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Chapter V Alkenes 2
Chapter V Alkenes 2
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5.15 Preparation of Alkenes: A Preview of
Elimination Reactions
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A Preview of Elimination Reactions
Alkenes are commonly made by elimination of HX
from alkyl halide: (dehydrohalogenation); using
heat and KOH
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A Preview of Elimination Reactions
elimination of H-OH from an alcohol (dehydration); requires
strong acids (sulfuric acid, 50 ºC)
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Dehydration in the Biosynthesis of Fats:
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Prac. Prob. 5.4: How many alkene
products from dehydration?
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Solution:
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5.16 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 too unreactive
Cl2 reacts as “Cl+ Cl-”; Br2 is similar
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Possible Mechanism (by analogy with HX)?
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BUT: Addition of Br2 to Cyclopentene
Addition is exclusively trans (stereospecific)
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Mechanism of Bromine Addition
Br+ adds to an alkene producing a cyclic cation: a
bromonium ion, in which bromine shares charge with
carbon
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Mechanism of Bromine Addition
Since the Br blocks one face, one must get anti
(trans) addition
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Addition of Br2 to Cyclopentene
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The Reality of Bromonium Ions
Bromonium were postulated more than 60 years ago to
expain the stereochemical course of the addition (to give the
trans-dibromide from a cyclic alkene
George Olah (Nobel Prize 1994) showed that bromonium ions
are stable in liquid SO2 with SbF5 and can be studied directly
by nuclear magnetic resonance spectroscopy
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5.17 Halohydrin Formation
This is formally the addition of HO-X to an
alkene (with “+OH” as the electrophile) to
give a 1,2-halo alcohol, called a halohydrin
The actual reagent is the dihalogen (Br2 or
Cl2 with water in an organic solvent)
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Mechanism:
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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
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5.18 Addition of Water to Alkenes:
Hydration
Hydration of an alkene is the addition of H-OH
to to give an alcohol
Acid catalysts are used in high temperature
industrial processes: ethylene is converted to
ethanol
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Mechanism:
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Oxymercuration/Demercuration
For laboratory-scale hydration of an alkene under mild
conditions (room temperature, neutral pH)
Use mercuric acetate in THF followed by sodium
borohydride reduction
Markovnikov orientation
◼ via mercurinium ion
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Mechanism: mercurinium ion
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Markovnikov Orientation:
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Problem 5.13: products of
oxymercuration?
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Problem 5.14: Which alkene?
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5.19 Addition of Water to Alkenes:
Hydroboration
H. C. Brown (1959) discovered hydroboration
Borane (BH3) is electron deficient: a Lewis acid
Borane adds to an alkene to give an organoborane
This is oxidized to the alcohol by hydrogen peroxide
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BH3 is a Lewis Acid
Six electrons in outer shell
Coordinates to oxygen electron pairs in
ethers
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Hydroboration-Oxidation Forms an
Alcohol from an Alkene
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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)
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Mechanism of
Hydroboration
Borane is a Lewis acid
Alkene (p-bond) is Lewis
base
Transition state involves
anionic development on B
The components of BH3 are
across C=C
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Hydroboration: Orientation in
Addition Step
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Steric Preference
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Two Possible Orientations: Practice
Problem 7.1
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Practice Problem 5.5: Which alkene?
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Which alkene would work best?
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This one: anti-Markovnikov
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Problem 5.15: Major Products?
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Problem 5.16: Which Alkenes?
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5.20 Addition of Carbenes to Alkenes
Carbenes are electrically neutral with
six electrons in the outer shell
They add symmetrically across double
bonds to form cyclopropanes
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Formation of Dichlorocarbene
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Dichlorocarbene Structure
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Reaction of Dichlorocarbene
Addition of dichlorocarbene is stereospecific cis
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Simmons-Smith Reaction
Equivalent to addition of CH2:
Reaction of diiodomethane with zinc-copper
alloy produces a carbenoid species
Forms cyclopropanes by cycloaddition
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Problem 5.17: Major products?
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5.21: Catalytic Hydrogenation
Addition of H-H across C=C
Reduction in general is addition of H2 or its equivalent
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5.21 Reduction of Alkenes:
Hydrogenation
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Syn Addition
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Mechanism
of Catalytic
Hydrogen-
ation
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Steric effect:
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Hydrogen Addition- Selectivity
With Pt or Pd catalysts, selective for C=C.
No reaction with C=O, C=N
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Hydrogen Addition- Selectivity
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Problem 5.18: Major Products?
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Solid Fats from Liquid Oils
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5.22 Oxidation of Alkenes: Epoxidation
Oxidation: decreases electron density on
carbon by:
◼ Adding –O, -N, or –X
◼ Removing –H
Epoxidation: forming a cyclic ether:
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Mechanism (schematic):
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Older method (from halohydrins):
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Diols from epoxides:
Anti-addition:
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Oxidation of Alkenes: Hydroxylation
Hydroxylation adds OH to each end of C=C
Oxidizing agent is osmium tetroxide
Stereochemistry of addition is syn
Product is a 1,2-dialcohol or diol (also
called a glycol)
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Formation of Diols via Osmium Tetroxide
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Problem 5.19: Which Alkene?
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Polymers:
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Polymers:
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Alkene Polymers:
Adding double bonds together, usually
head-to-tail, forms synthetic polymers like
polyethylene:
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Alkene Polymers by Radical Reactions:
Initiation:
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Alkene Polymers by Radical Reactions:
Propagation:
Termination:
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Other “Vinyl” Polymers:
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More Examples:
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Natural Rubber:
Made from the sap of a number of plants,
principally Hevea brasiliensis
Crude rubber (latex) is Z-polyisoprene
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5.23 Biological Alkene Addition
Reactions
Living organisms convert organic
molecules using enzymes as catalysts
Many reactions are similar to organic
chemistry conversions, except they occur
in neutral aqueous solution at 37oC
Usually very specific for reactant and
stereochemistry
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In the Laboratory:
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Prostaglandin
Biosynthesis:
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