Organic Chemistry, 6e

by L.G. Wade, Jr.

Chapter 15
Conjugated Systems,
Orbital Symmetry, and
Ultraviolet Spectroscopy
Christine Hermann
Radford University
Radford, VA
 2006, Prentice Hall

15.1 Identify the alkene with the

smallest heat of hydrogenation.

1,2-Pentadiene

Trans-1,3-pentadiene

1,4-Pentadiene

1-Pentyne

Level 2
Easy

1
 15.1 answer

1,2-Pentadiene

Trans-1,3-pentadiene

1,4-Pentadiene

1-Pentyne

Conjugated dienes have the lowest heat

of hydrogenation.
Level 2
Easy

15.2 Identify the highest energy

orbital of 1,3-butadiene.

π1 bonding MO

π2 bonding MO

π3* antibonding MO

π4* antibonding MO

Level 2
Easy

2
 15.2 answer

π1 bonding MO

π2 bonding MO

π3* antibonding MO

π4* antibonding MO

The π4* antibonding MO has the highest

energy.
Level 2
Easy

15.3 Name CH2=CH-CH2+

Allylic anion
Benzylic cation

Allylic radical
Benzylic anion

Allylic cation
Benzylic radical

Level 2
Easy

3
 15.3 answer

Allylic anion
Benzylic cation

Allylic radical
Benzylic anion

Allylic cation
Benzylic radical

The allylic cation has a double bond

next to a positive carbon.

Level 2
Easy

15.4 How does HX add to a

conjugated diene?

1,2-addition

1,3-addition

2,3-addition

1,4-addition

1,2- and 1,4-addition

Level 2
Easy

4
 15.4 answer

1,2-addition

1,3-addition

2,3-addition

1,4-addition

1,2- and 1,4-addition

Both products are formed by addition of HX to a

conjugated diene.
Level 2
Easy

15.5 Explain the reaction of HBr

with CH2=CHCH=CH2.

1,2-Product is the kinetic product; 1,4-
product is the thermodynamic product.

1,4-Product is the kinetic product; 1,2-
product is the thermodynamic product.

1,2- and 1,4-products are
thermodynamic products.

1,2- and 1,4-products are kinetic
products.
Level 2
Easy

5
 15.5 answer

1,2-Product is the kinetic product; 1,4-
product is the thermodynamic product.

1,4-Product is the kinetic product; 1,2-
product is the thermodynamic product.

1,2- and 1,4-products are
thermodynamic products.

1,2- and 1,4-products are kinetic
products.
Level 2
Easy

15.6 Give the mechanism for the

bromination of an alkene with
NBS.

Allylic elimination

Allylic substitution

Addition of bromine

Addition of hydrogen bromide

Level 2
Medium

6
 15.6 answer

Allylic elimination

Allylic substitution

Addition of bromine

Addition of hydrogen bromide

N-Bromosuccinimide produces a low

concentration of bromine, resulting in
allylic substitution.
Level 2
Medium

15.7 List a criteria for the Diels-

Alder reaction.

Four electrons in the conjugated diene
and two electrons in the dienophile.

Two electrons in the conjugated diene
and four electrons in the dienophile.

Eight electrons in the conjugated diene
and four electrons in the dienophile.

Four electrons in the conjugated diene
and eight electrons in the dienophile.
Level 2
Easy

7
 15.7 answer

Four electrons in the conjugated diene
and two electrons in the dienophile.

Two electrons in the conjugated diene
and four electrons in the dienophile.

Eight electrons in the conjugated diene
and four electrons in the dienophile.

Four electrons in the conjugated diene
and eight electrons in the dienophile.
Level 2
Easy

15.8 +

4-Ethylcyclohexene

Ethylbenzene

5-Ethyl-1,3-cyclohexadiene

1-Ethylcyclohexene

Level 3
Challenging

8
 15.8 answer

4-Ethylcyclohexene

Ethylbenzene

5-Ethyl-1,3-cyclohexadiene

1-Ethylcyclohexene

A cyclohexene is formed from a diene and

alkene in a Diels-Alder reaction.
Level 3
Challenging

15.9 Identify the alkene with the

highest UV wavelength.

1-Hexene

1,4-Hexadiene

2,4-Hexadiene

1,3,5-Hexatriene

Level 2
Challenging

9
 15.9 answer

1-Hexene

1,4-Hexadiene

2,4-Hexadiene

1,3,5-Hexatriene

The wavelength increases with the

addition of conjugated double bonds.
Level 2
Challenging

15.10 Identify the alkene with the

lowest UV wavelength.

1,3-Butadiene

1,3-Cyclohexadiene

3-Methylenecyclohexene

Level 2
Easy

10
 15.10 answer

1,3-Butadiene

1,3-Cyclohexadiene

3-Methylenecyclohexene

The UV wavelengths are as follows: 1,3-

butadiene - 217 nm; 1,3-cyclohexadiene
- 256 nm; and 3-methylenecyclohexene
- 232 nm.
Level 2
Easy

11