Chapter 3

Alkenes & Alkynes

Structure, Nomenclature, and an introduction to
Reactivity and Mechanism

Saturated and
Unsaturated Hydrocarbons

Saturated hydrocarbons have no double bonds.

Unsaturated hydrocarbons have one or more double bonds.

Nomenclature of Alkenes

Replace ane of alkane with ene.

The functional group gets the lowest possible number.

Stereoisomers May Be Named Using

a cis or trans Prefix

Nomenclature of Dienes

two double bonds = diene

Nomenclature of Alkenes

Number in the direction so that the functional group

gets the lowest number.

Nomenclature of Alkenes

Substituents are stated in alphabetical order.

Nomenclature of Cyclic Alkenes

A number is not needed to denote the position of the C=C functional group;
it is always between C1 and C2.

Vinylic and Allylic Common Names

Double Bonds Have

Restricted Rotation

The six carbon

atoms are in the
same plane

Rotation about a double bond breaks the bond.

Alkenes May Have cistrans Isomers

Cis: The hydrogens are on the same side of the ring.

Trans: The hydrogens are on opposite sides of the ring.

They have different configurations; they can be separated.

Sometimes cis and trans do not work

The E,Z System of Nomenclature

Z = Zusammen (together)

E = Entgegen (opposite)

Relative Priorities

The relative priorities of the two groups depends on the

atomic numbers of the atoms attached to the sp2 carbon.

The E and Z Isomers

(E) 1-chloro-3-(chloromethyl)-4-ethyl-5-methylhex-3-ene

Double Bonds

lower
higher

Break multiple bonds into

equivalent single bonds

Isotopes

Reactions of Organic Compounds

Electrophilic Addition (general)

Hydrohalogenation (more specific, could be HCl, HBr, or HI
Hydrobromination (specific for HBr)

Electrophiles

An electrophile is a Lewis acid and has:

a positive charge or
a partial positive charge or
an incomplete octet.

Nucleophiles

A nucleophile is a Lewis base and has:

a lone pair of electrons and/or
a negative charge

Reactive Intermediates
During the course of a reaction, a reactive
intermediate may be involved. We will limit our
study to the carbocation intermediate.
sp2, trigonal
planar
Empty p orbital

Increasing stability

Carbocation Stability

Alkyl groups:
decrease the concentration of positive charge on the carbon and
increase the stability of the carbocation.

Hyperconjugation Stabilizes a Carbocation

Bond Making and Bond Breaking

Reaction Mechanism

Arrows denote the flow of electrons from the Lewis base

to the Lewis acid

Functional Group Transformation

hydrohalogenation
(transformation)

Learn to recognize
the functional group
transformation.
In this case it is an
alkene going to an
alkyl chloride

Draw Notecards for each reaction

you are expected to learn (see course
handouts)

Me

Cl
HCl (g)
ether

Type: hydrohalogenation

Me

Reaction Mechanism
hydrohalogenation
(mechanism)

The curved arrow

notation is used to
describe bond
making and bond
breaking in a
mechanism

Draw Notecards for each reaction

mechanism you are expected to
learn (see course handouts)

How to Draw Curved Arrows

Exothermic and Endothermic Reactions

Transition
state
Eact

Ignore entropy G H
Reaction coordinate diagram

Bond Enthalpy
Endothermic or Exothermic

Bond
DH (kcal/mol)
Breaking
-bond
62
H-Br
88
COST
150

Bond Making
C-H
C-Br
GAIN

DH (kcal/mol)
101
71
172

150 kcal/mol 172 kcal/mol = 22 kcal/mol or exothermic

Reaction Coordinate Diagrams for Fast and Slow

Exothermic and Endothermic Reactions

Reactions in Chapter 4
name

class

1. Hydrohalogenation

electrophilic
addition

2. Hydration

electrophilic
addition
3. Halogenation
electrophilic
addition
4. Hydrogenation
electrophilic
addition
5. cis Di-hydroxylation oxidation
6. Oxidative cleavage oxidation
7. Epoxidation
oxidation

subclass

mechani
sm
hydrochlorination, yes
hydrobromination
, hydroiodination
yes
bromination,
chlorination
reduction

yes
no
no
no
no

Refer to the course map in the syllabus when studying the remainder
of the material in this course as we will not cover every reaction in the
textbook. Always refer to the 345 reactions summary in the course
materials folder in Blackboard. If the reaction has a yes under the
mechanism column, you are expected to learn the mechanism that
goes along with the reaction.