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Conjugated Compounds
and Ultraviolet Spectroscopy
Conjugated and Nonconjugated
Dienes
Compounds can have more than one double or triple bond
If they are separated by only one single bond they are
conjugated and their orbitals interact
The conjugated diene 1,3-butadiene has properties very
different from those of the nonconjugated diene, 1,5-
pentadiene
2
Conjugated compounds: common in nature
Extended conjugation leads to absorption of visible light, producing color
3
Learning Check:
Circle any conjugation in the following:
A. B. C.
CH2 CH C N
H2C
H
D. O E. CH3 F.
C C
C CH3 CH2
O CH2
4
Solution:
Circle any conjugation in the following:
A. B. C.
CH2 CH C N
H2C
Nonconjugated
H
D. O E. CH3 F.
C C
C CH3 CH2
O CH2
Nonconjugated
5
14.1 Conjugated Dienes:
Preparation: Typically by elimination of allylic halide
6
Stability of Conjugated Dienes:
Conjugated dienes are more stable than nonconjugated
based on heats of hydrogenation
8
Description of 1,3-Butadiene
The single bond between the conjugated double bonds is
shorter and stronger than sp3
9
Molecular Orbital Description
Isolated Double bond Conjugated Double bonds
11
Carbocations from Conjugated Dienes
Now: Addition of H+ gives delocalized 2o allylic carbocation
12
Addition Products to Delocalized Carbocation
13
Another Example:
14
Learning Check:
Give the likely products from reaction of 1 equiv HCl with
2-methyl-1,3-cyclohexadiene.
15
Solution:
Give the likely products from reaction of 1 equiv HCl with
2-methyl-1,3-cyclohexadiene.
16
14.3 Kinetic vs. Thermodynamic Control
17
Kinetic and Thermodynamic Control:
Example
Addition to a conjugated diene at or below room temperature normally
leads to a mixture of products in which the 1,2 adduct predominates
over the 1,4 adduct
18
19
_____ Kinetic control
_____ Thermodynamic control
20
14.4 The Diels-Alder Cycloaddition
Reaction
Conjugate dienes can combine with alkenes to form six-membered cyclic
compounds
Ring formation involves no intermediate (concerted formation of 2 bonds)
Discovered by Otto Paul Hermann Diels and Kurt Alder in Germany in the 1930’s
21
View of the Diels-Alder Reaction
Woodward and Hoffman showed to be an example of the general
class of pericyclic reactions
Involves orbital overlap, change of hybridization and electron
delocalization in transition state
The reaction is called a cycloaddition
Diene Dieneophile
22
14.5 Characteristics of Diels-Alder Reaction
The alkene component is called a dienophile
C=C is conjugated to an electron withdrawing group, such as C=O or
CºN
Alkynes can also be dienophiles
23
Stereospecificity of the Diels-Alder
Reaction
The reaction is stereospecific,
There is a one-to-one relationship between stereoisomeric
reactants and products
24
Endo vs Exo positions
Endo and Exo denote relative sterechemistry of groups in bicyclic
systems
25
Regiochemistry of the Diels-Alder Reaction
Reactants align to produce endo (rather than exo) product
26
Example:
27
Conformations of Dienes in the
Diels-Alder Reaction
The two double bonds
in the diene are “cis”
or “trans” to each
other about the single
bond (being in a plane
maximizes overlap)
These conformations
are called s-cis and s-
trans (“s” stands for
“single bond”)
28
Not all dienes can rotate to be s-cis
29
Learning Check:
Which can form an s-cis diene?
30
Solution:
Which can form an s-cis diene?
31
Learning Check:
Which would be good Diels-Alder dienophiles?
32
Solution:
Which would be good Diels-Alder dienophiles?
33
14.6 Diene Polymers: Natural and
Synthetic Rubbers
Conjugated dienes can be polymerized
The initiator for the reaction can be a radical, or an acid
Polymerization: 1,4 addition of growing chain to
conjugated diene monomer
34
Natural Rubber
A material from latex, in plant sap
In rubber repeating unit has 5 carbons and Z stereochemistry of all
C=C
Gutta-Percha is natural material with E in all C=C
Looks as if it is the head-to-tail polymer of isoprene (2-methyl-1,3-
butadiene)
35
Synthetic Rubber
Chemical polymerization of isoprene does not produce rubber
(stereochemistry is not controlled)
36
Vulcanization
Natural and synthetic rubbers are too soft to be used in products
Charles Goodyear discovered heating with small amount of sulfur
produces strong material
Sulfur forms bridges between hydrocarbon chains (cross-links)
37
14.7 Structure Determination in Conjugated
Systems: UV Spectroscopy
Conjugated compounds can absorb light in the ultraviolet region of the
spectrum
The electrons in the highest occupied molecular orbital (HOMO) undergo a
transition to the lowest unoccupied molecular orbital (LUMO)
The region from 2 x 10-7m to 4 x 10-7m (200 to 400 nm) is most useful in
organic chemistry
A plot of absorbance (log of the ratio of the intensity of light in over light
transmitted) against wavelength in this region is an ultraviolet spectrum –
38
Ultraviolet Spectrum of 1,3-Butadiene
Example: 1,4-butadiene has four molecular orbitals with the lowest
two occupied
Electronic transition is from HOMO to LUMO at 217 nm (peak is
broad because of combination with stretching, bending)
39
Quantitative Use of UV Spectra
Absorbance for a particular compound in a specific solvent at a
specified wavelength is directly proportional to its concentration
You can follow changes in concentration with time by recording
absorbance at the wavelength
40
14.8 Interpreting UV Spectra: The
Effect of Conjugation
max: wavelength where UV absorbance for a compound is greatest
Energy difference between HOMO and LUMO decreases as the
extent of conjugation increases
max increases as conjugation increases (lower energy)
1,3-butadiene: 217 nm, 1,3,5-hexatriene: 258 nm
41
Substituents on system increase max
1,3-butadiene: H2C=CH-CH=CH2 217 nm
42
Calculations of lmax
The lmax of the p p* transition for compounds with < 4 conjugated
double bonds can be calculated using Woodward-Fieser rules.
Start with a base number: O O
C H C R
CH2 CH CH CH2 C C C C
max = 217 nm max = 210 nm max = 215 nm
43
Example:
Calculate expected lmax for following:
Base = 217
3 alkyl substituents @ 5 each = 15
Calculated = 232
Observed = 232
44
Learning Check:
Calculate expected lmax for following:
O
47
b-Carotene,
11 double
bonds in
conjugation,
max = 455 nm
48
Vision:
Beta-Carotene
Vision:
H3C
H3C CH3 CH3 CH3
Liver Enzymes
Vitamin A
CH3 CH3 OH H3C CH3 CH3 CH3 O
H3C CH3
H
H
CH3 O
H
CH3 Retinal NH2 CH3 NH2
Metarhodopsin II
Light
FIND THE MAN IN THE COFFEE BEANS
Vision:
Vision:
Stare at the eye of the red parrot while you count slowly to 20, then look
immediately at one spot in the empty bird cage. The faint, ghostly image of a
bluegreen bird will appear in the cage.
Try the same thing with the green cardinal. A faint magenta bird will appear
in the cage.
The ghostly birds you see here are called afterimages. An afterimage is an
image that stays with you even after you have stopped looking at an object.
The back of your eye is lined with light sensitive cells, called cones, which are
sensitive to certain colors of light. When you stare at the red bird, your red-
sensitive cones adapt to the light and lose their sensitivity. When you shift your
gaze to the white background of the bird cage, you see white (minus red) where
the red-sensitive cells have become adapted. White light minus red light is
blue-green light. That's why the afterimage you see is blue-green and in the
shape of a parrot. The same thing happens when you stare at the green bird,
but this time it's the green-sensitive cones that adapt. White minus green light is
magenta light, so you see the afterimage as a magenta cardinal.
Look at the flag for
about 20 seconds, Vision:
then look down to the
white space below.
Notice how the
ghostly image of the
familar "stars and
stripes" appears. This
afterimage occurs
because red, white
and blue are the
complementary colors
of cyan,black and
yellow.
Which of the following is not conjugated?
20% 20% 20% 20% 20%
1. 2.
O
3.
5.
4.
O
1 2 3 4 5
How many π (pi) bonding molecular orbitals are
present in 1,3,5-hexatriene ?
20% 20% 20% 20% 20%
1. 2
2. 3
3. 4
4. 5
5. 6
1 2 3 4 5
Arrange the following alkenes in order of least
stable to most stable.
20% 20% 20% 20% 20%
A B C
1. A<B<C
2. B<C<A
3. B<A<C
4. A<C<B
5. C<A<B
1 2 3 4 5
Predict the expected major organic product of the
following reaction.
HBr
20% 20% 20% 20% 20%
55 ÞC
°C
1. 2.
Br Br
3.
Br
4. 5.
Br
Br 1 2 3 4 5
Predict the expected major organic product of the
following reaction.
O
Toluene 20% 20% 20% 20% 20%
+ O
heat
O
1. 2.
O
H O
O O
O H O
3.
H O
4. H O
H O 5.
O
O
O
H O 1 2 3 4 5
O
Which of the following dienes would be expected to
react fastest in a Diels-Alder reaction?
20% 20% 20% 20% 20%
1. 2.
3.
4. 5.
1 2 3 4 5
Which of the following dienophiles would be expected
to react fastest in a Diels-Alder reaction?
20% 20% 20% 20% 20%
1. 2.
OH O
3.
Cl
5.
4. OCH3
O
1 2 3 4 5
Which of the following dienes will not participate in a
Diels-Alder reaction?
25% 25% 25% 25%
1. 2.
3. 4.
1 2 3 4
Select the most appropriate name for the
following polymer:
F 20% 20% 20% 20% 20%
n
1. poly(methyl fluoride)
2. poly(ethyl fluoride)
3. poly(vinyl fluoride)
4. polyfluoromethane
5. polyfluoroethane
1 2 3 4 5
UV/Visible spectroscopy is based on _____
excitation.
25% 25% 25% 25%
1. electronic
2. rotational
3. nuclear
4. vibrational
1 2 3 4
If one knows the molar absorptivity for a molecule, then
one can determine its concentration by taking an
ultraviolet/visible absorption spectrum.
50% 50%
1. True
2. False
1 2
Which of the following wavelengths can be
classified as UV light?
20% 20% 20% 20% 20%
1. 900 nm
2. 725 nm
3. 500 nm
4. 450 nm
5. none of these
1 2 3 4 5
Which of the following statements is not true regarding
ultraviolet/visible spectroscopy?
1 2 3 4 5
Which of the following compounds is most likely to absorb in the
visible region of the electromagnetic spectrum?
1.
2.
3.
4. 5.
O
1 2 3 4 5
The electronic transition that occurs for conjugated
molecules in ultraviolet/visible spectroscopy is:
1. σ → π*
2. σ → σ*
3. π → π*
4. σ* → π*
1 2 3 4