Conjugated Systems, Orbital Symmetry, and

Ultraviolet Spectroscopy

© 2013 Pearson Education, Inc. Chapter 15 1

 Conjugated Systems

•  Conjugated double bonds are separated by one single bond.

•  Isolated double bonds are separated by two or more single bonds.
•  Conjugated double bonds are more stable than isolated ones.

© 2013 Pearson Education, Inc. Chapter 15 2

 Heat of Hydrogenation of Conjugated
Bonds

§  For conjugated double bonds, the heat of hydrogenation is less than the sum for
the individual double bonds.
§  The more stable the compound, the less heat released during hydrogenation.
§  Conjugated double bonds have extra stability.

© 2013 Pearson Education, Inc. Chapter 15 3

 Relative Stabilities

© 2013 Pearson Education, Inc. Chapter 15 4

 Structure of Buta-1,3-diene
Not only stability look at the bond length

§  The C2—C3 single bond is shorter than 1.54 Å.

§  Electrons are delocalized over the molecule.
§  There is a small amount of overlap across the central C2—C3 bond,
giving it a partial double bond character.

How do you explain ?

© 2013 Pearson Education, Inc. Chapter 15 5
 Molecular Orbitals (MOs)
§  All atoms of buta-1,3-diene are sp2 hybridized with overlapping p orbitals.
§  Each p orbital has two lobes with the wave function indicated by plus (+) and minus
(–) sign (not electrical charges).
§  When lobes overlap constructively (+ and +, or – and –), a pi bonding (π) MO is
formed.
§  When lobes overlap destructively (+ and –), a pi antibonding (π*) MO is formed.

Why ?
To understand and predict the properties
of conjugated systems

Remember Rules ???

© 2013 Pearson Education, Inc. Chapter 15 6

 MO for Buta-1,3-diene and Ethylene
§  The bonding MOs of both
buta-1,3-diene and ethylene
are filled and the antibonding
MOs are empty.

§  Buta-1,3-diene has lower

energy than ethylene.

§  This lower energy is the

resonance stabilization of the
conjugated diene.

© 2013 Pearson Education, Inc. Chapter 15 7

 π1 MO for Buta-1,3-diene

§  Lowest energy.

§  All bonding
interactions.
§  Electrons are
delocalized over
four nuclei.

Note the number of nodes

© 2013 Pearson Education, Inc. Chapter 15 8

 π2 MO for Buta-1,3-diene

§  Two bonding interactions.

§  One antibonding
interaction.
§  This is a bonding MO.
§  Higher energy than
π1 MO and not as strong.

Note the number of nodes

© 2013 Pearson Education, Inc. Chapter 15 9

 π3* MO for Buta-1,3-diene

§  Two antibonding and

one bonding
interaction.
§  Two nodes.
§  Vacant in the ground
state.

© 2013 Pearson Education, Inc. Chapter 15 10

 π4* MO for Buta-1,3-diene
§  Three nodes.
§  Strongly antibonding.
§  Highest energy MO.
§  Vacant at ground state.

© 2013 Pearson Education, Inc. Chapter 15 11

 Ethylene Pi MOs
Visualized using computational models

§  The combination of two p orbitals must give two molecular orbitals.
§  Constructive overlap is a pi bonding (π) MO.
§  Destructive overlap is an antibonding (π*) MO.

© 2013 Pearson Education, Inc. Chapter 15 12

 Allylic Radicals

§  Stabilized by resonance.

§  Radical stabilities: 1° < 2° < 3° < 1° allylic.
§  Substitution at the allylic position competes with addition to double
bond.
§  To encourage substitution, use a low concentration of reagent with
light, heat, or peroxides to initiate free radical formation.

© 2013 Pearson Education, Inc. Chapter 15 13

 Mechanism of Allylic Bromination

Initiation step:

Propagation steps:

© 2013 Pearson Education, Inc. Chapter 15 14

 Or use NBS/
Bromination Using N-Bromosuccinimide (NBS)

§  NBS provides a low, constant concentration of Br2.

§  NBS reacts with the HBr by-product to produce Br2 and to
prevent HBr addition across the double bond.

© 2013 Pearson Education, Inc. Chapter 15 15

 Allyl System
§  Geometric structure of the allyl
cation, allyl radical, and allyl
anion.
§  The three p orbitals of the allyl
system are parallel to each
other, allowing for the
extended overlap between C1–
C2 and C2–C3.

© 2013 Pearson Education, Inc. Chapter 15 16

 Allylic Anions

§  The allylic anion has two electrons in the π2 MO.

§  As with allyllic cations and radicals, the allylic anion is also
stabilized by resonance.

© 2013 Pearson Education, Inc. Chapter 15 17

 MOs for the Allylic Species

© 2013 Pearson Education, Inc. Chapter 15 18

 Stable molecules tend to have
filled bonding MOs and empty
antibonding MOs.

© 2013 Pearson Education, Inc. Chapter 15 19

 The Allylic Position

§  The allylic carbon is the one directly attached to an sp2 carbon.
§  Allylic cations are stabilized by resonance.

© 2013 Pearson Education, Inc. Chapter 15 20

 Allylic Cations

§  The positive charge is delocalized over two carbons by resonance,

giving the allyl cation more stability than nonconjugated cations.

© 2013 Pearson Education, Inc. Chapter 15 21

 Stability of Carbocations

§  Stability of 1° allylic ≈ 2° carbocation.

§  Stability of 2° allylic ≈ 3° carbocation.

© 2013 Pearson Education, Inc. Chapter 15 22

 §  During propagation an allylic radical is formed that is stabilized by
resonance.
§  Either radical can form the final product.

© 2013 Pearson Education, Inc. Chapter 15 23

 MO for Buta-1,3-diene and Ethylene
§  The bonding MOs of both
buta-1,3-diene and ethylene are
filled and the antibonding MOs
are empty.
§  Buta-1,3-diene has lower energy
than ethylene.
LUMO
§  This lower energy is the
resonance stabilization of the
LUMO
conjugated diene.

HOMO HOMO and LUMO

HOMO
HOMO: Highest occupied molecular orbital
LUMO: Lowest unoccupied molecular orbital

Identify HOMO and LUMO of both molecules

© 2013 Pearson Education, Inc. Chapter 15 24
 Electrophilic addition reactions of
conjugated dienes

© 2013 Pearson Education, Inc. Chapter 15 25

 1,2- and 1,4-Addition
to Conjugated Dienes
§  Electrophilic addition to the double bond produces the most stable
intermediate.
§  For conjugated dienes, the intermediate is a resonance-stabilized allylic
cation.
§  Nucleophile adds to either carbon 2 or 4, both of which have the
delocalized positive charge.

§  Addition of HBr to buta-1,3-diene produces: 3-bromobut-1-ene (1,2-addition)

§  and 1-bromobut-2-ene (1,4-addition).
© 2013 Pearson Education, Inc. Chapter 15 26
 Mechanism of 1,2- and 1,4-Addition

© 2013 Pearson Education, Inc. Chapter 15 27

 Kinetic Versus Thermodynamic Control

At different temperatures major product is different ?????

Regardless of the temperature which is the more stable product ? Is it 1-2 or 1-4
© 2013 Pearson Education, Inc. Chapter 15 28
 Kinetic Versus
Thermodynamic Control (Continued)

© 2013 Pearson Education, Inc. Chapter 15 29

 Kinetic Control at –80 °C
§  Transition state for the 1,2-addition has a lower Ea because it is a more stable secondary
carbocation.
§  The 1,2-addition will be the faster addition at any temperature.
§  The nucleophilic attack of the bromide on the C2 allylic carbocation is irreversible at this low
temperature.
§  The product that forms faster predominates (kinetic product).
§  Because the kinetics of the reaction determines the product, the reaction is said to be under
kinetic control.

© 2013 Pearson Education, Inc. Chapter 15 30

 Thermodynamic Control at 40 °C
§  The 1,2-addition is still the faster addition, but at 40 °C, the bromide attack is reversible.
§  The 1,2-product ionizes back to the allylic cation.
§  At 40 °C an equilibrium is established, which favors the most stable product.
§  The 1,4-addition is the most stable product (thermodynamic product) because it has a more
substituted double bond.
§  Because the thermodynamics of the reaction determines the product, the reaction is said to
be under thermodynamic control.

© 2013 Pearson Education, Inc. Chapter 15 31

 SN2 Reactions of Allylic Halides and Tosylates
§  Allylic halides and tosylates react quickly by the SN2 mechanism.
§  The transition state of the SN2 mechanism is stabilized through conjugation
with the p orbitals of the pi bond.
§  This transition state has a lower activation energy and explains the enhanced
reactivity of these allylic species.

© 2013 Pearson Education, Inc. Chapter 15 32

 SN2 Reactions with Organometallics

§  Allylic halides and tosylates react with Grignards

and organolithiums:

H2C═CHCH2Br + CH3Li à H2C═CHCH2CH3 + LiBr

© 2013 Pearson Education, Inc. Chapter 15 33

§  Named after Otto Diels and Kurt Alder. They received the Nobel prize in1950.

§  The reaction is between a diene and an electron-deficient alkene (dienophile).

§  Produces a cyclohexene ring.
§  The Diels–Alder is also called a [4 + 2] cycloaddition because a ring is formed by
the interaction of four pi electrons of the alkene with two pi electrons of the alkene
or alkyne.

A pericyclic reaction
© 2013 Pearson Education, Inc. Chapter 15 34
 Conformations of
Buta-1,3-diene for diels alder reaction
§  The s-trans conformer is more stable than the s-cis by 12 kJ/mol
(2.8 kcal/mol).
§  Easily interconvert at room temperature.

But for diels alder reaction s-cis is required

© 2013 Pearson Education, Inc. Chapter 15 35
 Mechanism of the Diels–Alder Reaction

§  One-step, concerted mechanism.

§  A diene reacts with an electron-poor alkene (dienophile) to give
cyclohexene or cyclohexadiene rings.

© 2013 Pearson Education, Inc. Chapter 15 36

 Examples of Diels–Alder Reactions

© 2013 Pearson Education, Inc. Chapter 15 37

 Stereochemical Requirements
§  Diene must be in s-cis conformation.
§  Diene’s C1 and C4 p orbitals must overlap with dienophile’s p orbitals to
form new sigma bonds.
§  Both sigma bonds are on same face of the diene: syn stereochemistry.

© 2013 Pearson Education, Inc. Chapter 15 38

 Explain using MO diagrams
As you may know there
are electron transitions in-
between two molecules……
So which MOs should
get involved

HOMO of diene and LUMO

of dieneophile
LUMO

Why ????

HOMO

© 2013 Pearson Education, Inc. Chapter 15 39

 Diels–Alder Rate for Dienes

§  Cyclopentadiene undergoes the Diels–Alder reaction readily because of its fixed s-
cis conformation.
§  When the diene is sterically hindered, the reaction slows down even though the
conformation can be s-cis.
§  s-trans dienes cannot undergo the Diels–Alder reaction.

© 2013 Pearson Education, Inc. Chapter 15 40

© 2013 Pearson Education, Inc. Chapter 15 41
 Rules of Diels alder reaction :1. Endo Rule

§  The p orbitals of the electron-withdrawing groups on the

dienophile have a secondary overlap with the p orbitals of C2
and C3 in the diene.

© 2013 Pearson Education, Inc. Chapter 15 42

 Examples of Endo Rule

© 2013 Pearson Education, Inc. Chapter 15 43

 Rule 2: Unsymmetrical Reagents:
1,4-Product

© 2013 Pearson Education, Inc. Chapter 15 44

 Unsymmetrical Reagents:
1,2-Product

© 2013 Pearson Education, Inc. Chapter 15 45

 Solved Problem 1
Predict the products of the following proposed Diels–Alder reactions.

Solution

© 2013 Pearson Education, Inc. Chapter 15 46

 Solved Problem 1 (Continued)
Predict the products of the following proposed Diels–Alder reactions.

Solution (Continued)

© 2013 Pearson Education, Inc. Chapter 15 47

 Pericyclic Reactions
§  Diels–Alder reaction is an example of a pericyclic reaction.
§  Woodward and Hoffmann predicted reaction products using their theory
of conservation of orbital symmetry.
§  MOs must overlap constructively to stabilize the transition state.

© 2013 Pearson Education, Inc. Chapter 15 48

 Symmetry-Allowed Reaction

§  Diene contributes/donates electrons from its highest energy occupied

orbital (HOMO).
§  Dienophile receives electrons in its lowest energy unoccupied orbital
(LUMO).

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 “Forbidden” Cycloaddition

§  [2 + 2] cycloaddition of two ethylenes to form cyclobutene has

antibonding overlap of HOMO and LUMO.

© 2013 Pearson Education, Inc. Chapter 15 50

 Photochemical Induction

§  Absorption of correct energy photon will promote an electron to

an energy level that was previously unoccupied.

© 2013 Pearson Education, Inc. Chapter 15 51

 [2 + 2] Cycloaddition

Photochemically allowed, but

thermally forbidden.

© 2013 Pearson Education, Inc. Chapter 15 52

 Ultraviolet Spectroscopy
§  200- to 400-nm photons excite electrons from a π bonding orbital to a π*
antibonding orbital.
§  Conjugated dienes have MOs that are closer in energy.
§  A compound that has a longer chain of conjugated double bonds absorbs light at
a longer wavelength.

© 2013 Pearson Education, Inc. Chapter 15 53

 IR spectroscopy also detects conjugated
double bonds by their lowered stretching
frequencies.
1640–1680 cm–1 isolated
1620–1640 cm–1 conjugated
1600 cm–1 aromatic

© 2013 Pearson Education, Inc. Chapter 15 54

 π → π* for Ethylene and Butadiene

© 2013 Pearson Education, Inc. Chapter 15 55

 Obtaining a UV Spectrum

§  The spectrometer measures the intensity of a reference beam

through solvent only (Ir) and the intensity of a beam through a
solution of the sample (Is).
§  Absorbance is the log of the ratio Ir/Is.

© 2013 Pearson Education, Inc. Chapter 15 56

 The UV Spectrum

§  Usually shows broad peaks.

§  Read λmax from the graph.
§  Absorbance, A, follows Beer’s law:
A = εcl
where ε is the molar absorptivity, c is the sample concentration
in moles per liter, and l is the length of the light path in
centimeters.

© 2013 Pearson Education, Inc. Chapter 15 57

 UV Spectrum of Isoprene

© 2013 Pearson Education, Inc. Chapter 15 58

 Sample UV Absorptions

© 2013 Pearson Education, Inc. Chapter 15 59

 Some good rules of thumb: An additional
conjugated C═C increases λmax about 30
to 40 nm; an additional alkyl group
increases it about 5 nm.
Useful base values:

© 2013 Pearson Education, Inc. Chapter 15 60

 Solved Problem 2
Rank the following dienes in order of increasing values of λmax. (Their actual absorption maxima are
185 nm, 235 nm, 273 nm, and 300 nm.)

Solution
These compounds are an isolated diene, two conjugated dienes, and a conjugated triene. The isolated
diene will have the shortest value of λmax (185 nm), close to that of cyclohexene (182 nm).
The second compound looks like 3-methylenecyclohexene (232 nm) with an additional alkyl
substituent (circled). Its absorption maximum should be around (232 + 5) nm, and 235 nm must be the
correct value.
The third compound looks like cyclohexa-1,3-diene (256 nm), but with an additional alkyl
substituent (circled) raising the value of λmax so 273 nm must be the correct value.
The fourth compound looks like cyclohexa-1,3-diene (256 nm), but with an additional
conjugated double bond (circled) and another alkyl group (circled). We predict a value of λmax about 35
nm longer than for cyclohexa-1,3-diene, so 300 nm must be the correct value.

© 2013 Pearson Education, Inc. Chapter 15 61