Chem - Chapter 7 and 9

Learning Objectives
John E. McMurry
(7.6)
 Stability of alkenes
www.cengage.com/chemistry/mcmurry (7.7)
 Electrophilic addition reactions of alkenes
(7.8)
 Orientation of electrophilic additions:
Chapter 7 Markovnikov’s rule
Alkenes: Structure and Reactivity (7.9)
 Carbocation structure and stability
© 2016 Cengage Learning. All Rights Reserved. © 2016 Cengage Learning. All Rights Reserved.
Learning Objectives Learning Objectives

(7.1) (7.10)
 Industrial preparation and use of alkenes  The Hammond Postulate
(7.2) (7.11)
 Calculating degree of unsaturation  Evidence for the mechanism of electrophilic
(7.3) additions: Carbocation rearrangements
 Naming alkenes
(7.4)
 Cis-Trans Isomerism in Alkenes
(7.5)
 Alkene Stereochemistry and the E,Z Designation
1
Alkene-Hydrocarbon With
Naming Alkenes
Carbon–Carbon Double Bond
 Alkene: Hydrocarbon containing a carbon-  Name the parent hydrocarbon
carbon double bond
 Sometimes called olefin
 Number the carbons in the chain so that double

bond carbons have lowest possible numbers
Industrial Preparation and Use

Naming Alkenes
of Alkenes
 Ethylene and propylene are the least complex  Name the parent hydrocarbon
alkenes
 Important organic chemicals produced industrially
 Number the carbons in the chain so that double

bond carbons have lowest possible numbers
2
Naming Alkenes Worked Example
 Give IUPAC names for the following compounds
 Write the full name  a)
 Number substituents:
 According to position in
chain
 Alphabetically
 Rings have cyclo as
 b)
prefix
Table 7.1 - Common Names of

Worked Example
Some Alkenes
 Solution:
 a)
 The longest chain is a pentene

 Consists of three methyl groups
 The methyl groups are attached to C3 and C4
 Using tri- before methyl and using numbers to signify
the location of the double bond
 The compound is 3,4,4-Trimethyl-1-pentene
3
Worked Example Worked Example
 Solution:
 a)
 b)
 The longest chain is a hexane

 The methyl group is attached to C3 1,2-Dimethylcyclohexene
 Using numbers to signify the location of the double  b)
bond
 The compound is 3-Methyl-3-hexene
4,4-Dimethylcycloheptene
Worked Example Cis-Trans Isomerism in Alkenes

 Name the following cycloalkenes:  Carbon atoms in a double bond are sp2-
hybridized
 a)  Three equivalent orbitals at 120°separation in
the plane
 Interaction of p orbitals, one bonding and one
antibonding  molecular orbital
 Rotation prevented by  bond
 b)
 Barrier to double-bond rotation must be as great
as the strength of p bond
 About 350 kJ/mol
4
Figure 7.3 - Cis and Trans
Cis-Trans Isomerism in Alkenes
Isomers of 2-Butene
 Rotation of  bond is prohibitive
 This prevents rotation about a carbon–carbon
double bond
Cis-Trans Isomerism in Alkenes Cis-Trans Isomerism in Alkenes

 Methyl groups in 2-butene are either on the  Cis-trans isomerization requires end groups to differ in
pairs
same side of the double bond or on opposite
sides  Not possible if one of the double-bond carbons is
attached to two identical groups
 Compound with substituents on the same side of
double bond is called cis-2-butene
 Isomer with substituents on opposite sides is
trans-2-butene
 Cis-trans isomerism occur whenever both
double-bond carbons are attached to two
different groups
5
Alkene Stereochemistry and the Alkene Stereochemistry and the
E,Z Designation E,Z Designation
 Tri- and tetra-substituted double bonds require  Rule 2
more general method  If atomic numbers are the same, compare at next
 E,Z system: Method used for describing alkene connection point at same distance
stereochemistry
 Uses Cahn–Ingold–Prelog sequence rules
Alkene Stereochemistry and the Alkene Stereochemistry and the

E,Z Designation E,Z Designation
 Rule 1  Rule 3
 Rank the substituent atoms according to the  Multiple-bonded atoms are equivalent to the
atomic number of the first atom same number of single-bonded atoms
 Higher atomic number gets higher priority
6
Alkene Stereochemistry and the
Worked Example
E,Z Designation
 Z geometry: Molecules which have higher  Solution:
ranked groups on each carbon are on the same
side of the double bond
 E geometry: Molecules which have higher-
ranked groups are on opposite sides
Worked Example Stability of Alkenes

 Assign stereochemistry (E or Z) to the double  Cis alkenes are less stable than trans alkenes
bond in the following compound  Less stable isomer is higher in energy and gives
 Convert the drawing into a skeletal structure (red off more heat
= O)  Tetrasubstituted > trisubstituted > disubstituted >
monosusbtituted
7
Electrophilic Addition of Alkenes Electrophilic Addition of Alkenes
 General reaction mechanism of electrophilic  Reaction is also successful with HCl, HI, and
addition H 2O
 Attack on electrophile, such as HBr, by  bond of  HI is generated from KI and phosphoric acid
alkene
 Produces carbocation and bromide ion
 Carbocation is an electrophile, reacting with a
nucleophilic bromide ion
Orientation of Electrophilic
Figure 7.7 - Mechanism
Additions: Markovnikov’s Rule
 In electrophilic addition reactions, unsymmetrical
substituted alkenes give a single product
 Regiospecific: Reaction in which only one of
two possible orientations of an addition occur
8
Markovnikov’s Rule Markovnikov’s Rule (restated)
 In the addition of HX to
an alkene
 H attaches to the
carbon with fewer alkyl
substituents
 X attaches to the
carbon with more alkyl
substituents
Markovnikov’s Rule (restated) Worked Example

 In the addition of HX to an alkene, more highly  Predict the products of the following reaction:
substituted carbocation forms as the
intermediate rather than the less highly
substituted one
 Solution:
 The reaction is electrophilic addition of HX to an
alkene
 Using Markovnikov's rule to predict orientation
9
Worked Example Worked Example
 What alkene is required to prepare the following  Show the structures of the carbocation
product: intermediates expected in the reaction
 Solution:
Worked Example
John E. McMurry
 Solution:
 Choose the alkene starting material for synthesis
of the desired haloalkane
www.cengage.com/chemistry/mcmurry
Chapter 9
Alkynes: An Introduction to
Organic Synthesis
10
Alkynes Naming Alkynes
 Hydrocarbons that contain carbon–carbon triple  Alkynyl groups are also possible
bonds
 Acetylene is the simplest alkyne
 Polyynes - Linear carbon chains of sp-hybridized

carbon atoms
Naming Alkynes Worked Example

 General hydrocarbon rules apply  Name the following alkynes:
 Suffix -yne indicates an alkyne
 Number of the first alkyne carbon in the chain is  A)
used to indicate the position of the triple bond
 B)
11
Worked Example
 Solution:
 A) 2,5-Dimethyl-3-hexyne
 B) 3,3-Dimethyl-1-butyne
© 2016 Cengage Learning. All Rights Reserved.
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Chem - Chapter 7 and 9

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Learning Objectives

Learning Objectives Learning Objectives

 Number the carbons in the chain so that double

Industrial Preparation and Use

 Number the carbons in the chain so that double

Table 7.1 - Common Names of

 The longest chain is a pentene

 The longest chain is a hexane

Worked Example Cis-Trans Isomerism in Alkenes

Cis-Trans Isomerism in Alkenes Cis-Trans Isomerism in Alkenes

Alkene Stereochemistry and the Alkene Stereochemistry and the

Worked Example Stability of Alkenes

Markovnikov’s Rule (restated) Worked Example

 Polyynes - Linear carbon chains of sp-hybridized

Naming Alkynes Worked Example

© 2016 Cengage Learning. All Rights Reserved.

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