Alkenes or Olefins

Alkenes are also called

olefins – comprise a
large collection of cyclic HYDROCARBONS
and acyclic alkenes as
well as dienes and
polyenes.
ALIPHATIC AROMATIC

Linear Cyclic Saturated Unsaturated

1
 Dienes and Polyenes

α-cardinene β-selinene zingiberene

oil of citronella oil of celery oil of ginger

β-carotene
red-orange pigment in plants and fruits 2
4. ALKENES and ALKYNES
A. Structure

B. Reactions

C. Chemical Tests
 Cis-trans isomers

small net dipole no net dipole

higher bp lower bp
Electrophilic Addition
Syn and Anti Addition
 Markovnikov’s Rule

H will add to the carbon with

fewer alkyl substituents and
X will add to the carbon with
more alkyl substituents.

Vladimir Markovnikov
 Carbocation Stability

Source: McMurry, 2012.

 Alkenes: Hydrohalogenation

 two-step reaction
 carbocation rearrangements are possible
 Markovnikov regiochemistry occurs
 syn and anti additions occur
9
Source: Smith, 2011.
 Alkenes: Hydrohalogenation

10
Source: Smith, 2011.
 Alkenes: Hydrohalogenation

11
Source: Smith, 2011.
 Alkynes: Hydrohalogenation

 two-step reaction for each HX

 resonance-stabilized carbocation forms
 Markovnikov orientation
12
Source: Smith, 2011.
 Alkenes: Halogenation

 two-step reaction
 bridged halonium ion is formed as intermediate
 Markovnikov regiochemistry occurs
 anti additions occur
13
Source: Smith, 2011.
 Alkynes: Halogenation

 Two-step reaction for each X2

 bridged halonium ions are formed
 anti addition occurs

14
Source: Smith, 2011.
 Alkenes: Hydrogenation

→ →

 a heterogeneous process
 catalysts = Pd, Pt, Ni, etc.
 syn addition occurs yielding a single product
15
Source: Wade, 2002.
Chemical Tests: Reaction with Br2

16
Chemical Tests: Reaction with KMnO4

syn addition

17
Synthetic Polymers
 Synthetic Polymers

19
Source: Smith, 2011.
Alkenes: Addition Polymerization

20
Source: Smith, 2011.
 vinyl chloride polyvinyl chloride (PVC)

tetrafluoroethylene polytetrafluoroethylene (Teflon)

styrene polystyrene (Styrofoam) 21

 Stereochemistry of Polymerization

22
Source: Smith, 2011.
 23
Source: Smith, 2011.