ORGANIC CHEMISTRY

OCHE220203
Lecturer: Dat P. Nguyen, Ph.D
Email: datnp@hcmute.edu.vn
Department of Chemical Technology
Faculty of Chemical and Food Technology 1
CHAPTER 6
ALKENES

2
 CONTENTS

1. Preparation of Alkenes
1.1. Elimination Reactions
1.2. Hydrogenation of Alkynes
2. Reactivity of Alkenes
2.1. Electrophilic Addition
2.2. Oxidation of Alkenes
2.3. Polymerization of Alkenes

3
 1. Preparation of Alkenes

Aldehydes/
Alkynes
Ketones

hydrogenation Wittig reaction

Halide/
Alcoholelimination elimination Amines

Alkenes

4
 1. Preparation of Alkenes
1.1. Elimination Reactions

Dehydration of Alcohols

5
 1. Preparation of Alkenes
1.1. Elimination Reactions

Unimolecular Elimination (E1)

Mechanism

• Reaction rate only depends on 1 compound (substrate)

• Reaction has 2 steps

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 1. Preparation of Alkenes
1.1. Elimination Reactions

Unimolecular Elimination (E1)

Mechanism – First step

Highest activation energy

→ 1st step is the rate determining step (RDS)
7
 1. Preparation of Alkenes
1.1. Elimination Reactions

Unimolecular Elimination (E1)

Mechanism – Second step

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 1. Preparation of Alkenes
1.1. Elimination Reactions

Unimolecular Elimination (E1)

Selectivity

Zaitsev product Hofmann product

More substituted C=C double bond → major product

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Elimination Reaction - Practice

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 1. Preparation of Alkenes
1.1. Elimination Reactions

Bimolecular Elimination (E2)

Mechanism

• Reaction rate depends on 2 compounds (substrate and base)

• Reaction has 1 step

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 1. Preparation of Alkenes
1.1. Elimination Reactions

Bimolecular Elimination (E2)

Mechanism
Leaving group must be anti to
the hydrogen being removed

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 1. Preparation of Alkenes
1.1. Elimination Reactions

Bimolecular Elimination (E2)

Selectivity

More substituted C=C double bond → major product

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 1. Preparation of Alkenes
1.1. Elimination Reactions

Bimolecular Elimination (E2)

Selectivity

More substituted C=C double bond → major product

14
 1. Preparation of Alkenes
1.1. Elimination Reactions

Bimolecular Elimination (E2)

Selectivity

Conjugated product → major product

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 1. Preparation of Alkenes
1.1. Elimination Reactions

Bimolecular Elimination (E2)

Normal base: NaOH, NaOEt or NaOMe

Zaitsev product
Bulky base:

Hofmann product
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 1. Preparation of Alkenes
1.1. Elimination Reactions

Bimolecular Elimination (E2)

Normal base
NaOH, NaOEt or NaOMe
Zaitsev product

Bulky base

Hofmann product

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Elimination Reaction - Practice

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Elimination Reaction - Practice

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 1. Preparation of Alkenes
1.1. Elimination Reactions

E1 vs. E2
E1 E2
Mechanism • First order (depends only on • Second order (depends on substrate
and Kinetics substrate) and base)
• 2-step mechanism (first step • 1-step mechanism
is RDS) • Does not form intermediate
• Forms carbocation
intermediate (3° > 2° > 1°)

Leaving Better leaving group → faster Better leaving group → faster reaction
group reaction
Strong base Not required Required
• Stronger base → faster reaction
• Bulky base → remove outer hydrogen

Solvent Favored by polar protic solvent Favored by polar aprotic solvent (e.g.,
(e.g., EtOH, MeOH, AcOH) MeCN, DMSO, DMF)

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 1. Preparation of Alkenes
1.1. Elimination Reactions

Hofmann Elimination (see Chapter 15)

• Form less substituted C=C double bond

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1. Preparation of Alkenes
1.2. Hydrogenation of Alkynes

Lindlar’s catalyst

or Ni2B (P-2 nickel)

22
 2. Reactivity of Alkenes

Hydrohalogenation +HX
Hydration +H2O
Hydroboration +BH3
Electrophilic Addition
(AE)
Hydrogenation +H2

Halogenation +X2
Alkenes Halohydrin formation +X2 + H2O

Epoxidation form epoxide

Dihydroxylation add 2 -OH

Oxidation
Ozonolysis +O3

Strong oxidation
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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

Electrophilic Addition

Mechanism

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

Mechanism

The 1st step is the RDS

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.1. Hydrohalogenation

Mechanism

X=H
Y = halogen

Y can also be CN- → Hydrocyanation

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.1. Hydrohalogenation
Selectivity

Markovnikov
product

Markovnikov’s rule: The AE reaction will proceed through

the most stable carbocation.
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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.1. Hydrohalogenation
Rearrangement of carbocation

Carbocation will rearrange

to more stable carbocation
if possible.

2 types of rearrangements:
• 1,2-hydride shift
• 1,2-alkyl shift

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.1. Hydrohalogenation
Rearrangement of carbocation

Carbocation will rearrange

to more stable carbocation
if possible.

2 types of rearrangements:
• 1,2-hydride shift
• 1,2-alkyl shift

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.1. Hydrohalogenation
Rearrangement of carbocation – Ring expansion
• 4-membered ring to 5-membered ring

• 5-membered ring to 6-membered ring

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.1. Hydrohalogenation

Nucleophile can attack

from both sides of the
carbocation
→ racemic mixture

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Hydrohalogenation - Practice

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.1. Hydrohalogenation

To get anti-Markovnikov product → Use HBr/peroxide

anti-Markovnikov

• Mechanism of this reaction is not Electrophilic Addition (AE),

but Radical Addition (AR)
• Radical Addition only occurs with HBr, not HF, HCl, HI

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.1. Hydrohalogenation
Hydrobromination with peroxide – Mechanism

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.2. Hydration

Mechanism

Step 1

Step 2

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.2. Hydration

Carbocation rearrangement can also occur in hydration

reaction

To avoid rearrangement, using Hg(OAc)2 and NaBH4

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Hydration - Practice

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.3. Hydroboration

Syn addition
H and OH are on
the same side

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.3. Hydroboration

Step 1:
Hydroboration

• This step can be repeated 3 • To avoid multiple additions

times until all 3 H of borane are of alkyl groups, other borane
replaced by alkyl groups reagents can be used:

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.3. Hydroboration
Mechanism

Step 2: Oxidation of
alkyl borane
alkyl borane
• All C-B bonds are
oxidized to C-O-B
• Borate is hydrolyzed
to boric acid and
alcohol

alcohol
borate boric acid
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 Hydroboration - Practice

OH bonds to less syn addition

substituted C

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Hydroboration - Practice

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Hydroboration - Practice

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.4. Hydrogenation

Metal catalyst

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.4. Hydrogenation

Stereospecificity

syn addition

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Hydrogenation - Practice

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Hydrogenation - Practice

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.5. Halogenation

Mechanism

If cyclic ion is
asymmetric →
Nucleophile add to
less substituted
carbon

anti addition 48
Halogenation - Practice

49
 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.6. Halohydrin Formation

Mechanism

anti addition 50
Halohydrin Formation - Practice

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 2. Reactivity of Alkenes
2.1. Electrophilic Addition

2.1.6. Halohydrin Formation

Mechanism

anti addition 52
 2. Reactivity of Alkenes
2.2. Oxidation of Alkenes

2.2.1. Epoxidation
peroxy acid epoxy

m-chloroperoxybenzoic acid
Mechanism

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 2. Reactivity of Alkenes
2.2. Oxidation of Alkenes

2.2.2. Dihydroxylation
Hydrolysis of epoxide

Mechanism

Nucleophile add to
anti addition
more substituted carbon 54
 2. Reactivity of Alkenes
2.2. Oxidation of Alkenes

2.2.2. Dihydroxylation
Reaction with KMnO4/OH-

Mechanism

syn addition
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 2. Reactivity of Alkenes
2.2. Oxidation of Alkenes

2.2.2. Dihydroxylation
Reaction with OsO4

Mechanism

syn addition
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 Addition to Alkenes - Summary
Reaction Reagent Product Note
Hydrohalogenation HX alkyl halide Markovnikov
Hydrobromination with HBr/peroxide alkyl bromide anti-Markovnikov
peroxide radical addition
Hydration H3 O + alcohol Markovnikov
1/ Hg(OAc)2 alcohol Markovnikov
2/ NaBH4 no rearrangement
Hydroboration-Oxidatio 1/ BH3/ether alcohol anti-Markovnikov
n 2/ H2O2/OH- syn addition
Hydrogenation H2/metal catalyst alkane syn addition
Halogenation X2 alkyl halide anti addition
Halohydrin formation X2 + H 2O halohydrin anti addition
Dihydroxylation 1/ mCPBA diol anti addition
2/ H3O+
KMnO4/OH- diol syn addition
OsO4 diol syn addition 57
Addition to Alkenes - Practice

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 2. Reactivity of Alkenes
2.2. Oxidation of Alkenes

2.2.3. Ozonolysis

Mechanism
• In the 2nd step, many
mild reductants can
be used: Me2S
(DMS), Zn/H+, PPh3

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 2. Reactivity of Alkenes
2.2. Oxidation of Alkenes

2.2.3. Ozonolysis
• Using strong reducing agent (e.g. NaBH4, LiAlH4), the
products will be alcohols

• Using oxidizing agent (e.g. H2O2), the products will be

ketones/carboxylic acids

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Addition to Alkenes - Practice

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 2. Reactivity of Alkenes
2.2. Oxidation of Alkenes

2.2.4. Strong Oxidation

In the present of strong oxidant (e.g. KMnO4/H+, K2Cr2O7),
alkenes will be oxidized to ketone/carboxylic acid/CO2.

Alkene can also undergo combustion.

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2. Reactivity of Alkenes
2.3. Polymerization of Alkenes

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