John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 8
Alkenes: Reactions
and Synthesis
Paul D. Adams • University of Arkansas
Diverse Reactions of Alkenes
 Alkenes react with many electrophiles to give useful
products by addition (often through special reagents)
Why this chapter?
 To begin a systematic description of major
functional groups
 Begin to focus on general principles and patterns
of reactivity that tie organic chemistry
8.1 Preparation of Alkenes: A
Preview of Elimination Reactions
 Alkenes are commonly made by
 elimination of HX from alkyl halide
(dehydrohalogenation)
 Uses heat and KOH
 elimination of H-OH from an alcohol (dehydration)
 requires strong acids (sulfuric acid, 50 ºC)
8.2 Addition of Halogens to
Alkenes
 Bromine and chlorine add to alkenes to give 1,2-dihaldes,
an industrially important process
 F2 is too reactive and I2 does not add
 Cl2 reacts as Cl+ Cl-
 Br2 is similar
Addition of Br2 to Cyclopentene
 Addition is exclusively trans
Mechanism of Bromine Addition
 Br+ adds to an alkene producing a cyclic ion
 Bromonium ion, bromine shares charge with carbon
 Gives trans addition
Bromonium Ion Mechanism
 Electrophilic addition of
bromine to give a cation is
followed by cyclization to
give a bromonium ion
 This bromoniun ion is a
reactive electrophile and
bromide ion is a good
nucleophile
The Reality of Bromonium Ions
 Bromonium ions were postulated more than 60 years
ago to explain the stereochemical course of the addition
(to give the trans-dibromide from a cyclic alkene)
 Olah showed that bromonium ions are stable in liquid
SO2 with SbF5 and can be studied directly
8.3 Halohydrins from Alkenes:
Addition of HOX
 This is formally the addition of HO-X to an alkene to give
a 1,2-halo alcohol, called a halohydrin
 The actual reagent is the dihalogen (Br2 or Cl2) in water
in an organic solvent)
Mechanism of Formation of a
Bromohydrin
 Br2 forms
bromonium ion,
then water adds
 Orientation
toward stable
C+ species
 Aromatic rings
do not react
An Alternative to Bromine
 Bromine is a difficult reagent to use for this reaction
 N-Bromosuccinimide (NBS) produces bromine in
organic solvents and is a safer source
8.4 Hydration of Alkenes: Addition
of H2O by Oxymercuration
 Hydration of an alkene is the addition of H-OH to
give an alcohol
 Acid catalysts are used in high temperature industrial
processes: ethylene is converted to ethanol
Oxymercuration Intermediates
 For laboratory-scale hydration of an alkene
 Use mercuric acetate in THF followed by sodium
borohydride
 Markovnikov orientation
 via mercurinium ion
8.5 Hydration of Alkenes: Addition
of H2O by Hydroboration
 Borane (BH3) is electron deficient
 Borane adds to an alkene to give an
organoborane
Hydroboration-Oxidation Forms an
Alcohol from an Alkene
 Addition of H-BH2 (from BH3-THF complex) to three
alkenes gives a trialkylborane
 Oxidation with alkaline hydrogen peroxide in water
produces the alcohol derived from the alkene
Orientation in Hydration via
Hydroboration
 Regiochemistry is opposite to Markovnikov orientation
 OH is added to carbon with most H’s
 H and OH add with syn stereochemistry, to the same
face of the alkene (opposite of anti addition)
Mechanism of Hydroboration
 Borane is a Lewis acid
 Alkene is Lewis base
 Transition state involves anionic development on B
 The components of BH3 are added across C=C
 More stable carbocation is also consistent with steric
preferences
8.6 Reduction of Alkenes:
Hydrogenation
 Addition of H-H across C=C
 Reduction in general is addition of H2 or its equivalent
 Requires Pt or Pd as powders on carbon and H2
 Hydrogen is first adsorbed on catalyst
 Reaction is heterogeneous (process is not in solution)
Hydrogen Addition - Selectivity
 Selective for C=C. No reaction with C=O,
C=N
 Polyunsaturated liquid oils become solids
 If one side is blocked, hydrogen adds to
other
Mechanism of Catalytic
Hydrogenation
 Heterogeneous –
reaction between
phases
 Addition of H-H is
syn
8.7 Oxidation of Alkenes:
Epoxidation and Hydroxylation
 Epoxidation results in a cyclic ether with an oxygen
atom
 Stereochemistry of addition is syn
Osmium Tetroxide Catalyzed
Formation of Diols
 Hydroxylation - converts to syn-diol
 Osmium tetroxide, then sodium bisulfite
 Via cyclic osmate di-ester
8.8 Oxidation of Alkenes: Cleavage
to Carbonyl Compounds
 Ozone, O3, adds to alkenes to form molozonide
 Molozonideis converted to ozonide that may be reduced
to obtain ketones and/or aldehydes
Examples of Ozonolysis of
Alkenes
 Used in determination of structure of an unknown alkene
Permangate Oxidation of
Alkenes
 Oxidizing reagents other than ozone also cleave alkenes
 Potassium permanganate (KMnO4) can produce carboxylic acids
and carbon dioxide if H’s are present on C=C
Cleavage of 1,2-diols
 Reaction of a 1,2-diol with periodic (per-iodic) acid,
HIO4 , cleaves the diol into two carbonyl compounds
 Sequence of diol formation with OsO4 followed by
diol cleavage is a good alternative to ozonolysis
8.9 Addition of Carbenes to
Alkenes: Cyclopropane Synthesis
 The carbene functional group is “half of an alkene”
 Carbenes are electronically neutral with six
electrons in the outer shell
 They add symmetrically across double bonds to
form cyclopropanes
Formation of Dichlorocarbene
 Base removes
proton from
chloroform
 Stabilized
carbanion remains
 Unimolecular
elimination of Cl-
gives electron
deficient species,
dichlorocarbene
Reaction of Dichlorocarbene
 Addition of dichlorocarbene is stereospecific cis
Simmons-Smith Reaction
 Equivalent of addition of CH2:
 Reaction of diiodomethane with zinc-copper alloy
produces a carbenoid species
 Forms cyclopropanes by cycloaddition
8.10 Radical Additions to Alkenes:
Chain-Growth Polymers

 A polymer is a very
large molecule
consisting of repeating
units of simpler
molecules, formed by
polymerization
 Alkenes react with
radical catalysts to
undergo radical
polymerization
 Ethylene is
polymerized to
polyethylene, for
example
Free Radical Polymerization:
Initiation
 Initiation - a few radicals are generated by the reaction
of a molecule that readily forms radicals from a
nonradical molecule
 A bond is broken homolytically
Polymerization: Propagation
 Radical from initiation adds to alkene to generate alkene
derived radical
 This radical adds to another alkene, and so on many
times
Polymerization: Termination
 Chain propagation ends when two radical chains combine
 Not controlled specifically but affected by reactivity and
concentration
Other Polymers
 Other alkenes give other common polymers
8.11 Biological Additions of
Radicals to Alkenes
 Severe limitations to the usefulness of radical addition
reactions in the lab
 In contrast to electrophilic additions, reactive
intermediate is not quenched so it reacts again and
again uncontrollably
Biological Reactions
 Biological reactions different from in the
laboratory
 One substrate molecule at a time is present in
the active site of an enzyme
 Biological reactions are more controlled, more
specific than other reactions
Pathway of Biosynthesis of
Prostaglandins
Let’s Work a Problem
Which Reaction would one predict to be faster,
addition of HBr to cyclohexene or to 1-
methylcyclohexene?
Answer
First, draw out both reactants with HBr. What we
should realize at this point is that the formation of
the intermediate that is more stabilized via
carbocation formation is the one that will form
product faster. At this point, we should see that the
intermediate formed via the 3˚ intermediate from 1-
methylcyclohexene (as opposed to the 2˚
carbocation intermediate in the case of
cyclohexene) will proceed faster.