Organic Chemistry II / CHEM

252
Chapter 13 – Conjugated
Unsaturated Systems
Bela Torok
Department of Chemistry
University of Massachusetts Boston
Boston, MA
1
 Introduction

- Conjugated unsaturated systems have a p orbital on a carbon adjacent

to a double bond
- The p orbital can come from another double or triple bond
- The p orbital may be the empty p orbital of a carbocation or a p
orbital with a single electron in it (a radical)
- Conjugation affords special stability to the molecule
- Conjugated molecules can be detected using UV spectroscopy

2
 Allylic Substitution

Reaction of propene with bromine varies depending on reaction conditions

- At low temperature the halogen adds across the double bond
- At high temperature or at very low concentration of halogen an
allylic substitution occurs

3
 Allylic Substitution
– Allylic Chlorination (High Temperature)
• Allylic chlorination - high temperature in the gas phase
• The reaction is a free radical chain reaction
– In the initiation step a low concentration of chlorine radical is
produced
– In the first propagation step an allyl radical is formed
– In the second propagation step the allyl radical reacts with
molecular chlorine

4
 Allylic Substitution
• Allylic radicals form readily because they are more stable than
ordinary primary, secondary, tertiary, or vinyl radicals
– This trend is reflected in their respective C-H bond dissociation
energies

• The relative stability of some carbon radicals is as follows:

5
 Allylic Substitution
– Allylic Bromination with N-Bromosuccinimide
• Propene undergoes allylic bromination with N-bromosuccinimide (NBS)
in the presence of light or peroxides
– NBS provides a continuous low concentration of bromine for the
radical reaction
– A low bromine concentration favors allylic substitution over addition

• The radical reaction is initiated by a small amount of bromine radical

formed by exposure of NBS to light or peroxides

6
 Allylic Substitution
• The propagation steps for allylic bromination with NBS are:
– A bromine radical reacts with propene to produce an allylic radical
and HBr
– HBr reacts with NBS to produce a bromine molecule
– A molecule of bromine reacts with a propene radical to regenerate a
bromine radical

7
 The Allyl Radical
• The Stability of the Allyl Radical
• Both molecular orbital theory and resonance theory can explain the
stability of allyl radicals
– Molecular Orbital Description of the Allyl Radical
• When an allylic hydrogen is abstracted, the developing p orbital on the
sp2 carbon overlaps with the p orbitals of the alkene
– The new p orbital is conjugated with the double bond p orbitals
– The radical electron and the π electrons are delocalized over the
entire conjugated system
– Delocalization of charge and electron density leads to increased
stability

8
 The Allyl Radical
• The three p orbitals combine to form three molecular orbitals
– The bonding molecular orbital contains two spin-paired
electrons and this orbital increases bonding between the
carbons
– The nonbonding orbital contains a lone electron which is
located at carbons 1 and 3 only

9
 The Allyl Radical
• Resonance Description of the Allyl Radical
• The allyl radical has two contributing resonance forms
– These resonance forms can be interconverted
– The resonance structures are equivalent
– Recall that equivalent resonance structures lead to much greater
stability of the molecule than either structure alone would suggest

• The true structure of the allyl radical as suggested by resonance theory is

as follows

10
 The Allyl Cation
• The allyl cation is intermediate in stability between a tertiary and
secondary carbocation

• The molecular orbital description of the allyl cation is very similar to

the allyl radical except it contains one fewer electrons
– Stability arises from the delocalization of the positive charge

11
 The Allyl Cation
• Resonance theory predicts that the allyl cation is a hybrid of
equivalent structures D and E
– Both molecular orbital theory and resonance theory suggest that
structure F (below) is the best representation for the allyl cation

12
 Rules of Resonance
• Summary of Rules for Resonance
Rules for Writing Resonance Structures
- Individual resonance structures are not real structures - A hybrid of all
major resonance structures gives an indication of the true structure
- Only electrons may be moved in resonance structures, not atoms
Only π and nonbonding electrons are moved
- All resonance structures must have the same number of paired and
unpaired electrons and must be proper Lewis structures

- All atoms in a delocalized π-electron system must be in a plane

– The molecule above does not behave like a conjugated diene
because the large tert-butyl groups twist the structure and prevent
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the diene from being planar
 Rules of Resonance

• The energy of the actual molecule is lower than the energy calculated
for any one contributing resonance structure
– Allyl cation has much lower energy than either 4 or 5

• A system with equivalent resonance structures is particularly stable

– The allyl cation has two equivalent resonance structures and is
therefore particularly stable
• The more stable a resonance structure is, the more important it is and
the more it contributes to the hybrid
– Structure 6 is a more stable tertiary carbocation and contributes
more than structure 7

14
 Stability of Resonance Structures
– Estimating the Relative Stability of Resonance Structures
• Structures with more covalent bonds are more important
– Structure 8 is more important than 9 or 10

• Structures in which all atoms have complete octets are more important
– Structure 12 is more important than structure 11

• Separation of charge decreases stability

– 13 is more important because it does not have a separation of charge

15
Alkadienes and Polyunsaturated Hydrocarbons
• Alkadienes contain two double bonds
– These are often referred to simply as dienes
– Alkadiynes contain 2 triple bonds and alkenynes contain a double
and a triple bond
• Polyunsaturated compounds can be classified as being cumulated,
conjugated or isolated
– Conjugated bonds affect each other when they react, isolated double
bonds react separately and do not affect each other

16
 Alkadienes and Polyunsaturated Hydrocarbons
• 1,3-Butadiene: Electron Delocalization
– Bond Lengths of 1,3-Butadiene
• The double bonds of 1,3-butadiene have the expected length of
regular double bonds
• The central bond is much shorter than a regular carbon-carbon
single bond
– Ethane has a carbon-carbon bond length of 1.54 Å

• The central bond in 1,3-butadiene is shorter than that in ethene

for two reasons
– The σ bond between C2 and C3 is made from sp2-sp2
overlap
– There is significant overlap between the C2-C3 p orbitals

17
Alkadienes and Polyunsaturated Hydrocarbons
– Conformations of 1,3-Butadiene
• There are two possible planar conformations of 1,3-butadiene
called s-cis and s-trans
– s Indicates the conformations originate from rotation
around a single bond
– s-Trans is more stable because it is less sterically hindered

18
Alkadienes and Polyunsaturated Hydrocarbons
– Molecular Orbitals of 1,3-Butadiene
• The first (lowest energy) π bonding molecular orbital in 1,3-butadiene
shows significant overlap of the p orbitals between C2 and C3
– The second π orbital in 1,3-butadiene is the highest occupied
molecular orbital (HOMO) and shows no overlap between C2 and C3

19
 Alkadienes and Polyunsaturated Hydrocarbons
• The Stability of Conjugated Dienes
• 1,3-butadiene has a lower heat of hydrogenation by 15 kJ mol-1 than two
molecules of 1-butene
– A lower heat of hydrogenation means 1,3-butadiene is more stable
– These molecules can be compared directly because upon
hydrogenation they lead to the same product

20
Alkadienes and Polyunsaturated Hydrocarbons

lycopene

Chlorophyll-a

heme
21
Alkadienes and Polyunsaturated Hydrocarbons

Mauveine-A Mauveine-B

William Perkin

Mauveine-C

22
Alkadienes and Polyunsaturated Hydrocarbons

23
Alkadienes and Polyunsaturated Hydrocarbons

Nobel Prize in Medicine

1967

Type 2 rhodopsin

George Wald Ragnar Granite Haldan K. Hartline

24
 Electrophilic Reactions
• Electrophilic Attack on Conjugated Dienes: 1,4 Addition
• When 1,3-butadiene reacts with one equivalent of HCl at room
temperature 78% of the 1,2 addition product and 22% of the
1,4 addition product are obtained

25
 Electrophilic Reactions
• In step 1 hydrogen chloride reacts to add hydrogen to a terminal carbon
which gives a stable allyl cation intermediate
– Addition of hydrogen to C2 leads to an unstable 1o carbocation

• In step 2 chloride can react at either end of the allyl cation

– This leads to either 1,2 or 1,4 product

• Other electrophilic reagents add to conjugated dienes in similar fashion

26
 Electrophilic Reactions
– Kinetic Control versus Thermodynamic Control of a Chemical Reaction
• When HBr adds to 1,3-butadiene the temperature of reaction greatly affects
the distribution of 1,2 and 1,4 products
– Low temperature (e.g., -80oC) favors 1,2-addition product
– High temperature (e.g., 40oC) favors 1,4-addition product
– When the mixture of products formed at low temperature is heated, the
product ratios change to favor 1,4-addition product

27
 Electrophilic Reactions
• Heating the 1,2-addition product leads to an equilibrium which
favors the 1,4-addition product
– Because equilibrium conditions favor the 1,4-addition
product it must be the most stable

28
 Electrophilic Reactions
• At lower temperatures the proportion of products is determined by the
relative rates of formation of product
– 1,2-addition product forms faster and is the major product
– The ∆G‡ for formation of 1,2- product is lower than for 1,4- product
– At low temperatures fewer molecules have enough energy to overcome the
higher ∆G‡ for formation of the 1,4-addition product
– The reaction is said to be under kinetic control
• At higher temperatures when an equilibrium is established, the most stable
product predominates
– Enough energy is available to overcome ∆G‡ barriers for formation of both
products and for the reverse reactions
– An equilibrium situation exists and the most stable product is the major one
– 1,4-addition product is more stable and is the major product
– The reaction is said to be under thermodynamic control
• The 1,4 product is most stable - disubstituted double bond
• The 1,2-addition product forms faster because the allyl cation has more δ+
charge density at the 2o rather than the 1o carbon
29
 The Diels-Alder Reaction
• The Diels-Alder Reaction: A 1,4-Cycloaddition Reaction of Dienes
• Heating 1,3-butadiene and maleic anhydride gives a 6-membered ring
product in 100% yield

• The simplest Diels-Alder reaction forms a cylohexene product

– Overall, two new σ bonds are formed at the expense of two π bonds
– The conjugated diene is a 4π-electron system
– The dienophile (“diene lover”) is a 2π-electron system
– The product is called an adduct

30
 The Diels-Alder Reaction
– Factors Favoring the Diels-Alder Reaction
• The simplest possible example of a Diels-Alder reaction goes at very low
yield and requires high temperatures

• To proceed in good yield and at low temperature the dienophile should

have electron-withdrawing groups
– It also helps if the diene has electron-releasing groups
– Dienes with electron-donating groups and dienophiles with electron-
withdrawing group can also react well together

31
 The Diels-Alder Reaction
– Stereochemistry of the Diels-Alder Reaction
• The Diels-Alder reaction is stereospecific i.e. the reaction is a syn
addition, and the configuration of the dienophile is retained

• The diene must be in the s-cis conformation to react

– s-Trans conformation would lead to formation of a highly unstable
trans bond in a 6-membered ring
– Cyclic dienes (rigid s-cis conformation!) are highly reactive

32
 The Diels-Alder Reaction
• Cyclopentadiene is so reactive it spontaneously undergoes Diels-Alder
reaction with itself at room temperature
– This dimer can be “cracked” (undergo retro-Diels-Alder reaction) by
heating and the cyclopentadiene product isolated by distillation.

• The Diels-Alder reaction occurs primarily in an endo rather than an exo

fashion when the reaction is kinetically controlled
– A group that is exo in a bicyclic ring system is anti to the longest
bridge
– A group that is endo is on the same side as the longest bridge

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 The Diels-Alder Reaction

Nobel Prize in
Chemistry
1950

Otto P. H. Diels Kurt Alder

Nobel Prize in
Chemistry
Interpretation
1981

Robert B.
Woodward

Roald Hoffmann Kenichi Fukui 34