Chapter 20

Conjugated Systems

20-1

Conjugated Dienes Heats of Hydrogentaion

From heats of hydrogenation, we can compare relative stabilities of conjugated and unconjugated dienes.
N ame Structural Formula H0 kJ (kcal)/mol -127 (-30.3) -126 (-30.1) -120 (-28.6) -115 (-27.6) -237 (-56.5) -226 (-54.1) -254 (-60.8)

Longer chain has little

1-Butene 1-Penten e

effect. of Number Steric cis- 2-Butene substituents.

trans- 2-Buten e 1,3-Butadien e

Effects

Conjugation t rans- 1,3-Pentad iene stabilizes.

1,4-Pentadien e

20-2

Conjugated Dienes Butadiene

Conjugation of the double bonds in 1,3-butadiene gives an extra stability of approximately 17 kJ (4.1 kcal)/mol . If double bonds independent:
2 + 2 H2 catalyst 2 H 0 = 2(-127 kJ/mol) = -254 kJ/mol) catalyst catalyst 2 H + 2 + 2H 2 2 2 Experimental data does not
0 H 0 = -237 kJ/mol H = 2(-127 kJ/mol) Conjugation

agree:

is important and stabilizing.

+ 2 H2 catalyst

= -254 kJ/mol) H 0 = -237 kJ/mol

20-3

Conjugated Dienes Butadiene

Conjugation

of double bonds in butadiene gives the molecule an additional stability of approximately 17 kJ/mol.

20-4

Conjugated Systems
Systems containing conjugated double bonds, not just those of dienes, are more stable than those containing unconjugated double bonds.
O O

2-Cyclohexenone (more s table)

3-Cycloh exenone (less s table)

20-5

Structure of Butadiene MOs

Combination

of four parallel 2p atomic orbitals gives two p-bonding MOs (this screen) and two p-antibonding MOs (the next screen).

20-6

Structure of Butadiene MOs

the

two p-antibonding MOs of butadiene (higher in energy).

20-7

How do we form the orbitals of the pi system

First count up how many p orbitals contribute to the pi system. We will get the same number of pi molecular orbitals.

Three overlapping p orbitals. We will get three molecular orbitals.

20-8

If atomic orbitals overlap with each other they are bonding, nonbonding or pi type anti-bond antibonding

sigma type anti-bonding

Anti-bonding, destabilizing. Higher Energy

non-bonded

But now a particular, simple case: distant atomic orbitals, on atoms not directly attached to each other. Their interaction is weak and does not affect the energy of the system. Non bonding If atoms are directly attached to each other the interactions is strongly bonding or antibonding. Bonding, stabilizing the system. Lower energy.
pi type bond sigma type bonding
or or

or

or

Molecular orbitals are combinations of atomic orbitals.

They may be bonding, antibonding or nonbonding molecular orbitals depending on how the atomic orbitals in them interact.

Example: Allylic radical

Two antibonding interactions. Only one weak, antibonding (nonbonding) interaction.

All bonding interactions.

Allylic Radical: Molecular Orbital vs Resonance

Molecular Orbital. We have three pi electrons (two in the pi bond and the unpaired electron). Put them into the molecular orbitals.

Note that the odd electron is located on the terminal carbons.

Resonance Result
Again the odd, unpaired electron is only on the terminal carbon atoms.

But how do we construct the molecular orbitals of the pi system? How do we know what the molecular orbitals look like?

Key Ideas:
For our linear pi systems different molecular orbitals are formed by introducing additional antibonding interactions. Lowest energy orbital has no antibonding, next higher has one, etc.

2 antibonding interaction 1 weak antibonding Interaction, nonbonding

Antibonding interactions are symmetrically placed.

0 antibonding interact

This would be wrong.

Another example: hexa-1,3,5-triene

Three pi bonds, six pi electrons. Each atom is sp2 hybridized.

Have to form bonding and antibonding combinations of the atomic orbitals to get the pi molecular orbitals. Expect six molecular orbitals. # molecular orbitals = # atomic orbitals Start with all the orbitals bonding and create additional orbitals. The number of antibonding interactions increases as we generate a new higher energy molecular orbital.

1,2- and 1,4-Addition

Addition

of one mol of HBr to butadiene at -78C gives a mixture of two constitutional isomers.
CH2 = CH- CH= CH2 + HBr 1,3-Butadiene Br H Br H CH2 = CH- CH- CH 2 + CH2 - CH= CH- CH 2 3-Bromo-1-butene 1-Bromo-2-butene 90% 10% (1,2-addition) (1,4-addition) -78C

We account for these products by the following twostep mechanism.

20-14

1,2- and 1,4-Addition

The key intermediate is a resonance-stabilized allylic carbocation.
CH2 = CH- CH = CH 2 + H- Br H + CH2 = CH- CH -CH2 _ Br Br H CH2 = CH- CH -CH2 (1,2-Addition) Br H Br CH2 -CH = CH -CH2 (1,4-Addition) H + CH 2 -CH = CH -CH2 _

20-15

1,2- and 1,4-Addition

Addition

of one mole of Br2 to butadiene at -15C also gives a mixture of two constitutional isomers.
CH2 = CH- CH= CH2 + Br2 1,3-Butadiene Br Br -15C Br + Br

CH2 - CH- CH = CH 2 3,4-Dibromo-1-buten e (54%) (1,2-addition)

CH2 - CH= CH- CH 2 1,4-Dibromo-2-buten e (46%) (1,4-addition)

We account for the formation of these 1,2- and 1,4addition products by a similar mechanism.
20-16

Experimental Information
For addition of HBr at -78C and Br2 at -15C, the 1,2addition products predominate; at higher temperatures (40 to 60C), the 1,4-addition products predominate. If the products of the low temperature addition are warmed to the higher temperature, the product composition becomes identical to the higher temperature distribution. The same result can be accomplished using a Lewis acid catalyst, such as FeBr3 or ZnBr2. If either pure 1,2- or pure 1,4- addition product is dissolved in an inert solvent at the higher temperature and a Lewis acid catalyst added, an equilibrium mixture of 1,2- and 1,4-product forms. The same equilibrium mixture is obtained regardless of which isomer is used as the starting material. 20-17

1,2- and 1,4-Addition

We

interpret these results using the concepts of kinetic and thermodynamic control of reactions. Kinetic control: The distribution of products is determined by their relative rates of formation.
In addition of HBr and Br2 to a conjugated diene, 1,2addition occurs faster than 1,4-addition.
+ CH2 = CH-CH-CH3 a 2 allylic carb ocation (greater contribu tion ) + CH 2 -CH=CH-CH 3 a 1 allylic carbocation (less er con trib ution)

20-18

1,2- and 1,4-Addition

Thermodynamic

control: The distribution of products is determined by their relative stabilities.

In addition of HBr and Br2 to a butadiene, the 1,4addition product is more stable than the 1,2-addition product.
Br BrCH2 CHCH=CH2 3,4-D ibromo-1-bu tene (less stable alk ene) + H BrCH2 C C CH2 Br H

(E)-1,4-D ib romo-2-b utene (more stab le alkene)

20-19

1,2- and 1,4-Addition

Kinetic

vs thermodynamic control. A plot of Gibbs free energy versus reaction coordinate for Step 2 of addition of HBr to butadiene.

20-20

UV-Visible Spectroscopy
Region of Spectrum near ultraviolet visib le Energy Wavelength (nm) k cal/mol k J/mol 200-400 400-700 299-598 171-299 71.5 - 143 40.9 - 71.5

Absorption

of radiation in these regions give us information about conjugation of carbon-carbon and carbon-oxygen double bonds and their substitution.

20-22

UV-Visible Spectroscopy
Typically, UV-visible spectra consist of one or a small number of broad absorptions.

20-23

UV-Visible Spectroscopy
Beer-Lambert

law: The relationship between absorbance, concentration, and length of the sample cell (cuvette):
Beer-Lambert Law: A = e c l
A = absorbance (unitless): A measure of the extent to which a compound absorbs radiation of a particular Io wavelength.
Absorbance (A) = log I

e = molar absorptivity (M-1cm-1): A characteristic property of a compound; values range from zero to 106 M-1cm-1. I = length of the sample tube (cm)
20-24

UV-Visible Spectroscopy
The visible spectrum of b-carotene (the orange pigment in carrots) dissolved in hexane shows intense absorption maxima at 463 nm and 494 nm, both in the blue-green region.

b-carotene m ax 463 (log e 5.10); 494 (log e4.77)

20-25

UV-Visible Spectroscopy
A p to p* transition in excitation of ethylene.

20-26

UV-Visible Spectroscopy
A p to p* transition in excitation of 1,3-butadiene

20-27

UV-Visible Spectroscopy
Wavelengths and energies required for p to p* transitions of ethylene and three conjugated polyenes
N ame Ethylene 1,3-Butadiene (3E)-1,3,5-Hexatrien e (3E,5E)-1,3,5,7-Octatetraene En ergy m ax Structural Formula (nm) [kJ (kcal)/mol] 165 217 268 290 724 (173) 552 (132) 448 (107) 385 (92)

20-28

UV-Visible Spectroscopy
Absorption

of UV-Vis radiation results in promotion of electrons from a lower-energy, occupied MO to a higher-energy,unoccupied MO.
The energy of this radiation is sufficient to promote electrons in a pi- bonding (p) MO to a pi-antibonding (p*) MO. Electrons in sigma bonding MOs are lower in energy and the UV radiation energy is no longer sufficient to promote the electrons to the empty anti-bonding MOs. Following are three examples of conjugated systems.
O O 1,3-Butadien e 3-Bu ten-2-on e H Ben zaldehyde

20-29

UV-Visible Spectroscopy
UV-Visible

spectroscopy of carbonyls.

Simple aldehydes and ketones show only weak absorption in the UV due to an n to p* electronic transition of the carbonyl group. If the carbonyl group is conjugated with one or more carbon-carbon double bonds, intense absorption occurs due to a p to p* transition.
O O O

2-Pentanone m ax 180 nm (e 900)

3-Penten-2-one m ax 224 nm (e 12,590)

Acetophenone ma x 246 nm (e 9,800)

20-30

Diels Alder Reaction/Symmetry Controlled Reactions Quick Review of formation of chemical bond.

Elect ron dono r

Electro n accept or

Note the overlap of the hybrid (donor) and the s orbital which allows bond formation.

For this arrangement there is no overlap. No donation of electrons; no bond formation.

20-31

Diels Alder Reaction of butadiene and ethylene to yield cyclohexene. We will analyze in terms of the pi electrons of the two systems interacting. The pi electrons from the highest occupied pi orbital of one molecule will B donate into an lowest HOMO donates into energy pi empty of the other. Works in both directions: A A LUMO Note donates into B, B donates into A. LUMO the accept overlap LUMO or leading accept to bond A HOMO donates into orHOM HOMB LUMO formati Note O O on the B dono dono overlap r A r 20-32 leading

Try it in another reaction: ethylene + ethylene cyclobutane

LU MO HOM O

LUM O
HOMO Equal bonding and antibonding interaction, no overlap, no bond formation, no reaction
20-33