An alkene, sometimes called an olefin, is a

hydrocarbon that contains a C=C.

Alkenes occur abundantly in nature. Ethylene for
instance is a plant hormone that induce ripening
in fruit.
- carotene a compound contains 11 C=C. an
orange pigment responsible for color of carrots
and it is a valuable dietary source of Vit A so it
offer some sort of protection against cancer.
 Ethylene and propylene, are the two important
organic chemicals produced industrially .
26 million tons of ethylene and 17 million tons of
propylene are produced each year in USA for the
use in the synthesis of polyethylene,
polypropylene, ethylene glycol, acetic acid, and
acetaldehyde.
Ethylene and propylene and butene are
synthesized industrially by thermal cracking of
light (C2 C8) alkanes.
 Because of the double bond, an alkene has fewer
hydrogens than alkane with the same number of
carbons CnH2n for alkene versus CnH2n+2 for an
alkane.
This fewer number of hydrogen referred to as
unsaturation, ethylene for example has formula
C2H4, whereas ethane has formula C2H6.
 In general, each ring or double bond in a molecule
corresponds to a loss of two hydrogens from alkane
formula CnH2n+2.
Using this relationship, its possible to calculate a
molecule degree of unsaturation the number of
rings and or multiple bonds present in a molecule.
Lets assume unknown hydrocarbon Mwt 82, which
corresponds to molecular formula C6H10. Since the
saturated C6 alkane (hexane) has formula C6H14, the
unknown compound has two fewer pair of hydrogen
H14 H10 = H4 = 2H2 and its degree of unsaturation is 2.
The unknown therefore contains two double bonds, or
one ring one double bond or two ring or triple bond.
 Similar calculation can be carried out for compounds
containing elements other than just carbon and
hydrogen
Organohalogen compounds (C,H, X where X = F, Cl, Br, I)
A halogen substituent acts simply as a replacement for
hydrogen in an organic molecule, so we can add number
of halogens and hydrogen to arrive at an equivalent
hydrocarbon formula from which degree of unsaturation
can be found.
Example organohalogen formula C4H6Br2 equivalent to
hydrocarbon C4H8 and thus degree of unsaturation is
one.
Organooxygen compounds (C, H, O):
Oxygen forms two bonds, so it doesnt affect the
formula of an equivalent hydrocarbon and can be
ignored when calculation the degree of unsaturation.
We can convince our self by seeing when oxygen atom
inserted into an alkane bond C-C becomes C-O-C or C-
H becomes C-O-H, there is no change in numbers of
hydrogen atoms.
Example the formula C5H8O is equivalent to
hydrocarbon formula C5H8 has two degree of
unsaturation.
Organonitrogen compounds (C, H, N):
Nitrogen forms three bonds, so an organonitrogen
compounds has one hydrogen more than a related
hydrocarbon, so we subtract the number of nitrogen
from the number or hydrogen from the
organonitrogen to reach the equivalent hydrocarbon
formula then degree of unsaturation is calculated.
We can also convince our self by seeing what happens
when a nitrogen atom is inserted into an alkane bond
C-C becomes C-NH-C or C-H becomes C-NH2,
meaning one additional hydrogen atom has been
added, we must then subtract this extra hydrogen
atom to arrive at equivalent hydrocarbon formula.
Example C5H9N equivalent to C5H8 thus two degree
of unsaturation.
To summarize:
Add the number of halogens to the number of hydrogens.
Ignore the number of oxygens.
Subtract the number of nitrogens from the number of
hydrogens.
Problem 1: Calculate the degree of unsaturation in the
following formula and then draw as many structures as you
can for each:
a) C4H8 b) C4H6 c) C3H4

Problem 2: Calculate the degree of unsaturation in the

following formulas:

a) C6H5N b) C6H5NO2 c) C8H9Cl3

d) C9H16Br2 e) C10H12N2O3 f) C20H32ClN
 Alkenes are named using a series of rules similar to
that of alkanes, with the suffix ene instead of ane.
Three steps:
Step 1 name the parent hydrocarbon, find the longest
chain containing the double bond and name the
compound accordingly using suffix ene.
Step 2:
Number the carbon atoms in chain. Begin at the
end nearer the double bond or, if the double bond
is equidistant from the two ends, begin at end
nearer the first branch point. This rule ensures
that double-bond carbons receive the lowest
possible numbers.
Step 3:
Write the full name. number the substituents
according to their position in the chain, and list
them alphabetically. Indicate the position of the
double bond by giving the number of the first alkene
carbon and place that number before the parent
name. if more than one double bond is present,
indicate the position of each and use one of the
suffixes diene , triene and so on
IUPAC system recommend placing of the position immediately
before the suffix ene rather than the parent compound but
still the old way is used
Cycloalkenes:
Cycloalkenes are named similarly to open-chain
alkenes, but because no chain end to begin from,
we number the cycloalkene so that the double
bond is between C1 and C2 and the first
substituent has as low a number as possible.
Example of common names and groups:

=CH2 substituent called methylene as per

ethylene CH2=CH2.
H2C=CH- substituent is called vinyl group.
H2C=CH-CH2- is called ally group.
 Essentially free rotation is possible around single
bonds, whereas this not true for the double bond.
For rotation to occur around a double bond the
bond must break and re-form.
The barrier to double-bond rotation must be as great
as the strength of the bond itself (84 kcal/mol)
whereas rotation a round single bond in ethane is (2.9
kcal/mol).
The lack of rotation around C=C is of a chemical
importance, imagine a disubstitueted alkene such as
2-butene CH3-CH=CH-CH3 the two methyl group
either on the same side of the double bond or on
opposite sides in a situation similar to disubstituted
cycloalkanes
 Cis-2-butene trans-2-butene
Since rotation cant occur, the two 2-butene cant
interconvert spontaneously, the are different, isolable
compounds.
Such compounds as in the case of disubstituted
cycloalkane we call them cis-trans stereoisomers.
Cis-trans isomerism is not limited to disubstituted
alkenes. It occur whenever both double-bond carbons
are attached to two different groups.
If one of the double bond carbon attached to two
identical groups cis-trans isomerism is not possible.
 These two compounds are identical
they are not cis-trans isomers

These two compounds are not

identical they are cis-trans
isomers

Problem: which of the following can exist as cis-trans

isomers? Draw each pair and indicate the geometry
of each isomer
Problem 2:
 The cis-trans naming system used in the previous slide
works only with disubstitued alkene.
With trisubstituted and tetra substituted double bonds
more general method is needed to describe the geometry
around the C=C.
According to E,Z system of nomenclature a set of sequence
rules is used to assign priorities to the substituent groups
on the double bond.
Consider each doubly bonded carbon separately, the rules
are used to decide which of the two attached group of
higher priority.
If the higher priority group of each carbon at the same side
of the double bond alkene is designated Z for the German
zusammen meaning together.
If the higher priority group of each carbon at the opposite
side of the double bond alkene is designated E for the
German entgegen meaning opposite.
 Rule 1 : consider the double bondcarbons
separately, look at the two atoms directly attached
to each and rank them according to atomic
number. An atom with higher atomic number
receives higher priority than lower atomic
number atom .
Br 35 > Cl17 > S16 > P15 > O8 > C6 > H2 >H1
 Rule 2: if a decision cant be reached by ranking
the first atoms in the substituent, look at the
second, third or fourth atoms away from the
double bond carbon until the first difference is
found. A CH2CH3 substituent and a CH3 are
equivalent according to rule 1 both have carbon as
first atom, by rule 2 ethyl receive higher priority
because in ethyl second atom is Carbon and in
methyl second atom is H.
 Rule 3: multiple-bonded atoms are equivalent to
the same number of single bonded atoms. For
example an aldehyde substituent (-CH=O) which
has a carbon atom double-bonded to one oxygen,
is equivalent to a substituent having a carbon
atom single bonded to two oxygens.
 Taking all the sequence rules into account, we can
assign the configurations shown in the following
examples
Problem:
 Although the cis-trans interconversion of alkene
isomers does not occur spontaneously, it can be
brought about by treating the alkene with strong
acid catalyst.

After interconversion cis -2-butene with trans-2-

butene and allow them to reach equilibrium, we
can find that they are not equal stability.
The trans isomer is more stable than cis isomer by
0.66 kcal/mol at room temp in 76:24 ratio.
 Cis alkenes are less stable than their trans
isomers because of steric strain between the two
large groups on the same side as in the steric
effect in case of axial conformation of
methycyclohexane.
 From heat of hydrogenation (heat evolve when
double bond hydrogenation i.e reduced) alkenes
become more stable with increasing substitution.
 For example, ethylene has Hhydrog = -32.8
kcal/mol, but when one alkyl substituent is
attached to the double bond, as in 1-butene, the
alkene become approximately more stable
(Hhydrog = -30.2).
Further increasing the degree of substitution
leads to still further stability.
As general rule. Alkenes follow the stability order:

Tetrasubstituted > trisubstituted > disubstituted > monosubstituted

 The stability order of alkenes is due to combination of
two factors:
1- stability interaction between the C=C bond and
adjacent C-H bonds on substituents which called
hyperconjugation. The more substituent around
double bond is the more such interaction and is the
more stable.

2- alkenes stability is due to bond strength, a bond

between an sp2 carbon and sp3 carbon is to somewhat
stronger than a bond between two sp3 carbons. Thus
comparing 1-butene and 2-butene the mono
substituted isomer has one sp3-sp3 and one sp3-sp2
while the disubstitueted has two sp3-sp2, that is more
highly substituted alkene s have high ration of sp3-
sp2.
Problem:
 Alkenes behave as nucleophiles (Lewis base) in polar
reaction.
Nucleophile is Greek word mean nucleus lover.
The C=C is electrons-rich and can donate a pair of
electrons to an electrophile (electrons lover) Lewis
acid.
For example reaction of 2-methylpropene with HBr
yields 2-bromo-2-methylpropane in a reaction called
electrophilic addition reaction.
The reaction begins with the attack on the
electrophile HBr by the electrons of the nucleophillic
bond.
The two electrons from the bond form a new bond
between the entering hydrogen and an alkene carbon.
 H Br Br
H 3C H
H3C H Br H
C C C C H H 3C C C H

H3C H H 3C H
H 3C H

Carbocation intermediate

In the above reaction the carbocation intermediate

itself is electrophile accept electrons pair from the
nucleophile Br- ion to form C-Br bond and a neutral
addition product formed.
 In the previous reactions unsymmetrical substituted
alkene react with HX and give only one product not a
mixture.
Such reactions are said to be regiospecific when only
one of two possible orientation of addition occurs.

After looking at the result of many reaction, the

Russian chemist Vladmir Markovnikov proposed in
1869 what has become known as Markovnikov rule.
 Since carbocation is involve as intermediate in the
these reactions Markovnikov rule can be restated.
In the addition of HX to an alkene, the more highly
substituted carbocation is formed as the
intermediate rather than the less substituted one.
Why should this be?
 Evidence has shown that the carbocations are
planar, its sp2 hybridized as it is a trivalent, the
three substituent oriented to corner of an
equilateral triangle
 2-methylpropene when react with H+ to form
carbocation, it give carbocation with three alkyl
substituent i.e tertiary carbocation 3 or it might
give carbocation with one alkyl substituent i.e
primary carbocation 1.
H3C H Cl H
H
H3C H
C C H H3C C C H C C
H H3C H
H3C H3C H

Since the reaction leads to 2-chloro-2-

methylpropane as only product, formation of the
tertiary carbocation is favour .
Thermodynamic show that the stability of
carbocation increase with increasing substitution
so the order of stability is 3> 2 > 1 > CH3+
 The highly substituted carbocation is more stable
because of electronegativity inductive effect, as we
said later in polar bond electrons shift towards the
more electronegative atom.
in the case of the carbocation the positive charge
made the carbon more electronegative than adjacent
one therefore electrons shift in response of
electronegativity and its more from alkyl group than
from a hydrogen.
H3C H Cl H
C C H H3C C C H
H3C H H3C H
 1930 Whitmore found that in the reaction between
HCl and 3-methyl-1-butene a substantial amount
of 2-chloro-2-methylbutane in addition to the
expected product 2-chloro-3-methybutane were
produced
 Once 2-chloro-2-methylbutane is formed this can
show that the reaction leads to this product take place
in several steps, which can explain the rearrangement.
The secondary carbocation intermediate formed by
the protonation of the 3-methyl-1-butene rearranges
to a more stable tertiary carbocation by a hydride
shift-the shift of a hydrogen atom and its electron pair
(a hydride ion :H-) between neighbouring carbons.
 Note the similarities between the two carbocation
rearrangements:
1-In both case a group (:H-,or :CH3-) moves to an
adjacent positively charged carbon taking its bonding
electrons pair with it.
2-A less stable carbocation rearrange to a more stable
one.
Importance of the rearrangement in biological
synthesis in steroids.
Problem: