Alkenes:

Reactions and
Synthesis

1-1
Alkenes

Hydrocarbons containing double bonds

C C

double bond
the functional group
center of reactivity

1-2
Molecular Formula of Alkene
Noncyclic alkene: Cyclic alkene:
CnH2n CnH2n–2
CH3CH2=CH2

1-3
Systematic Nomenclature of Alkenes
•Longest continuous chain containing the
functional group

1-4
•Cite the substituents in alphabetical order

•Name with the lowest functional group number and

then the lowest substituent numbers

1-5
•No numbering of the functional group is needed in
a cyclic alkene

1-6
Special Nomenclatures

1-7
Conversion of alkene isomers requires breaking of
the p bond between the two sp2 carbons

1-8
Cis-Trans Interconversion in Vision

1-9
E and Z isomers

1-10
Naming by the E,Z System
Rule 1: Consider the atomic number of the
atoms bonded directly to a specific sp2
carbon.

1-11
Rule 2: If there is a tie, consider the atoms
attached to the tie.

1-12
Rule 3: Multiple bonds are treated as attachment
of multiple single bonds.

1-13
Rule 4: Rank the priorities by mass number in
isotopes.

1-14
An alkene is an electron-rich molecule
A nucleophile
Nucleophile: an electron-rich atom or molecule
that shares electrons with electrophiles

Examples of Nucleophiles

1-15
Nucleophiles are attracted to electron-deficient
atoms or molecules (electrophiles)

Examples of Electrophiles

1-16
Electrophilic Addition of HBr to Alkene

1-17
Curved Arrows in Reaction Mechanisms
Movement of a pair of electrons

Movement of one electron

1-18
Utilization of Curved Arrows

1-19
Rules for Use of Curved Arrows

1-20
Rules for Use of Curved Arrows

1-21
1-22
Diverse Reactions of Alkenes
 Alkenes react with many electrophiles to give useful products by addition (often
through special reagents)

1-23
Preparation of Alkenes: A Preview of Elimination Reactions

1-24
Electrophilic Addition of Alkenes

1-25
Addition of Hydrogen Halides

1-26
 What is the product?

Which do you think is produced more?

1-27
Carbocation formation is the rate-limiting step
a more stable
carbocation

You might produce ~1% of it !

1-28
Carbocation Stabilities

1-29
 Markovnikov’s Rule
The electrophile adds to the sp2 carbon that is bonded to
the greater number of hydrogens

electrophile

In a regioselective reaction, one constitutional isomer is the

major or the only product

1-30
Addition of Water to Alkene

1-31
 Acid-Catalyzed Addition of Alcohol
-The reaction depends on the presence of an acid; H+
-The proton will seek electrons from the oxygen of the
alcohol and binds to it

1-32
 Rearrangement of Carbocation
1,2-hydride shift a more stable
carbocation

1-33
 Rearrangement of Carbocation
a more stable
1,2-methyl shift carbocation

1-34
Carbocation does not always rearrange …

1-35
 Carbocation Rearrangement

Ring Expansion

a more stable
carbocation

1-36
Addition of Halogens to Alkene

1-37
1-38
Addition of Halogens
in the Presence of Water

1-39
Consider the transition states …

1-40
Oxymercuration and Mercuration
of Alkene

1-41
 Demercuration by Reduction

This is how we can produce an alcohol without the presence

Of an acidic medium !

1-42
 Addition of Borane
Hydroboration–Oxidation
Anti-Markovnikov’s rule in product formation

1-43
Anti-Markovnikov Markovnikov
addition addition

(a pericyclic reaction)

1-44
Formation of Alkyl Boranes

1-45
OH Replacement of Boron

1-46
Anti-Markovnikov Addition
of an OH Group

1-47
Reaction of Carbene with Alkene

1-48
 Synthesis of Bromobutane

Peroxide is the initiator!

1-49
Generation of Radicals

1-50
Addition of Radicals to Alkene

1-51
1-52
Relative Stabilities of Alkyl Radicals

1-53
Addition of Hydrogen to Alkenes

1-54
Catalytic Hydrogenation of an Alkene

1-55
 Addition of HBr or HCl

Markovnikov Addition

CH3 H Br H
HBr CH3 H
C C C C
CH3 H CH3 H
Markovnikov

H Br
CH3 H
C C
CH3 H
not formed

1-56
HBr Addition with RO-OR

Anti-Markovnikov

HBr H Br

RO-OR, h

1-57
 Free-Radical Mechanism

Initiation: .
RO-OR 2 RO
. .
RO + HBr Br + ROH

. Br
Propagation: i) + Br .

Br H Br
ii) . .
+ H-Br + Br

1-58
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

1-59
Addition of Br2 to Cyclopentene

 Addition is exclusively trans

1-60
Mechanism of Bromine Addition

 Br+ adds to an alkene producing a cyclic ion

 Bromonium ion, bromine shares charge with carbon
• Gives trans addition

1-61
 Bromonium Ion Mechanism

 Electrophilic addition of bromine to give a cation is followed

by cyclization to give a bromonium ion
 This bromonium ion is a reactive electrophile and bromide ion
is a good nucleophile
 Stereospecific anti addition

1-62
Addition of Hypohalous Acids to Alkenes: Halohydrin
Formation

 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)

1-63
 Unsymmetrical Bromonium ion

H2O opens ring at more hindered

site

+

Br Br
+ CH3

CH3 HO H
H
H 2O

1-64
Catalytic Hydrogenation Mechanism

1-65
Oxidation of Alkenes: Epoxidation and Hydroxylation
 Oxidation is addition of O, or loss of H
 Epoxidation results in a cyclic ether with an oxygen atom
 Stereochemistry of addition is syn
 MCPBA in CH2Cl2 are the usual conditions
 Addition of acid results in a trans-1,2-diol

 Treatment of the epoxide with aqueous acid give a trans diol

1-66
Oxidaton of Alkenes:Cleavage to Carbonyl Compounds

 Ozone, O3, adds to alkenes to form molozonide

 Reduce molozonide to obtain ketones and/or aldehydes

1-67
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

1-68
 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 1-69
1-70
1-71
1-72
 Alkynes

• Recall that the triple bond consists of 2 p bonds and 1  bond.

• Each carbon is sp hybridized with a linear geometry and bond
angles of 1800.

1-73
 Alkynes

• Terminal alkynes hydrogen atom is directly bonded to

a carbon atom of the triple bond.
• Internal alkynes have a carbon atom bonded to each
carbon atom of the triple bond.
• An alkyne has the general molecular formula CnH2n-2,

1-74
 Alkynes
Nomenclature:

• Alkynes are named in the same general way that

alkenes are named.
• In the IUPAC system, change the –ane ending of
the parent alkane name to the suffix –yne.
• Choose the longest continuous chain that
contains both atoms of the triple bond and
number the chain to give the triple bond the
lower number.
• Compounds with two triple bonds are named as
diynes, those with three are named as triynes
and so forth.

75 1-75
 Alkynes
Nomenclature:

• Compounds both a double and triple bond are

named as enynes. The chain is numbered to give
the first site of unsaturation (either C=C or CC)
the lower number.
• If numbering is equal the ene gets the lower
number.
• However, yne is still the parent ending

CH3-CC-CH=CH-CH3 is 2-hexen-4-yne

76 1-76
 Alkynes

Nomenclature:

1-77
 Alkynes
Alkyne Reactions: Additions

1-78
 Alkynes
Alkyne Reactions: Additions

1-79
 Alkynes

Hydrohalogenation: Electrophilic Addition of HX

• Alkynes undergo hydrohalogenation, i.e the, addition

of hydrogen halides, HX (X = Cl, Br, I).

• Two equivalents of HX are usually used: addition of

one mole forms a vinyl halide, which then reacts with
a second mole of HX to form a geminal dihalide.
1-80
Alkynes

81 1-81
Alkynes

1-82
 Alkynes
Alkyne Reactions: Addition of HX

• Electrophilic addition of HX to alkynes is slower

than electrophilic addition of HX to alkenes, even
though alkynes are more polarizable and have
more loosely held p electrons than alkenes.

1-83
 Alkynes
Alkyne Reactions: Addition of HX

• Markovnikov addition in step [3] places the H on

the terminal carbon to form the more substituted
carbocation A, rather than the less substituted
carbocation B.

84 1-84
 Alkynes

Halogenation: Addition of Halogen

• Halogens X2 (X = Cl or Br) add to alkynes just as they

do to alkenes. Addition of one mole of X2 forms a
trans dihalide, which can then react with a second
mole of X2 to yield a tetrahalide.

85 1-85
Alkynes

86 1-86
 Alkynes
Hydration: Electrophilic Addition of Water

• In the presence of strong acid or Hg2+ catalyst, the

elements of H2O add to the triple bond. The initial
addition product, an enol, is unstable and rearranges to
a product containing a carbonyl group—that is, a C=O,
before the second addition can occur. A carbonyl
compound having two alkyl groups bonded to the C=O
carbon is called a ketone.

1-87
 Alkynes

• Internal alkynes undergo hydration with concentrated

acid, whereas terminal alkynes require the presence of
an additional Hg2+ catalyst—usually HgSO4—to yield
methyl ketones by Markovnikov addition of water.

88 1-88
 Alkynes

• Tautomerization, the process of converting one

tautomer into another, is catalyzed by both acid and
base.
89 1-89
 Alkynes

Hydration: Electrophilic Addition of Water

90 1-90
Alkynes

91 1-91
 Alkynes

Hydroboration—oxidation is a two step reaction sequence

that converts an alkyne to a carbonyl compound.

1-92
 Alkynes

• Hydroboration—oxidation of an internal alkyne forms

a ketone.
• Hydroboration of a terminal alkyne adds BH2 to the
less substituted, terminal carbon. After oxidation to
the enol, tautomerization yields an aldehyde, a
carbonyl compound having a hydrogen atom bonded
to the carbonyl carbon.

93 1-93
 Alkynes
Acetylide anions
• Because sp hybridized C—H bonds are more acidic than
sp2 and sp3 hybridized C—H bonds, terminal alkynes are
readily deprotonated with strong base in a BrØnsted-
Lowry acid-base reaction. The resulting ion is called the
acetylide ion.

94 1-94
 Alkynes

• Acetylide anions react with unhindered alkyl halides

to yield products of nucleophilic substitution.

1-95
 Alkynes
Synthesis:
• You can now begin to consider (for example) how to
prepare a five-carbon product from three smaller
precursor molecules using the reactions you have
learned.

1-96
 Addition of Radicals to Alkenes: 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 poyethylene, for
example

1-97
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

1-98
 Polymerization: Propagation
 Radical from initiation adds to alkene to generate alkene
radical
 This radical adds to another alkene, and so on many times

 Chain propagation ends when two radical chains combine

 Not controlled specifically but affected by reactivity and
concentration

Termination

1-99
Other Polymers

 Other alkenes give other common polymers

 Radical stability: 3o > 2o > 1o (just like with

carbocations)

1-100
Reactions of Dienes

1-101
Hydrocarbon containing
two double bonds: diene
three double bonds: triene
four double bonds: tetraene
many double bonds: polyene

1-102
Different Kinds of Dienes

1-103
 Nomenclature of Alkenes with More
than One Functional Group
1. Identify the longest continuous chain containing
both double bonds

2. Give the double bonds the lowest possible number

3. The numbers indicating the double bonds are cited

either before the name of the parent compound or
before the suffix

4. Substituents are cited in alphabetical order

1-104
1-105
When the multiple bonds are a double bond and a triple
bond

1-106
If there is a tie, the double bond gets the lowest number

1-107
A chain is numbered to give the lowest number to the
functional group with the highest priority

CH3 NH2
H2C CHCH2OH CH3C CHCH2CH2OH H2C CHCH2CH2CH2CHCH3
2-propen-1-ol 4-methyl-3-penten-1-ol 6-hepten-2-amine

CH3 NH2
OH
6-methyl-2-cyclohexenol 3-cyclohexenamine 1-108
Electrophilic Addition Reactions of Isolated
Dienes

One product produced !

Addition can occur at only one of the double bonds when

1 mole of HBr is available 1-109
Electrophilic Addition Reactions of
Conjugated Dienes

Two products produced !

1-110
(resonance)

1-111
A conjugated diene undergoes both 1,2- and 1,4-addition

1-112
Compare the two addition product distribution at different
reaction temperatures

kinetic control
(product coming from most
stableTransition state)

thermodynamic or
equilibrium control
(product based on Zaitsev’s rule)

1-113
Thermodynamic Versus Kinetic Control

• The thermodynamic product is the most stable product

• The thermodynamic product predominates when the

reaction is reversible (thermodynamic control)

• The kinetic product is the product that is formed most

rapidly

• The kinetic product predominates when the reaction is

irreversible (kinetic control)
1-114