10.

4 HALOGENOALKANES (old names 'haloalkanes' or 'alkyl halides')

10.4.1 Introduction to halogenoalkane reactivity

• Halogenoalkanes owe their reactivity, especially compared to the unreactive

alkanes, to two principal reasons.
• R3C-X = halogenoalkane/haloalkane/alkyl halide/halogenated alkane etc. X =
halogen e.g. Cl, Br or I
• The carbon-halogen bond is polar, Cδ+-Xδ- due to the difference in electronegativity
between carbon and the halogen. The Cδ+ carbon is then susceptible to nucleophilic
attack by electron pair donor neutral molecules (e.g. :NH3, H2O:) or ions (e.g. :OH-,
-
:CN).
• The carbon-halogen bond is usually the weakest bond in the molecule and
significantly weaker than the carbon-carbon or carbon-hydrogen bonds.
o Average bond enthalpies/kJmol-1: C-C 348, C-H 412, both relatively high
requiring high activation energies for reaction.
o Average bond enthalpies/kJmol-1: C-Cl 338, C-Br 276, C-I 238, generally
lower resulting in lower activation energies.
 Even the lowering of the bond enthalpy by 10kJ from C-C to C-Cl,
combined with the polarity of the C-Cl bond, makes all the difference
when comparing alkane and halogenoalkane reactivity.
• A comparison of aliphatic halogenoalkanes and aromatic halides is dealt with in
FURTHER COMMENTS.
• IMPORTANT NOTE on structure classification
o In the mechanism diagrams you will see part of the molecular structure
shown as R3C
o PLEASE do not assume this means a tertiary (tert) halogenoalkane
(haloalkane).
o R3C- is used repeatedly to minimise the number of graphic images
needed.
o In general an halogenoalkane (haloalkane) has the structure R3C-X
where R = H, alkyl or aryl.
o A primary halogenoalkane (haloalkane) can be shown as RCH2-X where
R = H, alkyl or aryl.
o A secondary (sec) halogenoalkane (haloalkane)can shown as R2CH-X
where R = alkyl or aryl.
o A tertiary (tert) halogenoalkane (haloalkane) can be shown as R3C-X
where R = alkyl or aryl.

10.4.2 Nucleophilic substitution of halogenoalkane by hydroxide ion

(hydrolysis with OH-)

• Hydrolysis with NaOH(aq): [see mechanisms 1, 2, 33 and 34 below]

• R3C-X + OH- ==> R3C-OH + X-
• The halogenoalkane is usually refluxed with aqueous sodium hydroxide,
NaOH(aq), but some RX molecules are reactive enough to hydrolyse when just mixed
with water (see further down).
• The reaction can proceed by two different mechanisms, which can occur
simultaneously!, and are sometimes referred to as SN1 'unimolecular' and SN2
'bimolecular', BUT these 'molecular' terms are based on kinetic studies of the
reaction and refer to the overall order of the reaction (see reaction kinetics). The
vast majority of reaction steps occur via bimolecular collisions, even if its only with the
solvent (as in the case of step (1) of the SN1 mechanism below), so beware of
terminology.
mechanism 1 - nucleophilic substitution of a halogenoalkane by hydroxide ion (SN1
'unimolecular' via carbocation)

• SN1 unimolecular, a two step ionic mechanism via carbocation formation

[mechanism 1 above]
o In step (1) the Cδ+-Xδ- polar bond of the halogenoalkane splits
heterolytically to form a carbocation and a free halide ion (X-, e.g. chloride
or bromide) and this is a reversible reaction. The C-Cl bond is most likely to
break because it is a weaker bond than the C-C or C-H bond AND breaks
heterolytically because of the big difference in electronegativity between
carbon (2.1) and chlorine (3.0) giving a polar Cδ+-Clδ- bond. So the C-Cl
bonding pair of electrons leaves with the Cl atom as the Cl- ion.
o In step (2) the hydroxide ion is a negative electron pair donor and rapidly
combines with the carbocation, forming the C-O bond in the alcohol product.
o Step (1) is the rate determining step with the much larger activation energy
(see reaction profile diagram 45)
o This mechanism is most likely with tertiary halogenoalkanes.
o Primary halogenoalkanes tend to react by the SN2 mechanism NOT involving
a carbocation.
o Secondary halogenoalkanes react via both mechanisms at the same time!
The relative rate order for the SN1 mechanism is tert > sec > prim i.e.
following the pattern of decreasing stability of the carbocation (see extra
discussion points).

Three diagram 'styles' are shown below for the SN2 bimolecular mechanism that
does NOT involve a carbocation.

style (a)

mechanism 2 - nucleophilic substitution of a halogenoalkane by hydroxide ion

(SN2 'bimolecular')

style (b)

mechanism 34 - nucleophilic substitution of a halogenoalkane by hydroxide ion

(SN2 'bimolecular')
 style (c)

mechanism 33 - nucleophilic substitution of a halogenoalkane by hydroxide ion

(SN2 'bimolecular')

o SN2 'bimolecular', a one step bimolecular collision mechanism [mechanisms

2, 34 and 33 above]
 The Cδ+-Xδ- bond is polar because of the difference in
electronegativity between carbon (2.1) and chlorine (3.0), so the
electron rich nucleophile, the hydroxide ion, attacks the slightly
positive carbon.
 The nucleophile acts as an electron pair donor (Lewis base) to
bond with the Cδ+ carbon to make the C-O bond in the newly formed
C-OH alcohol group.
 Simultaneously the chlorine atom is ejected, taking with it the C-X
bond pair, so forming the chloride ion on expulsion.
 This mechanism is most likely with primary halogenoalkanes.
Tertiary halogenoalkanes tend to react by the SN1 mechanism
involving a carbocation, secondary halogenoalkanes react via both
mechanisms (see extra discussion points).
o Diagram styles and explanation:
 Style (a) Does not show the 'activated complex' or 'transition state' at
the point where the hydroxide ion ('incoming') and the chloride ion
('outgoing') are 'half-bonded' to the central carbon atom of the
functional group.
 Style (b) Shows a simplified version of the 'activated complex' or
'transition state'. The blue .... represent 'half-bonds' (not weak inter-
molecular forces) in the sense that the hydroxy/hydroxide group is
'coming in' and the chloro/chloride group is 'going out'!
 The change can also be represented as a simple reaction
progress-profile diagram 41.
 Note that 'activated complex' or 'transition state' is not
the same as an intermediate like a carbocation which is
a definite entity in its own right, however short its
lifetime.
 Style (c) Shows the reaction in terms of the stereochemistry. This is
not a particularly important 'style' unless the original halogenoalkane
is chiral (see note on chirality below).

Also read the FURTHER COMMENTS for this reaction * mechanism

index

o Direct hydrolysis with H2O: [mechanisms 10 and 35 below]

o R3C-X + 2H2O ==> R3C-OH + X- + H3O+
mechanism 10 - nucleophilic substitution of a halogenoalkane by water (SN1
unimolecular via carbocation)

o SN1 unimolecular, a two step ionic mechanism via carbocation formation.

[mechanism 10 above]
 In step (1) the halogenoalkane splits heterolytically to form a
carbocation and a free halide ion (e.g. chloride or bromide) and this
is a reversible reaction. The C-X bond is most likely to break because
it is a weaker bond than C-C or C-H AND breaks heterolytically
because of the big difference in negativity between carbon (2.1) and
chlorine (3.0) giving a polar Cδ+-Xδ- bond. So the C-Cl bonding pair
of electrons leaves with the Cl atom as the Cl- ion. Step (1) is the
rate determining step (rds) and the rate effectively only depends on
the halogenoalkane concentration.
 In step (2) the water is an electron pair donor and rapidly
combines with the carbocation, forming the C-O bond in the
protonated alcohol.
 In step (3) a water molecules rapidly removes a proton to leave the
free alcohol product.
 The overall change can also be represented as a reaction
progress-profile diagram 42.
 This mechanism above is most likely with tertiary
halogenoalkanes.
 Primary halogenoalkanes tend to react by the SN2 mechanism NOT
involving a carbocation, though very slow with water if it reacts at all.
Secondary halogenoalkanes tend to react via both mechanisms at
the same time (see extra discussion points).

mechanism 35 nucleophilic substitution of a halogenoalkane by water (SN2

bimolecular)

o SN2 'bimolecular', a two step bimolecular collision mechanism but NOT

involving a carbocation. [mechanism 35 above]
 Step (1): The Cδ+-Xδ- bond is polar because of the difference in
electronegativity between carbon (2.1) and chlorine (3.0), so the
electron rich nucleophile, the water molecule, attacks the slightly
positive carbon. The nucleophilic water acts as an electron pair donor
(Lewis base) to bond with the 'delta positive' carbon to give the C-O
bond of the protonated alcohol. Simultaneously the chlorine atom
is ejected, taking with it the C-X bond pair, so forming the chloride
ion on expulsion. Step (1) is the rate determining step (rds) and
the rate effectively only depends on the halogenoalkane
concentration.
  In step (2) another water molecule rapidly accepts the proton from
the protonated alcohol to leave the free alcohol product.
 The reaction profile would be similar to diagram 45
 BUT the intermediate is [R3COH2]+ NOT an R3C+
carbocation.
 This mechanism is most likely with primary halogenoalkanes,
but very slow if at all with water, much faster with the hydroxide ion, a
more powerful nucleophile (negative ion as well as an electron pair
donor). Tertiary halogenoalkanes tend to react by the SN1
mechanism involving a carbocation, secondary halogenoalkanes
react via both mechanisms (see extra discussion points).
o FURTHER COMMENTS on these halogenoalkane (haloalkane)
nucleophilic substitution reactions
 Comparison of aliphatic halogenoalkane and aromatic halide
hydrolysis.
 Halogenoalkanes hydrolyse much more readily than aryl
halides which are aromatic compounds with a halogen atom
directly bonded to the benzene ring. The carbon-halogen
bond is stronger and less polar in aromatic compounds
compared to halogenoalkanes. This is because in the
aromatic halogen compounds there is some
overlap/delocalisation of the lone pairs of electrons of the
chlorine with the ∏ electrons of the benzene ring. This
makes the aromatic ring C-Hal bond stronger and less
easy to break, hence less polar and less susceptible to
nucleophilic attack.

 However, if the halogen is in an alkyl

side chain off the benzene ring, hydrolysis will
readily take place.
 e.g. refluxing chloromethylbenzene
(phenylchloromethane, above left) with
aqueous/ethanolic sodium hydroxide gives
phenylmethanol.
 C6H5CH2Cl + NaOH ==> C6H5CH2OH + NaCl

 or or Whereas hydrolysis
of any of the three other isomeric aromatic halogen
compounds, namely chloro-2/3/4-methylbenzene
(above left) where the Cl atom is attached to the ring,
is very difficult to achieve to produce a phenol
(where the OH hydroxy group is directly attached to
a benzene ring) by hydrolysis.
 ClC6H4CH3 + NaOH ==> HOC6H4CH3 + NaCl
 is NOT EASY! though it can be brought about at
higher temperatures and high pressures than normal
reflux conditions in the school laboratory, but in an
'industrial' sealed reaction vessel.
 Rate of reaction, OH- versus H2O:
 Only applies to the SN2 mechanism: Irrespective of the
structure of the halogenoalkane, the hydrolysis will be
 faster with aqueous sodium hydroxide than just water
because the hydroxide ion is a more powerful
nucleophile. Although they are both electron pair donors,
the hydroxide ion carries a full negative charge compared
to the electrically neutral water molecule.
 The rate determining formation of the carbocation in the SN1
mechanisms means the rate is not affected by using alkali or
just water (read about the kinetics below).
 Reaction kinetics: The possibility of two reaction mechanisms has
consequences for the rate expressions when the rates of
halogenoalkane (RX) nucleophilic substitution reactions are studied.
 The SN1 mechanism is referred to as a 'unimolecular', despite it
being a two/three step mechanism of bimolecular collisions, because
the rate is only dependent on one reactant, the R3C-X is shown in
step (1), but it still has to collide with the solvent!
 [see mechanism 1 or mechanism 10 and reaction profile
42]
 Experimental results produce the overall 1st order rate
expression: rate = k1[RX]
 This is because the activation energy of the 1st step, forming
the carbocation by heterolytic bond fission, is so high, that
the speed is relatively low, so step (1) alone determines the
speed of the reaction. This is referred to as the rate
determining step (or rds in shorthand!). Step (2) has a
much lower activation energy and is much faster (see
reaction profile diagram 42). You would register zero order
for the order of reaction with respect to sodium hydroxide (or
more specifically, the hydroxide ion concentration).
 The SN2 mechanism is referred to as a 'bimolecular'.
 [see mechanisms 2/33/34 or mechanism 35 and reaction
profile 41]
 Experimental results produce the overall 2nd order rate
expression: rate = k2[RX][OH]
 This is because it is a one step mechanism involving the
bimolecular collision of the two reactant molecules/ions (see
also reaction profile diagram 41). The rate depends on
both the halogenoalkane and hydroxide ion concentrations
(individually, 1st order with respect to both).
 The relative reactivity of the C-X bond, where X = F, Cl, Br or I.
 In general the reactivity order is C-I > C-Br > C-Cl > C-F.
 This is due to the decrease in bond enthalpy as the
halogen atom radius increases the bond gets longer and
weaker, i.e. easier to form the carbocation in the SN1
mechanism or easier to release a X- ion from the 'activated
complex' in the SN2 mechanism.
 Average bond enthalpies/kJmol-1: C-F 484, C-Cl 338,
C-Br 276, C-I 238
 This bond strength factor overrides any increase in bond
polarity, which on face value, since the order of becoming
less polar is: C-F > C-Cl > C-Br > C-I, which would suggest
an increase in susceptibility to nucleophilic attack at the delta
positive carbon, but that's not what is observed!
 So bond enthalpies override the bond polarity
trend.
 Carbon chain structure and relative reactivity.
 Generally speaking the reactivity order is tert > sec > prim
halogenoalkane, but unfortunately it isn't quite that simple!
 For the SN1 mechanism the reactivity trend is tert
> sec > prim halogenoalkane.
  The reason for this is that alkyl groups have
a small electron charge donating inductive
effect (+I effect). Its actually the positive
charge on the carbon (from the C-X bond)
attracting the electron charge of the alkyl
group(s) which helps stabilise the
carbocation by 'spreading' the charge and
lowering the potential energy of the
intermediate carbocation.
 So a typical reactivity series is (CH3)3CBr >
(CH3)2CHBr > CH3CH2Br > CH3Br
 because the order of carbocation
stability would be ...
 (CH3)3C+ > (CH3)2CH+ > CH3CH2+ >
CH3+
 where 3, 2, 1 and 0 methyl groups
are available to stabilise the
carbocation.
 The reason for this carbocation
stability trend is often referred to as
an increasing +I or inductive
effect of an increasing number of
alkyl groups. The alkyl group is
considered to 'donate' electron
charge to the positive carbon atom
to stabilise the carbocation.
However, it is better considered that
the postive charge on the positive
carbon attracts the greater electron
clouds of the alkyl groups compared
to hydrogen atoms and so spreads
the charge more widely stabilising
the carbocation, hence the more
alkyl groups on the functional group
carbon, the more stabilisation can
occur.
 SN1 is also favoured by polar solvents like
water or ethanol, which help stabilise the
carbocation by solvation.
 For the SN2 mechanism the reactivity trend is
prim > sec > tert halogenoalkane because of steric
hindrance, that is alkyl groups get in the way of the
incoming nucleophile such as the hydroxide ion or
water molecule. It is usually very slow with water, but
no problem if the R3C-X is warmed/refluxed with
aqueous sodium hydroxide, though some alcohol
can be added to increase the solubility of R3C-X to
increase the rate of hydrolysis.
 The SN1 mechanism is favoured by tertiary
halogenoalkanes because of the greater stability of
tertiary carbocations formed.
 Secondary halogenoalkanes often react by either
the SN1 or SN2 mechanisms simultaneously.
 Primary halogenoalkanes tend to react by the
SN2 mechanism, because on heterolytic C-X bond
fission, they would form the least stable primary
carbocations.
 For a given halogen, overall tertiary
halogenoalkanes tend to be the most reactive
 and tend to undergo nucleophilic substitution via
the SN1 carbocation mechanism and primary
halogenoalkanes tend to be the least reactive
and react via the SN2 mechanism BUT it is a very
complicated situation!
 Con-current nucleophilic substitution AND elimination reactions
are discussed at the end of the section on the elimination mechanism
where things get even more complicated.
 Some points concerning the STEREOCHEMISTRY of the
reaction :-
 What happens if the original haloalkane has chirality?
 AND what is the optical activity of the product?
 If the haloalkane has three different R groups on the carbon
of the C-Hal bond, i.e. RR'R''CX, then there are four different
groups bonded to the carbon of the C-Hal bond. Therefore
the molecule is chiral and can exhibit optical isomerism
(non-super imposable mirror image forms). If the initial
halogenoalkane is an optical isomer, the stereochemical
consequences depend on which mechanism by which the
halogenoalkane reacts. The results can be very complex and
their full explanation goes beyond this level. However there
are two product formation trends.


 (Apologies for repeating diagrams but it helps to
appreciate these stereochemical points)
 In the SN1 carbocation mechanism (e.g.
mechanism 1 above), the three bonds of the R
groups of the carbocation formed in step (1), are in a
trigonal planar arrangement >C-. This means the
nucleophile (e.g. OH- or H2O) can attack the
carbocation with equal probability on each side.
This results in a tendency for a racemic mixture to
form, that is an optically inactive mixture of equal
amounts of the two optical isomers.
 (What you actually get in practice is a
significant reduction in optical activity in the
product)
 For an optically active halogenoalkane reactant,
the considerable reduction in optical activity in a
nucleophilic substitution reaction is evidence of
the SN1 unimolecular mechanism i.e. the
formation of a trigonal planar carbocation.


 However, in the case of the SN2 mechanism (e.g.

mechanism 33 above), racemisation does NOT take
 place and chirality and optical activity is
completely preserved in the molecule, BUT
inversion takes place i.e. the absolute 3D
configuration of the product is completely opposite to
that of the reactant. Stereochemically the most
successful line of attack for SN2 substitution, is if the
nucleophile hits the carbon of the C-Hal bond on the
opposite side to the halogen atom. The result has
been likened to an umbrella being blown inside out in
a gale! The three single bonds for the -CRR'R'' are
pushed through and so the configuration inverted!
[see mechanism 33 style (c)]
 For an optically active halogenoalkane reactant,
the retention of complete optical activity in a
nucleophilic substitution reaction is evidence of
the SN2 bimolecular mechanism.
 Reaction progress profiles to show the progress of SN1 and SN2
nucleophilic substitutions.

SN1 with
-
OH

SN1 with H2O

 Reaction profiles above:

 Diagram 45 corresponds to mechanism 1 and diagram 42
corresponds to mechanism 10.
 The 'progress' of an SN1 reaction for e.g. tertiary halogenoalkane
hydrolysis with sodium hydroxide or water, can be represented
by a 'double/triple hump' diagram where the troughs represents the
formation of the intermediates. The 2nd activation energy, Ea2, is
much smaller than the 1st activation energy, Ea1, because, unlike the
1st step, no bond is broken in the 2nd step and the water/hydroxide
ion readily bonds to the carbocation. Ea3 is also small for the water
hydrolysis because protons are readily transferred in acid-base
reactions.
  Reaction profile - diagram 41 above (corresponds to mechanism
diagrams 2/33/34) The 'progress' of an SN2 reaction e.g. for
primary halogenoalkane hydrolysis with sodium hydroxide, can
be represented by a 'single hump' diagram where the peak
represents the formation of 'activated complex' or 'transition state', in
which the 'outgoing' Cl and the 'incoming' OH are 'half-bonded' with
the functional group carbon atom.

10.4.3 The nucleophilic substitution of halogenoalkane by

cyanide ion

 R3C-X + CN- ==> R3C-CN + X- [see mechanisms 36 and 8 below]

 This is usually achieved by refluxing the halogenoalkane with
ethanolic potassium cyanide to form the nitrile.

mechanism 36 - nucleophilic substitution of a halogenoalkane by

cyanide ion (SN1 'unimolecular' via carbocation)

 SN1 unimolecular, a two step ionic mechanism via carbocation

formation [mechanism 36 above]
 In step (1) the polar Cδ+-Brδ- bond of the halogenoalkane
splits heterolytically to form a carbocation and a free
bromide ion, and this is a reversible reaction.
 In step (2) the negative cyanide ion rapidly adds to the
positive carbocation to form the C-N bond and give the nitrile
product. The cyanide ion donates a pair of electrons to form
the new C-C bond.
 mechanism 8 - nucleophilic substitution of a halogenoalkane by
cyanide ion (SN2 'bimolecular')

 SN2 'bimolecular', a one step mechanism [mechanisms 8 above]

 The Cδ+-Brδ- bond is polar, so the electron rich negative
nucleophile, the cyanide ion, attacks the slightly positive
carbon. The nucleophile (CN-) acts is acting as an electron
pair donor (Lewis base) to bond with the 'positive' carbon.
 Simultaneously the bromine atom is ejected, taking with it the
C-Br bond pair of electrons, so forming the nitrile and a
bromide ion.
 FURTHER COMMENTS
 The mechanisms are the same for chloroalkanes, but
slower, due to the stronger C-Cl bond enthalpy.
 In industry chloroalkanes are more likely to be used
because they are cheaper.
 Many of the comments for hydrolysis apply to this
reaction.

10.4.4 Nucleophilic substitution of a halogenoalkane with

ammonia or primary aliphatic amine

 With ammonia a primary aliphatic amine is formed: [see

mechanisms 37 and 9 below]
 R3C-Br + 2NH3 ==> R3C-NH2 + NH4+Br-
 The halogenoalkane is heated with excess concentrated
ethanolic ammonia in a sealed vessel to form a primary
amine, though it may be as its bromide salt.
 The primary amine is completely freed by adding strong
alkali e.g. aqueous sodium hydroxide, NaOH(aq).
 R3C-NH3+ + OH- ==> R3C-NH2 + H2O

mechanism 37 - nucleophilic substitution of a halogenoalkane by

ammonia (SN1 unimolecular via carbocation)

 SN1 unimolecular, a three step ionic mechanism via carbocation

formation [mechanism 37 above]
 In step (1) the Cδ+-Brδ- polar bond of the halogenoalkane
splits heterolytically to form a carbocation and a free halide
ion (e.g. chloride or bromide) and this is a reversible reaction.
 In step (2) the nucleophilic electron pair donating ammonia
molecule rapidly adds to the carbocation to give the
protonated amine product R3C-NH2+.
  In step (3) one of the excess ammonia molecules can
remove a proton to leave the primary amine product.
 Note: Alkali still needs to be added at the end
because the primary amine formed is usually a
stronger base than ammonia.

mechanism 9 - nucleophilic substitution of a halogenoalkane by

ammonia (SN2 bimolecular)

 SN2 'bimolecular', a two step mechanism [mechanism 9 above]

 Step (1) the Cδ+-Brδ- bond is polar, so the electron rich
nucleophile, the ammonia molecule, attacks the slightly
positive carbon. The nucleophile acts as an electron pair
donor (Lewis base) to bond with the 'positive' carbon.
Simultaneously the bromine atom is ejected, taking with it the
C-Br bonding pair of electrons, so forming the bromide ion.
 In step (2) one of the excess ammonia molecules can
remove a proton to leave the primary amine product.
 Note: Alkali still needs to be added at the end
because the primary amine formed is usually a
stronger base than ammonia.
 Further substitution can take place because the amine product
itself is a nucleophile.
 e.g. if you start with bromomethane and react it with
ammonia, the following products can be formed ..
 CH3Br + NH3 ==> [CH3NH3]+Br-
 Excess ammonia favours the formation of the primary
amine i.e. reduces the formation of the secondary and
tertiary amines and the quaternary ammonium salt.
 the primary amine, methylamine, CH3NH2, as its bromide
salt
 CH3NH2 + CH3Br ==> [(CH3)2NH2]+Br-
 the secondary amine, dimethylamine, (CH3)2NH, as
its bromide salt
 (CH3)2NH + CH3Br ==> [(CH3)3NH]+Br-
 the tertiary amine, trimethylamine, (CH3)3N,
as its bromide salt
 (CH3)3N + CH3Br ==> [(CH3)4N]+Br-
 and eventually the quaternary salt,
tetramethylammonium bromide
 With a primary aliphatic amine a secondary aliphatic amine is
formed: [mech's 38 and 11 below]
 The reaction of a halogenoalkane and excess primary amine can
be written as ...
 R3C-Br + 2R'-NH2 ==> R3C-NHR' + [R'-NH3]+Br-
 The halogenoalkane is heated with excess concentrated
ethanolic solution of the primary amine in a sealed vessel to
form a secondary amine.
 The secondary amine product is freed by adding strong
alkali e.g. aqueous sodium hydroxide, NaOH(aq).
  [R3C-NH2R']+ + OH- ==> R3C-NHR' + H2O
 The mechanisms for the reaction of primary amines with
halogenoalkanes are essentially the same as for ammonia
above. So all the general comments for ammonia apply here too, so
I will not repeat them, where it says ammonia, just say primary
amine! In step (3) one of the excess primary amine molecules can
remove a proton to leave the primary amine product.
 Note: Alkali still needs to be added at the end because the
secondary amine formed is usually a stronger base than
ammonia.

mechanism 38 - nucleophilic substitution of a halogenoalkane by a

primary amine (SN1 unimolecular via carbocation)

mechanism 11 - nucleophilic substitution of a halogenoalkane by a

primary amine (SN2 bimolecular)

 Further substitution can take place because the product itself is

a nucleophile.
 e.g. if you start with bromoethane and react it with
ethylamine, the following products can be formed ..
 CH3CH2Br + CH3CH2NH2 ==> [(CH3CH2)2NH2]+Br-
diethylamine, (CH3CH2)2NH, as its bromide salt
 (CH3CH2)2NH + CH3CH2Br ==> [(CH3CH2)3NH]+Br-
triethylamine, (CH3CH2)3N, as its bromide salt
 (CH3CH2)3NH + CH3CH2Br ==>
[(CH3CH2)4N]+Br- tetraethylammonium
bromide
 FURTHER COMMENTS
 Many of the comments for hydrolysis apply to this
reaction.

 Aromatic amines, e.g. phenylamine, , do NOT

readily react with halogenoalkanes. When the
amine/amino group is directly attached to the benzene ring
(via the N), the lone pair of electrons on the nitrogen is
partially delocalised with the pi electrons of the benzene ring,
consequently they are less readily donated. This causes
 aromatic amines to be much weaker electrophiles than
aliphatic amines where no such effect can take place.

10.4.5 The elimination of hydrogen bromide from a

bromoalkane

 e.g. R2CH-CBrR2 + KOH ==> R2C=CR2 + H2O + KBr

[mech's 26 and 27 below]
 or R2CH-CBrR2 + OH- ==> R2C=CR2 + H2O +
Br- (more correctly)
 The halogenoalkane is refluxed with ethanolic potassium
hydroxide (NOT aqueous).
 Compared to nucleophilic substitution, elimination is favoured
by using a stronger base like KOH, ethanol as the solvent,
rather than water and a tertiary structured halogenoalkane.

mechanism 26 elimination of HBr from a halogenoalkane by hydroxide

ion (E2 'bimolecular')

 E2 mechanism via single step bimolecular collision process.

[mechanism 26 above]
 The hydroxide ion acts both as a strong base (proton
accepting) and as a nucleophile (electron pair donor), by
removing a proton from the halogenoalkane to form water.
 As the C-H bond pair of electrons (bottom left) shifts to
complete the C=C double bond of the alkene product,
simultaneously, the C-Br bond pair (bottom right) leaves with
the bromine atom to give the bromide ion.

mechanism 27 - elimination of HBr from a halogenoalkane by hydroxide

ion (E1 'unimolecular')

 E1 mechanism, two step process via carbocation formation.

[mechanism 27 above]
 In step (1) the polar and weakest bond, Cδ+-Brδ-, breaks
heterolytically to form a carbocation and bromide ion.
 In step (2) the strongly basic and nucleophilic hydroxide ion
abstracts a proton from the carbocation to form water and
 simultaneously the C-H bond pair (bottom left) shifts to complete the
C=C double bond of the alkene.
 FURTHER COMMENTS
 Con-current nucleophilic substitution AND elimination reactions
for RX = halogenoalkane/haloalkane/alkyl halide/halogenated
alkanes.
 i.e. nucleophilic substitution to give an alcohol versus
elimination to give an alkene.
 With halogenoalkanes of at least C2, the use of strong alkali
like sodium hydroxide can also produce alkene products by
an elimination whose mechanism is discussed above.
 e.g. R2CH-CBrR2 + NaOH ==> R2C=CR2 + H2O +
NaBr
 as well as/versus R2CH-CBrR2 + NaOH ==> R2CH-
C(OH)R2 + NaBr
 In both cases R = H, alkyl or aryl.
 Elimination E2 is favoured by ethanol solvent and
substitution is favoured by water/aqueous media.
 One explanation is that in ethanol, the ethoxide ion is
formed, and is a stronger base than water, hence
better at abstracting a proton in the E2 mechanism
and competes with the nucleophilic attack of the OH-
ion at the Cδ+-Xδ- bond in the SN2 nucleophilic
substitution mechanism.
 CH3CH2OH + OH- CH3CH2O- + H2O
 Also, although ethanol is polar, it is less polar than
water and a more polar solvent favours substitution.
 A lower temperature also favours elimination and
ethanol boils at 79oC, 21oC lower than water (bpt.
100oC).
 Elimination E1 is more favoured by increase in alkyl
groups attached to the carbon of the C-halogen bond,
therefore yield of alkene increases in the order tert RX
>sec RX > prim RX
 This is due to the with the greater stability of the
intermediate carbocation which is more likely to be
formed in the order tert RX > sec RX > prim RX (as
is the preference of the SN1 mechanism!),
 so carbocation stability is tert R3C+ > sec
R2CH+ > prim RCH2+ (R = alkyl),
 therefore increasing stability of the
carbocation, increases the chance of proton
loss from the carbocation to give the alkene
(see carbocation stability discussion).
 Elimination E2 is favoured by an even stronger base,
particularly in the less polar ethanol, than sodium hydroxide
e.g. like potassium hydroxide since in the E2 mechanism the
hydroxide ion abstracts a proton from the halogenoalkane.
 See comments under using ethanol solvent, and
probably more significant for prim > sec > tert
halogenoalkanes.
 Its worth noting that with weak bases like ammonia
very little elimination occurs.
 Examples of data on con-current nucleophilic substitution
versus elimination reactions.
 (i) Refluxing bromoethane (prim) with ethanolic
sodium hydroxide (CH3CH2OH/NaOH) solution (at
~80oC), gives 1% ethene (and 99% ethanol),
 whereas refluxing with 2-bromopropane (sec) gives
80% propene (and 20% propan-2-ol).
 (ii) Refluxing 2-bromo-2-methylpropane (tert) with
aqueous-ethanol/NaOH (at ~100oC) gives 19%
methylpropene (81% 2-methyl-propan-2-ol), whereas
2-bromopropane (sec) gives 5% propene (95%
propan-2-ol).
 Note in the 2nd example, the presence of
water significantly reduces the alkene yields,
i.e. more nucleophilic substitution, but the
tert alkene yield is greater than for the sec
haloalkane.
 Further note that ethanol is often added to
the aqueous NaOH/KOH to increase the
solubility of the halogenoalkane.
 Summing up: The 'classic' conditions to maximise the
yield of an alkene are refluxing the halogenoalkane with
ethanolic potassium hydroxide. Compared to water, it
involves the less polar ethanol and a lower reaction
temperature. The method also uses the strongest
'common' base and further more, the yield of alkene will
increase for tert RX > sec RX > prim RX