CHEMISTRY 126

STUDY UNIT 7
ALKENES AND ALKYNES
Alkenes and Alkynes

• Alkenes contain double bonds (C=C)

• a double bond (C=C) consists of 1 σ and 1 π bond

• Alkynes triple bonds (C≡C)

• a triple bond (C≡C) consists of 1 σ and 2 π bonds.

• Alkenes are also known as olefins

• “unsaturated compounds ” – those that
contain a double or triple C to C bond
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Alkenes and Alkynes
They contain less H atoms than the
corresponding alkane & hence generic
chemical formulas are:
General formulae
NB : Alkanes: CnH2n+2
• CnH2n = alkenes Cycloalkanes: C nH2n
• CnH2n-2 = alkynes
Eg Ethane(C2H6), Ethene (C2H4), Ethyne(C2H2)

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General Properties
• With multiple (double or triple) bonds three
possible arrangements arise:
• Cumulative system
• Conjugated system
• Isolated system.
e.g
Cumulative Conjugated Isolated
C=C=C C=C-C=C C=C-C-C=C
C=C=C=C C≡C-C≡C C≡C-C-C-C≡C

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 Bonding in Alkenes
• Alkenes C atoms are sp2 hybridized at the double bond
• Bond angles are trigonal planar and about ~120°
• C=C bond length is ~1.34 Å, C-C single bond length is ~1.54 Å
• A C=C bond is stronger than a C-C single bond
• free rotation along C=C bond is very limited

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 Alkenes
• CH2=CH2 (ethene/ethylene) is a raw material for
a number of industrial products
• e.g. ethanol, acetic acid, ethylene glycol etc.
• Ethene (also called Ethylene) is a plant hormone
which causes seeds to sprout, flowers to bloom,
fruit to ripen, etc.

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 Nomenclature
1. To name alkenes and alkynes the suffix “ane” of the
corresponding alkane is replaced with “ene” or “yne”
respectively e.g.
ethane (CH3-CH3),
ethene (CH2=CH2),
ethyne (HC≡CH)
• If there is more than one double or triple bond use the
suffix “diene”, “triene”, etc.
2. The parent name is selected as the longest continuous
C-chain that includes both carbons of the multiple bond
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Nomenclature

e.g. NOT

• NB :parent chain is a butene above and not a 5C chain !!

3. Number the parent chain from the end nearest /closest to the
multiple bond and give preference to the double bond if a triple
bond is also present in the molecule

4. Indicate the position of the multiple bond by citing the lower

number of carbons forming the multiple bond eg
5 3 1
2-pentene
4 2
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Nomenclature

• If the multiple bond is equidistant from both

ends of the chain, number the chain from the
end nearest the first branch point or
substituent.
1 3

2 4

2-methyl-2-butene

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Nomenclature
1
3
2 4 2-ethyl-1-butene

5 3 1
4 2
6 1
2 4
5
6 2-methyl-3-hexene
3
5-methyl-3-hexene

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Cis – Trans Isomerism

• The double bond in an alkene is rigid – thus it will not rotate

freely.
• Therefore substituents on the alkene carbon atoms will
produce geometric isomers called cis isomers or trans isomers
• Cis isomer has the identical or smallest group on each alkene C-
atom on the same side of the double bond and are also called Z
isomers
• Trans isomer (E isomers ) has identical or smallest group on
each alkene C atom on opposite side of the double bond

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 Cis – Trans Isomerism
• If the two non-hydrogen atoms or groups are:
– on the same side of the double bond it is a cis- arrangement
– on opposite sides a trans- arrangement

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 Cis – Trans Isomerism
• If the two non-hydrogen atoms or groups are:
– on the same side of the double bond it is a cis- arrangement
– on opposite sides a trans- arrangement

2 2

1 1

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 Cis – Trans Isomerism
• If the two non-hydrogen atoms or groups are:
– on the same side of the double bond it is a cis- arrangement
– on opposite sides a trans- arrangement

2 2 1 2

cis trans
1 1 2 1

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Cis – Trans Isomerism
• Note that they have different physical properties
• this is because their dipole moments are different.

Additive effect Subtractive effect

Polar molecule Non-polar molecule

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 Cis – Trans Isomerism
cis trans
1 1 2 1
1.
2 2 1 2

2 1
2. 1 1

2 2 1 2

NB: In its simplest form, there must be two atoms/groups that are identical
at each of the double-bonded C atoms, while the other atoms/groups
must be different from these, whether they are identical or not.
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Nomenclature of Cycloalkenes
• Ring is numbered so that the double bond is between C-1
and C-2 1

• Thus no need to indicate position of double bond here

• Number substituents to give lowest possible position
• Prefix cyclo precedes name of the alkene with number of C
atoms in the ring e.g.
Br

1 2 7
8 3 6 1

7 4 5 2
6 5 4 3
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1,3,5,7-cyclooctatetraene 7-bromo-1,3,5-cycloheptatriene
Chemical Reactivity

• Alkenes undergo addition reactions only

• The π bond is weaker than the σ bond - therefore
easier to break.
• A reagent will add across the double bond resulting in
an addition reaction.

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 Carbocations
• Are e- deficient species which carry a positive charge at
a C-atom (C+); and also called carbonium ions.
• They are formed as intermediates in addition reactions
across a C=C bond.
• Not all carbocations are equally stable – tertiary
carbonium ions are most stable and primary and
methyl the lowest stability
CH 3
CH 3
H H
+ + + +
C > H
C > H
C > C
H 3C CH 3
CH 3
CH 3 H H

3° Most stable 2° 1° least stable methyl

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 Symmetry and Addition Reactions
• Halogenation of ethene is a
symmetry reaction
• both the reagent (Br2) and
the substrate (ethene) are
symmetric → only a single
product is formed.
• For asymmetric reactions?
Two products are possible.

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 Markovnikov’s Rule
• States that when an unsymmetrical reagent adds to a
unsymmetrical double bond, the electrophilic part of the
reagent(ie the H from HCl or the H from water etc ) adds
preferentially to the alkene carbon carrying the most hydrogen
atoms directly attached to it

CH2=CH-CH3 + Hᵟ+-Clᵟ- → CH2Cl-CH2-CH3 Minor/anti Markovnikov product

+ CH3-CHCl-CH3 Major/Markovnikov Product
Example
H H 3C H H 3C H
H 3C

C C
+ Hᵟ+-Clᵟ- H C C H + H C C H

H H H Cl Cl H

(minor) (major)
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Markovnikov’s Rule

• Why? Because this mode of addition will always

proceed via the most stable carbocation intermediate,
i.e. consider the addition of H+ to propene:
H
1o carbocation
+
ANTI-Markovnikov product
H+
+
H
2o carbocation
Markovnikov product

• Then the carbocation subsequently reacts with the Cl

anion if e.g. HCl is the reagent
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Hydration
• Addition of water (H2O) across the double bond i.e.
adding H and OH across the double bond
• Product is an alcohol
• Requires an acid as a catalyst O H
H2SO4 major
+ H2O
HO
minor

H2SO4 O H

+ H2O major

HO minor
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Hydrogenation and halogenation
• Addition of H2 or X2 across the double bond to
produce an alkane or a vicinal dihalide
• [Vicinal: when 2 atoms are attached to adjacent/
neighbouring C-atoms]
• Hydrogenation (H2) requires a metal catalyst, e.g.
Pt or Pd, but not halogenation (X2)

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 Oxidation of an alkene with
Potassium Permanganate (KMnO4)
• Used as a chemical test for
alkene presence
• Product is a glycol (1,2-vicinal
diol) and manganese oxide
• Color change from purple to
brown/black which is the MnO2
solid
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Oxidation: Permanganate reaction
• Complex reaction mechanism
• Both O atoms are transferred from the
permanganate ion.

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Relative stability of alkenes
• Dependent on the number of alkyl groups bonded to
the C=C atoms
• The higher the number of alkyl groups, the higher the
stability, with R being alkyl chains
R H

R H
v
R R R R R H R H

> > >

R R H R H R H H

R v R

Tetra substituted is most stable monosubstituted is least stable

H H
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 Examples
1. Ethene is unsubstituted alkene (least
stable)
2. Propene is a mono-substituted alkene
(stable)
3. 2-methyl-2-butene is a tri-substituted
alkene (more stable)
4. 1,2-dimethylcyclobutene is a tetra-
substituted alkene (most stable)
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 Revision:
Draw: Cl

• 3-chloro-4-ethyl-2-methyloct-3-ene

• 3-isopropyl-2-heptane

• Name 3-methylhexa-2,4-diene

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Nomenclature
C H C H
2

C H C H C H C H C H C H
2 2 2

cyclohexene cyclooctene
5
3
2 4
1
3-vinyl-1,5-hexadiene
These double bonds are not assigned
with E or Z geometry: not possible to trans-cyclodecene cis-cyclodecene
assign priority

1 Br
octa-
5
1 5 3,5-diene
4 2 3 8 3-bromo
3 4 6 3Z
2-phenyl-1,3-cyclopentadiene (3Z,5E)-3-bromoocta-3,5-diene 5E
These rings are not assigned
with E or Z geometry 30
 hexa
3-methyl
2,4-diene
(E) 2
(E) 4

(2E,4E)-3-methylhexa-2,4-diene

Reactions:
Br

? + HBr CH3CH2CHCH2CH2CH3

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3-Hexene as starting material: 2-Hexene as starting material

H H H
H
OR
H 2 3
H

H-Br H-Br

H H H Br H H H Br

=
3 3 OR
3 2
Br H H H Br H H H

3-Hexene only gives 3-bromohexane as 2-Hexene as the starting material, gives

the product. two possible compounds that can be
formed (i.e. 2-bromohexane and 3-
bromohexane).
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Nomenclature

5,6-dimethyl-2,4-heptadiene

3-phenyl-1-propene

7
6 1

5 2

4 3
7-methylene-1,3,5-cycloheptatriene
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Reactivity
• Rank alkenes in order of stability:

2 1 3
Highest Lowest
• trisub- tetrasub- disub-alkene

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Revision

CH
C H 3 CH3
3
Br
H-Br + H
H
H
H H
Br

Markovnikov/ Anti Markovnikov/

Major Product Minor Product

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Revision

+ H-Cl Cl
Major Product
H

+ H-Cl Major Product

Cl H
H H

H
H
CH 2
H
+ H-I I Major Product

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 Alkynes
• Alkynes have sp hybridized C’s
• Linear – bond angle 180°
• C≡C double bond ~ 1.21 Å
• Reminder: general formula is CnH2n-2

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Alkynes: Nomenclature
• Same as alkenes, except use the suffix “-yne”
1. Longest continuous carbon chain
2. Carbons are numbered from the end closest to the
triple (or double) bond
– If you have a choice, put double bond at the lowest #
3. If the position is the same from either side, number
so that the position of the substituents have the
lowest numbers
4. Multiple bonds: di, tri, tetra etc.

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Nomenclature
5 4 3 2 1 1-penten-4-yne pent-1-en-4-yne
CH2=CH-CH2-C≡CH 4-penten-1-yne
1 2 3 4 5

1 2 3 4 5
H2C=C-C≡C-CH3 2-methyl-1-penten-3-yne

CH3
Hex
6 2 1 Br 1,1,3,4,5,5 5 en
1 5 4 3
3 4 5 6 1,2,3,4,5,6 1 yne
2 NO
2 1-bromo
3-nitro
4-methyl
5-phenyl
1-Bromo-4-methyl-3-nitro-5-phenyl-5-hexen-1-yne
1-Bromo-4-methyl-3-nitro-5-phenyl-hex-5-en-1-yne 39
Alkynes: Reactions
• Most of the reactions discussed for alkenes also
apply to alkynes, although the alkynes usually react
slower.

• There are a couple of differences though.

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 Alkynes: Reactions

Hydrogenation:

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Alkynes: Reactions

Halogenation:

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Alkynes: Reactions
Addition of hydrogen halides (hydrohalogenation):

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Hydration of Alkynes

• Enols tend to be unstable and isomerise to the keto form

• π bond shifts from the C=C to the C=O
• Called keto-enol tautomerism

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Acidity of Alkynes

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Acetylenic protons

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