ide ion is beha"ing as a nucleophile in this reaction.
0g bromoethane  ethanol
Br C
CH
3
H
H
HO:
-
OH C
CH
3
H
H
+ Br
-
0g 1-chlororoane  roan-1-ol
Cl C
CH
3
H
HO:
-
OH C
CH
3
H
+ Cl
-
CH
3
CH
3
b) ith cyani!e ions
Cyanide ions are nucleohiles and react with halogenoalkanes by nucleohilic
substitution to gi"e nitriles. The halogenoalkane should be boiled under re#lu' with
,C) in a+ueous ethanol.
--X ! C)
-
 --C) ! X
-
The mechanism is e'actly the same as with the hydro'ide ion.
X C
CH
3
H
H
NC:
-
CN C
CH
3
H
H
+
X
-
)ote that the C)
-
ion has the #ollowing structure&
C N
:
-
Thus the lone air o# electrons is on the carbon, not the nitrogen. It is thus the carbon
which attaches itsel# to the organic molecule.
0g bromoethane  roanenitrile
Br C
CH
3
H
H
NC:
-
CN C
CH
3
H
H
+
Br
-
0g 1-chlororoane  1-methylroanenitrile
Cl C
CH
3
H
NC:
-
CN C
CH
3
H
+
Cl
-
CH
3
CH
3
The reaction with cyanide ions is signi#icant because it increases the number o#
carbon atoms on the chain, so it pro#i!es a ay o$ ascen!ing the ho%ologous
series. It is thus "ery use#ul in organic synthesis.
c) ith a%%onia
I# a halogenoalkane is heated with ethanolic ammonia in a sealed tube, a rimary
amine is #ormed&
--X ! 1)H
*
 --)H
1
! )H
2
X
The mechanism is again nucleohilic substitution&
CH
3
CH
3
C
H
H
X
NH
3
C
N
H
H
H
+
H
H
:
+
X
-
The initial substitution ste #orms the intermediate --)H
*
!
ion. The H is remo"ed by
another ammonia molecule to #orm the amine&
CH
3
NH
3
C
N
H
H
H
+
H
H
:
CH
3
C
N
H
H
+
H
H
:
+
NH
4
0g bromoethane  aminoethane
CH
3
NH
3
C
N
H
H
H
+
H
H
:
CH
3
C
N
H
H
+
H
H
+
NH
4
CH
3
C
H
H
NH
3
:
Br
+
Br
-
0g 1-chlororoane  1-aminoroane
CH
3
NH
3
C
N
H
H
H
+
H
:
CH
3
C
N
H
H
+
H
+
NH
4
CH
3
C
H
NH
3
:
Cl
+
Cl
-
CH
3
CH
3
CH
3
&. Eli%ination o$ hy!rogen hali!es
I# halogenoalkanes are boiled with an ethanolic solution o# ,(H instead o# with an
a+ueous solution, they will undergo elimination o# an HX molecule to gi"e an alkene&
-
3
-
1
CH-
*
-
2
CBr ! (H
-
 C
1
H
2
! Br
-
! H
1
(
)a(H is not used since it is only saringly soluble in ethanol. This reaction works
best i# distillation aaratus is used since the alkene roduct is "olatile.
The hydrogen is always lost #rom a carbon atom ad$acent to the carbon atom attached
to the halogen .all the hydrogen atoms which could be remo"ed ha"e been circled/.
4ometimes this can result in more than one ossible roduct&
Br
C C
H H
H H
H
C
C
H
H
H
H
bromoethane ethene
Cl
C C
H H
H H
H
C
C
H
H
H
C
H
H
CH
3
3-chlororoane roene
Cl
C C
H H
H H
H
C
C
H
H
H
C
H
H
CH
3
1-chlororoane roene
Br
C C
H H
H H
H
C
C
H
H
H
H
C
H
C
2
H
5
H
C
H
3-bromobutane but-3-ene
5uring the abo"e elimination reactions there is only one ossible roduct.
Br
C C H
H
H H
H C
C
H
H
H
H
C
H
C
2
H
5
H
C
H
1-bromobutane but-3-ene
In this reaction, losing an H atom on the other side o# the Br atom results in two
di##erent roducts&
C
C
H
H
CH
3
CH
3
C
C
H
H
CH
3
CH
3
or
Br
C C H
H
H H
H
H
C
H
H
C
H
1-bromobutane cis but-1-ene or trans but-1-ene
The mechanism o# this reaction in"ol"es the hydro'ide ion attacking a hydrogen atom
on the haloalkane&
C C
H
R
R
X
R
R
HO
+ X +
:
-
-
C C
R R
R
R
H
2
O
)ote that the hydro'ide ion is beha"ing as a base, not a nucleohile
0g 3-chlororoane  roene
C C
H
H
X
H
H
HO
+ X +
:
-
-
C C
H
H
H
H
2
O
CH
3
CH
3
'. (ates o$ reaction o$ halogenoal)anes
The rate o# substitution or elimination o# halogenoalkanes deends on the ease with
which the C-X bond can be broken. This deends on the strength o# the C-X bond,
which in turn deends on the length o# the bond.
4ince the C-F bond is "ery short, it is "ery strong and di##icult to break. Thus
#luoroalkanes react "ery slowly.
The C-Cl bond is longer and weaker than the C-F bond, and the C-X bonds become
rogressi"ely longer and weaker on descending the grou. Thus the C-I bond is the
longest, weakest and easiest to break and thus iodoalkanes react the most +uickly.
Thus rates o# reactions decrease in the order&
Iodoalkanes 6 bromoalkanes 6 chloroalkanes 6 #luoroalkanes
%s the halogen atom becomes larger, the C-X bond becomes longer, weaker and more
di##icult to break and the corresonding halogenoalkanes react more +uickly.
*. Su%%ary o$ reactions o$ haloal)anes
Haloalkane  alcohol
-eagent& )a(H.a+/ or ,(H.a+/
Conditions& warm under re#lu'
0+uation& --X ! (H
-
 --(H ! X
-
7echanism& nucleohilic substitution
-ole o# hydro'ide ion& nucleohile
Haloalkane  nitrile
-eagent& ,C) in a+ueous ethanol
Conditions& boil under re#lu'
0+uation& --X ! C)
-
 --C) ! X
-
7echanism& nucleohilic substitution
Haloalkane  %mine
-eagent& ammonia in ethanol in a sealed tube
Conditions& heat
0+uation& --X ! 1)H
*
 --)H
1
! )H
2
X
7echanism& nucleohilic substitution
Haloalkane  alkene
-eagent& ,(H in ethanol
Conditions& heat
0+uation&

C C
H
R
X
R
R
+ X +
-
C C
R R
R
H
2
O R
R
7echanism& elimination
-ole o# hydro'ide ion& base