John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 14
Conjugated Compounds and
Ultraviolet Spectroscopy

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Stability of Conjugated Dienes:
Molecular Orbital Theory
 Conjugated dienes are typically formed by
elimination of HX from an allylic halide

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Stability of Conjugated Dienes:
Molecular Orbital Theory
 Significant properties of conjugated dienes
 Possess a shorter central single bond

 Possess an increased stability as indicated by

heats of hydrogenation

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Table 14.1 - Heats of Hydrogenation for
Some Alkenes and Dienes

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Stability of Conjugated Dienes:
Molecular Orbital Theory
 According to the valence bond theory, orbital
hybridization is the reason behind the stability of
conjugated dienes
 Central C–C single bond is caused by σ overlap
of sp2 orbitals on both carbons
 sp2 orbitals possess 33% s character and sp3 orbitals
possess 25% s character

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The Molecular Orbital Theory
 Interaction between the π orbitals of a
conjugated diene causes an increased stability
 According to the molecular orbital theory, two π
molecular orbitals result when a π bond is
formed by the combination of two p orbitals
 One π molecular orbital possesses lesser energy
than the starting p orbitals causing it to be
bonding
 The other π molecular orbital possesses a higher
energy than the starting p orbitals and has a
node between nuclei, causing it to be antibonding

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Figure 14.2 - Four π molecular
orbitals in 1,3-butadiene

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Worked Example
 Allene, H2C=C=CH2, has a heat of
hydrogenation of –298 kJ/mol (–71.3 kcal/mol)
 Rank a conjugated diene, a nonconjugated
diene, and an allene in order of stability
 Solution:
 If the heat of hydrogenation for each double bond
were the same as that for an isolated bond:

∆H hydrog = –126 + (–126) = - 252 kJ / mol

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Worked Example
 The measured Δhhydrog, –298 kJ/mol, is 46 kJ/mol
more negative than the negative value
 Allene is higher in energy (less stable) than a
conjugated diene, which in turn is less stable
than a conjugated diene

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Electrophilic Additions to Conjugated
Dienes: Allylic Carbocations
 The behaviour of conjugated dienes in
electrophilic addition reactions is markedly
different from that of typical alkenes

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Electrophilic Additions to Conjugated
Dienes: Allylic Carbocations
 Conjugated dienes undergo electrophilic
reactions to produce a mixture of products
 1,4-addition products are formed due to the
intermediate action of allylic carbocations

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Products of Addition to
Delocalized Carbocation
 The reaction between Br– the allylic cation
occurs either at C1 or C3 as both carbons share
the positive charge

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Worked Example
 Give the structures of both 1,2 and 1,4 adducts
resulting from reaction of 1 equivalent of HBr
with the following compound

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Worked Example
 Solution:

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Kinetic versus Thermodynamic
Control of Reactions
 Addition to a conjugated diene at or below room
temperature normally leads to a mixture of
products in which the 1,2 adduct predominates
over the 1,4 adduct
 At higher temperature, the product ratio
changes and the 1,4 adduct predominates

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Kinetic versus Thermodynamic
Control of Reactions
 Consider a reaction with B and C as products

 B forms faster than C

 ΔGǂB < ΔGǂC
 C is more stable than B
 ΔG˚C > Δ G˚B

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Figure 14.5 - Energy Diagram
for Competing Reactions

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Kinetic versus Thermodynamic
Control of Reactions
 Reactions under kinetic control
 Product of an irreversible reaction depends only
on relative rates and not on stability
 B is the major product
 Reactions under thermodynamic control
 Product of a readily reversible reaction depends
only on stability and not on relative rates
 C is the major product

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Kinetic versus Thermodynamic
Control of Reactions
 Applying the principles of kinetic control and
thermodynamic control to the electrophilic
addition reactions of conjugated dienes

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Worked Example
 Determine why 1,4 adducts of 1,3-butadiene are
generally more stable than 1,2 adducts
 Solution:

 Disubstituted bonds are more stable than

monosubstituted double bonds
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The Diels-Alder Cycloaddition
Reaction
 Reaction in which conjugated dienes undergo
an addition reaction with alkenes to yield
substituted cyclohexene products

 Used to create cyclic molecules

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The Diels-Alder Cycloaddition
Reaction
 The Diels-Adler reaction is a pericyclic process
 Pericyclic reactions are single-step reactions that
take place in a cyclic redistribution of bonding
electrons

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Characteristics of the Diels-
Alder Reaction
 The Denophile (diene lover)
 If the dienophile possesses an electron-
withdrawing substituent, the Diels-Adler reaction
takes place at a high speed

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Stereospecificity of the Diels-
Alder Reaction
 The Diels-Adler reaction is stereospecific
 Forms a single product stereoisomer
 Retains the stereochemistry of the dienophile

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Characteristics of the Diels-
Alder Reaction
 The orientation of the diene and dienophile
partners favors the formation of the endo
product instead of the exo product
 Endo substituent - Syn to the larger of the 2
bridges
 Exo substituent - Trans to the larger of the 2
bridges

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Regiochemistry of the Diels-
Alder Reaction
 Diels-Adler reactions yield endo products
because the reactants are positioned directly
above one another
 Increased overlap of diene and dienophile
orbitals

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Conformations of Dienes in the
Diels-Alder Reaction
 Dienes can undergo a Diels-Adler reaction only
if they adopt an s-cis conformation
 Carbons 1 and 4 are close enough to react
through cyclic transition, unlike the s-trans
conformation

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Characteristics of the Diels-
Alder Reaction
 Dienes that are unable to adopt a s-cis
conformation do not undergo Diels-Adler
reactions

 Some dienes that are set only in the correct s-

cis geometry readily react in the Diels-Adler
cycloaddition
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Characteristics of the Diels–
Alder Reaction
 Biological Diels-Adler reactions occur but are
rare
 The biosynthesis of lovastatin contains an
intramolecular Diels-Adler reaction of a triene

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Worked Example
 Predict the product of the following Diels-Adler
reaction

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Worked Example
 Solution:
 Rotating the diene to the s-cis conformation is
necessary for the reaction to take place

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Diene Polymers: Natural and
Synthetic Rubbers
 Conjugated dienes can be polymerized
 The initiator for the reaction can be a radical, or
an acid
 Polymerization is a 1,4 addition of growing chain
to conjugated diene monomer

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Natural Rubber
 Mostly derived from the sap of Hevea
brasiliensis
 Double bonds of rubber exhibit Z
stereochemistry
 Gutta-Percha occurs naturally

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Synthetic Rubber
 Diene polymerization is used in the commercial
production of rubber
 Polymerization of chloroprene yields neoprene
 Expensive synthetic rubber with good weather
resistance

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Vulcanization
 Natural and synthetic rubbers are too soft to be
used in products
 Vulcanization involves heating rubber with sulfur
which causes the rubber to harden
 Sulfur forms bridges between hydrocarbon
chains (cross-links)
 Elasticity of rubber is due to the irregular
structure of polymer chains caused by the
double bonds
 Double bonds cause polymers to bend

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Worked Example
 Show the mechanism of the acid-catalysed
polymerization of 1,3-butadiene
 Solution:

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Ultraviolet Spectroscopy
 Specifically used to determine the molecular
structure of conjugated compounds
 Not used as widely as mass spectrometry,
infrared spectroscopy, or nuclear magnetic
resonance
 Examines the nature of conjugated π electron
system

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Ultraviolet Spectroscopy
 Ultraviolet region of electromagnetic spectrum
 Short-wavelength of the visible region to the long-
wavelength end of the X-ray region
 Scientist’s preferred area of study is the narrow
range (2×10–7 m – 4×10–7 m)

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Principle of UV Spectroscopy
 Organic molecules absorb enough energy from
UV radiation to cause an electron shift from a
lower-energy orbital to a higher-energy orbital
 UV irradiation causes a π electron to shift from
the highest occupied molecular orbital
(HOMO) to the lowest unoccupied molecular
orbital (LUMO)
 Termed pi to pi star (π to π*) excitation

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Figure 14.11 - Ultraviolet
Excitation of 1,3-butadiene

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Recording an Ultraviolet
Spectrum
 A sample is irradiated with UV light whose
wavelength alternates continuously
 Energy is absorbed when the wavelength
matches the energy required to cause electron
displacement
 Absorbed energy is detected and displayed on a
chart that plots wavelength versus absorbance
(A)
I0
A = log
I
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Molar Absorptivity (ɛ)
 It is the expression of absorbed UV light
A
ε=
c×l
 A = Absorbance
 c = Concentration in mol/L
 l = Sample pathlength in cm
 To determine the concentration of the sample
when A, ɛ, and l are known
A
c=
ε .l
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Worked Example
 Calculate the concentration of vitamin A on a
sample whose absorbance at 325 nm is A =
0.735 in a cell with a pathlength of 1.00 cm
 Pure vitamin A has λmax = 325 (ɛ = 50,100)

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Worked Example
 Solution:
A
ε=
c×l

 In this problem:
 ɛ = 50,100 = 5.01×104 L/mol.cm
 l = 1.00 cm
 A = 0.735

A 0.735 –5
=c = = 1.47 × 10 M
ε × l 5.01×10 L / mol.cm ×1.00 cm
4

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Interpreting UV Spectra:
The Effect of Conjugation
 Wavelength of UV radiation that causes pi to pi
star excitation in a conjugated molecule
ultimately depends on the nature of the
conjugated system
 Degree of conjugation has a significant
influence on the wavelength of UV absorption
 Energy difference between HOMO and LUMO is
inversely proportional to the degree of
conjugation

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Table 14.2 - Ultraviolet Absorptions of
Some Conjugated Molecules

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Worked Example
 Determine if the following compound exhibits
ultraviolet absorptions in the 200 to 400 nm
range

 Solution:
 Since the compound possesses multiple
alternate bonds, it would show ultraviolet
absorption in the 200–400 nm range
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Conjugation, Color, and the
Chemistry of Vision
 Pigmentation of compounds are caused by the
chemical structures of colored molecules and
the human perception of light
 The visible region of the electromagnetic
spectrum lies between 400 to 800nm
 The ultraviolet spectrum lies adjacent to the
visible region of the electromagnetic spectrum
 Conjugation systems of some compounds cause
their UV absorptions to extend into the visible
region

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Figure 14.13 - Ultraviolet
Spectrum of β-carotene

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Conjugation, Color, and the
Chemistry of Vision
 Human vision is possible through the functions
of rods and cones in the eye
 Rods function in dim light and cones function in
bright light

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Summary
 Conjugated diene comprises alternating double
and single bonds
 Conjugated dienes are more stable than
nonconjugated dienes
 The formation of 1,4-addition products are
exclusive to reactions with conjugated dienes
 In a reaction involving formation of 1,2 NS 1,4-
addition products, kinetic control is believed to
cause the 1,2 adduct and thermodynamic
control is believed to cause the 1,4 adduct

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Summary
 Diels-Adler cycloaddition is another reaction
unique to conjugated dienes
 Reaction is stereospecific
 Ultraviolet spectroscopy is specifically used in
the determination of conjugated π-electron
systems
 Upon UV irradiation, energy is absorbed that
causes the π electron to shift from the highest
occupied molecular orbital (HOMO) to the
lowest unoccupied molecular orbital (LUMO)

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