Alkene Preparation and Reactions

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Alkene Preparation and Reactions

ALKENES
• Also called olefins (form oily liquids on reaction with chlorine gas)
• Contain at least one carbon-carbon double bond (C=C)
• General formula, CnH2n (n=2,3,…)
• Classified as unsaturated hydrocarbons (compound with double or
triple carbon-carbon bonds that enable them to add hydrogen atoms.
• sp2 -hybridized
Naming Alkenes
RULE 1. Select the longest continuous
carbon chain that contains a double bond.

This chain
contains 6
carbon atoms
RULE 2. Name this compound as you would an alkane, but
change –ane to –ene for an alkene.

This chain Name


This isthe
theparent
longest
contains 8 compound
continuous octene.
chain.
carbon atoms Select it as the parent
compound.
RULE 3. Number the carbon chain of the parent
compound starting with the end nearer to the
double bond. Use the smaller of the two
numbers on the double-bonded carbon to
indicate the position of the double bond. Place
this number in front of the alkene name.
IUPAC RULES
The name of the parent compound is
1-octene.
4 3 2 1

5
6
7
8
RULE 4. Branched chains and other groups are treated as in
naming alkanes. Name the substituent group, and designate its
position on the parent chain with a number.
• A compound with more than one double bond.
- Two double bond: diene
- Three double bond: triene
- Four double bond: tetraene
* Numbers are used to specify the locations of the double bonds.

1 4 7 6 5 4 3 2 1
2
CH23 C CH2 CH3 C C C C C CH2
C H H H H H
H H
IUPAC names: 1,3-butadiene 1,3,5-heptatriene
new IUPAC names: buta-1,3-diene hepta-1,3,5-triene

1 2
8 3

7 4
6 5
IUPAC names: 1,3, 5, 7-cyclooctatetraene
new IUPAC names: cycloocta-1,3,5,7-tetraene
ALKENES AS SUBSTITUENTS
• Alkenes names as substituents are called alkenyl groups.
• Can be named systematically as ethenyl, propenyl, etc. or
by common names such as vinyl, ally, methylene and
phenyl groups.

CH2 -CH=CH2 -CH2-CH=CH2

methylene group vinyl group allyl group


(ethenyl group) (2-propenyl group)

CH=CH2
CH2 CHCHCH2CH
3-methylenecyclohexene CH2
3-vinyl-1,5-hexadiene
3-vinylhexa-1,5-
diene
CYCLOALKENES
• Contains C=C in the ring

cyclopropene cyclobutene cyclopentene cyclohexene

• Nomenclature of cycloalkenes:
- Similar to that alkenes
- Carbons atoms in the double bond are designated
C1 and C2
6 CH3 5
5 1 4 1
4 2 3 2
3
1-methylcyclohexene 1,5-dimethylcyclopentene
Preparation of Alkenes

Alkenes can be prepared in the following ways:


i) Dehydration of alcohols
conc. H2SO4
R-CH2-CH2-OH R-CH=CH2 + H2O
• Saytzeff rule:
- A reaction that produces an alkene would favour the
formation of an alkene that has the greatest number of
substituents attached to the C=C group.

Dehydration of alcohols
H+ CH3CH2-CH=CH2 + H2O
CH3CH2-CH-CH3 1-butene
OH H+
CH3CH=CH-CH3 + H2O
2-butanol
2-butene
major product
Preparation of Alkenes

ii) Dehydrohalogenation of haloalkanes

R-CH2-CH2-X

NaOH can be replaced by KOH


Preparation of Alkenes

3) By Dehalogenation of Vicinal dihalides


Preparation of Alkenes

4)By Controlled Hydrogenation of Alkanes


5) By Cracking of Alkanes
Reactivity of Alkenes
More reactive than alkanes because:
• A carbon-carbon double bond consists of a σ and a π
bond. It is easy to break the π bond while the σ bond
remains intact.
• The π electrons in the double bond act as a source of
electrons (Lewis base). Alkenes are reactive towards
electrophiles which are attracted to the negative charge
of the π electrons.
• π bond will broken, each carbon atom becomes an
active site which can form a new covalent bond with
another atom. One π bond is converted into 2 σ bonds.
Reactions of Alkenes
Catalytic hydrogenation:
-hydrogenation: addition of hydrogen to a double bond and
triple bond to yield saturated product.
-alkenes will combine with hydrogen in the presence
of catalyst to form alkanes.

Pt or Pd
C C H o
C
25-90 C
H C
H H
Addition of hydrogen halides:
- Addition reaction with electrophilic reagents.
-Alkenes react with hydrogen halides (in gaseous state or
in aqueous solution) to form addition products.
-The hydrogen and halogen atoms add across the double
bond to form haloalkanes (alkyl halides).
- General equation:

H X
C C HX C
C
alkene
haloalkane
-
Reactivity of hydrogen halides : HF < HCl < HBr < HI
MARKOVNIKOV’S RULE
• There are 2 possible products when hydrogen halides react
with an unsymmetrical alkene.
• It is because hydrogen halide molecule can add to the C=C
bond in two different ways.

HH HH
CH3 C H-I CH3 C
CH CH
1-iodopropane
H
HH HH
I
CH3 C H-I CH3 C
CH CH
2-iodopropane
I
(major product)
Markovnikov’s rules:

- the addition of HX to an unsymmetrical


alkene, the hydrogen atom attaches itself
to the carbon atom (of the double bond)
with the larger number of hydrogen atoms.
Mechanism of electrophilic addition reactions:
- C=C : electron rich part of the alkene molecule
- Electrophiles: electron-seeking

Step 1: Formation of carbocation.


Attack of the pi bond on the electrophile to form carbocation.

δ+ δ-
C C E C Y-

Y
C carbocation
E
Step 2: Rapid reaction with a negative ion.
The negative ion (Y-) acts as nucleophile and attacks the
positively charged carbon atom to give product of the addition
reaction.

C Y- C
C
ADDITION OF HYDROGEN HALIDES TO
UNSYMMETRICAL ALKENES AND
MARKOVNIKOV’S RULE

CH3CHCH2
1
3 2
HCl H Cl
CH3CH=CH2 + 1-chloropropane
Propene
CH3CHCH2
Cl H
2-
chloropropane
(major product)
according to Markovnikov's
rules
MECHANISM:

Step 1: Formation of carbocation


H H H H HH
H Cl HC C C or H C C C Cl-
CH3 C C H
H H H H H H
less stable carbocation more stable carbocation
(1o carbocation) (2o carbocation)

- 2o carbocation is more stable than 1o carbocation.


- 2o carbocation tends to persist longer, making it more likely to combine with
Cl- ion to form 2-chloromethane (basis of Markovnikov's rule).

Step 2: Rapid reaction with a negative ion

H HH H HH
HCC CH Cl- HCCCH
H H H Cl H
2-chloromethane
(major product)
Addition reaction with concentrated sulfuric
acid: hydration of alkenes

-the alkene is absorbed slowly when it passed


through concentrated sulfuric acid in the cold
(0-15oC).
-involves the addition of H atom and HSO4
group across the carbon-carbon double bond.
- follows Markovnikov’s rule.
H H H H
H C CH H OSO3H H C C H
(H2SO4) H
OSO3H
ethyl hydrogensulphate
When the reaction mixture is added(CH
to water and warmed,
3CH2HSO4)
ethyl hydrogensulphate is readily hydrolysed to ethanol

CH3CH2OSO3H + H-OH CH3CH2OH + H2SO4


(H2O)

*ethene reacts with concentrated H 2SO4 to form


ethanol*

or
Addition of Water (Hydration)

Alkenes react with water in the presence of a strong


acidic catalyst (dilute H2SO4)to form an alcohol.
Markonikov rule is followed.

H OH
C C H2O H+ C C
alkene alcohol
MECHANISM OF ACID CATALYSED HYDRATION OF ALKENES

Step 1: Protonation to form carbocation


H H HHH
CH3 C C H H+ HCCCH
H
more H
stable carbocation
(2o carbocation)

Step 2: Addition of H2O to form a protonated alcohol


HHH
H C C C
O H CH3CHCH3
H H O H
H
H
H
Step 3: Loss of a proton (deprotonated) to form alcohol

CH3CHCH3
CH3CHCH3 +
O H H
OH
H+ = catalyst
ANTI-MARKOVNIKOV’S
RULE: FREE RADICAL
ADDITION OF
HYDROGEN BROMIDE
• When HBr is added to an alkene in the absence of peroxides
it obey Markovnikov’s rule.
• When HBr (not HCl or HI) reacts with unsymmetrical alkene
in the presence of peroxides (compounds containing the O-
O group) or oxygen, HBr adds in the opposite direction to
that predicted by Markovnikov’s rule.
• The product between propene and HBr under these
conditions is 1-bromopropane and not 2-bromopropane.

peroxide
CH3CH=CH2 HBr CH3CH2CH2Br
1-bromopropane
(major product)
anti-Markovnikov's orientation
• Anti-Markovnikov’s addition:

- peroxide-catalysed addition of HBr occurs


through a free radical addition rather than a
polar electrophilic addition.
- Also observed for the reaction between HBr and
many different alkenes.
- Not observed with HCl or HI.

- (The HCl bond (103 kcal/mol) is stronger than HBr bond (87kcal/mol).It is
not broken by the alkoxy free radicals obtained from peroxide)

- The HI bond (71 kcal/mol) is weaker than HBr bond )87kcal/mol).It is


broken by the alkoxy free radical obtained from peroxides. But the iodine
atom so formed readily combine with each other to yield iodine molecules
rather than attack the double bond in alkenes)
ANTI-MARKOVNIKOV’S RULE: FREE RADICAL
ADDITION OF HYDROGEN BROMIDE-Mechanism
Combustion of alkenes:
 The alkenes are highly flammable and burn
readily in air, forming carbon dioxide and
water.
 For example, ethene burns as follows :
C2H4 + 3O2 → 2CO2 + 2H2O
OXIDATION
• Oxidation: reactions that form carbon-
oxygen bonds.

• Oxidation reaction of alkenes:


i)epoxidation
iii)Ozonolysis
E P O XID AT IO N O F AL K E N E S
• Epoxide / oxirane: a three-membered cyclic ether.
O O O
C R C OH
R C OO H C C
C
peroxyacid epoxide (oxirane) acid
alkene

• Examples of epoxidizing reagent:

O O
O
Cl
CH3 C O O H COOH H
peroxyacetic acid peroxybenzoic acid O
m-chloroperoxybenzoic
O acid
(PhCO3H) (MCPBA)
O Z O N O L YS IS O F AL K E N E S
• Ozonolysis:
- The reaction of alkenes with ozone (O3) to form an ozonide, followed
by hydrolysis of the ozonide to produce aldehydes and /or ketone.

- Widely used to determine the position of the carbon-carbon double


bond.

- Ozonolysis is milder and both ketone and aldehydes can be


recovered without further oxidation.

R R' R O R' R R'


C C O3 C C + C O O C
O O H2O, Zn/H
R H R H
R ozonide H ketone aldehyde
POLYMERIZATION OF ALKENES
• Polymer: A large molecule composed of many smaller
repeating units (the monomers) bonded together.

• Alkenes serves as monomers for some of the most


common polymers such as polyethylene (polyethene),
polypropylene, polystyrene, poly(vinyl chloride) and
etc.

• Undergo addition polymerization /chain-growth


polymer:
- a polymer that results from the rapid addition of one
molecule at a time to a growing polymer chain, usually
with a reactive intermediate (cation, radical or anion) at
the growing end of the chain.
repeating unit

CI H CI H CI Cl
H H Cl H
CI H
C C C C C C C C C
H C C
H H H H H
C
vinyl chloride H poly(vinyl
H H chloride)
H H
H
n
UNSATURATION TESTS FOR ALKENES
• Reactions of alkenes with KMnO4

- KMnO4 is a strong oxidising agent.


-alkenes undergo oxidation reactions with
KMnO4 solution under two conditions:
a)Mild oxidation conditions using cold,
dilute, alkaline KMnO4 (Baeyer’s test).
b)Vigorous oxidation conditions using hot,
acidified KMnO4.
• Reaction of alkenes with cold, dilute, alkaline
KMnO4 (Baeyer’s test)

- the purple colour of KMnO4 solution disappears


and a cloudy brown colour appears caused by the
precipitation of manganese (IV) oxide, MnO2.

- test for carbon-carbon double or triple bonds.

- a diol is formed (containing two hydroxyl groups


on adjacent carbon atoms).
KMnO4 (aq), OH-
C C C C MnO2
cold
OH
OH
a diol
Reaction of alkene with hot kmno4

When treated with hot concentrated potassium


permanganate solution , alkenes split at the double bond to
form ketone and acid.
b) Bromine

-A solution of bromine in inert solvent (CH2CI2 or CCI4)


and dilute bromine water are yellow in colour.

-The solution is decolorised when added to alkenes or


organic compounds containing C=C bonds.
Mechanism
Pharmaceutical Uses of Alkene

• Alkenes are the raw materials for the manufacture of chemicals


like alcohols, aldehydes etc.
• Alkenes are also used as general anesthesia.
• Ethene is a plant hormone which controls growth, seed
germination and fruit development. Therefore, ethene is used for
artificial ripening of fruits, flower maturation, etc.
Uses of alkene
Alkenes are produced from the alkanes in crude oil by a process
called cracking. Cracking uses heat and a catalyst to decompose
alkanes.
The cracking process is important because it turns less useful
alkanes into more useful smaller ones and produces very useful
alkenes like ethene, the starting material for many plastics.
• Alkenes are extremely important in the manufacture of plastics.
All plastics are in some way related to alkenes. The names of
some plastics (Polythene or Poly Ethene, Polypropene), relate to
their alkene partners. Plastics are used for all kinds of tasks, from
packaging and wrapping, to clothing and outdoor apparel.
Uses of alkene

• Lower alkenes are used as fuel and illuminant. These may be


obtained by the cracking of kerosene or petrol.
• For the manufacture of a wide variety of polymers, e.g.,
polyethene, polyvinylchloride (PVC) and Teflon etc.
• As raw materials for the manufacture of industrial Chemicals
such as alcohols, aldehydes, and etc.
• Besides, alkenes also used for artificial ripening of fruits, as a
general anesthetic, for making poisonous mustard gas (War gas)
and ethylene-oxygen flame.

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