Problem Set #5 11 points possible OC 13.47, SUP 13.1, 13.4, 13.6, 13.7, 13.8, 13.14, 13.19, 13.

23,
13.25 (2 pts)

OC 13.47 The compound shown below was synthesized by Proffessor I M Dimm who was astonished
to find that it was exceedingly stable. Prof. Dimm had expected world renown for making what he
thought would be an unstable compound. Dimm reasoned that with six double bonds and a triple bond
in the molecule there would be 16 π electrons and thus, no aromatic character (4n, n=4, not 4n+2).
Where was his reasoning wrong?

Two of the electrons in the triple bond are not part of the conjugated π system. They are in a π orbital
that is perpendicular to the rest of the p orbitals that make the conjugated π system. The conjugated π
system thus only contains 14 electrons. 14 = 4n + 2 for n =3. So this molecule is aromatic.

SUP 13.1 Which of the following species are expected to be aromatic?

The first species is not a fully conjugated species. One of the carbon atoms is sp3 hybridized so it is
neither aromatic nor anti-aromatic.
The cyclopropenyl radical is also neither aromatic nor anti-aromatic. It is a fully conjugated, cyclic
system but it has 3 electrons in its pi system. 3 is neither 4n nor (4n +2).
The cyclopentadienyl cation is also a fully-conjugated, cyclic system but it has 4 pi electrons in this
system so it is anti-aromatic.
The two remaining species are aromatic. Both are fully conjugated, one has 6 electrons and the other
has 10 electrons.

SUP 13.4 Azulene and calicene are fairly polar molecules despite the fact that they do not contain any
electronegative atoms. Explain why.

Resonance structures that Resonance structures that

For each of these molecules, there is a polarized resonance structure where each of the rings is
aromatic. Because aromaticity is so favorable, these resonance structures are major contributors to the
real structure of the molecule (at least they are more major than the resonance structures with opposite
dipole that make the rings antiaromatic) and so the molecule is polar

SUP 13.6 Which of the following bromides would ionize most rapidly to form a carbocation? Justify
your reasoning
 Br
Br
Br

Br

A B C D
The bromides above form the carbocations shown below. B forms the most stable carbocation because
the cycloheptatrienyl cation is aromatic.

SUP 13.7 Which of the following heteroatom-containing compounds are expected to be aromatic?

S Not aromatic because it is not fully conjugated. The top carbon atoms has 2 C and 2 Hs
attached to it so it is sp3 hybridized.

All the other compounds are (or can be) cyclic, fully-conjugated systems. Each atom can donate one p
orbital to the pi system. In order for the nitrogen or sulfur atoms to do so they must either be part of a
double bond or they must donate the two electrons in a lone pair to the pi system. The boron has an
empty p orbital that it can donate without donating electron.
CH3
H

N N
S

N H
B
N N
N N
H CH3
H
Aromatic compounds
In the first there are 6 electrons in the pi system all coming from the double bonds. In the second there
are also six electrons: four from the double bonds and one from the lone pair of sulfur. In the third
compound, there are 4 electrons from the double bonds and two electrons from the lone pair of the
uncharged nitrogen. The fourth has 6 electrons all from the pi system. The fifth has four electrons from
the double bonds and 2 from the lone pair of the N. The last has 6 electrons from the double bonds and
none from the boron.
(CH3)3C C(CH3)3

N
S
(CH3)3C

Anti-aromatic compounds
The sulfur containing molecule has 8 electrons total in its pi system, 6 from the double bonds and 2
from the lone pair of S. The other compound has 4 electrons in the pi system. (The nitrogen can only
donate either a double bond or a lone pair to the pi system, not both.)
SUP 13.8 Pyridine and pyrrolidine react rapidly with dilute aqueous HCl to form the corresponding
hydrochloride salts. However pyrrole, which is another nitrogen containing heterocycle, does not
react under these conditions. Explain.
aromatic aromatic not aromatic not aromatic

HCl
HCl

N N N N
H
H H H

aromatic not aromatic

HCl So unfavorable that no reaction occurs with dilute HCl

N N
H
H H
When a nitrogen atom acts as a base it donates its lone pair to form the N-H bond. Pyridine and
pyrrolidine can easily use their lone pairs for this purpose. The lone pair of pyrrole is a part of the
aromatic system and so is not easily donated. When that pair is used to make a N-H bond, the resulting
compound is no longer aromatic.

SUP 13.14 Draw the molecular orbitals of cyclopentadienyl anion pi system in order of increasing
energy and
a) indicate how many electrons will occupy which orbitals
b) indicate the number and positions of the nodes present
c) identify the HOMO and LUMO orbitals of the cyclopentadienyl anion

LUMO

Energy

HOMO

SUP 13.19 Depending on the electronic nature of group G, Birch reduction gives either A or B as the
major (often the only) product in the following reaction:
If G is electron donating A is formed: if G is electron withdrawing, B is produced. Provide the
mechanistic explanation for the observed regiochemistry of the Birch reduction.
G G G

Na/NH3
EtOH

A B
This question is wrong so everyone should get a point for it. I only really care about it because we
use the same types arguments to explain regiochemistry of electrophilic aromatic substitution.
The regiochemistry of the Birch reduction can be understood by considering the anionic intermediates
of the reaction. The precursor to A has a negative charge on the carbon to which the G is attached. This
intermediate is stabilized by an electron withdrawing group so if G is electron withdrawing then A is
formed. The precursor to A is destabilized if G is electron-donating so B will be formed instead.
G G

H
H
H H

intermediate before A intermediate before B

SUP 13.23 Benzyne is a highly reactive molecule that is produced as a short-lived intermediate in
certain organic reaction.
a) Would you expect benzyne to be aromatic?
b) Why do you think benzyne is so reactive?
Yes benzyne would be aromatic for the same reasons that the molecule in OC13.47 (above) is
aromatic. Only one of the pi bond in the triple bond is part of the conjugated pi system so there are still
6 electrons in the cyclic conjugated pi system. It is so reactive because it has tremendous angle strain in
the ring. To make the second pi bond in the triple bond the bond angles at each of those two carbon
atoms should be 180 degrees. This is not possible in a six membered ring so the pi bond that is not part
of the conjugate system has horrible overlap between the atomic orbitals that make it up.

SUP 13.25 (2 pts) Provide reasonable synthetic sequences to prepare each of the following compounds
from the indicated starting materials and any other necessary reagents.
a)
NBS KOH Br
Br2

Br Br

Because the benzyilic position is so stable I can brominates this position with NBS.
b)
mCPBA OH
H2 CF3CO3H HBr
or another O
Lindlar's catalyst peracid Br

I must first make an epoxide and then open the epoxide under acidic conditions to get the primary
alcohol. If I try to use Br2 in H2O to add the bromine and OH to the double bond then I will get the
opposite regioisomer.
c) retrosynthetic analysis
CO2H CO2H CO2H

via
The middle from
Diels-Alder
Birch reduction of
from

I look at the product and see that the outer two rings are six membered rings with one double bond.
You should immediately think Diels-Alder when you see such rings.
CO2H
CO2H CO2H

1) Na/NH3 2 eq
EtOH

2) H3O+ heat

d) retrosynthetic analysis
O H

Br

I can make the butynyl anion and benzyl bromide easily from my starting material. Benzyl bromide
should easily undergo the SN2 reaction with the anion to form the carbon-carbon bond. I use
dissolving metal reduction to get the trans alkene so that I can then get the trans epoxide.
NaNH2

NBS
Br
heat

O H
CH3CO3H
Na / NH3 or another peracid