MODULE 2
CHE 214
Lecture 6B
The Chemistry of
Alkenes and Alkynes
Alkene Structure and Reactivity
DEPARTMENT OF CHEMICAL ENGINEERING
UNIVERSITY OF SANTO TOMAS
MANILA, PHILIPPINES
Intended Learning Outcomes
•Predict the mechanism and outcome of addition
reactions of alkenes given the conditions and
starting materials.
UST DEPARTMENT OF CHEMICAL ENGINEERING (L.LAPITAN 2014) 2
This PowerPoint presentation is developed based
from the following references:
Mc Murry, J.E. Organic Chemistry 9th edition
Mc Murry, J.E. Foundations of Organic Chemistry
Solomons and Frhyles Organic Chemistry
UST DEPARTMENT OF CHEMICAL ENGINEERING (L.LAPITAN 2014) 3
Diverse Reactions of Alkenes
Alkenes react with many electrophiles to give useful
products by addition (often through special reagents)
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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)
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Preparation of Alkenes: A Preview
of Elimination Reactions
❖ Dehydrohalogenation of Alkyl Halides
H
H H H H
base
C C
H -HX
X H H
H
❖ Dehydration of Alcohols
H
H H H+, heat H H
C C
H OH -HOH H H
H
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2. Addition of Halogens to
Alkenes
Bromine and chlorine add to alkenes to give 1,2-dihalides, an
industrially important process
F2 is too reactive and I2 does not add
Cl2 reacts as Cl+ Cl-
◦ Br2 is similar
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Addition of Br2 to Cyclopentene
Addition is exclusively trans
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Mechanism of Bromine Addition
Br+ adds to an alkene producing a cyclic ion
Bromonium ion, bromine shares charge with carbon
◦ Gives trans addition
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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
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)
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Mechanism
H2O
Br Br +
H2O H3C
H3C H
+Br
OH H
CH 3 Br
H3C H
Br
Ch. 8 - 12 UST DEPARTMENT OF CHEMICAL ENGINEERING (L.LAPITAN 2014)
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
Dimethyl sulfoxide (DMSO) is a
widely used solvent that is miscible
with water and a wide range of
organic solvents.
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4. Hydration of Alkenes: Acid catalyzed
hydration
▪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
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Mechanism
H
H O H H 2O
H H
slow fast
(step 1) (step 2)
O
more stable H H
3o cation
fast H 2O
(step 3)
H H
H O H +
Ch. 8 - 15
OH
UST DEPARTMENT OF CHEMICAL ENGINEERING (L.LAPITAN 2014)
5. Hydration of Alkenes:
Oxymercuration-Demercuration
For laboratory-scale hydration of an alkene
Use mercuric acetate in THF followed by sodium
borohydride Tetrahydrofuran (THF), or oxolane, is an organic
compound with the formula (CH2)4O. The
Markovnikov orientation compound is classified as heterocyclic compound,
specifically a cyclic ether. It is a colorless, water-
miscible organic liquid with low viscosity. It is
◦ via mercurinium ion mainly used as a precursor to polymers.
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Mechanism of Oxymercuration
❖ Does not undergo a “free carbocation”
−
OAc
+Hg +
HgOAc
OAc
AcO + +
H 2O
HgOAc HgOAc
H 2O
HO O H
H
Ch. 8 - 17 UST DEPARTMENT OF CHEMICAL ENGINEERING (L.LAPITAN 2014)
❖ Stereochemistry
● Usually anti-addition
H 2O
Hg(OAc) 2 +
THF-H2O H3C
H3C H +Hg(OAc)
OH H
CH3 Hg(OAc)
Ch. 8 - 18 UST DEPARTMENT OF CHEMICAL ENGINEERING (L.LAPITAN 2014)
6. Hydration of Alkenes: Hydroboration -
Oxidation
▪ Borane (BH3) is electron deficient
▪ Borane adds to an alkene to give an
organoborane
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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
▪ Lewis acids accept an electron pair.
▪ Lewis Acids are Electrophilic, meaning that they are electron-attracting.
▪Alkene is Lewis base
▪ Lewis Bases donate an electron pair.
▪ Lewis Bases are Nucleophilic meaning that they “attack” a positive charge
with their lone pair.
▪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
Mechanism of Hydroboration
Summary of Alkene Hydration
Methods
Summary of Methods for Converting Alkene to Alcohol
Occurrence of
Reaction Regiochemistry Stereochemistry Rearrangements
Acid-catalyzed Markovnikov Not controlled Frequent
hydration addition
Oxymercuration- Markovnikov Not controlled Seldom
demercuration addition
Hydroboration- Anti-Markovnikov Stereospecific: Seldom
oxidation addition syn addition of
H – and –OH
Ch. 8 - 23 UST DEPARTMENT OF CHEMICAL ENGINEERING (L.LAPITAN 2014)
Examples via H
1,2-hydride
H shift
H+ OH with
H rearrangement
H2O
OH
1. Hg(OAc)2, THF-H2O H
2. NaBH4, OH−
Markovnikov addition of H2O
without rearrangement
H anti-Markovni-
1. BH3-THF OH kov, syn addition
2. H2O2, OH−
of H2O
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7. 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)
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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
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Mechanism of Catalytic
Hydrogenation
Heterogeneous – reaction
between phases
Addition of H-H is syn
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8. Oxidation of Alkenes: Epoxidation and
Hydroxylation
▪Epoxidation results in a cyclic ether with an oxygen atom
▪Stereochemistry of addition is syn
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9. Osmium Tetroxide Catalyzed
Formation of Diols
▪Hydroxylation - converts to syn-diol
▪Osmium tetroxide, then sodium bisulfite
▪Via cyclic osmate di-ester
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10. Oxidation of Alkenes: Cleavage to
Carbonyl Compounds
Ozone, O3, adds to alkenes to form
molozonide
Molozonide is converted to ozonide
that may be reduced to obtain ketones
and/or aldehydes
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Examples of Ozonolysis of
Alkenes
Used in determination of structure of an unknown alkene
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Examples of Ozonolysis of
Alkenes
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11. Permanganate
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
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Cleavage of 1,2-diols
▪Reaction of a 1,2-
diol with 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
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12. 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 https://www.britannica.com/science/carbene
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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
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13. Simmons-Smith Reaction
▪Equivalent of addition of CH2:
▪Reaction of diiodomethane with zinc-copper alloy produces a
carbenoid species
▪Forms cyclopropanes by cycloaddition
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