Part 02

Physical & Chemical properties

  Generally, trans isomer is more stable than cis as cis
isomer has more steric repulsion.
 The first three alkenes are gases, the next fourteen
members are liquids, and the higher ones are solids.
 Alkenes are more reactive than alkanes because the
 They are colourless and odourless (except ethylene
−electrons of the double bond are located much far
which has a faint sweet smell), practically insoluble in
from the carbon nuclei and are thus less firmly bound
water but fairly soluble in non−polar solvents like
to them. −bond is weaker than −bond and more
benzene, petroleum ether, etc. As polarity increases,
easily broken.
solubility in polar solvents increases. Generally,
solubility of cis > trans in polar solvents.  The reactivity order of alkenes (inverse of stability
order) is dependent on two factors: (i)
 Generally, for type of alkenes dipole Hyperconjugation and (ii) Steric Hindrance.
moment of cis > trans.
 These are reflected in the heat of combustion or heat
 Melting point increases as molecular weight increases. of hydrogenation of isomeric alkenes.
Generally due to more packing efficiency, melting
point of trans > cis.

 Boiling point increases as molecular weight increases.

Generally, branching decreases boiling point, while
polarity increases boiling point. Generally, boiling
point of cis > trans. Page 1 Page 2
 Stability order of some alkenes.  Alkenes give the following type of reactions: (i)
Addition Reaction, (ii) Oxidation Reaction, (iii)
Substitution Reaction, (iv) Polymerization Reaction,
(v) Isomerization Reaction.

 These are generally, Electrophilic Addition reactions.

Page 3 Page 4
  Step 2 : The polarized bromine molecule transfers a
positive bromine atom (with six electrons in its
valance shell) to the alkene resulting in the formation
of cyclic bromonium ion.

 Alkenes react rapidly with a halogen molceule in a

non-polar solvent at room temperature and in the
absence of light. The product is vicinal dihalide.
 Whenever an electrophile has a lone pair, it
 If bromine in is added to an alkene, the immediately attacks the electrophilic carbon to form
red−brown colour of the bromine disappears almost a three membered intermediate.
instantly as long as the alkene is present in excess.
This serves as a test for the detection of unsaturation  Step 3: The attack of − ion on the cyclic ion takes

of = or  type. place from the side opposite to side where bromine

atom is already present in order to minimise steric
hindrance . This is SN2 with SN1 character.
 Step 1 : A bromine molecule becomes polarized as it −
approaches the alkene.
−

Page 5 Page 6
 This is type of pseudo carbocation character is called  The addition of halogen molecule to alkene is an
non-classical carbocation. example of Markovnikov’s addition.

 This mechanism is called anti-addition as both

halogens attack from opposite side of the alkene.

 Reactivity of halogens:

 Addition of is exothermic reaction so it is difficult

to control.

 reacts slowly with alkenes to form Vicinal di-

iodides which are unstable and eliminate to give
back the alkene.

 Markovnikov's rule : When molecule of polar reagents

of the general structure − (such as −, −
−, −) add on an unsymmetrical
unsaturated hydrocarbon, the negative atom/part
goes to the unsaturated carbon atom bearing lesser
number of hydrogen atoms.

Page 7 Page 8
  Water acts as a nucleophile since it is in excess.

 Reactivity:

 The reaction of halogen in water ( / ) or

hypohalous acid ( ) follows anti and Markovnikov’s
addition.

 The difference between addition in and water is

that in the last step the nucleophile attacking is
instead of −.

 Addition of HX on unsymmetrical alkenes takes place

according to Markovnikov's rule.

Page 9 Page 10
 −

 Since carbocation ion is formed rearranged products

are also likely.

 In cases where rearrangement is not possible the

major product will form according to Markovnikov’s
Rule.

 If the carbon, where the nucleophilic halide ion

attacks, becomes chiral and no other carbon is chiral,
then a pair of enantiomers are formed as the
carbocation is planar. Page 11 Page 12
 1. Chain Initiation Step
 Order of reactivity of :
 

Due to lone pair – lone pair repulsion − bond is

The addition of to propene, , under


weak 
polar conditions (in absence of peroxide) yields
2−Bromopropane. However, in the presence of
peroxide (or under other conditions that promote
radical formation), the addition proceeds via a rapid
chain reaction to yield 1−Bromopropane.  − bond is stronger than − bond

2. Chain Propagation Step

 This addition of on unsaturated unsymmetrical
compounds takes place contrary to Markovnikov's
rule. This addition of in presence of peroxide is
generally referred to as the peroxide effect or
Kharasch effect leading to anti−Markovnikov addition
proposed by Morris Selig Kharasch in 1933.
Page 13 Page 14
 Secondary Radical is more stable than a Primary
Radical.

  − for −
−

 Only for both steps are exothermic. For others

 − is stronger than − bond. heat has to be given in at least one step.

 is the only one of the four hydrogen halides that

will add readily to alkenes via a radical pathway. The
reason for this is reflected in the  values ( − )  Alkenes react with conc. to produce alkyl
for the two steps of the chain reaction for addition of hydrogen sulphates, which give alcohol on hydrolysis.
to = . This reaction is used to separate an alkene from a
mixture of alkane and alkene.

  − for − − −
Page 15 Page 16
 Propene and higher alkenes react with water in the
presence of an acid to form alcohol. This reaction is
known as Hydration Reaction. Intermediate in this
reaction is carbocation, so rearrangement may take
place.

 Product is alcohol (just like addition of water).

 Major product is Markovnikov’s product. No

rearrangement. Therefore, no carbonium ion is
formed.

Page 17 Page 18
 Mercuric acetate in is treated with an alkene.
The addition product on reduction with sodium boro
hydride in aqueous solution gives alcohol. It
follows the Markovnikov's rule. − − −

−
−

 The hydrogen atom is abstracted by carbon from the

same side as .

Page 19 Page 20
 Instead of if we use , ether will be produced.
This is known as Alkoxymercuration-Demercuration.

 This reaction, as the previous two, leads to the

formation of alcohol from alkene.

 But, unlike the previous two, this gives an anti-

Markovnikov’s product. − 
 Though the product is anti-Markovnikov’s, the
addition to the alkene is Markovnikov’s.

Page 21 Page 22
 −

− −
− −

−
− −

Page 23 Page 24
 −
 Syn addition because and attack from the
same side. Then − ion attacks . After this the
alkyl group shifts from to . And we know that in
rearrangement when a group shifts it will leave and
attack from the same side of the alkyl group.

 After getting trialkylborane, if we use an acid in step

3 instead of oxidation, then we will get an alkane.
−

−
−  This is an effective method for hydrogenation of an
alkene without using molecular H2 with catalyst.
− Page 25 Page 26
 Trialalkylboranes, where at least two alkyl groups are
highly hindered, cannot react on a hindered double
bond.  Alkenes react with Carbon monoxide and hydrogen
at − ° temperature and high pressure (
 This means we can selectively make an anti- ) in the presence of Cobalt catalyst to produce an
Markovnikov’s alcohol on an unhindered double bond aldehyde. The net reaction is the addition of a
and also reduce the unhindered double bond −atom to one of the Olefinic bond and a formyl
selectively. (− ) group to the other. It does not follow
Markovnikov's rule.

 In presence of or at dimerization of
isobutylene take place to give two isomer of octene.

Page 27 Page 28
Page 29 Page 30
  Addition of Tilden reagent on unsymmetrical alkene
follow Markovnikov's rule. But no rearrangement
occurs as it forms through the non-classical
carbocation.

− −

Page 31 Page 32
  
 Discussed in Alkanes.

 When ozone is passed through an alkene in an inert

solvent, it adds across the double bond to form an
 Alkenes on combustion gives and . ozonide. Ozonides are explosive compound they are
not isolated.

 On warming with and , ozonides cleave at the

site of the double bond, the products are carbonyl
compounds (aldehydes or ketones) depending on the
nature of the alkene.
 The addition of ozone on double bonds and
subsequent hydrolysis of the ozonide formed is
termed as ozonolysis.

   
− 
  

Page 33 Page 34
    

 

(1)

 Product of ozonolysis depends upon what we treat

the Ozonide with.
Page 35 Page 36
(2) (5)

(6)

(3)

(7)

(4)

Page 37 Page 38
(9) (11)

 Alkenes are readily oxidized to acid or ketone by

treating them with acidic Permagnate or acidic
dichromate. lf, is formed, it is further
oxidized to and . However, no further
oxidation of ketones will take place.
(10)
(1)

Page 39 Page 40
(2) (5)

(6)
(3)

(4)

Page 41 Page 42
 Dihydroxylation is the addition of two − groups to
(1)
an alkene.

 Dihydroxylation can be done either as syn or as anti

addition.

 Alkenes on passing through dilute alkaline cold

(i.e., Baeyer's reagent) decolourise the pink
colour of and gives brown precipitate of •
It is an example of syn addition.

Page 43 Page 44
(2)

− −

− − −

−
−
− −

− − − −
− −
−
−

− −
−
Page 45 Page 46
 Osmium tetroxide ( ) adds to alkene to form
cyclic osmic ester which can be made to undergo
ready hydrolytic cleavage of their − bonds to yield
the vic−diol.

 The disadvantage of this reaction as a preparative

method is expense and toxicity of . However, this
can be overcome by using it in catalytic quantities in
association with which re−oxidises the osmic
acid, , formed to .

 To dihydroxylate by anti addition, we need to first

− convert the alkene to an epoxide.

Page 47 Page 48
 There are two ways of doing epoxidation.

 Alkenes reacts with oxygen in the presence of

catalyst at − to form epoxide.

 When an alkene is treated with peroxyacid, an  M.C.P.B.A(metachloroperoxybenzoic acid) and

epoxide is formed. Such epoxidation is known as peroxytrifluoroacetic acid ( ) is a very good
Prileschiave reaction. reagent for epoxidation.

Page 49 Page 50
 (5)

(1)

(2)

(6)

(3)

(4)

Page 51 Page 52
(7) (9)

(8)

 More substituted alkenes undergo epoxidation faster.

Page 53 Page 54
−

 When alkenes are treated with or at high

temp., one of their allylic hydrogen is replaced by
halogen atom. Allylic position is the carbon adjacent
to one of the unsaturated carbon atoms. It is a free
radical substitution reaction.
−
 Already discussed in alkyl halides.

−
 Many molecules of same compound unite with each
other to form a long chain molecule with same
empirical formula. This long chain molecule having
repeating structural units called polymer, and the
starting simple molecule as monomer and process is
called polymerization.

Page 55 Page 56
  Alkene on heating at − or on heating in
presence of catalyst [ or )3] undergo
isomerization.

 Molecular weight of polymer is simple multiple of

monomer (in case of addition polymer).

 Polymerization can be carried out by free radical or

ionic mechanism.

 The presence of oxygen initiates free radical

mechanism.

 Addition polymerization can also be carried out by

ionic mechanism by using Ziegler-Natta Catalysts
( )

Page 57 Page 58
Part 02

Physical & Chemical properties