Chapter 3
The Nature of Organic Reaction
Reactions: Alkenes
Alkene, sometimes called olefins, are hydrocarbons
that contain a carbon-carbon double bond, C=C
Ethene
Alkynes are hydrocarbons that contain a carbon-
carbon triple bond, C≡C.
3.1 Naming Alkenes and Alkynes
Ethene Ethyne
Step 1 : Name the parent hydrocarbon
Fine the longest carbon chain that contains the double bond,
and name the compound using the suffix –ene in place of –ane
Step 2 : Number the carbon atom in the chain
Begin numbering at the end nearer the double bond.
This rule ensures that the double-bond carbons receive
the lowest possible numbers.
Step 3 : Write the full name
We number the cycloalkene so that the double bond is
between C1 and C2 And the first substituent has as low
a number as possible.
Alkynes
4 3 2 1 4 3 2 1
Worked Example 3.1
What is the IUPAC name of the following alkene?
2,6,6-trimethylhept-2-ene
p. 82
Problem 3.1
Give IUPAC name for the following compounds:
******* *******
(a) 3,4,4-Trimethylpent-1-ene
(b) 3-Methylhex-3-ene
(c) 4,7-Dimethylocta-2,5-diene
(d) 6-Ethyl-7-methylnon-4-ene
Problem 3.2
Name the following cycloalkenes:
(a) 1,2-Dimethylcyclohexene
(b) 4.4-Dimethylcycloheptene
(c) 3-Isopropylcyclopentene
Problem 3.3
Draw structures correspounding to the following IUPAC names:
(a)2-Methylhex-1-ene (b) 4,4-Dimethylpent-2-yne
(c) 2-Methylhex-1,5-diene (d) 3-Ethyl-2,2-dimethylhept-3-ene
2
5 1 3
Problem 3.4
Name the following alkyne
1 3
5 3 2 1
3 4 5
32
(a) 2,5-Dimethylhex-3-yne
(b) 3,3-Dimethylbut-yne
(c) 3,3-Dimethyloct-4-yne
(d) 2,5,5-Trimethylhept-3-yne
3.2 Electronic Structure of Alkenes
Figure 3.1 The bound must break momentarily for rotation around a
Carbon-carbon double bond to take place, requiring a large amount of Energy.
Figure 3.1 The bound must break momentarily for rotation around a
Carbon-carbon double bond to take place, requiring a large amount of Energy.
3.3 Cis-Trans Isomers of Alkene
Figure 3.2 cis and trans isomers of but-2-ene. The Cis isomer
has the two methyl groups on the same side of the double bound,
and the trans isomer has the methyl groups on opposite sides.
Figure 3.3 The requirement for cis-trans isomerism in alkenes. Both double
-bond carbons must be bonded to two different groups.
high high
low high
high low low low
Worked Example 3.2
Draw the cis and trans isomers of 5-chloropent-2-ene
5 4 1 1
3 2 3 2
5 4
3.4 Sequence Rules: The E,Z Designation
Rule 1 :
Considering the double-bond carbons separately, look at the
atoms directly attached to each carbon and rank them
according to atomic number.
For example:
Rule 2 :
If a decision can’t be reached by ranking the first atoms
In the substituents, look at the second, third, or fourth
atoms away from the double-bond carbons until the
First difference is found.
Rule 3 :
Multiple-bonded atoms are equivalent to the same
number of single-bonded atoms..
Worked Example 3.3
Assigning E,Z stereochemistry to an alkene
3.5 Kinds of Organic Reactions
• Addition reactions
• Elimination reactions
• Substitution reactions
• Rearrangement reactions
3.6 How Reactions Occur: Mechanisms
Symmetrical cleavage is said to be homolytic
Unsymmetrical cleavage is said to be heterolytic
Radical reactions typically involve the movement of a lone
electron.
Polar reactions in which two electrons move together when
bonds are formed or broken.
The Electronegativities of Common Elements
Green (metal); blue (nonmetal); gray (metalloids)
Note that the transition metals do not follow these trend
9.5
Figure 3.4 Some onestep
Worked Example 3.4
Predicting the polarity of a bond
Worked Example 3.5
Identifying Electrophiles and Nucleophiles
3.7 Mechanisms of Polar Reactions
Polar reaction
Worked Example 3.4
Predicting the polarity of a bond
Worked Example 3.5
Identifying Electrophiles and Nucleophiles
3.8 The Mechanism of an Organic Reaction:
Addition of HCl to Ethylene
Figure 3.5 A comparison of carbon-carbon single and double bonds.
Figure 3.6 The mechanism of the electrophilic addition of the HCl
to ethylene. The reaction takes place in two steps and involves an
intermediate carbocation.
Worked Example 3.6
Predicting the product of an Electrophilic Addition Reaction
3.9 Describing a Reaction: Reaction Energy
Diagrams and Transtition States
Figure 3.7 An energy diagram for the reaction of ethylene with HCl.
Two separate steps are involved, each with its own activation energy,
Transition state, and energy change. The energy minimum between
the twosteps represents the carbocation reaction intermediate.
3.10 Describing a Reaction: Energetics and
Catalysis
Figure 3.8 A reaction energy diagram showing the catalyzed and uncatalyzed
reaction of ethylene and H2.
Worked Example 3.7
Drawing an Energy Diagram
