Conjugated

C j d Systems,
S
Orbital Symmetry,
Symmetry and
p py
Ultraviolet Spectroscopy
 Wave Properties of Electrons

• Standing wave vibrates in fixed location.

• Wave function, ψ, is a mathematical description of
size,
i shape,
h and
d orientation.
i t ti
• Amplitude may be positive or negative.
• Node: Amplitude is zero.
2
 Wave Interactions

• Linear combination of atomic orbitals:

– between different atoms is bond
formation.
– on the same atom is hybridization.
• Conservation of orbitals
• Waves that are in phase add together.
Amplitude increases
increases.
• Waves that are out of phase cancel out.

3
 Sigma Bonding

• Electron density lies between the nuclei.

• A bond may be formed by s-s, p-p, s-p, or
hybridized orbital overlaps.
• The bonding molecular orbital (MO) is
lower in energy than the original atomic
orbitals.
• The antibonding MO is higher in energy
than the atomic orbitals.

4
 σ Bonding MO

Formation of a σ-bonding MO: When the 1s orbitals of two hydrogen

atoms overlap in phase with each other, they interact constructively to
form a bonding MO
MO.
5
 σ∗ Antibonding MO

Formation of a σ* antibondingg MO: When two 1s orbitals overlap

p out of
phase, they interact destructively to form an antibonding MO.
Chapter 2 6
H2: s-s Overlap

Chapter 2 7
 Cl2: p-p Overlap

• When two p orbitals overlap along the line between

the nuclei, a bonding orbital and an antibonding
orbital result.
• Most of the electron densityy is centered along
g the line
between the nuclei.
• This linear overlap is another type of sigma bonding
MO
MO.
8
Carbon: sp3 hybridization
 Methane

109.5o

Each of the four C-H bonds results from head-on ((s)) overlapp
of a singly occupied carbon sp3 hybrid orbital with a singly
occupied hydrogen 1s orbital. Sigma bonds are formed by
head to head overlap between the hydrogen s orbital and a
head-to-head
singly occupied sp3 hybrid orbital of carbon.
 Carbon: sp2 hybridization

- three hybrid sp2 orbitals that lie on the same plane at 120o
- a third p orbital that is lying perpendicular to the plane
 Carbon: sp hybridization

The carbon atoms forms: two hybrid sp orbitals and two p

orbitals.
 Definitions
• Conjugated double bonds
are separated
dbby one single
i l
bond. Example: 1,3-
pentadiene.

• Isolated double bonds are

separated by two or more
g bonds. Example:
single p 1,4-
,
pentadiene.

H C H
• Cumulated double bonds are C C
on adjacent carbons.
H CH2CH3
Example: 1,2-pentadiene.
Stabilities of Dienes
 Structure of 1,3-Butadiene
• Most stable conformation is planar.
• Single bond is shorter than 1.54 Å.
• Electrons are delocalized over molecule.
 Constructing Molecular Orbitals
• π molecular
l l orbitals
bi l are the
h sideways
id overlap
l off p
orbitals.

• p orbitals have 2 lobes. Plus (+) and minus (-)

indicate the opposite phases of the wave function
function,
not electrical charge.

• When lobes overlap constructively, (+ and +, or -

and -) a bonding MO is formed
formed.

• When + and - lobes overlap

overlap, waves cancel out
and a node forms; antibonding MO.
 Ethylene π MO’s

• The combination of
two p orbitals must
give
i ttwo molecular
l l
orbitals.
• Constructive overlap
is a bonding MO.
• Destructive overlap
is an anti-bonding
MO.
 π1 MO for 1,3-Butadiene

• Lowest energy.
• All bonding
interactions.
• Electrons are
delocalized over
four nuclei
nuclei.
 π2 MO for 1,3-Butadiene

• 2 bonding
interactions.
• 1 antibonding
interaction.
• A bonding MO.
 π3* MO for 1,3-Butadiene
,

• Antibonding MO.
• Empty at ground
state.
• Two nodes.
 π4* MO for 1,3-Butadiene

• All antibonding
interactions.
interactions
• Highest energy.
• Vacant at ground
state.
MO Energy Diagram

The average
energy of
electrons is
lower in the
conjugated
compound.
 Conformations of 1,3-Butadiene

• s-trans conformer is more stable than the s-

cis by 12 kJ/mol (2
(2.8
8 kcal/mol)
kcal/mol).

• Easily interconvert at room temperature

temperature.

H H
H H
H H
H H
H H
H
ss-trans
trans s-cis H
 Allylic Cations

• Carbon adjacent to C=C is allylic.

• Allylic cation is stabilized by resonance
resonance.
• Stability of 1° allylic ≈ 2° carbocation.
• Stability ll li ≈ 3° carbocation.
St bilit off 2° allylic b ti

H H
+ +
H2C C CH2 H2C C CH2
1,2- and 1,4-Addition to Conjugated
Dienes
Di
• Electrophilic addition to the do
double
ble bond
produces the most stable intermediate.

• For conjugated dienes, the intermediate is a

resonance stabilized allylic cation
cation.

• Nucleophile adds to either carbon 2 or 4

4, both
of which have the delocalized positive charge.
Addition of HBr

_ _
Br Br

H H H H
H3C C C CH2 H3C C C CH2
Br Br
1,2-addition
, product
p 1,4-addition p
product
Kinetic vs. Thermodynamic Control

Major product
at 40°C

Major
M j product
d t
at -80°C
 Allylic Radicals

• Stabilized by resonance.

• Radical stabilities: 1° < 2° < 3° < 1° allylic.

• Substitution at the allylic position competes with

addition
dditi tto d
double
bl bbond.
d

• To encourage substitution
substitution, use a low concentration
of reagent with light, heat, or peroxides to initiate
free radical formation.
 Allylic Bromination
Br2 hν
2 Br

H H H
Br
+ HBr
H H H
H H H H

Br Br Br Br

H H
B
Br
+ Br •
H H
H Br H
 Bromination Using NBS

• N-Bromosuccinimide (NBS) provides a low,

constant concentration of Br2.

• NBS reacts with the HBr by-product to

produce Br2 and prevent HBr addition.
MO’s for the Allylic System
SN2 Reactions of Allylic Halides
and Tosylates
 Diels-Alder Reaction
• Otto Diels, Kurt Alder; Nobel prize, 1950

• Produces cyclohexene ring

• Diene + alkene or alkyne with electron-

withdrawing group (dienophile)

33
Examples of Diels-Alder Reactions

34
 Stereochemical Requirements

• Diene must be in s-cis conformation

conformation.

• Diene’s C1 and C4 p orbitals must overlapp

with dienophile’s p orbitals to form new
sigma bonds.

• Both sigma bonds are on same face of the

diene: syn stereochemistry.

35
 s-cis Conformation of the Diene

• When the diene is in s-trans conformation, the end

p orbitals are too far apart to overlap with the p
orbitals of the dienophile

36
Cyclopentadiene: Diels-Alder Reaction
to Form Dicyclopentadiene

Cyclopentadiene

37
 Concerted Mechanism

4 + 2 cycloaddition Î concerted cyclic movement of 6 electrons

Îtransition state must have a geometry that allows overlap of
the 2 end p orbitals of the diene with those of the dienophile
38
 syn Stereochemistry
• TheDiels-Alder
Diels Alder reaction is a syn addition with respect to both
diene and dienophile

• The dienophile adds to one face of the diene, and the diene
adds to one face of the dienophile

• Substituents that are on the same side of the diene or

dienophile will be cis in the newly formed ring

39
 Endo Rule
• The p orbitals of the electron
electron-withdrawing
withdrawing groups
on the dienophile have a secondary overlap with
the p orbitals of C2 and C3 in the diene
diene.

40
 Regiospecificity
• The 6-membered ring product of the Diels-Alder
reaction will have electron-donating and electron-
withdrawinggg p Î1,2
groups , or 1,4
, but not 1,3.
,

41
 Pericyclic Reactions

• Diels-Alder reaction is example.

• Woodward and Hoffmann predicted reaction

products using their theory of conservation of
orbital symmetry.

• MO’s must overlap constructively to stabilize

the transition state.

42
 Symmetry-Allowed Reaction

• Diene contributes
electrons from its
highest energy
occupied orbital
(HOMO).

• Dienophile receives
electrons in its
lowest energy
unoccupied
p orbital
(LUMO).
43
 “Forbidden” Cycloaddition

• [2 + 2] cycloaddition
of two ethylenes to
form cyclobutene has
anti-bonding
anti bonding overlap
of HOMO and LUMO.

44
 Photochemical Induction
• Absorption of correct energy photon will
promote an electron to an energy
gy level that
was previously unoccupied.

45
 [2 + 2] Cycloaddition

• Photochemically
allowed, but
thermallyy forbidden.

46
 Ultraviolet Spectroscopy

• 200-400 nm photons excite electrons from a π

bonding orbital to a π
π* antibonding orbital
orbital.

• Conjugated dienes have MO’s

MO s that are closer
in energy.

• A compound that has a longer chain of

conjugated double bonds absorbs light at a
longer wavelength.

47
π → π* Transition for Ethylene and Butadiene

48
 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
Ab b iis th
the llog off th
the ratio
ti Ir / Is
49
 The UV Spectrum
• Usually shows broad peaks.

• Read λmax from the graph.

• Absorbance, A, follows Beer’s Law:

A = εcl
cl

where ε is the molar absorptivity

absorptivity, c is the
sample concentration in moles per liter, and l
is the length of the light path in centimeters.
50
UV Spectrum of Isoprene

51
Sample UV Absorptions

52
Woodward-Fieser Rules

53
 Problem on
Diels-Alder Cycloaddition

54
SOLVED PROBLEM 15-1
Use the endo rule to predict the product of the following cycloaddition.

Solution
Imagine this diene to be a substituted cyclopentadiene; the endo product will be formed.

55
SOLVED PROBLEM 15-1 (continued)
Solution (continued)
In the imaginary reaction, we replaced the two inside hydrogens with the rest of the cyclopentadiene ring.
Now we put them back and have the actual product.

56
SOLVED PROBLEM 15-2
Predict the products of the following proposed Diels–Alder reactions.

S l ti
Solution

57
SOLVED PROBLEM 15-2 (continued)
Solution (continued)

58
Provide the structure of the major organic product
i th
in the ffollowing
ll i reaction.
ti

59