Conjugated Systems

Double bonds in conjugation behave differently than isolated double bonds

With conjugated double bonds resonance structures can be drawn

With isolated double bonds cannot draw resonance structures including both alkenes

 Leads directly to energy differences

As expected, those structures that can draw resonance structures are more stable,

therefore conjugated double bonds are more stable than isolated double bonds

More stable

Remember that internal double bonds are more stable than terminal double bonds

-in addition we can classify dienes, and other multiple alkene structures,

by whether the alkenes are in conjugation

 Another type of multiple alkene is an allene

Allenes, shortest form of a cumulene (parent name), have two double bonds

with common carbon atom in both alkenes

Cumulenes are less stable than both conjugated and isolated double bonds

The double bonds are orthogonal to each other

Leads to a less stable structure

 Molecular Orbitals

We can understand, and predict, many properties of conjugated systems

by considering the molecular orbitals

Remember when we discussed bonding in organic compounds

we formed bonds by combining atomic orbitals

Either sigma (σ) or pi (π) bonds were formed depending upon the symmetry

of the resultant bond upon addition of the atomic orbitals

 Sigma Bonds

Formed by combining two atomic orbitals

(shown here with two atomic s orbitals)

Sigma (bonding)

If combine two atomic orbitals MUST obtain two molecular orbitals

Sigma* (antibonding)

 The same process occurs when considering conjugated dienes

Rules for combining orbitals:

1) Always get the same number of molecular orbitals as

number of atomic orbitals used to combine

2)
As the number of nodes increase, the energy of the molecular orbital increases

3) The molecular orbitals obtained are the region of space where the electrons my reside

(on time average)

 First consider an isolated alkene

Simplest is ethylene

We can separate the sigma and pi framework

With alkenes, we are interested in the pi framework

since this is what controls the reactivity

The molecular orbitals obtained computationally appear same

as the approximation used by combining atomic p orbitals

π bond
π* bond

 Can draw electronic configuration for the π system

Again consider ethylene

Since there are 2 π electrons in this molecule, will place 2 electrons in MO diagram

Always place electrons in lowest energy orbital first

Each orbital can accommodate two electrons

E
 Use same procedure for larger conjugated systems

With butadiene there are 4 p orbitals in conjugation

Realize if we add 4 p orbitals then we must obtain 4 molecular orbitals

The difference between the 4 orbitals will be the sign of adjacent atomic orbitals

Lowest energy molecular orbital for butadiene

-has three bonding interactions between adjacent orbitals

 We will obtain 4 molecular orbitals with different number of nodes

0 nodes
1 node
2 nodes
3 nodes

We can also predict the relative energy levels of these molecular orbitals

by the number of nodes (as nodes increases, energy increases)

The electronic configuration can thus also be determined by knowing there are 4 π electrons

 In order to allow electron delocalization the p orbitals must be aligned

This constrains the geometry of conjugated systems

The p orbitals must be in the same direction – thus the carbon framework is planar

 Molecular Orbital Picture for Allylic Systems

An allylic system refers to 3 conjugated p orbitals

 With 3 conjugated p orbitals, must obtain 3 molecular orbitals

2 nodes

E
1 node

0 nodes

Depending upon number of π electrons the electronic configuration can be determined

Allyl cation has 2 π electrons

Allyl radical has 3 π electrons

Allyl anion has 4 π electrons

Implies that excess negative charge of anion is located on the terminal carbons

(size of coefficients correlates with probability of electron density

Similar to resonance description

 Addition to Conjugated Dienes

As we have already seen, alkenes can react with electrophiles to create a carbocation

With conjugated dienes this reaction will create an allylic carbocation

The nucleophile can then react with either resonance form in the second step

 Kinetic versus Thermodynamic Control

What forms faster (kinetic product) and what is more stable (thermodynamic product)

need not be the same

Consider the addition to conjugated dienes

H2O !+

!+ Reaction at 2˚ cation site has a

H2O H2O!+ more stable transition state

E

H+ !+
OH

Generate allylic cation in first step

Allylic cation can have water react at two sites
OH
Reaction at 2˚ site
Reaction a 1˚ site, though,

Reaction at 1˚ site
generates more stable product

(more substituted double bond)

Thus the kinetic product has The thermodynamic product has

water reacting at 2˚ site
water reacting at 1˚ site

 Formation of Allylic Radical

Remember that we form allylic radicals with free radical halogenation with an alkene

Another way to generate the bromine radical is to use NBS (N-bromosuccinimide)

 SN2 Reactions of Allylic Halides

Allylic halides react faster with a nucleophile in a SN2 reaction

than halides without allylic stabilization

The conjugated π system stabilizes the developing charge in the transition state

Due to this enhancement, allylic halides react with Grignard reagents well,

remember that Grignard reagents often have poor yields with unactivated alkyl halides

 Pericyclic Reactions

Reactions involving concerted bond formation, or bond breakage,

with a ring of interacting orbitals

Ring of interacting orbitals

-Orbitals must form a continuous loop

Therefore each orbital must be able to interact with the adjacent orbital

 Interactions between orbitals on different reactants

Electrons are located in Molecular Orbitals (MO’s)

When two molecules react, a molecular orbital on one molecule interacts

with a molecular orbital on the second molecule which causes an energy gain

(if reaction is favorable)

With conjugated π systems we can consider only the π framework

 Butadiene

Consists of four interacting p orbitals which form the π framework

4 π electrons in 4 continuous p orbitals

As we learned in forming σ bonds – the energy of a MO (or a bond)

is dependent upon the symmetry of the interacting orbitals

 Molecular Orbitals for Butadiene

Lowest unoccupied MO

(LUMO)

E
Highest occupied MO

(HOMO)

4 electrons are placed in these molecular orbitals by pairing

the lowest energy MO’s until all electrons are placed in orbitals

The molecular orbital that is highest in energy that contains electrons is called

the highest occupied molecular orbital (HOMO)

The molecular orbital that is lowest in energy that does not contain electrons is called

the lowest unoccupied molecular orbital (LUMO)

 Ethylene

The molecular orbitals for ethylene can be obtained in a similar manner

Lowest unoccupied MO

E (LUMO)

Highest occupied MO

(HOMO)

2 electrons are placed in 2 MO’s

derived from the two conjugated p orbitals

After determining the electronic configuration,

the HOMO and LUMO orbitals can be determined

 Energy Gain in a Reaction

Remember that these molecular orbitals on two molecules

combine to form new orbitals in a reaction

Consider the interaction of HOMO and LUMO orbitals on different molecules

HOMO HOMO LUMO LUMO

If two HOMO orbitals react then

two new MO’s will be obtained

(one lower and one higher in energy)
HOMO LUMO

The 4 electrons will be placed and

thus there is no energy gain

The only energy gain is when a HOMO

from one molecule reacts with a LUMO

from the other molecule

 In order for the HOMO of one molecule to interact with the

LUMO of another molecule the SYMMETRY of the orbitals must be correct

If the symmetry is wrong, then we cannot have interacting orbitals

Butadiene HOMO

Ethylene LUMO

Consider butadiene reacting with ethylene

The symmetry of the interacting orbitals is correct,

therefore butadiene reacting with ethylene is symmetry allowed

 Ethylene, however, cannot react with itself

The orbitals cannot align themselves with proper symmetry

Ethylene HOMO

Ethylene LUMO

Therefore this reaction is symmetry forbidden

 Excitation

Photolysis (if the energy of light is correct!) can excite an electron to a higher MO

h!
E

This process changes the symmetry of the HOMO

Therefore a reaction can be made “symmetry allowed” by photolysis

Ethylene, for example, will react under photolysis but not thermally

 Diels-Alder Reaction

The reaction between butadiene and ethylene is called a Diels-Alder reaction

Obtain cyclohexene functional units after a Diels-Alder reaction

 Diels-Alder Reaction is favored by a lower HOMO-LUMO energy gap

In addition to requiring the correct symmetry, the energy gap between the

HOMO and LUMO orbitals determines the amount of energy gain in a reaction

LUMO
LUMO

HOMO
HOMO energy gain
energy gain

As the energy gap between the HOMO and LUMO becomes smaller

the reaction rate is favored

 Adjusting Energy Levels

Electron withdrawing groups lower the energy of a molecular orbital,

Electron donating groups raise the energy of a molecular orbital

Usually the butadiene reacts through the HOMO and ethylene reacts through the LUMO,
therefore a Diels-Alder reaction is favored with electron withdrawing groups on ethylene and
electron donating groups on butadiene

 Reaction Products

Always try to find the cyclohexene unit in the product,

this will indicate what was the initial butadiene and ethylene parts

 Stereochemistry of Addition

Butadiene must be in a s-cis conformation,

not s-trans

NOT

Therefore the rate of the reaction will be affected by diene substituents

> >
 Orientation Between the Diene and Alkene

The two components can react to form two different stereoproducts

These two products are diastereomers

Which is favored?

 Endo Rule

The Diels-Alder reaction favors the endo product

H
ENDO

O2N O2N NO2

H

EXO
H
NO2 NO2 NO2

Endo means “inside” the pocket formed by the Diels-Alder reaction,

exo is “outside” of this pocket

 Energetic Basis of Endo Rule

This stereochemical preference is due to ENERGY

In the endo position the orbitals on the electron withdrawing group

can favorably interact with the orbitals of the diene

Endo position

NC C
H N
Exo position

In endo position, orbitals on alkene substituents can interact with p orbitals of butadiene

In exo orientation this interaction is not present

 Regiochemistry of Unsymmetrically Substituted Diels-Alder Products

When a monosubstituted butadiene and a monosubstituted alkene react,

different regioproducts can be obtained

OCH3
OCH3 OCH3
NO2 ! NO2
or
NO2

Can predict favored product by understanding location of charge in molecules

OCH3 OCH3 OCH3 O O

1 N N
2 1 O O
3 2
4
Consider resonance forms
Consider resonance forms

Negative charge is located on C2 and C4
Positive charge located on C2

The negative charge will react preferentially

with the positive charge to obtain one regioproduct

 Using this analysis we can predict regioproducts

A Diels-Alder reaction can therefore control both regio- and stereochemistry

 Ultraviolet-Visible Spectroscopy

(UV-VIS)

Another analytical tool to determine organic structures is UV-VIS spectroscopy

Similar to IR, this is another spectroscopic technique,

therefore a sample is irradiated with light of a particular wavelength

If the compound absorbs the light, the detector will record the intensity of absorbance

In an UV-VIS spectrum the light used is between ~200 nm to ~700 nm

(UV range is ~200 nm to ~370 nm, while visible light is ~370 nm to 700 nm)

Remember that in IR the wavelength of light used was 2.5 – 25 µm

(between one to two orders of magnitude larger than UV light)

 UV light is thus much higher in energy than IR light

Instead of causing molecular vibrations,

UV-VIS light causes electronic excitations

An electron is excited from the HOMO to the LUMO

Ethylene LUMO

h!
E
Ethylene HOMO

If the correct amount of energy is applied (i.e. the correct wavelength of light),

the excitation of one electron from the HOMO to the LUMO will occur

The amount of energy required is thus the energy gap between the HOMO and LUMO

As the HOMO-LUMO gap changes, the wavelength required for excitation changes

(remember that a lower wavelength is higher in energy)

The HOMO-LUMO energy gap is affected by the amount of conjugation

A conjugated diene system has a lower HOMO-LUMO energy gap

than an isolated double bond

Therefore a more conjugated system has a higher wavelength of absorbance

(higher wavelength is lower in energy, therefore smaller energy gap)

 Information Obtained from a UV-VIS

The major piece of information is the point of maximum absorbance

(called λmax)

In addition an absorbance is characterized by how strongly the molecule absorbs

Beer’s law:

A = ε•c•l

c = concentration of sample

l = path length of sample

ε = molar absorbtivity (extinction coefficient)

*characteristic of sample

If the molecule absorbs more strongly, it has a higher ε

 λmax

As seen earlier, the position of the λmax indicates the HOMO-LUMO energy gap

A more conjugated system has a lower HOMO-LUMO energy gap,

therefore the λmax will be of a longer wavelength

Only conjugated alkenes will cause a shift in λmax

As the conjugation increases, the shift will increase

Compounds that are colored to our eye therefore must be very conjugated

(the lowest wavelength human eyes detect is ~370 nm)