Loudon Chapter 15 Review: Dienes, Resonance and Aromaticity

CHEM 3331, Jacquie Richardson, Fall 2010 - Page 1

This chapter looks at the behavior of carbon-carbon double bonds when several of
them are in a group. This makes their behavior quite different from that of normal,
isolated alkenes like what we saw in Chapters 4 and 5.
C or

Isolated or ordinary Conjugated diene - Cumulated diene -

diene - same stability more stability than less stability than
as two normal alkenes two normal alkenes two normal alkenes
Because of their lower stability, we wont see much of cumulated alkenes - most
of this chapter deals with conjugated alkenes.

The Diels-Alder reaction

This is probably the most important part of this chapter it will come up in
syntheses in the future. The general idea is that you bring together a four-carbon piece
and a two-carbon piece to make a six-membered ring. The four-carbon piece has two
double bonds and is called the diene; the two-carbon piece has either a double or a triple
bond and is called the dienophile. The electrons all move around the ring at the same time.
This is one example of a cycloaddition.
R
R R
R C
CR2
CR2 C
R
R R
Diene Dienophile R Diene Dienophile
The R groups hanging from the dienophile can be an H or any sort of R group.
However, each dienophile must have at least one electron-withdrawing group for this
reaction to work well, although you can force it to go by using higher temperatures and
pressures. The diene can have pretty much any substituents, with a few exceptions.
The dienophile must have at least one of these:
O O O O O O
C H C R C OR C OH C O C R C N
As another note, numbering is extremely useful in keeping track of what happens
during this reaction. You can also draw in a faint dotted line to indicate where the bonds
are about to form, so that you can track connections more easily. Here, youre making a
bond from C2 to C3, and from C6 to C1. C7 and C8 dont participate in the reaction at all
they just fold out of the way and allow the reaction to happen. Thats why they end up
as a bridge across the newly-formed six-membered ring.
O O
6 7
6 1 O
1 CH3 8
5 CH3 5 6
7 7 8 5
8 4
or 1 CH3
4 2 4 3
2 3 2
3
Here, the new bonds are C1-C6 and C2-C7. C5 folds out of the way, and C8, C9
and C10 dont participate at all. Even though this molecule doesnt have any electron-
withdrawing groups, the reaction still goes under reasonable conditions in this particular
case.
5
1 6 10
2 heat 1 6
2
5 9 10
3 7 3 4
4 8 7 9
8
Loudon Chapter 15 Review: Dienes, Resonance and Aromaticity
CHEM 3331, Jacquie Richardson, Fall 2010 - Page 2

Another requirement for this to happen is that the diene has to be able to curl into
a C-like shape it must be s-cis. If a molecule is prevented from forming this shape,
Diels-Alder cant happen. If its locked so that its always s-cis, the reaction will be
easier than on a normal linear molecule.

Can't do Diels-Alder Great at Diels-Alder

The general rule is that the more time the molecule spends s-cis, the easier this
reaction will be. Sometimes the diene will appear to be freely rotating but is hindered by
some bulky R groups. We can label the four groups coming off the ends of the diene as
Ro or Ri, depending on whether theyre on the outside or inside. The rule is that the
bigger the Ri groups are, the less time the molecule will spend in this shape, and the
harder it will be to do Diels-Alder.
Ro CH3 H H

Ri H CH3 CH3
Ri H H CH3

Ro CH3 H H
Ro = outside group No steric hindrance in s-cis Some steric hindrance in s-cis Lots of steric hindrance in s-cis
Ri = inside group Good at DA Mediocre at DA Bad at DA

1,2 vs. 1,4 addition

A lot of the different chemistry that these molecules do is caused by resonance.
The position one away from a double bond is called the allylic position. Any time you
have a charge or a radical there, it can move around by resonance.

Because of this, conjugated alkenes can behave differently from regular alkenes.
If you put them under conditions that would add HBr to regular alkenes, you get some
product that looks as if the molecule is acting normally and adding an H and a Br to
adjacent carbons. But you also get some product where it adds the new atoms four
carbons apart from one another.
2 4 Br
HBr 2 4
1 H Br
3 2 4
1
H
1 3 3

1,2-product 1,4-product
If you step through the mechanism, this makes sense once you factor in resonance.
Either one of the two resonance forms can get attacked by the bromine, giving the two
different products.
Loudon Chapter 15 Review: Dienes, Resonance and Aromaticity
CHEM 3331, Jacquie Richardson, Fall 2010 - Page 3

H Br
Br
Br
H H

Br
H H
Br
Based on what we know of alkene stability, the 1,4-product is the most stable
because it has the most groups attached to the alkene. But the 1,2-product is usually faster
to form, because the bromine is closer to carbon 2 at first. This means that the 1,2-
product is favored under low-energy conditions and is the kinetic product. The 1,4-
product is favored under high-energy conditions that allow it to equilibrate back and forth
before it settles into one state, so its the thermodynamic product. You can skew the
amounts of products towards the kinetic side by using lower temperatures and towards
the thermodynamic side by using higher temperatures.

Aromaticity
Even though weve done a lot of reactions on alkenes, none of them work on
benzene. Thats because aromatic rings have totally different behaviors from normal
alkenes. They are much more stable than they would be if the alkenes had no interactions
at all. In fact, the alkenes dont even exist as distinguishable double bonds they average
out around the ring, so that every bond is halfway between single and double.
Benzene

Benzene is not the only molecule that fits this description lots of others have the
same behavior. There are four conditions that a molecule must meet to be aromatic:
1. It has to be cyclic
2. It has to be planar
3. All of the atoms around the ring have to have some involvement in the pi system,
either through pi bonds, lone pairs (maybe due to a negative charge), empty
orbitals (often due to a positive charge) or radicals.
4. If it has 4n+2 pi electrons, its aromatic. If it has 4n electrons, its antiaromatic. It
doesnt matter what n is as long as its an integer.
Not all carbons have involvement in pi system = nonaromatic

All carbons have involvement in pi system, and there are 6 pi electrons altogether = aromatic

All carbons have involvement in pi system, and there are 8 pi electrons altogether = antiaromatic (if it's planar)

Aromatic means that the molecule is more stable than it would otherwise be, due
to this effect. Antiaromatic means that its less stable. Nonaromatic means that it has no
Loudon Chapter 15 Review: Dienes, Resonance and Aromaticity
CHEM 3331, Jacquie Richardson, Fall 2010 - Page 4

change in either direction, because one or more of these rules arent being met. The
reasons for the changes in stability have to do with orbital levels it turns out that
aromatic molecules always have all bonding orbitals filled, while antiaromatic molecules
have two half-filled orbitals. The book has a good explanation of this on page 722, under
the name of Frost Circles.
In the case of larger rings, if the rules work out to them being antiaromatic, theyll
usually bend out of shape to avoid it. COT is the best-known example of this. It behaves
just like a regular alkene, with no unusual behavior due to aromaticity or antiaromaticity.

Cyclooctatetraene (COT) would be antiaromatic, but it twists up to avoid

the penalty of lowered stability. This makes it nonaromatic instead.
Sometimes you have the option of whether to include a lone pair towards the total
pi electrons or not. This is often the case for heterocycles, rings with atoms other than
carbon. Sometimes the lone pairs are excluded anyway due to geometry, especially if the
atom already has a double bond. The molecule will choose the best outcome, based on
stability.
If you count the lone pair: 6 pi electrons, so it's aromatic
If you don't count the lone pair: not every atom has an involvement in the pi system,
N so it's nonaromatic.
H Best outcome: count the lone pair (LP is p-hybridized)

If you count the lone pair: 8 pi electrons, so it's antiaromatic

If you don't count the lone pair: 6 pi electrons, so it's aromatic
N Best outcome: don't count the lone pair (LP is sp2-hybridized)

If you don't count either lone pair: not every atom has an involvement in the pi system,
so it's nonaromatic.
O
If you count one lone pair: 6 pi electrons, so it's aromatic
If you count both lone pairs: 8 pi electrons, so it's antiaromatic
Best outcome: count only one lone pair (one LP is p-hybridized and the other is sp2)
There are also ways to explain the participation or nonparticipation of a lone pair
based on geometric requirements. For instance, pyridine (the middle molecule above)
couldnt have its lone pairs participating anyway, since the hybridization of the nitrogen
forces the lone pair to point out away from the ring. In general, a participating lone pair
will be p-hybridized (which allows that atom to be part of the pi-system) and a non-
participating lone pair will be whatever hybridization is left over on that atom.