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Conjugated Compounds

This document discusses conjugated compounds and ultraviolet spectroscopy. Some key points: 1) Conjugated compounds have alternating double and single bonds where the π orbitals interact, making them more stable than nonconjugated compounds. This extended conjugation can cause absorption of visible light and produce color. 2) UV-visible spectroscopy can be used to study conjugated systems. Increased conjugation causes absorption peaks to shift to longer wavelengths. 3) The UV spectrum of 1,3-butadiene shows absorption peaks around 217nm from transitions between its highest occupied and lowest unoccupied molecular orbitals.

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141 views

Conjugated Compounds

This document discusses conjugated compounds and ultraviolet spectroscopy. Some key points: 1) Conjugated compounds have alternating double and single bonds where the π orbitals interact, making them more stable than nonconjugated compounds. This extended conjugation can cause absorption of visible light and produce color. 2) UV-visible spectroscopy can be used to study conjugated systems. Increased conjugation causes absorption peaks to shift to longer wavelengths. 3) The UV spectrum of 1,3-butadiene shows absorption peaks around 217nm from transitions between its highest occupied and lowest unoccupied molecular orbitals.

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fawkes316
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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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