14.
Conjugated Compounds and Ultraviolet Spectroscopy
Based on McMurrys Organic Chemistry, 7th edition
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, 1,5-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 16 kJ/mol
less heat than 1,4-pentadiene
Molecular Orbital Description of 1,3-Butadiene
The single bond between the conjugated double
bonds is shorter and stronger than sp3 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
14.2 Electrophilic Additions to Conjugated Dienes: Allylic Carbocations
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)
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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, product ratio changes and 1,4 adduct predominates
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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
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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)
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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 = ecl e is molar absorptivity (extinction coefficient) c is concentration in mol/L l is path of light through sample in cm
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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
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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 b-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
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