CHEM1011 Worksheet 13
Model 1: Aromaticity
Certain cyclic molecules exhibit extraordinary stability, attributed to lower than expected potential energy.
These molecules are called aromatic molecules.
The racetrack analogy explains this stability as follows: electrons can race endlessly around a ‘racetrack’ of
conjugated p orbitals. This allows them to adopt a longer wavelength and thus a lower energy. Such a
‘racetrack’ of p orbitals is called a cyclic conjugated p system.
'Racetrack'
represented as electrons go round and
round in circles
Benzene
Aromatic conjugated π system
represented as not a racetrack!
'Normal' conjugated π system
Aromaticity requires 3 things:
1) Conjugation
2) That the conjugated system is cyclic
3) That the cyclic conjugated system contains 4n + 2 p electrons (Hückel’s rule) where n = 0, 1, 2, 3, etc
Note: for a molecule to be aromatic it only needs to contain a cyclic conjugated p system that meets
these requirements
Critical thinking questions:
1) For the molecules below find the largest possible cyclic conjugated p system “racetrack” and label it
with the total number of electrons involved in the p bonds of that racetrack.
2) Identify which of these molecules meet the requirements for aromaticity and label these “aromatic”.
N
3) Pyrrole is an aromatic heterocyclic compound (i.e. atoms other than carbon in the ring), but at first
glance it doesn’t appear to contain enough p electrons to be aromatic (only 2 p bonds = 4 p electrons).
On the orbital diagram below, place the lone pair of electrons on the nitrogen atom in an appropriate
orbital to allow them to be counted as p electrons. Does this satisfy the criteria for aromaticity?
H
N
N H
pyrrole
Model 2: Carboxylic Acids and their Derivatives
Critical thinking questions
1. Carboxylic acids are, as the name suggests, capable of undergoing acid-base reactions. We also know
that amines are basic. Use this to predict the outcome of the following reactions.
Carboxylic acid derivatives are formed from the condensation of a carboxylic acid with a second functional
group, such as an alcohol or an amine. In some cases they can be formed directly. More often, the carboxylic
acid must be converted to a more reactive intermediate, such as an acid chloride but the process of
condensation is essentially the same:
2. Using the reaction above as a model, predict the products of the condensation of an acid chloride with an
amine.
Model 3: Amino acids and peptides
Amino acids are bifunctional organic compounds containing carboxyl and amine groups. These two groups can
react to form an amide, with what is known as a peptide bond:
The dipeptide shown below has all of the ionisable groups in their conjugate acid forms, together with their pKa
values.
1. Draw the structure of the amino acids that formed this dipeptide.
2. Draw the structure of another dipeptide containing both of the amino acids in the dipeptide drawn above.
Hint: rearrange the order of the amino acids – they can react at either end. What type of isomer is this
compared to the peptide above?
3. Draw the structure of the dipeptide at the following pH values:
pH = 5
pH = 12