Alkene Preparation and Reactions
Alkene Preparation and Reactions
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.
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.
CH=CH2
CH2 CHCHCH2CH
3-methylenecyclohexene CH2
3-vinyl-1,5-hexadiene
3-vinylhexa-1,5-
diene
CYCLOALKENES
• Contains C=C in the ring
• 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
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
R-CH2-CH2-X
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:
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:
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
or
Addition of Water (Hydration)
H OH
C C H2O H+ C C
alkene alcohol
MECHANISM OF ACID CATALYSED HYDRATION OF ALKENES
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:
- (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)
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.
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