Chap 8 L

CHAPTER 8
Reactions of
Alkenes and Alkynes
Alkene Reactions
Reactions of Alkenes
 Addition of a halogen to give 1,2-dihalide
 Addition of a hypohalous acid to give
halohydrin
 Addition of water to give alcohol
 Addition of hydrogen to give alkane
 Addition of single oxygen to give three-
membered cyclic ether: epoxide
 Addition of two hydroxyl groups to give
1,2-diol
 Addition of a hydrogen halide to give
halide
 Oxidative cleavage to form a carbonyl
compound
 Addition of carbene to form cyclopropane
8-1 Preparing Alkenes: A Preview of
Elimination Reactions
Preparation of alkenes: elimination reactions
Precursors to alkenes
 Biological systems – usually alcohols
 Laboratory – either alcohols or alkyl halides
Alkenes and alcohols are chemically related through addition and
elimination reactions
 Alkenes add H2O to form alcohols
 Alkenes add HX to form halides
 Alcohols eliminate water to form alkenes
 Alcohols eliminate HX to form alkenes
Preparing Alkenes: A Preview of Elimination
Reactions
Dehydrohalogenation
 Loss of HX from alkyl halide
 Usually occurs by reaction of an alkyl halide with a strong
base
Reactions
Dehydration
 Loss of water from an alcohol
 Usually occurs by treatment of an alcohol with a strong acid
Reactions
In biological pathways dehydrations normally take place
on substrates in which –OH is positioned two carbons
away from a carbonyl group
Problem 8.1 8.2
8-2 Halogenation of Alkenes
Halogenation
 Addition reaction of alkenes
 Addition of Br2 and Cl2 to alkenes to yield 1,2-dihalides
Halogenation of Alkenes
Halogenation of cycloalkenes
 Only trans-stereoisomer of dihalide product is formed
 Reaction occurs with anti stereochemistry – the two
halogen atoms come from opposite faces of double-
bond, one from top face and one form bottom face
Reaction occurs through an intermediate bromonium ion
(R2Br+), formed by interaction of the alkene with Br2 and
simultaneous loss of Br-
Bromonium ion shields one side of molecule so that
reaction with Br- ion occurs only from opposite side
Alkene halogenation reaction
 Common laboratory reaction
 Limited primarily to marine organisms in nature
 Carried out by enzymes called haloperoxidases that oxidize
Br- or Cl- ions to a biological equivalent of Br+ or Cl+
Problem 8.3 8.4
8-3 Halohydrins from Alkenes
Halohydrin Formation (electrophilic addition)
 Reaction of alkenes with hypohalous acids HO-Cl or
HO-Br to yield 1,2-halo alcohols called halohydrins
 In marine organisms halohydrin formation is carried out

by haloperoxidases that oxidize Br- or Cl- ions to
corresponding HOBr or HOCl bonded to a metal atom
in the enzyme for subsequent addition to the double
bond of substrate
Halohydrins from Alkenes
 Br2 reacts with
alkene to give
cyclic bromonium
ion intermediate
 Intermediate
bromonium ion is
intercepted by
water nucleophile
 Oxygen loses
proton to give the
neutral halohydrin
product
Problems 8.5
What product would you expect from the reaction of cyclopentene with Br2
and water? Show the stereochemistry.
Problems 8.6
When an unsymmetrically substituted alkene such as propene is treated
with Br2 and water, the major product has the bromine atom bonded to
the less highly substituted carbon atom. Is this Markovnikov or non-
Markovnikov orientation? Explain.
8-4 Hydration of Alkenes
Alkenes undergo an acid catalyzed addition reaction with
water to yield alcohols
 Hydration of ethylene is not of much use in the laboratory
because of the high temperatures often required
 Uncommon in biological pathways

Hydration of Alkenes
Acid-catalyzed hydration of double bond adjacent to carbonyl
group
 More common in biological pathways
 Adjacent carbonyl group required for elimination of water
 Not an electrophilic addition mechanism
Laboratory hydrations of alkenes
 Oxymercuration
 Electrophilic addition of Hg2+ to alkene on treatment with
mercury(II) acetate [(CH3CO2)2Hg, or Hg(OAc) 2] in aqueous
tetrahydrofuran (THF) solvent
 Reaction yields an alcohol
 Product corresponds to Markovnikov regiochemistry (more
highly substituted alcohol formed)
Laboratory hydrations of alkenes
 Oxymercuration
 Closely analogous to halohydrin formation
1. Electrophilic addition of Hg2+ gives cyclic mercurinium ion
2. Nucleophilic addition of water to mercurinium ion followed by
deprotonation gives organomercury product
3. Demercuration (involving radicals) with sodium borohydride
gives alcohol
 Hydroboration/oxidation
 Addition of a B-H bond of borane, BH3, to an alkene
 Occurs in single step
 No carbocation intermediate
 Reaction yields an alcohol
 Syn stereochemistry
 Both C-H and C-B bonds form at the same time and
from the same face of the double-bond
 Product has non-Markovnikov regiochemistry
Alkene Hydroboration
Worked Example 8.1
Predicting the Products of a Hydration Reaction
What products would you obtain from reaction of 2-
methylpent-2-ene with:
(a) BH3, followed by H2O2,OH-

(b) Hg(OAc)2, followed by NaBH4
Worked Example 8.1
Strategy
 Determine type of reaction being carried out
 Two methods of hydration
 Hydroboration/oxidation
 Occurs with syn stereochemistry
 Gives non-Markovnikov alcohol
 Oxymercuration
 Occurs with anti stereochemistry
 Gives the Markovnikov alcohol
Worked Example 8.1
Solution
Worked Example 8.2
Synthesizing an Alcohol
How might you prepare the following alcohol?
Worked Example 8.2
Strategy
 To synthesize a specific target molecule work backwards
 Target molecule is a secondary alcohol
 –OH bearing carbon in the product must have been a
double-bond carbon in the alkene reactant
 Devise a method and select possible reactants
Worked Example 8.2
Solution
Note: 4-methylhex-2-ene has a disubstituted double and would

probably give a mixture of two alcohol products with either
hydration method
Prob 8.7
Problem 8.8
8-5 Reduction of Alkenes: Hydrogenation
Hydrogenation
 Addition reaction process by which alkenes are
reduced to alkanes
Reduction
 Increases electron density on carbon by
 Forming C-H
 Breaking C-O, C-N, or C-X bond
Reduction of Alkenes: Hydrogenation
Catalytic hydrogenation
 A heterogeneous process that takes place on the surface of
insoluble catalyst particles
 Common catalysts for alkene hydrogenation:
 Platinum – PtO2 (Adams’ Catalyst)
 Palladium – very fine powder supported on inert material such as
charcoal (Pd/C)
 Occurs with syn stereochemistry
 Both hydrogens add to the double bond from the same side
Mechanism of catalytic
hydrogenation
Other unsaturated functional groups are much less reactive
toward catalytic hydrogenation under normal reaction
conditions.
Hydrogenation
 Unsaturated vegetable oils reduced to produce
saturated fats used in margarine and cooking
products
 Vegetable oils
 Triesters of glycerol, HOCH2CH(OH)CH2OH, with
three long-chain carboxylic acids called fatty acids
 Fatty acids
 Polyunsaturated carboxylic acids containing long
hydrocarbon chains
 Double bonds have cis stereochemistry
Catalytic hydrogenation of polyunsaturated fats
Catalytic hydrogenation of polyunsaturated fats
 Complete hydrogenation leads to saturated fatty acids
 Incomplete hydrogenation results in isomerized trans fats that
release trans fatty acids upon digestion, increasing blood cholesterol
levels
Biological hydrogenation (reduction) of isolated double bonds

 Double bond must be adjacent to a carbonyl group
 The reduction of isolated double bonds is rare in biological
pathways
 Process occurs in two steps
1. NADPH (coenzyme reduced nicotinamide adenine dinucleotide
phosphate) adds hydride ion (H:-) to double bond to produce an
ion
2. Protonation of an anion by acid HA leading to an overall addition
of H2
Biological reduction of double bond in trans-Crotonyl
ACP leads to the formation of Butyryl ACP
8-6 Oxidation of Alkenes: Epoxidation
Oxidation
 A reaction that results in a loss of electron
density by carbon
 Decreases electron density on carbon by:
 Breaking C-H bond
 Forming C-O, C-N, or C-X bond
Note: oxidation often adds oxygen; reduction often adds hydrogen

Oxidation of Alkenes: Epoxidation
Alkenes on treatment with a peroxyacid, RCO3H, are
oxidized to give epoxides
Epoxide (oxiranes)
 Cyclic ethers with an oxygen atom in a three-membered
ring
Synthesis of epoxides from alkenes
 Peroxyacid transfers oxygen to alkene
 Both C-O bonds form on the same face of the double
 One step mechanism
 No intermediates
Synthesis of epoxides from halohydrins
 Preparation of halohydrin through electrophilic addition of
HO-X to alkene
 Treatment of halohydrin with base deprotonates OH
 O- nucleophile reacts with C-Cl electrophile substituting C-
O bond for C-Cl bond
 Cl- eliminated yielding the epoxide
Epoxides in biological
pathways:
 Epoxides prepared
from alkenes as
intermediates
 Peroxyacids are not
involved
 FADH2 used in
biological reactions
 Conversion of squalene
into 2,3- oxidosqualene;
a key step in the
biosynthesis of steroids
Problem 8.11
8-7 Oxidation of Alkenes: Hydroxylation
Hydroxylation
 The addition of an –OH group to each of the two double-bond
carbons
 Two step alkene epoxidation-hydrolysis process:
1. Epoxidation
2. Hydration
 Epoxides undergo an acid-catalyzed reaction with water to
give corresponding 1,2-dialcohol, or diol
Oxidation of Alkenes: Hydroxylation
Acid catalyzed epoxide-opening takes place by:
1. Protonation of the epoxide increasing the electrophilicity of
carbon
2. Nucleophilic addition of water followed by deprotonation
 Trans-1,2-diol formed
Epoxides in biological pathways
 Epoxide hydrolyses are common
 Pathways animals use to detoxify harmful substances
 Benzo[a]pyrene
 Carcinogenic substance found in cigarette smoke, chimney
soot, and barbecued meat
 Detoxified by conversion to a diol epoxide
Hydroxylation in the Laboratory
 Carried out directly by oxidation of an alkene with osmium
tetroxide, OsO4
 Catalytic amount of OsO4 used in the presence of stoichiometric
amount of N-methylmorpholine N-oxide (NMO)
 No carbocation intermediate
 Occurs through cyclic osmate intermediate
Hydroxylation in the Laboratory
 OsO4 is very expensive and toxic
 Laboratory hydroxylation usually done in presence of a
stoichiometric amount of N-methyl-morpholine-N-oxide, NMO, to
reoxidize OsO4
Problem 8.12
8-8 Oxidation of Alkenes: Cleavage to
Carbonyl Compounds
Ozone (O3) is useful double-bond cleavage reagent
 Ozone is generated by passing a stream of oxygen through a high-
voltage electrical discharge
 Ozone adds rapidly to C=C bond at low temperature to give molozonide
which spontaneously rearranges to ozonide
 Ozonide is treated with reducing agent to convert it to carbonyl
compounds
Oxidation of Alkenes: Cleavage to Carbonyl
Compounds
 If tetrasubstituted double bond is ozonized, two ketone fragments result
 If a carbon of the alkene is bonded to hydrogen, ozonolysis will cleave
the double bond to yield an aldehyde
Compounds
Potassium permanganate (KMnO4) in neutral or acidic
solution cleaves alkenes to give carbonyl-containing
products
 If a carbon of the alkene is bonded to hydrogen a carboxylic acid is
produced
 If a carbon of the alkene is bonded to two hydrogens, CO2 is formed
Compounds
Alkenes are also cleaved by hydroxylation to a 1,2-diol
followed by treatment with periodic acid, HIO4.
 If the two –OH groups of the diol are in an open chain, two carbonyl
compounds result
 If the two –OH groups of the diol are on a ring, a single, open-chain
dicarbonyl compound is formed
Worked Example 8.3
Predicting the Reactant in an Ozonolysis
Reaction
What alkene would yield a mixture of cyclopentanone
and propanal on treatment with ozone followed by
reduction with zinc?
Worked Example 8.3
Reaction
Strategy
 Reaction of alkene with ozone, followed by reduction with
zinc, cleaves the carbon-carbon double bond and gives two
carbonyl-containing fragments
 Working backward, the alkene precursor can be found by
removing the oxygen from each product and joining the two
carbon atoms to form a double bond
Worked Example 8.3
Reaction
Solution
Problem 8.13
8-9 Addition of Carbenes to Alkenes:
Cyclopropane Synthesis
A carbene, R2C:, is a neutral molecule containing a
divalent carbon with only six electrons in its valence
shell
 One simple method for generating dichlorocarbene is by
treatment of CHCl3 with KOH
 Carbenes behave as electrophiles, adding to alkenes to
yield cyclopropanes
Addition of Carbenes to Alkenes: Cyclopropane
Synthesis
Mechanism of the formation of dichlorocarbene
Synthesis
 Dichlorocarbene carbon atom is sp2-hybridized with a
vacant p orbital extending above and below the plane of the
three atoms with an unshared pair of electrons occupying
the third sp2 lobe
Synthesis
 Reaction of dichlorocarbene with an alkene results in a
dichlorocyclopropane
 Addition is stereospecific, meaning that only a single
stereoisomer is formed as product
Problem 8.15
 What product would you expect from the following
reaction?
8-10 Radical Addition to Alkenes: Alkene
Polymers
Radicals add to alkene double bonds
 Radicals remove one electron from double bond
 One electron left behind yielding a new radical
Polymer
 A large molecule built up by repetitive bonding together of
many smaller molecules called monomers
 Cellulose (glucose polymer)
Radical Addition to Alkenes: Alkene Polymers
 Proteins (amino acid polymers)
 Nucleic acid (nucleotide polymer)

Simplest polymerization
 Result when an alkene is treated with a small
amount of a radical as an initiator
Initiation
1. Small amount of benzoyl peroxide catalyst is heated breaking
weak O-O bonds and yielding radicals
2. Benzoyloxy radical adds to C=C bond of ethylene forming a
carbon radical
3. a) One electron from C=C bond pairs up with electron of
benzoyloxy radical to form C-O bond
b) Other electron remains on carbon (a carbon-centered
radical)
Propagation
 Polymerization occurs when the carbon radical adds to
another ethylene molecule to yield another radical
Termination
 Chain process ends by a reaction that consumes a radical
 Combination of two growing chains
2-R–CH2CH2• → R–CH2CH2CH2CH2–R
Vinyl monomers
 Substituted ethylene
 Undergo polymerization to yield polymer with substituted
groups regularly spaced in alternating carbon atom long chain
 Polypropylene
 Styrene
Polymerization of unsymmetrically substituted vinyl
monomers
Propylene or Styrene
 Radical addition steps can take place at either end of the
double bond to yield:
 A primary radical intermediate (RCH2.)
 A secondary radical (R2CH.)
 Similar to electrophilic addition reaction
 More highly substituted, secondary radical is formed
Worked Example 8.4
Predicting the Structure of a Polymer
Show the structure of poly(vinyl chloride), a polymer

made from H2C=CHCl, by drawing several
repeating units
Worked Example 8.4
Strategy
 Mentally break the carbon-carbon double bond in the
monomer unit, and form single bonds by connecting
numerous units together
Worked Example 8.4
Solution
The general structure of poly(vinyl chloride) is

8-11 Biological Additions of Radicals to
Alkenes
Radical vs. Electrophilic Addition Reactions
Electrophilic addition
 Reaction occurs once
 Intermediate is then quenched and reaction stops.
Biological Additions of Radicals to Alkenes
Radical vs. Electrophilic Addition Reactions
Radical addition
 Difficult to control
 Limited use in the laboratory
 Reaction intermediate is not quenched so reaction continues
Biological Reactions
 Only one substrate molecule at a time is present in
the active site of the enzyme where the reaction
occurs (necessary reactant groups nearby)
 More controlled
 More common than laboratory radical reactions
Step 1 – formation of a carbon radical at C13 of arachidonic acid
by iron-oxy radical
Step 2 – C13 radical reacts with O2 at C11 through resonance
form
Step 3 – Oxygen radical reacts with C8-C9 double bond
forming carbon radical at C8
Step 4 – C8 radical adds to C12-C13 double bond forming
carbon radical at C13
Step 5 – Resonance form of C13 carbon radical adds at C15
to a second O2 molecule
Step 6 – Reduction of O-O bond gives prostaglandin H2
8-12 Conjugated Dienes
Sites of unsaturation
 Many compounds have numerous sites of unsaturation
 If sites are well separated in molecule they react independently
 If sites are close together they may interact with one another
Conjugated double bonds
 Double bonds that alternate with single bonds
Conjugated Dienes
Heats of Hydrogenation
Conjugated dienes are more stable than nonconjugated
dienes
Conjugated Dienes
Buta-1,3-diene is approximately 16 kJ/mol (3.8 kcal/mol)
more stable than expected
Conjugated Dienes
Explanations for conjugated diene stability
1) Valence Bond Theory
 Stability due to orbital hybridization
 Alkanes
 C-C single bonds
 σ overlap of sp3 orbitals on both carbons
 Conjugated dienes
 σ overlap of sp2 orbitals (shorter and stronger)
Conjugated Dienes
2. Molecular Orbital Theory
 Interaction between the p orbitals of the two double
bonds
 Two p orbitals combine to form two p molecular orbitals
 Both electrons occupy the low-energy bonding orbital
leading to a net lowering of energy and formation of a
stable bond
Conjugated Dienes
 Four adjacent p atomic orbitals of a conjugated diene
Four molecular orbitals of buta-1,3-diene

Conjugated Dienes
In a conjugated diene, the lowest p MO (y1) has a
favorable bonding interaction between C2 and C3
that is absent in the nonconjugated diene
 Certain amount of double-bond character to C2-C3 bond,
making that bond stronger and shorter that a typical single
bond
8-13 Reactions of Conjugated Dienes
Conjugated dienes
 Undergo electrophilic addition reactions readily
 Mixture of products obtained
 Addition of HBr to buta-1,3-diene yields mixture of
two addition products
Reactions of Conjugated Dienes
Allylic carbocation is an intermediate
 Allylic means next to a double bond
 When buta-1,3-diene reacts with H+ electrophile two
carbocation intermediates are possible:
1. A primary carbocation
2. A secondary allylic carbocation (stabilized by resonance
between two forms)
 Secondary allylic carbocation is more stable and forms faster
than the nonallylic carbocation
Reactions of Conjugated Dienes
Allylic carbocation reacts with Br- to complete the
electrophilic addition
 Reaction can occur at C1 or C3
 Both carbons share positive charge
 Mixture of 1,2- and 1,4-addition products results
Worked Example 8.5
Predicting the Products of Electrophilic Addition to
a Conjugated Diene
Give the structures of the likely products from reaction

of 1 equivalent of HCl with 2-methylcyclohexa-1,3-
diene. Show both 1,2- and 1,4- adducts.
Worked Example 8.5
a Conjugated Diene
Strategy
Electrophilic addition of HCl to a conjugated diene involves the
formation of allylic carbocation intermediates
First –
 Protonate the two ends of the diene
 Draw resonance forms of the two allylic carbocations that
result
Second –
 Allow each resonance form to react with Cl- to generate four
possible products
Worked Example 8.5
a Conjugated Diene
Solution
Problem 8.18
 Give the structures of both 1,2- and 1,4-adducts
resulting from reaction of 1 equivalent of HCl with
penta-1,3-diene.
8-14 The Diels-Alder Cycloaddition Reaction
Conjugated dienes undergo reactions with alkenes

to yield substituted cyclohexene products
The Diels-Alder Cycloaddition Reaction
Diels-Alder cycloaddition reaction is a Pericyclic
reaction
 Pericyclic reactions take place in a single step by a cyclic
redistribution of bonding electrons
 In the Diels-Alder transition state, the two alkene carbons
and carbons 1 and 4 of the diene rehybridize from sp2 to
sp3 to form two new single bonds, while carbons 2 and 3
of the diene remain sp2 hybridized to from the new double
bond in the cyclohexene product
 Diels-Alder cycloaddition reaction occurs most rapidly if
the alkene component, or dienophile (“diene lover”), has
an electron-withdrawing substituent group
 The double or triple bond of the dienophile is adjacent to the
positively polarized carbon of an electron-withdrawing
substituent
 The double-bond carbons in these substances are
substantially less electron-rich than the carbons in ethylene
 Diels-Alder reaction is stereospecific
 Reactant stereochemistry is also maintained
 Diene must adopt an s-cis conformation, meaning “cis-like”
about the single bond
 Some dienes cannot adopt the s-cis conformation and cannot
undergo Diels-Alder cycloaddition reactions
 Some dienes are fixed in the s-cis conformation and are
highly reactive in Diels-Alder cycloaddition reactions
 A few biological Diels-Alder reactions are known
 Biosynthesis of lovastatin involves an intramolecular Diels-
Alder reaction in the key step
Worked Example 8.6
Predicting the Product of a Diels-Alder Reaction
Predict the product of the following Diels-Alder reaction

Worked Example 8.6
Strategy
Draw the diene so that the ends of the two double

bonds are near the dienophile double bond. Then
form two single bonds between the partners,
convert the three double bonds into single bonds,
and convert the former single bond of the diene into
a double bond. Because the dienophile double
bond is cis to begin with, the two attached
hydrogens must remain cis in the product
Worked Example 8.6
Solution
Problem 8.21
 Predict the product of the following Diels-Alder
reaction:
Problem 8.22
 Which of the following alkenes would you expect to
be good Diels-Alder dienophiles?
Problem 8.23
 Which of the following dienes have an s-cis
conformation, and which have an s-trans
conformation?
8.15 Reactions of Alkynes
Alkyne Addition Reactions
 Alkynes behave similarly to alkenes
 Alkynes are less reactive than alkenes
 Various reactions can often be stopped at the
monoaddition stage if one molar equivalent of
reagent is used
Reactions of Alkynes
Problem 8.25
Mercury(II)-Catalyzed Hydration of Alkynes
 Alkynes are resistant to reaction with aqueous acid
 Undergo hydration readily in the presence of
mercury(II) sulfate as a Lewis acid catalyst
 Reaction occurs with Markovnikov regiochemistry
Mercury(II)-Catalyzed Hydration of Alkynes
 Isolated product is typically a ketone
 Ketone formed by keto-enol tautomerism
Mechanism of Mercury(II)-Catalyzed Hydration of Alkynes
Mechanism of Mercury(II)-Catalyzed Hydration of Alkynes
 Unsymmetrically substituted internal alkynes produce a
mixture of both possible ketones when hydrated
 Terminal alkyne for a methyl ketone
Problem 8.26
Alkyne acidity
 Terminal alkynes (RC≡CH) are relatively acidic
 RC≡CH treated with a strong base NaNH2
 Terminal hydrogen is removed forming and acetylide anion
Alkyne acidity
 BrØ nsted-Lowry Acid
 A substance that donates H+
 Acidity order:
 Established by measuring acid dissociation constants and
expressing the results as pKa values
Low pKa = strong acid
High pKa = weak acid
 Amide ion (NH2-), the conjugated base of ammonia (pKa = 35),
is often used to deprotonate terminal alkynes
Terminal alkynes more acidic than alkenes or alkanes
 Acetylide ions are more stable than vinylic (alkenyl) or alkyl ions
 Increasing s character of hybridized carbon atom places negative
charge closer to carbon nucleus and stabilizes the anion
 Acetylide anion has sp-hybridized carbon
 Presence of negative charge and an unshared electron pair on
carbon makes acetylide anions strongly nucleophilic
 Nucleophilic substitutions not limited to acetylene

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CHAPTER 8

 In marine organisms halohydrin formation is carried out

 Uncommon in biological pathways

(a) BH3, followed by H2O2,OH-

Note: 4-methylhex-2-ene has a disubstituted double and would

Biological hydrogenation (reduction) of isolated double bonds

Note: oxidation often adds oxygen; reduction often adds hydrogen

 Nucleic acid (nucleotide polymer)

Show the structure of poly(vinyl chloride), a polymer

The general structure of poly(vinyl chloride) is

Four molecular orbitals of buta-1,3-diene

Give the structures of the likely products from reaction

Conjugated dienes undergo reactions with alkenes

Predict the product of the following Diels-Alder reaction

Draw the diene so that the ends of the two double

 Nucleophilic substitutions not limited to acetylene

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