10.

3 Reaction mechanisms of ALKENES

Electrophilic addition of bromine and hydrogen bromide
Part 10.3 ALKENES - introduction to the reaction mechanisms of alkenes. Electrop
hilic addition of hydrogen bromide [HBr(conc. aq) and HBr(g/non-polar solvent)]
to form halogenoalkanes. These revision notes include full diagrams and explanat
ion of the ionic electrophilic addition reaction mechanisms of alkenes and the '
molecular' equation and reaction conditions and other con-current reaction pathw
ays and products are also explained.
Part 10.3 ALKENES
10.3.1 Introduction
Alkenes are reactive molecules, particularly when compared to alkanes.
They are reactive towards electron pair accepting electrophiles because of t
he high density of negative electron charge associated with the ? pi electrons o
f the double bond.
However they can also readily undergo free radical reactions e.g. their per
oxide catalysed polymerisation to form a poly(alkane) and these reactions also i
nvolve the interaction of free radicals with the ? pi electrons.
The electrophilic addition reactions of alkenes are compared with the nucleo
philic addition to carbonyl compounds in the aldehydes and ketones section.
10.3.2 The electrophilic addition of hydrogen bromide to alkene
The organic synthesis of bromoalkanes by reacting hydrogen bromide with alkenes
Examples of the addition of hydrogen bromide to alkenes
(i) ethene + hydrogen bromide ==> bromoethane
alkenes structure and naming (c) doc b + HBr ==> (c) doc b
(ii) propene + hydrogen bromide ==> 2-bromopropane
alkenes structure and naming (c) doc b+ HBr ==> (c) doc b
some of the isomer 1-bromopropane is also formed in this reaction
minority product (c) doc b from a con-current reaction.
What is the reaction mechanism for the addition of hydrogen bromide to an al
kene?
Does the mechanism change if the solvent is changed?
Do the products of the reaction depend on the solvent used?
Can isomeric products be formed in the addition of hydrogen bromide to an al
kene?
AQUEOUS media: [see mechanism 39 below]
If a liquid alkene is mixed with, or a gaseous alkene is bubbled through
, concentrated hydrobromic acid, HBr(aq) (hydrogen bromide dissolved in water) a

bromoalkane is formed.
overall reaction: R2C=CR2 + HBr ==> R2CH-CBrR2
In water, hydrogen bromide is a strong acid i.e. completely ionises to g
ive the oxonium ion and bromide ion.
HBr(g/aq) + H2O(l) ==> H3O+(aq) + Br-(aq)
organic reaction mechanisms
mechanism 39 - electrophilic addition of hydrogen bromide to an alkene in aqueou
s media
In the acid solution via step (1) the H3O+ or oxonium ion (hydrated prot
on) is the 'attacking electrophile' and protonates the alkene to form the interm
ediate positive carbocation R2CHCR2+. The oxonium ion is an electrophile because
it accepts a pair of electrons from the alkene ? bond to form the new C-H bond.
In step (2) the (already present) negative bromide ion rapidly combines
with the carbocation to form the bromoalkane product. The bromide ion donates a
pair of electrons to form the new C-Br bond.
With the high concentration of water present, a water molecule could
also interact with the carbocation to eventually form a small amount of the alc
ohol R2CHCR2OH, this again provides evidence of an ionic mechanism.
NON-AQUEOUS media: [mechanism 3 below] Addition will also occur if the alken
e is mixed with hydrogen bromide gas, or the HBr gas is dissolved in a non-polar
organic solvent and mixed with the alkene.
organic reaction mechanisms
mechanism 3 - electrophilic addition of hydrogen bromide to an alkene in non-aqu
eous media
In this case, for step (1), the attacking electrophile is the already polari
sed hydrogen bromide molecule, Hd+Brd-, which splits heterolytically to protonat
e the alkene, forming the carbocation and a bromide ion. The HBr molecule is an
electrophile because it accepts a pair of electrons from the alkene ? bond to fo
rm the new C-H bond.
In step (2) the bromide ion formed in step (1) rapidly combines with the car
bocation to form the bromoalkane. The bromide ion donates a pair of electrons to
form the new C-Br bond.
FURTHER COMMENTS
EVIDENCE for an IONIC MECHANISM
Below is a general comment for all the electrophilic addition reacti
ons of alkenes.
If the reaction is carried out in the presence of other negative ion
s e.g. chloride ion from adding sodium chloride salt to an aqueous reaction mixt
ure, then some chloroalkane is produced via step (2).
R2CH-CR2+ + Cl- ==> R2CH-CR2Cl
Without a carbocation intermediate formed it is difficult to

explain the formation of such products.

In fact any anion present, X-, produces some R2CH-CR2X
A symmetrical alkene is when the atoms/groups are the same on either sid
e of the C=C double bond.
e.g. ethene H2C=CH2 or but-2-ene CH3-CH=CH-CH3
This means which ever way round the HX addition takes place onto the
double bond, you always get the same product.
An non-symmetrical alkene is when the atoms/groups are NOT the same on e
ither side of the C=C double bond e.g.
propene CH3-CH=CH2, methylpropene (CH3)2C=CH2 or but-1-ene CH2=CH-CH
2-CH3
This means that when addition to the double bond with a non-symmetri
cal reagent itself, e.g. like H-X, you have the possibility of two different iso
meric addition products.
e.g. CH3-CH=CH2 + H-X ==> CH3-CHX-CH3 or CH3-CH2-CH2-X
Which begs the questions, which isomer predominates? and why?
The Markownikoff rule predicts which isomer is likely to predominate for
adding a non-symmetrical reagent to a non-symmetrical alkene and the rule can b
e stated in various ways but the IUPAC definition of 1997 states: For the hetero
lytic addition of a polar molecule to an alkene (or alkyne), the more electroneg
ative (nucleophilic like OH- or Br- etc.) atom (or part) of the polar molecule b
ecomes attached to the carbon atom bearing the smaller number of hydrogen atoms
[or you can say the least electronegative (most electrophilic like Br+ or H+ etc
.) will attach to the carbon atom bonded with the most H atoms). BUT the 'rule'
only applies to the ionic mechanism, you can get the opposite effect in free rad
ical addition in the presence of peroxides!
The orientation of the products from non-symmetrical addition (HX or
Br2(aq) see later) is governed by the stability of the carbocation intermediate
formed by the protonation of the alkene by the attacking H-X electrophile, and
explains the Markownikoff rule.
The order of carbocation stability is tertiary > secondary > primary
, because alkyl groups give a slight electron donating inductive effect (+I) via
the attraction of the positively charged carbon atom. This spreads the positive
charge of the carbocation and gives the carbocation more stability by lowering
its potential energy. It is a general rule of physics that spreading out electri
c charge lowers the potential energy and increases the stability of a situation.
The most stable carbocation will be the one most likely to exist wit
h a sufficient life-time to be hit by the electron pair donating ion (e.g. X-) o
r any other electron pair donor, including water (see addition of bromine water)
. NOTE: The positive carbon of the most stable carbocation, has attached to it t
he most alkyl groups and the least hydrogen atoms.
e.g. from protonating propene CH3CH=CH2 you expect the carbocati
on stability to be ...
CH3CH+CH3 (sec) > CH3CH2CH2+ (prim)

or from protonating 2-methylbut-2-ene (CH3)2C=CHCH3 you expect t

he carbocation stability to be ...
(CH3)2C+CH2CH3 (tert) > (CH3)2CHC+HCH3 (sec)
So for adding HX to a non-symmetrical alkene you would expect the ma
jor isomer to be e.g.
from propene, CH3CH=CH2 you expect mainly CH3CHX-CH3
and some CH3CH2-CH2X
from methylpropene, (CH3)2C=CH2 you expect mainly (CH3)2CX-CH3
and some (CH3)2CH-CH2X
from 2-methylbut-2-ene you expect mainly (CH3)2CXCH2CH3 > and so
me (CH3)2CHCHXCH3
from but-1-ene, CH2=CHCH2CH3 you expect mainly CH3-CHXCH2CH3
with some XCH2-CH2CH2CH3
What happens in terms of optical isomers/activity if the product has a c
hiral carbon*?
An example of a chiral carbon results from when four different atom
s or groups (a to d) is bonded to the same carbocation i.e. *Cabcd, so the carbo
cation has a plane of symmetry. This symmetrical arrangement means that if the p
roduct is potentially optically active, a racemic mixture will be formed because
the e.g. bromide ion, can add with equal probability on both sides of the carbo
cation. This will result in equal quantities of the optical isomers (enantiomers
), giving an optically inactive racemic mixture.
e.g. but-1-ene, CH2=CHCH2CH3 on adding HX, will give a racemic mixtu
re of the optical isomers of CH3*CHXCH2CH3 with some XCH2-CH2CH2CH3 which is inc
apable of optical isomerism because it does not have a chiral carbon.
FURTHER COMMENTS
Free radical addition of hydrogen bromide
The addition of hydrogen bromide using a peroxide catalyst produces
'anti-Markownikoff' addition.
e.g. propene, CH3CH=CH2 produces mainly CH3CH2-CH2Br
but only hydrogen bromide gives this peroxide effect, the additi
on of H-Cl, Br2(aq) and H2SO4 etc. all broadly follow the Markownikoff addition
rule.
Addition of mixed halogen compounds (inter-halogen compounds), such as i
odine(I) chloride ICl, will also add to the alkene double bond.
e.g. CH3CH=CH2 + ICl ==> CH3CHI-CH2Cl or CH3CHCl-CH2I
From the Markownikoff rule 2-chloro-1-iodopropane should be the prin
cipal product because chlorine is more electronegative than iodine, so think of
it as the addition of Id+-Cld-.