• Unsaturated chemical compound

containing at least one carbon-carbon

double bond, where rotation about the
C=C is very difficult.

• To show the presence of the double

bond, the –ane suffix from the alkane
name is changed to –ene.

• Also called olefins( fat dissolving)

• sp2 atomic orbitals
• Trigonal planar, 120o degree
 Geometric Isomerism
• Cis-trans isomerism
-isomers that have same order
of atom attachment but a
different arrangement of
their atoms in space.
 General Formula

CnH2n
• where n is the number of
carbon atoms in the
molecule
 Physical Properties
• Physical state -The first lower
member like ethene, propene and
butene are colorless gases.
•  Density - lighter than water.  
• Solubility - insoluble in water and
soluble in nonpolar organic solvents.
• more reactive than alkanes due to
their double carbon-carbon bond.
• Boiling point -The boiling points
of alkenes gradually increase with
an increase in the molecular
mass.
•  The cis isomer ( example cis-2-
butene, b.p.= 3.7°C) is higher in
bpt than its trans isomers
(example, trans-2-butene, b.p.=
1°C) 
• Melting point 
The melting points of alkenes
increase with an increase in
the molecular mass.
 Natural Sources
• Isolated from petroleum.
• Plant material like plant
hormone, like Ethylene – a
natural ripening agent and
Terpenes – found in essential oil.
 Some Common Alkene Polymers and their Uses

•Ethylene H2C=CH2 Polyethene, Polythene Packaging, cable

insulation, films and sheets
•Tetrafluoroethene F2C=CF2 Polytetrafluoroethene, PTFE,
Teflon Coatings, gaskets.
•Chloroethene (vinyl chloride) H2C=CHCl Polyvinyl chloride,
PVC, Tedlar Insulation, films, pipes
•Styrene H2C=CHC6H5 Polystyrene, Styron Foam for packaging
etc.
•Vinyl acetate H2C=CHOCOCH3 poly(vinyl acetate), PVA
•Paints, adhesives.
 Preparations of Alkenes

1. Dehydrohalogenation of Alkyl
halides
2. Dehydration of Alcohol
3. Dehalogenation of Vicinal Halides
4. Reduction of Alkynes
 Preparations of alkenes
1. Dehydrohalogenation of alkyl halides

C C + KOH
alcohol
C C + KX + H 2O

Ease of dehydrohalogenation of alkyl halides

H X
3° > 2° > 1°

Example:
KOH
CH3CH2CH2CH2Cl CH3 CH2 HC CH2
n-butyl chloride 1-butene
- +
KOH is an OH donor use to abstract H

CH3CH2CHClCH 3 KOH
sec - butyl chloride
CH3 HC CHCH3
2 - butene (80%)
+ CH3CH2HC CH2
1 - butene (20%)
 Dehydrohalogenation of Alkyl Halides
• Is an Elimination reaction. The term "elimination"
describes the fact that a small molecule is lost
during the process.
Different mechanisms are possible:
– Loss of the LG to form a carbocation,  removal of
H+ and formation of C=C bond
– Simultaneous H+ removal, C=C bond formation
and loss of the LG
– Removal of H+ to form a carbanion, loss of the LG
and formation of C=C bond.
2. Dehydration of alcohol

acid
C C C C + H2 O
alkene
H OH
Ease of dehydration of alcohols
3° > 2° > 1°

ex.
H H H H
H2SO 4
H C C H H C C H + H2O
ethylene
H OH
ethyl alcohol

+
acid serves as H donor
 H2SO4
CH3CH2CH2CH2OH CH3CH2 HC CH2 CH3 HC CHCH3

n-butyl alcohol 1-butene 2-butene

(chief product)

H2SO 4
CH3CH2 HC CH3
Al 2O 2 in
CH3 HC CHCH3 + CH3CH2 HC CH2

OH heated tube

sec-butyl alcohol 2-butene 1-butene

(chief product)
 Dehydration of Alcohols
• It is the elimination of water
molecule from alcohol to convert
into alkene.
• Lost of H and OH from adjacent
carbons
• An acid catalyst alkene.
 Mechanism of Alcohol Dehydration

Step 1 : Alcohol unites with a hydrogen

ion to form the protonated alcohol
Step 2 : Alcohol associates into water
and carbonium ion.
Step 3 : The carbonium ion then loses
a hydrogen ion to form alkene.
3. Dehalogenation of vicinal dihalides
(same side)

C C + Zn C C + ZnX2

X X
dihalides

Example:

Zn
CH3 HC CH CH3 CH3 HC CHCH3 + ZnX2

Br Br

2,3- Dibromobutane 2- butene

4. Reduction of alkynes

R R
Pd, NiBr
C C syn (cis)
Lindlar
Catalyst H H

R C C R

R H
Na or Li NH3
C C anti (trans)

H R
 Reduction of Alkynes
• Reducing Alkynes to form trans or cis
Alkenes.
Using Na/ NH3
Step 1:
Sodium transfer an electron to the alkyne
giving a radical anion.
Step 2: The radical anion removes a proton
from the ammonia in an acid/base
reaction
Step 3:
A second atom of sodium transfers
another electron to the alkyne giving an
anion.
Step 4 :
the anion removes proton from the
ammonia in an acid/base reaction.
 Reactions of Alkene
• Halogenation
• Hydration
• Hydrogenation
• Addition of hydrogen Halides
• Addition of sulfuric acid
• Addition of Carbenes
• Addition of Free Radical
• Allylic Hydrogenation • Hydroboration-
• Dimerazation oxidation
• Alkylation • Epoxidation
• Polymerization
• Hydroxylation
• Halohydrins formation
• Ozonolysis
 Reactions of Alkenes

1. Addition of Halogens (X2)

X2 = CL2, Br 2
C C + X2 C C I 2 - unreactive with alkane
X X

Example.

Br2 CCl4
HCH3C CH2 CH3CHBrCH2Br
propene(propylene) 1,2 dibromopropane (propylene bromide)
 Halogenations – Addition of
Halogens
• When an alkene is treated at room temperature
with a solution of bromine or chlorine in carbon
tetrachloride or some other inert solvent, the
halogens adds rapidly to the double bond of the
alkene to give the corresponding vicinal dihalide (
two halogens attached adjacent carbons
2. Addition of Hydrogen (catalytic hydrogenation)

Pt, Pd or Ni
C C + H2 C C
H H

Ex.
H2, Ni
HCH3C CH2 CH3CH2CH3
propene(propylene) propane
 Hydrogenation of Alkenes
• The relationship between reactants and
products in addition reactions can be
illustrated by the hydrogenation of alkenes
yield alkanes.Hydrogenation is the addition of
H2 to a multiple bond.
3. Addition of hydrogen halides

C C + HX C C HX = HCL, HBr, HI
H X
Ex.
HCH3C CH2 HI
CH3CHICH 3
propene 2 - iodopropane ( isopropyl halides)

Br
H 3C C CH3 Markovnikov addition.
no peroxides
H
2 - bromopropane
HBr
HCH3C CH2 (Isopropyl bromide)

peroxides CH3CH2CH2Br anti - Markovnikov addition.

1 - bromopropane
(n - propyl bromide)
Ex. I
H
HCH3C CH2 + HI H3C CH CH2

H3C CH CH2
+ HI H3C CHI CH3 actual product
 HI
CH2=CHCl CH3CHICl
- - -
vinyl chloride 1 Chloro 1 iodoethane

CH3 CH3

H3CHC=C CH3
+ HI I CCH2CH3

CH3

CH3CH=CHCH3 + HI CH3CHICH2CH3
 Addition of hydrogen halides
– In the addition of an acid to the C=C of an
alkene, the hydrogen of the acid attaches
itself to the carbon that already holds the
greater number of hydrogens
– The reactivity of alkene, with halogen
acids is in the order;.
HI > HBr > HCl
4. Addition of sulfuric acid

C C + H2SO 4 C C
H OSO3H
alkyl hydrogen sulfates

Ex.

80% H 2SO 4 OSO 3H H2O, heat

HCH3C CH2 H3C CHCH3
H3C CHCH3
propene OH
Isopropyl alcohol
 98%H2SO 4 H2O, heat
CH 2=CH 2 CH 3CH 2OSO 3H CH 3CH 2OH + H 2SO 4

CH3
63%H2SO 4
H2C CCH3
5. Addition of water. HYDRATION

+
H
C C + HOH C C
H OH
Ex.
OH
+
H2O, H
HCH3C CH2 H3C CHCH3
propene Isopropyl alcohol (2 - propanol)

H3C +
CH3
H2O, H
H3C C CH2 H3C C CH3
Isobutylene CH4
OH
tert - butyl alcohol
 Addition of Water - Hydration
– When heated with water in the presence of an
acid catalyst, alkenes yield alcohol ROH.
– The process is called hydration of alkenes because
it involves the addition of water across the double
bond.
– The addition of the HOH across the double
bonded carbon that bears the greater number of
hydrogen atoms and the hydroxyl groups goes to
the other double-bonded carbon
 6. Halohydrin formation

C C + X2 + H 2O C C + HX X2 = Cl 2, Br 2
H OH

Ex.
Cl 2, H2O
HCH3C CH2 H3C CH CH2 follow Markovnikov rul
propylene HO Cl
(propene)
propylene chlorohydrin
Sterospecific:
H3C H CH3
C Cl H
Cl2, H 2O
3 - chloro - 2 - butanol
C
H OH
H3C H
cis - 2 - butene CH3
threo (stereospecific)
H CH3 CH3
C H Cl
Cl2, H 2O
C 3 - chloro - 2 - butanol
H3C H OH
H
trans 2 - butene CH3
erythro
 7. Dimerization (di = two, mer = part, product contains exactly twice
the # of C & H atom as the original).

CH3 CH3 CH3 CH3 H3C

CH3
H2SO 4
H3C C CH2 + H3C C CH2 H3C C CH C CH3+ H3C C CH2 C CH2
isobutylene isobutylene CH3 CH3
2,4,4 - trimethyl - 2 - pentene 2,4,4 - trimethyl - 1 - pent
 Mechanism:

CH3 CH3
addition of a hydrogen ion
H 3C C CH2 + H:Br H3C C
+
CH3 + : Br to isobutylene to form
the carbon

CH3 CH3 CH3 CH3 CH3 H3C

H 3C C
+
CH3 + H 3C C CH 2 H3C C CH 2 C
+
CH3 H 3C C CH C CH3
H3C H3C

Addition of the tert-butyl cation to iso butylene; the orientation of addition is

duch to yield the more stable tertiary cation. Step(2) brings about the union
of two : isobutylene units, which is of course necessary for the product.
8. Alkylation

acid
C C + R H C C

H R
ex.

CH3 CH 3 CH3 CH3

H2SO 4
H 3C C CH2 + H 3C C H H 3C C CH 2 C CH3
isobutylene
CH 3 H CH3
isobutane 2, 2, 4 - trimethyl pentane
 mechanism:

CH3 CH3
Addition of a hydrogen
ion to form carbocation
H 3C C CH2 + H:B H3C C CH3 + :B
+
CH3 CH3 CH3 CH3 Addition of a
tert-butyl
H3 C C CH2 + H3 C C + H3 C C CH2 C CH3 carbocation to
+ isobutylene
CH3 CH3
Carbocation
abstracts a
CH3 CH3 CH3 CH3 CH3 hydrogen atom with
its pair of electrons
H 3C C CH2 C CH3 + H C CH3 H3 C C CH2 C CH3 + from a molecule of
alkane. This
+ CH3 abstraction of
CH3 CH3 H hydride ion yields
CH3 an alkane of 8
carbons and a new
carbocation to
+C CH3
continue the chain.
CH3
 A carbocation may:

a.) combine with a negative ion or other basic molecule

b.) rearrange to a more stable cabocation

c.) eliminate a hydrogen ion to form an alkene

d.) add to an alkene to form a larger carbocation

e.) abstract a hydride ion from an alkane

9. Oxymercuration - demercuration

oxymercuration demercuration

NaBH4
C C + H2O + Hg(OAc)2 C C C C
mercuric acetate
HO AcOHg HO H
organomercurial cmpd. alcohol
Markovnikov orientation

•Oxymercuration – involves addition to the C=C of OH and HgOAc

(mercuric ion)

•Demercuration – the HgOAc is replaced by H

Ex. OH
Undergo the process
of oxymercuration,
Hg(OAc) 2, H2O NaBH 4 involves addition to
H3C(H 2C) 3HC CH 2 H3C CH(CH 2)3CH 3 the carbon – carbon
1 - hexene double bond of –OH+
2- hexanol -HgOAc

CH3
CH3
Hg(OAc)2, H2O NaBH4
CH2CH3C CH2 CH2CH3C CH3 Follows Markovnikov
2 - methyl - 1 - butene addition
OH
tert - pentyl alcohol

CH3 Hg(OAc) 2, H 2O NaBH4 CH3

OH
1 - methylcyclopentene 1 - methylcyclopentanol

CH3 CH3
Hg(OAc)2, H 2O NaBH4
H3C C CH CH2 H3C C HC CH3

CH3 CH3 OH
3, 3 - dymethyl - 1 - butene 3, 3 - dymethyl - 2 - butanol
 10. Hydroboration – oxidation

H2O 2
C C + (BH3)2 C C
OH
- C C
Diborane
H B H OH

Anti - markovnikov orientation

With the reagent Diborane, alkenes undergo hydroboration to yield alkylboranes,

which on oxidation give alcohols.

H2C=CH2 H2C=CH2 H2C=CH2

(BH3)2 CH3CH2BH 2 (CH3CH2)2BH (CH3CH2)3B
diborane triethylboron

-
OH
(CH3CH2)3B + 3H2O2 3CH 3CH2OH + B(OH) 3
ethanol boric acid
Mechanism:

C C + H-B C C C C
hydroboration oxidation
B OH

H B = H - BH2, H - BHR, H - BR2

Hydroboration involves the addition of the double bond of BH3 w H becoming

attach to one doubly bonded carbon and boron to the other. The alkylborane can
then undergo oxidation in which the boron is replaced by –OH. Thus, the 2 –
stage reaction process of hydroboration oxidation permits the effect. The addition
to the carbon – carbon double bond of elements of H-OH.
 -
CH3CH=CH2 (BH3)2 H2O 2, OH CH3CH2CH2OH
-
propylene n propyl alcohol

CH3 -
CH3
(BH 3)2 H2O 2, OH
H3C C=CH2 H3C CHCH2OH
Isobutylene Isobutyl alcohol

-
(BH 3)2 H2O 2, OH
CH3CH2CH=CH 2 CH3CH2CH2CH2OH
- -
1 butene n propyl alcohol
11. Addition of free radicals

peroxides
C C + Y Z
or light C C
Y Z

n - C6H13CH CH2 + BrCCl 3 peroxide n - C6H13CH CH2 CCl 3

1 - octane bromotrichloromethane
Br
3 - bromo - 1,1,1 - trichlorononane
stability of radical: 3º > 2º > 1º CH3

peroxides
RCH CH 2 + CCl 4 RCH CH2 CCl 3

Cl
Mechanism:

peroxides rad.

Rad. + Cl:CCl3 Rad:Cl + .CCl3

.CCl3 + RCH=CH2 RCH - CH2 - CCl3
RC.H - CH2 - CCl3 + Cl:CCl 3 RCH - CH2 - CCl3 + .CCl3

Cl
 Electrophilic addition : Markonikov orientation

H3C CH CH3 H3C CH CH3

+
2º cation Br
isopropyl bromide
HBr
HCH3C CH2
propylene

H3C CH2 CH2 +

1º cation
 Free – radical Addition : Anti – Markovnikov orientation

H3C
.CH CH2Br
2º free radical
HBr
H3C CH2 CH2Br

Br.

.
HCH 3C CH2
propylene

H3C CH2 CH2

Br
1º free radical
12. Polymerization of Alkenes

Polymerization – the joining together of many small molecules to form very large
molecules.
Monomers – the simple compounds form which polymers are made.

Ex.
O 2, heat, pres
nCH2 CH2 H 2C CH2 CH2 CH2 CH2 CH2
or
H2C CH2
polythylene
(plastic material of packaging film)

•5 processes of polymerization

1. Free - radical polymerization

2. Cationic polymerization
3. Anionic polymerization
4. Condensation polymerization
5. Coordination polymerization
 Free – radical polymerization
peroxide
nCH2 CH H2 C CH CH 2 CH CH2 CH CH2
Cl Cl Cl Cl
or
H2 C CH2
Cl n
poly (vinyl chloride)

Polyvinyl chloride - use to make phonograph, records, plastic pipes, when plasticized with
high boiling esters – raincoats, shower curtains and coatings for metal and upholstery fabrics.
Peroxide – initiator, required in small amount in polymerization
-Free radical initiator

.
Mechanism:

peroxide rad decomposition of peroxides to form free radical

Free radical adds to
molecule of alkenes
which for another free
radical
 rad H2C CH
G
radCH 2 CH
G
. chain initiating step

This radical adds to another

molecule of alkene to generate
another free radical. This radical
adds to another molecule of alkene
to generate a still larger radical

radCH2 CH

G
.+ H2C CH
G
radCH2 CH

G
CH2 CH

G
. chain propagating step
13. Addition of Carbenes. Cycloaddition
carbenes – derivative of methylene

+ - UV light
H2C N N photolysis CH2 + N2
diazomethans methylene

UV light
H2C C O CH2 CO +
ketene methylene
Methylene exist into 2 different forms
singlet methylene – unshared electrons are paired, less stable

:
& generated first in photolysis : stereospecific addition

CH2 or H
.
:. .. C

..
triplet methylene – unshared electrons are not paired,
free radical (diradical) : nonstereospecific addition

H :.. C H
 Cycloaddition: addition of the carbon – carbon double bond
light
HCH3C CHCH3 +
CH2N2 HCH3C CHCH3 + N2
2 - butene diazomethane
CH2
1, 2 - dimethycyclopropane

Sterospecific: (addition of methylene can occur with 2 different kinds of

stereochemistry.)

Photolysis of diazomethane into in liquid

cis - 2 -butene + CH2N2 cis 1, 2 - dimethylcyclopropane

And in liquid

trans 2 -butene + CH2N2 trans 1,2 -dimethylcyclopropane

CH2 :+ C C C C C C

CH2 CH2
Singlet methylene
Stereospecific
Electrophilic addition
Electron deficient and
can find electrons at

. .+
CH2 C C C
.
C
the C-C double bondingle
C C

CH2 . CH2

Non – stereospecific: cis/trans2 – butene + CH2N2 both cis and trans 1,2 -
dimethylcyclopropane

Triplet methylene
Non - Stereospecific
Free radical addition
ff. by addition
 Methylene undergoes intersection

C H + CH2 C CH2 H

Addition of substituted carbenes: 1,1 - elimination

- +
t - BuO K
HCH2C CHCH3 + CHCl3 HCH3C CHCH3 + t - BuOH + KCl
2 - butene chloroform
C

Cl Cl
3, 3 - dichloro - 1, 2 - dimethylcyclopropane
Mechanism:

..-+ .. .. -
+ .. Reaction involves
a divalent carbon

..
t - BuO H CCl3 CCl3 t - BuO H
CCl3
- ..CCl2 + Cl -
compound, a
derivative of
methylene:
dichlorocarbene dichlorocarbene:
CU2.

HCH3C CH3CH .
+. CCl 2 HCH3C
Generated in 2
CHCH3 steps, initiated by
attack on
chloroform by the
C strong base tert-
butoxide ion and
Cl Cl then adds to the
alkene.

Because of the presence of halogen atom, the singlet form is the more
stable form of dichlorocarbene and is the one adding to the double bond.
 Addition of Carbenes
• Carbenes are intermediates of the general
formula CH2:. The derivatives of methylene
(CH2) are the carbenes.
• Methylene is formed by the photolysis of
either diazomethane, CH2N2 or ketene,
CH2=C=O.
 14. Hydroxylation. Glycol formation

C C + KMnO 4 or HCO 2OH C C

OH OH
Example.
cold, dil. KMnO4 or HCO2OH
HCH 3C CH2 H 3C CH CH2 + 2MnO2
propylene OH OH
1,2 - propanediol (propylene glycol)

Oxidizing agents that bring about hydroxylation

a. cold alkaline potassium permanganate, KMnO4
b. peroxy acids, such as peroxyformic acid HCO2OH
KMnO4 -
syn hydroxylation

HO OH
- -
cis 1,2 cyclopentanediol

HCO2OH -
OH + HO anti hydroxylation

OH HO
- -
trans 1,2 cyclopentanediol
15. Halogenation. Allylic substitution ( same mechanism with substitution in alkene

heat
H C C C + X2 X C C C X2 = Cl 2, Br 2
low conc.
Ex.
HCH3C CH2 Cl 2, 600º
Cl - CH 2CH CH2
propylene allyl chloride
Br

+ NBS
N - bromosuccinimide
cychlohexene 3 - bromocyclohexene
 -
CH2=CH CH3

- -
alkene like site of addition alkane like site of substitution

-
CH2=CH CH3

-
heterolytic attack, addition Free radical attack, substitution
Can we direct the attack to just one of these sites? Yes, by our choice of
rxn. Conditions.

Conditions:
1.alkenes undergo substitution by halogen at high temp. or under the influence of
UV light, generally in gas phase.
2.it can also undergo addition of halogen at low temp. in the absence of light and
generally in liquid state(phase).

low T
H3C CH CH2
CCl4 soln
heterolytic add'n
Cl Cl
Cl2 1,2 - dichloropropane
H3C CH CH2
propylene

500 - 600º Cl CH2 CH CH2 HCl free radical subs

gas phase 3 - chloro -1 - propane
N – bromosuccinimide a reagent used
for the specific purpose of brominating
alkenes at the allylic position provides
a constant low conc. of bromine.

O
O
C
C CH2 N H
HBr +
CH2 N Br Br 2 + CH2 C
CH2 C
O
O
NBS succinimide
 C H
vinylic hydrogen: hard to abstract
C H

C H allylic hydrogen: easy to abstract

.
H
Vinylic hydrogen- hydrogens attached to C=C
Alylic hydrogen – hydrogens attached to a carbon atom next to a double bond

Ease of abstraction of hydrogen atoms: Allylic >3º > 2º > 1º > CH4 > Vinylic

Ease of formation of free radicals: allyl > 3º > 2º > 1º > CH3. > vinyl
Example:

NBS
CH3(CH2)3CH2CH2CH=CH2
16. Ozonolysis (Cleavege rxn)

O H2O, Zn
C C + O3 O O C O + O C
ozone aldehyde ketone
O O
ozonide

Cleavage – a rxn in which the double bond is completely broken and the alkene
molecules converted into 2 smaller molecule.
Reducing agent (Zn) – prevent formation of hydrogen peroxide
will not react with aldehyde and ketone (aldehyde are often
converted to acid, RCOOH for ease of isolation.)
 O3 H2O, Zn
CH3CH2CH=CH2 CH3CH2CHO + CH2=O

CH3 H3C H
H3C C=CH2
O3 H2O, Zn
H3C C=O + O CH
 H2O, Zn O3
CH3CH2CH2CH=CHCH3
CH3CH2CH2CHO + CH3CHO

H H H H
H2O / Zn O3
CH 2CH 3C O + O C CH 2CH3 CH2CH3C C CH2CH3
aldehydes 3 - hexene

H CH3 H CH3
H2O / Zn O3
CH2CH3C O + O C CH3 CH2CH3C C CH3
aldehydes ketone 2 - methyl - 2 - pentene

Ozonolysis – is a typical means of degradation

17. Cleavage with periodate ( cleavage with a diol)

KMnO4 NaIO4
C C C C acids, ketones. CO2
cold, dil.
OH OH

RCOOH are generally obtained instead of aldehydes, RCHO a

terminal ==CH2 group is oxidized to CO2.
Example.

CH3 CH3
KMnO 4
CH3COOH + O C CH3
NaIO 4
H3C CH C CH3
carboxylic acid ketone 2 - methyl - 2 - butene

KMnO4
CH3CH2CH2COOH + CO2
NaIO4
HCH 2CH2CH3C CH2
carboxylic acid carbon dioxide
 Cleavage of cycloalkenes
CH 2
O3 H2O, Zn H 2C CHO
di - aldehyde
H 2C CHO
CH2
CH 2
H 2C CH
H 2C CH
CH2 CH2
KMnO 4 H2C COOH
di - acid
NaIO 4 H2C COOH
CH2
18. Epoxidation of Alkenes

O O

C=C +CH3COOH C C + CH3COH

O

Alkene Peroxyacetic Acid Epoxide Carboxylic acid

 Example
O O

H2C=CH(CH2)9CH3 + CH3COOH CH2-CH(CH2)9CH3 + CH3COH

1-Dodecane Peroxyacetic acid 1,2-epoxydodecane Acetic acid