Chapter 3

Alkenes and Alkynes: The Nature

of Organic Reactions
Jae Woong Jung
Kyung Hee University

에너지나노소재연구실
Energy Nanomateials Laboratory
3. Alkenes and Alkynes: The
Nature of Organic Reactions
 Alkene s- Hydrocarbon with carbon-carbon double
Bonds
 Also called an olefin but alkene is better
 Alkynes - Hydrocarbons that contain carbon-carbon
triple bonds
 Includes many naturally occurring materials
 Flavors, fragrances, vitamins

3
Why this Chapter?

 C-C double bonds are present in most

organic and biological molecules
 To examine consequences of alkene
stereoisomerism
 To focus on general alkene reaction:
electrophilic addition
 We will use alkyne chemistry to begin looking
at general strategies used in organic
synthesis

4
3.1 Naming of Alkenes and Alkynes

 Name the parent hydrocarbon

 Number carbons in chain so that double bond carbons
have lowest possible numbers
 Write the full name

5
1. Name the parent hydrocarbon: suffix –ene in plase of -ane

2. Number carbons in chain so that double bond

carbons have lowest possible numbers

6
3. Write the full name

7
IUPAC changed its naming rules in 1993

8
Many Alkenes Are Known by Common Names

9
Alkynes
- General hydrocarbon rules apply with “-yne” as a
suffix indicating an alkyne
- Numbering of chain with triple bond is set so that
the smallest number possible for the first carbon of
the triple bond

Alkenyl and alkynyl groups

10
 3.2 Electronic Structure of Alkenes
 Carbon atoms in a double bond are sp2-hybridized
 Three equivalent orbitals at 120º separation in plane
 Fourth orbital is atomic p orbital

 Combination of electrons in two sp2 orbitals of two atoms

forms  bond between them
 Additive interaction of p orbitals creates a  bonding
orbital
 Occupied  orbital prevents rotation about -bond
 Rotation prevented by  bond - high barrier, about 268
kJ/mole in ethylene

11
12
3.3 Cis-Trans Isomers of Alkenes
 The presence of a carbon-carbon double bond can
create two possible structures
 cis isomer - two similar groups on same side of
the double bond
 trans isomer - similar groups on opposite sides
 Each carbon must have two different groups for these
isomers to occur

13
 Cis, Trans Isomers Require That End Groups
Must Differ in Pairs
 180°rotation superposes
 Bottom pair cannot be superposed without breaking C=C

14
Interconversion of cis and trans alkene isomers

15
3.4 Sequence Rules: The E,Z Designation
 Neither compound is clearly “cis” or “trans”
 Substituents on C1 are different than those on C2
 We need to define “similarity” in a precise way to
distinguish the two stereoisomers
 Cis, trans nomenclature only works for disubstituted
double bonds

16
E,Z Stereochemical Nomenclature
 Priority rules of Cahn, Ingold, and Prelog
 Compare where higher priority groups are with
respect to bond and designate as prefix
 E -entgegen, opposite sides
 Z - zusammen, together on the same side

17
Ranking Priorities: Cahn-Ingold-Prelog Rules
RULE 1
 Must rank atoms that are connected at comparison point
 Higher atomic number gets higher priority

18
RULE 2
 If atomic numbers are the same, compare at next
connection point at same distance
 Compare until something has higher atomic number
 Do not combine – always compare

19
RULE 3
 Substituent is drawn with connections shown and no
double or triple bonds
 Added atoms are valued with 0 ligands themselves

20
21
 3.5 Kinds of Organic Reactions
 In general, we look at what occurs and try to learn how
it happens
 Common patterns describe the changes
- Addition reactions – two molecules combine

- Elimination reactions – one molecule splits into two

22
- Substitution – parts from two molecules exchange

- Rearrangement reactions – a molecule undergoes

changes in the way its atoms are connected

23
3.6 How Reactions Occur: Mechanisms

 In a clock the hands move but the mechanism

behind the face is what causes the movement
 In an organic reaction, we see the transformation
that has occurred. The mechanism describes the
steps behind the changes that we can observe
 Reactions occur in defined steps that lead from
reactant to product

24
Types of Reaction Mechanisms
 Bond formation or breakage can be symmetrical or
unsymetrical
 Symmetrical- homolytic : radical reactions
 Unsymmetrical- heterolytic : polar reactions

25
Indicating Steps in Mechanisms

 Curved arrows indicate breaking

and forming of bonds
 Arrowheads with a “half” head
(“fish-hook”) indicate homolytic
and homogenic steps (called
‘radical processes’)
 Arrowheads with a complete head
indicate heterolytic and
heterogenic steps (called ‘polar
processes’)

26
Polar Reactions
 Molecules can contain local unsymmetrical electron
distributions due to differences in electronegativities
 This causes a partial negative charge on an atom and a
compensating partial positive charge on an adjacent atom
 The more electronegative atom has the greater electron
density
 Elements such as O, F, N, Cl more electronegative than
carbon

27
Generalized Polar Reactions
 An electrophile, an electron-poor species,
combines with a nucleophile, an electron-rich
species
 The combination is indicate with a curved arrow
from nucleophile to electrophile

28
29
3.7 The Mechanism of an Organic
Reaction: Addition of HCl to Ethylene
 HCl adds to the  part of C-C double bond
 The  bond is electron-rich, allowing it to function as
a nucleophile
 H-Cl is electron deficient at the H since Cl is much
more electronegative, making HCl an electrophile

30
31
 Mechanism of Addition of HCl to Ethylene

 General reaction
mechanism:
electrophilic addition
 Attack of electrophile
(such as HCl) on  bond
of alkene
 Produces carbocation
and chloride ion
 Carbocation is an
electrophile, reacting
with nucleophilic
chloride ion

32
 3.8 Describing a Reaction: Transition
States and Intermediates

 The highest energy point in a reaction step is

called the transition state
 The energy needed to go from reactant to
transition state is the activation energy (DG‡)

33
34
 If a reaction occurs in more
than one step, it must
involve species that are
neither the reactant nor the
final product
 These are called reaction
intermediates or simply
“intermediates”
 Each step has its own free
energy of activation
 The complete diagram for
the reaction shows the free
energy changes associated
with an intermediate

35
3.9 Describing a Reaction: Catalysis

Catalyst: a substance that increases the rate of a

chemical transformation

36
Terpens: Naturally Occurring Alkenes

37
38