Conjugated Unsaturated Systems Benzene, C6H6

•  Resonance contributors are imaginary,

Chapter 16 but the resonance hybrid is real.
•  Benzene is a planar molecule.
•  All six of the C-C bond lengths are
identical.
•  Each p electron is shared by all six
carbons in a π-bonding system.
•  The π electrons are delocalized.

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E-2

Conjugation & Delocalization H H H

•  Conjugation occurs whenever p orbitals Localized C H

H C H
can overlap on three or more adjacent atoms.
vs. H3C C C N
H
•  The four p orbitals on adjacent atoms make a 1,3-diene a conjugated system. Delocalized H H H
•  The p orbital at the allylic position is in conjugation with the double bond. Electrons localized
electrons
•  Having three or more p orbitals on adjacent atoms allows p orbitals to overlap and
electrons to delocalize. localized
electrons

O O O

H3C C H3C C = H3C C

O O O
delocalized
electrons

E-4
 Conjugated, unsaturated, π-delocalized systems Dienes •  1,4-Pentadiene is an isolated diene.

•  The π bonds in 1,4-pentadiene are too far apart to be conjugated

and are isolated from each other by a sp3 carbon.

E-5

Resonance, Hybridization, and Conjugation p-Orbitals Required for Conjugation O O

H3C C H3C C

There are two Lewis structures (A and B) for the resonance-stabilized acetone
•  Continue to consider the acetone enolate C C
enolate anion (CH3COCH2)- anion and its resonance structures.

•  The electron pair on the oxygen atom adjacent to the C=O can only be delocalized if
it has a p orbital that can overlap with two other p orbitals on adjacent atoms.

•  The terminal carbon atom is sp2 hybridized with trigonal planar geometry.

•  Three adjacent p orbitals make the anion conjugated.

•  The actual hybrid has more of the charge on the oxygen and more C=C double bond
character.

•  Based on structure A, the indicated carbon is sp3 hybridized, with the lone
pair of electrons in an sp3 hybrid orbital.

•  Based on structure B, however, it is sp2 hybridized with the unhybridized p

orbital forming the π portion of the double bond.
 Conjugation of Allylic Cations Stability of Allyl Cations
•  Conjugation of the p-orbitals stabilizes the allyl carbocation. •  Experimental data show that the stability of the allyl cation is comparable
to a more highly substituted 2° carbocation.
•  Delocalizing the charge stabilizes the allyl carbocation, making it more
stable than a normal 1° carbocation.

Common Examples of Resonance Common Examples of Resonance

Type [1] The Three Atom Allyl System, X = Y − Z*
Type [2] Conjugated Double Bonds

•  Cyclic, completely conjugated rings like benzene have two resonance structures,
drawn by moving the electrons in a cyclic manner around the ring.
•  Three resonance structures can be drawn for other conjugated dienes, two of
which involve separation of charge.

Examples are the allyl cation and the acetate anion. The two resonance structures
differ in the location of the double bond, and either the charge, the radical, or the
lone pair, generalized by [*].
 Common Examples of Resonance Common Examples of Resonance

Type [3] Cations Having a Positive Charge Adjacent to a Lone Pair Type [4] Double Bonds Having One Atom More Electronegative Than the Other

•  The overall charge is the same in both resonance structures.

•  Based on formal charge, a neutral X in one structure must bear a (+)
charge in the other.

The Resonance Hybrid is a Combination of Resonance Forms

Resonance (Valence Bond) Description of the Allyl Radical
•  The actual hybrid resembles the most stable resonance structure(s).
•  The allyl radical has two contributing resonance forms.
•  Three rules guide the assessment of the relative stability of resonance structures.
•  The resonance structures are equivalent.
•  Recall that equivalent resonance structures lead to much greater
stability of the molecule than either structure alone would suggest.

Arrow-pushing (to get from A to B):

•  The true structure of the

allyl radical as suggested
by resonance theory:

E - 16
Allyl Radical Formation & p-Orbital Overlap (Valence Bond Theory) Molecular Orbitals
•  Molecular Orbitals (MO) Theory describes the molecular orbitals in molecules
based on the mathematical combination of the wave functions for the overlapping
atomic orbitals involved.

•  Molecular orbital theory and valence bond (VB) theory (involving resonance) often
describe very similar structures for compounds and predict very similar
reactivities.

•  However, VB theory does not properly account for some observed phenomena in
reaction mechanisms and spectroscopy.
X Transition State Orbital description of the
H
•  MO theory is more consistent with observed data.
resonance hybrid C below
•  For most of the reaction systems we study, both give a good approximation of the
nature of the compounds and reactions.

•  Wave functions and amplitude:

–  The lobes of the molecular orbitals are depicted with different colors,
representing positive versus negative amplitudes of the wave functions.
=
–  In reactions, overlap of amplitudes with the same sign (or color) suggests a
favorable interaction (lower energy) and overlap of opposite sign an
unfavorable interaction (higher energy).
E - 17 E - 18

Molecular orbital description Molecular orbitals in the allylic radical

Resonance Hybrid
(VB Theory): of the allyl radical
•  The three p orbitals of the allylic system combine to form three molecular
orbitals.

•  The bonding molecular orbital contains two spin-paired electrons and this orbital
LUMO
increases bonding between the carbons.
Lowest Unoccupied
Molecular Orbital •  The nonbonding orbital contains a lone electron which is located at carbons 1
and 3 only.

•  The shape of the lowest energy molecular orbital is similar to the fully-
conjugated system described by VB theory.
HOMO
Highest Occupied
Molecular Orbital
•  The shape of the HOMO, or the Highest Occupied Molecular Orbital is
consistent with the partial radical character on the two outer carbons in the
resonance hybrid.

•  The shape of the highest energy molecular orbital (which in this case also
happens to be the LUMO or Lowest Unoccupied Molecular Orbital) is most
similar to the shapes of the original p-orbitals, with the amplitudes inverted.

•  In general, reactions of compounds involve either the HOMO, LUMO, or both.

E - 19 E - 20
 Polyunsaturated Hydrocarbons
The Allyl Cation – Molecular Orbital Theory
•  Polyunsaturated compounds can be classified as being cumulated, conjugated or isolated.
•  Conjugated dienes affect each other when they react, isolated double bonds react
separately and do not affect each other.

Valence Bond Theory

Resonance Hybrid:

The molecule below does not behave

like a conjugated diene because the
large tert-butyl groups twist the structure
and prevent the diene from being planar.

NOT conjugated
NOT conjugated

E - 21

Valence Bond Theory & 1,3-butadiene Molecular Orbitals of 1,3-Butadiene

F - 24
Conjugated Diene Conjugated Diene
Bond Lengths: Conformations:

Conjugated Diene
Resonance: Stereoisomers:

Be sure not to confuse conformational differences & stereoisomers:

Percent s-orbital Character:

Note: Only the s-trans

conformer is possible for this
stereoisomer; the s-cis
conformer would be too
sterically hindered.

Stability of Conjugated Dienes vs. Isolated Dienes Ultraviolet-Visible Spectroscopy

•  When hydrogenation gives the same alkane from two dienes, the •  Conjugated compounds absorb energy in the ultraviolet (UV) and visible (Vis)
more stable diene has the smaller heat of hydrogenation. regions on the electromagnetic spectrum.
•  The conjugated diene is more stable by ~ 30 kJ/mol. •  The wavelength of radiation absorbed and the intensity of the absorption
depend on the structure of the molecule.

•  A UV-Vis spectrum is typically measured from 200-800 nm, spanning the near
UV and visible regions.

Energy Diagram:
 Absorbance in UV-Vis Spectroscpy UV absorption spectrum of 2,5-dimethyl-2,4-hexadiene
•  In UV-Vis spectroscopy the electrons are excited from lower energy levels to higher ones.
(in methanol at a concentration of 5.95 x 10-5 M in a 1.0 cm cell)
•  The electron is generally excited from the highest occupied molecular orbital (HOMO) to the
lowest unoccupied molecular orbital (LUMO).

•  Alkenes and nonconjugated dienes have absorptions below 200 nm because the energy
difference between the HOMO and LUMO is large.

•  In conjugated dienes these

energy levels are much
closer together and the
wavelengths of absorption
are longer than 200 nm

•  Ethene has λmax at 171 nm

and 1,3-butadiene has λmax
at 217 nm.

Conjugated Dienes and Ultraviolet Light Increasing Conjugation and Ultraviolet Light
•  With molecules having eight or more conjugated π bonds, the
absorption shifts from the UV to the visible region.
•  The compound takes on the color of the light it does not absorb.

Carbonyl Compounds
•  Carbonyl compounds also absorb light in the UV region.
•  An unshared electron on oxygen is promoted to a p* orbital.
•  β-Carotene has 11 conjugated double bonds and an absorbance maximum
at 497 nm which is in the blue-green region of the visible spectrum.

•  β-Carotene is perceived as red-orange, the complementary color of blue-

green.
Conjugated Dienes and Visible Light Sunscreens
•  UV radiation from the sun is high enough in energy to cleave bonds, forming
•  The longer the conjugated system, the smaller the energy difference between the radicals that can prematurely age skin and cause cancer.
HOMO and the LUMO.
•  However, since much of this radiation is filtered out by the ozone layer, only UV
•  Lycopene absorbs visible light at λmax = 470 nm, in the blue-green region of the light having wavelengths >290 nm reaches the earth s surface.
visible spectrum.
•  Much of this UV light is absorbed by melanin, the highly conjugated colored
•  Because it does not absorb light in the red region, lycopene appears bright red. pigment in the skin that serves as the body s natural protection against the
harmful effects of UV radiation. Prolonged exposure to the sun can allow more UV
radiation to reach your skin than melanin can absorb.
•  Sunscreens can offer some protection, because they contain conjugated
compounds that absorb UV light, thus shielding the skin (for a time) from the
harmful effects of UV radiation. Sunscreens are given an SPF rating (sun
protection factor), according to the amount of sunscreen present.
•  Two sunscreens that have been used for this purpose are para-aminobenzoic acid
(PABA) and padimate O.

Products of Electrophilic Addition

•  Electrophilic addition of one equivalent of HBr to an isolated diene yields
one product and Markovnikov s rule is followed.

•  Electrophilic addition in conjugated dienes gives a mixture of two

products, called the 1,2- and 1,4-addition products.
Addition to 1,3-dienes: Reaction Conditions and Products How Kinetic vs. Thermodynamic Products Form (General)

•  The amount of 1,2- and 1,4-addition products formed in •  The rate of a reaction is determined by its energy of activation (Ea),
electrophilic addition reactions of conjugated dienes depends whereas the amount of product present at equilibrium is determined by its
greatly on the reaction conditions. stability.

Kinetic Effects for 1,2-Products Greater Stability of 1,4-Products

•  The 1,4-product is more stable because it has two alkyl groups

bonded to the carbon–carbon double bond, whereas the 1,2-
product has only one.

The 2º carbon (C2) bears more of the +

charge than the 1º carbon (C4). In other
words the resonance structure on the right
is a bigger contributor to the resonance
hybrid.
 Kinetic vs. Thermodynamic Products Energy Diagram for the Two-Step Mechanism
for the addition of HBr to 1,3-butadiene
•  When a reaction mixture containing predominantly the 1,2-product is
heated, the 1,4-addition product becomes the major product at
equilibrium.

•  At low temperature, the lower energy of activation pathway is followed, since most
molecules do not have enough energy to overcome the higher barrier.

•  At higher temperature, most molecules have enough kinetic energy to reach either
transition state and equilibrium favors the more stable product.

The Diels–Alder Reaction Examples of the Diels–Alder Reaction

•  The Diels–Alder reaction is an addition reaction between a 1,3-diene and an
alkene (called a dienophile), to form a new six-membered ring.

•  Because each new σ bond is ~ 80 kJ/mol stronger than a π bond that is broken, a
typical Diels–Alder reaction releases ~ 160 kJ/mol of energy.

•  Heating is sometimes necessary to overcome the activation energy barrier, even

though the reaction is exothermic.
 Synthesis Using the Diels–Alder Reaction

46

Rules of the Diels–Alder Reaction Rules of the Diels–Alder Reaction

1.  The diene can react only when it adopts the s-cis conformation. 2. Electron-withdrawing substituents in the dienophile increase the
reaction rate.

•  In a Diels–Alder reaction, the conjugated diene acts as a

nucleophile and the dienophile acts as an electrophile.
•  Electron-withdrawing groups make the dienophile more
electrophilic (and thus more reactive) by withdrawing electron
•  This rotation is prevented in cyclic alkenes.
density from the carbon–carbon double bond.
•  When the two double bonds are constrained to an s-cis conformation, the
•  If Z is an electron-withdrawing group, then the reactivity of the
diene is unusually reactive.
dienophile increases as follows:
•  When the two double bonds are constrained in the s-trans conformation,
the diene is unreactive.
 Dienophiles in the Diels–Alder Reaction Rules of the Diels–Alder Reaction

•  A carbonyl group adjacent to the double bond is an effective electron- 3. The stereochemistry of the dienophile is retained.
withdrawing group because it bears a partial positive charge (δ+), which
withdraws electron density from the carbon–carbon double bond of the
dienophile.
•  Some common dienophiles are shown below:

49

Fused and Bridged Bicyclic Ring Systems Formation of Fused Ring Systems
•  A cyclic dienophile forms a bicyclic product.
•  A bicyclic system in which two rings share a common C–C bond is called
a fused ring system.
•  The two H atoms of the ring fusion must be cis, because they were cis in
the starting dienophile.
•  A bicyclic system of this sort is said to be cis fused.

52
Formation of Bridged Bicyclic Ring Systems Rules of the Diels–Alder Reaction
4. Preference for Endo Orientation
•  When ethylene reacts with 1,3-cyclopentadiene, a new six-membered ring
forms and above the ring there is a one atom bridge. •  When cyclopentadiene reacts with a substituted alkene as the
dienophile (CH2=CHZ), the substituent Z can be oriented in one of
•  Thus, the product is bicyclic, but the carbon atoms shared by both rings
two ways in the product, exo or endo.
are nonadjacent.
•  In these cases, the endo product is preferred.
•  A bicyclic ring system in which the two rings share nonadjacent carbon
atoms is called a bridged ring system.

Endo Addition Mechanism for Endo and Exo Addition

•  The transition state leading to the endo product allows more interaction between
Figure 16.11
the electron-rich diene and the electron-withdrawing substituent Z on the
dienophile.

•  This is an energetically favorable arrangement.

 Reaction of maleic anhydride and cyclopentadiene Retrosynthetic Analysis
To draw the starting materials from a given Diels–Alder adduct:

Notes:
•  Retain the stereochemistry of substituents on the C=C of the dienophile.

http://www.chemtube3d.com/DAendo_vs_exo,cyclopentadiene_and_maleic_anhydride.html •  Cis substituents on the six-membered ring give a cis dienophile.

Diels–Alder Reaction Dimers The Retro Diels–Alder Reaction

•  When heated, dicyclopentadiene undergoes a retro Diels–Alder reaction,
•  A reactive molecule like 1,3-cyclopentadiene readily undergoes a Diels– and two molecules of cyclopentadiene are
Alder reaction with itself: that is, 1,3-cyclopentadiene dimerizes because re-formed.
one molecule acts as the diene and another acts as the dienophile.
•  If the newly produced cyclopentadiene is immediately treated with a
different dienophile, it reacts to form a new Diels–Alder adduct with this
dienophile.

•  This is how cyclopentadiene, used in Diels–Alder reactions, is produced.

•  The formation of dicyclopentadiene is so rapid that it takes only a few

hours at room temperature for cyclopentadiene to completely dimerize.
Steroid Synthesis Some Common Steroids
•  Diels–Alder reactions have been widely used in the laboratory synthesis
of steroids. •  Steroids exhibit a wide range of biological properties, depending on the
substitution pattern of the functional groups on the rings.
•  Steroids are tetracyclic lipids containing three six-membered rings and
one five-membered ring. •  Some examples of steroids are below:

•  The four rings are designated as A, B, C, and D.

Steroid Synthesis Synthesis Using the Diels–Alder Reaction

•  The key Diels–Alder reactions used to prepare the C ring of estrone
and the B ring of cortisone are as follows: