University of Zakho

Faculty of Science
Department of Chemistry

Diene

Prepared by:
Yousif Idrees Abdulghafar

Supervisor by:
Dr.Huda

Content
Subject page
2019-2020
1. Introduction 2
2. Nomenclature 3
2.1. Naming diene in the IUPAC system 3
2.2. We name cyclic dienes as follows: 3
3. Physical properties 4
3.1. Relative Stabilities of Dienes 4
4. Preparations of dienes 6
4.1. Dehydrogenation of butane 6
4.2. Elimination reactions of unsaturated alkyl halides 6
4.3. Elimination reactions of unsaturated alcohols 6
5. Reactions of dienes 7
5.1. Electrophilic addition to Isolated Dienes. 7
5.2. Electrophilic addition to conjugated Dienes 8

Introduction
Many hydrocarbons are known that contain more than one double or triple bond.
A hydrocarbon that contains two double bonds is called an alkadiene.[1]
1
Double bonds can interact with each other if they are separated by just one single
bond. Such interacting double bonds are said to be conjugated. Double bonds
with two or more single bonds separating them have little interaction and are
called isolated double bonds.[2]
Dienes are compounds that possess two C=C bonds. Depending on the proximity
of the π bonds, they are classified as cumulated, conjugated, or isolated. [3]
 In cumulated dienes, also called allenes, the π bonds are adjacent.[3]

 In conjugated dienes, the π bonds are separated by exactly one s bond.[3]

 In isolated dienes, the π bonds are separated by two or more s bonds. [3]

The observed bond distances can be explained by looking at hybridization. Each

carbon atom in 1,3butadiene is sp2 hybridized, so the central C–C single bond is
formed by the overlap of two sp2 hybridized orbitals, rather than the sp3
hybridized orbitals used to form the C–C bond in CH3CH3. [4]

• Based on hybridization, a Csp2–Csp2 bond should be shorter than a Csp3–Csp3

bond because it is formed from orbitals having a higher percent s-character. [4]

*Nomenclature
Naming diene in the IUPAC system

2
 Compounds with two double bonds are named as dienes by changing the -ane
ending of the parent alkane to the suffix -adiene. Always choose the longest chain
that contains both atoms of the double bond [4]
The positions of the double bonds are given by a number for each one, as shown
in the examples below [5]

We name cyclic dienes as follows:

1. Name the ring size; cyclobuta-, cyclopenta-, and so forth. [5]

2. After the ring has been named, determine the number of double bonds: diene,
triene, and so forth. [5]

3. Select one carbon atom of one double bond in the ring as C-1, then indicate
the position of the second double bond with the smallest number. A few
examples are shown below. Note that in these structures, the double bonds in
cyclopentadiene and 1,3-cyclohexadiene are conjugated; the double bonds in 1,4-
cyclohexadiene are isolated or nonconjugated. [5]
Figure 1

3
Physical properties
Relative Stabilities of Dienes
the relative stabilities of alkenes can be assessed from their heats of
hydrogenation. Figure 2 compares these values for the isolated diene 1,4-
pentadiene and its conjugated isomer (E)-1,3-pentadiene. The figure shows that
an isolated pair of double bonds behaves much like two independent alkene
units. The measured heat of hydrogenation of the two double bonds in 1,4-
pentadiene is 252 kJ/mol (60.2 kcal/mol), exactly twice the heat of hydrogenation
of 1-pentene. Furthermore, the heat evolved on hydrogenation of each double
bond must be 126 kJ/mol (30.1 kcal/mol) because 1-pentene is an intermediate in
the hydrogenation of 1,4-pentadiene to pentane. By the same reasoning,
hydrogenation of the terminal double bond in the conjugated diene (E)-1,3-
pentadiene releases only 111 kJ/mol (26.5 kcal/mol) when it is hydrogenated to
(E)-2-pentene. Hydrogenation of the terminal double bond in the conjugated
diene [6]
Figure 2

evolves 15 kJ/mol (3.6 kcal/mol) less heat than hydrogenation of a terminal

double bond in the diene with isolated double bonds. A conjugated double bond

4
is 15 kJ/mol (3.6 kcal/ mol) more stable than an isolated double bond. This
increased stability due to conjugation is the delocalization energy, resonance
energy, or conjugation energy.[6]
The cumulated double bonds of an allenic system are of relatively high energy.
The heat of hydrogenation of allene is more than twice that of propene.[6]

Thus, the order of alkadiene stability decreases in the order: conjugated diene
(most stable) → isolated diene → cumulated diene (least stable). To understand
this ranking, we need to look at structure and bonding in alkadienes in more
detail. [6]

Preparations of dienes
Dehydrogenation of butane
The conjugated diene 1,3-butadiene is used in the manufacture of synthetic
rubber for automobile tires and is prepared on an industrial scale in vast
quantities. In the presence of a suitable catalyst, butane undergoes thermal
dehydrogenation to yield 1,3-butadiene. [6]

Elimination reactions of unsaturated alkyl halides

Conjugated dienes can be prepared from allylic halides via an elimination process.
[3]

5
A sterically hindered base, such as potassium tert-butoxide, is used to prevent the
competing SN2 reaction from occurring. Conjugated dienes can also be formed
from dihalides via two successive elimination reactions. [3]

Elimination reactions of unsaturated alcohols

Laboratory syntheses of conjugated dienes involve elimination reactions of
unsaturated alcohols. In the example that follow, the conjugated diene is
produced in high yield even though an isolated diene is also possible. [6]

Reactions of dienes
For another example of how delocalized electrons can affect the product of a
reaction, we will compare the products formed when isolated dienes (dienes that
have only localized electrons) undergo electrophilic addition reactions to the
products formed when conjugated dienes (dienes that have delocalized
electrons) undergo the same reactions.[7]

Electrophilic addition to Isolated Dienes.

The reactions of dienes with isolated double bonds are just like the reactions of
alkenes. If an excess of the electrophilic reagent is present, two independent
electrophilic addition reactions will occur. In each reaction, the electrophile adds

6
to the sp2 carbon bonded to the most hydrogens because that results in
formation of the most stable carbocation. [7]

The reaction proceeds exactly as we would predict from our knowledge of the
mechanism for the reaction of alkenes with electrophilic reagents. [7]
MECHANISM FOR THE REACTION OF AN ISOLATED DIENE WITH EXCESS HBr

Figure 3

Step 1: The electrophile (H+) adds to the sp2 carbon bonded to the most
hydrogens in order to form the more stable carbocation. [7]
Step 2: The bromide ion adds to the carbocation. [7]
Step 3: Because there is an excess of the electrophilic reagent, there is enough
reagent to add to the other double bond; again the H+ adds to the sp2 carbon
bonded to the most hydrogens. [7]
Step 4: The bromide ion adds to the carbocation. [7]

Electrophilic addition to conjugated Dienes.

Addition of one mole of HBr to 1,3-butadiene at -78◦C gives a mixture of two
constitutional isomers, 3-bromo-1-butene and 1-bromo-2-butene.[8]

7
 The designations “1,2-” and “1,4-” used here to describe additions to conjugated
dienes and other systems do not refer to IUPAC nomenclature. Rather, they refer
to the four-atom system of two conjugated double bonds and indicate that
addition takes place at either carbons 1 and 2 or carbons 1 and 4 of the four-atom
system. For example, the Michael reaction is referred to as a 1,4-addition. The
bromobutenes formed by addition of one mole of HBr to butadiene can in turn
undergo addition of a second mole of HBr to give a mixture of dibromobutanes.
Our concern at this point is only with the products of the fi rst reaction. [8]
Addition of one mole of Br2 at -15◦C also gives a mixture of 1,2-addition and 1,4-
addition products. [8]

MECHANISM 1,2- AND 1,4-ADDITION TO A CONJUGATED DIENE

Step 1: Make a new bond between a nucleophile (p bond) and an electrophile—
add a proton. Electrophilic addition is initiated by the reaction of a terminal
carbon of one of the double bonds with HBr to give an allylic carbocation
intermediate, which can best be represented as a resonance hybrid of two
contributing structures. Formation of this stabilized cation is the rate determining
Figure 4

step. [8]

8
Step 2: Make a new bond between a nucleophile and an electrophile. Reaction of
bromide at one of the carbons bearing partial positive charge gives the 1,2-
addition product; reaction at the other gives the 1,4-addition product. [8]
Figure 5

References
1. T.W. Graham Solomons & Craig B. Fryhle & Scott A. Snyder .(2014).organic
chemistry.11thed. John Wiley & Sons,591.

2. L.G. WADE, JR.( 2013).organic chemistry.8thed. Pearson Education,667.

3. D.Klein( 2015). organic chemistry.2thed. John Wiley & Sons,783,784.

4. J. G. Smith(2011). organic chemistry.3thed.The McGraw-Hill

Companies,582,262.

5. R. J. Ouellette & J.D. rawn (2014). organic chemistry. Elsevier,357.

6. F. A. Carey & R. M. Giuliano (2014). ). organic chemistry.9 thed. The McGraw-Hill

Companies,382,383,386.

7. P.Y. Bruice (2016). organic chemistry.8thed. Pearson Education,347.

9
8. W.H. Brown & Ch.S. Foote & B.L. Iverson & E.V. Anslyn & B.M. Novak
(2012).organic chemistry.6thed.Cengage Learning,814,815.

10