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Conjugated Compounds & UV Spectroscopy

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© All Rights Reserved
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John E.

McMurry

[Link]/chemistry/mcmurry

Chapter 14
Conjugated Compounds and
Ultraviolet Spectroscopy

Paul D. Adams • University of Arkansas


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 that
are very different from those of the nonconjugated diene,
1,4-pentadiene.
Why this Chapter?
 Conjugated compounds are common in nature
 Extended conjugation leads to absorption of visible light,
producing color
 Conjugated hydrocarbon with many double bonds are
polyenes (lycopene is responsible for red color in
tomatoes)
 Examine properties of conjugated molecules and reasons
for the properties
14.1 Stability of Conjugated
Dienes: Molecular Orbital Theory
 Typically by elimination in allylic halide
 Specific industrial processes for large scale
production of commodities by catalytic
dehydrogenation and dehydration
Measuring Stability
 Conjugated dienes are more stable than nonconjugated based on heats of
hydrogenation

 Hydrogenating 1,3-butadiene produces 17 kJ/mol less heat than 1,4-pentadiene


Relative Stability of Alkenes
Relative Stability of Alkenes
Increasing Stability Order
Molecular Orbital Description of
1,3-Butadiene
 The single bond between the conjugated double bonds is
shorter and stronger than normal
 The bonding -orbitals are made from 4 p orbitals that
provide greater delocalization and lower energy than in
isolated C=C
 The 4 molecular orbitals include fewer total nodes than in
the isolated case (See Figures 14-1 and 14-2)
 In addition, the single bond between the two double bonds
is strengthened by overlap of p orbitals
 In summary, we say electrons in 1,3-butadiene are
delocalized over the  bond system
 Delocalization leads to stabilization
Molecular Orbital
Molecular Orbital of 1, 3 Butadiene

C C C C 4

C C C C 
3
E

C C C C 2

C C C C 
1
LCAOs MOs
14.2 Electrophilic Additions to
Conjugated Dienes
 Review: addition of electrophile to C=C
 Markovnikov regiochemistry via more stable carbocation
Carbocations from Conjugated
Dienes
 Addition of H+ leads to delocalized secondary allylic
carbocation
Products of Addition to
Delocalized Carbocation
 Nucleophile can add to either cationic site
 The transition states for the two possible products are not
equal in energy
14.3 Kinetic vs. Thermodynamic
Control of Reactions
 At completion, all reactions are at equilibrium and the
relative concentrations are controlled by the differences in
free energies of reactants and products
(Thermodynamic Control)
 If a reaction is irreversible or if a reaction is far from
equilibrium, then the relative concentrations of products
depends on how fast each forms, which is controlled by
the relative free energies of the transition states leading to
each (Kinetic Control)
Kinetic vs. Thermodynamic control
Kinetic vs. Thermodynamic control
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
 At higher temperature, the product ratio changes
and the 1,4 adduct predominates
Kinetic and Thermodynamic
Product
14.4 The Diels-Alder
Cycloaddition Reaction
 Conjugate dienes can combine with alkenes to form six-membered
cyclic compounds
 The formation of the ring involves no intermediate (concerted
formation of two bonds)
 Discovered by Otto Paul Hermann Diels and Kurt Alder in
Germany in the 1930’s
View of the Diels-Alder
Reaction
 Woodward and Hoffman showed this reaction 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
14.5 Characteristics of the Diels-
Alder Reaction
 The alkene component is called a dienophile
 C=C is conjugated to an electron withdrawing group, such as
C=O or CN
 Alkynes can also be dienophiles
Stereospecificity of the Diels-Alder
Reaction
 The reaction is stereospecific, maintaining
relative relationships from reactant to product
 There is a one-to-one relationship between
stereoisomeric reactants and products
Regiochemistry of the Diels-Alder
Reaction
 Reactants align to produce endo (rather than exo) product
 endo and exo indicate relative stereochemistry in
bicyclic structures
 Substituent on one bridge is exo if it is anti (trans) to
the larger of the other two bridges and endo if it is syn
(cis) to the larger of the other two bridges
Conformations of Dienes in the
Diels-Alder Reaction
 The relative positions of 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”)
 Dienes react in the s-cis conformation in the Diels-Alder reaction
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
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)
Synthetic Rubber
 Chemical polymerization of isoprene does not produce rubber
(stereochemistry is not controlled)

 Synthetic alternatives include neoprene, polymer of 2-chloro-1,3-


butadiene

 This resists weathering better than rubber


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)
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 – see Figure 14-11
Ultraviolet Spectrum of 1,3-
Butadiene
 Example: 1,3-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)
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
 Beers’ law: absorbance = cl
 “” is molar absorptivity (extinction coefficient)
 “c” is concentration in mol/L
 “l” is path of light through sample in cm
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
 Substituents on  system increase max
 See Table 14-2
Vision : Rod and Cone cells
14.9 Conjugation, Color, and the
Chemistry of Vision
 Visible region is about 400 to 800 nm
 Extended systems of conjugation absorb in visible region
 -Carotene, 11 double bonds in conjugation, max = 455 nm
 Visual pigments are responsible for absorbing light in eye and
triggering nerves to send signal to brain
Let’s Work a Problem

Explain why 2,3-di-tert-butyl-1,3-butadiene does not undergo


Diels-Alder reactions.
Answer

This compound has the tertiary butyl groups in a cis


relationship with each other. This brings about a steric strain
from the proximity of the bulky substituents. As a result, the
compounds undergoes a change to a trans conformation to
relieve strain, but Diels-Alder reaction cannot take place.
Homework
 20
 24
 27
 31
 36
 39
 46
 51

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