Molecules to Materials

The Organic Chemistry of Materials

Part 1: Conjugation & dyes
Question 1
What property must an auxochrome have to permit it to tune the colour of a dye?

Answer
An auxochrome must increase the delocalization of electrons (extend conjugation). It can
achieve this if it has a lone pair of electrons (electron donating) or can accept electrons (it has
a double bond in conjugation with the chromophore).

Question 2
Why is the first compound coloured and the second colourless?
H
N N
N N
H
yellow colourless

Answer
The first compound is fully conjugated while the second has a break in conjugation (the two
aromatic rings are isolated from each other).

Question 3
Draw the curly arrows that connect these two resonance structures:

N O N O

H H H

Answer
Remember, curly arrows represent the redistribution of electrons. The tail of a curly arrow
starts where the electrons are in the original molecule and the head shows where these two
electrons will be re-drawn in the second resonance structure.

Curly arrows will always flow from an area of high electron density to an area of low electron
density.

The answer is:

N O N O

H H H

Question 4
Draw the resonance structure indicated by these curly arrows:

O N
O

Answer
This is effectively the reverse of the question above. Here we have told you where the
electrons will be in the second resonance structure so all you have to do is draw it.

Remember that none of the atoms will exceed the octet rule (that is, have more than eight
valence electrons). Remember that as we are sharing electrons formal charges may be
created, but if they are their total must be the same on both sides of the delocalization arrow
(i.e. the two resonance structures must have the same overall charge).

The answer is:

N N

O N O N
O O

Question 5
For this question you need to draw the curly arrows that show how the electrons could be
redistributed to give a resonance structure that has no formal charges, then draw that
resonance structure:

H O
N
H
OH

O O O
H

Answer
This is the hardest of these three questions on resonance structures as it gives you the least
information. Basically, it is a combination of the two previous questions, just you need to show
how the electrons would flow from the negative charge (electron rich) towards the positive
charge (electron poor). The answer is:
 H O H O
N N
H H
OH OH

O O O O O O
H H

Question 6
What is the product of the nitration reaction shown below? Pay special attention to the
regiochemistry (which isomer is favoured). This is an example of electrophilic aromatic
substitution.

OH
HNO3

?
H2SO4

Answer
The mechanism for this reaction is in the lecture notes. The taxing part is considering what is a
better electron donating group, the hydroxyl group or the methyl? The stronger electron do-
nating group will activate the aromatic ring more and will control which position the nitration
occurs at.
OH OH
HNO3
H2SO4 NO2

The hydroxyl group is the more electron donating – one of the resonance structures formed
when the electrophile adds ortho to this group has every atom obeying the octet rule. This is
good. Substitution next to the methyl group results in an intermediate that always has one
atom with only six valence electrons.

Question 7
Using the curly arrow notation, propose a reaction mechanism for the following example of
electrophilic aromatic substitution:

O N
N AlCl3
+ + HCl
Cl

Answer
This is an example of a reaction known as the Friedel-Crafts acylation. It is a classic method for
functionalizing aromatic rings. Like all the previous reactions, the first step is to create a
powerful electrophile. This is achieved by treating the acyl chloride with a Lewis acid, a
compound that can accept two electrons (why can aluminium trichloride accept electrons?
Think about its valence shell. It is in group 13 this means it has three valence electrons. When
it forms three covalent bonds it has a total of six valence electrons. It may be neutral, but it is
not obeying the octet rule and it desperately wants to). So the first step is:

O Cl
Cl O
Al Al Cl
Cl Cl
Cl Cl Cl

The next step is identical to all the previous examples of electrophilic aromatic substitution.
The electron rich aromatic ring is going to attack the oxonium species.

N
N O O
Cl
H

This gives the charged intermediate. Re-aromatization is achieved by elimination of a proton.

Question 8
What is the product of the following electrophilic aromatic substitution? Use the curly arrow
notation to help explain the regiochemistry (what position the electrophile adds to) of the
reaction.

?
F
FeBr3
+ Br Br

Answer
It’s the same reaction again. It is like we think this is an important transformation. This time we
are adding a halogen, bromine, to the ring. The FeBr3 is simply present to generation the
powerful electrophile we require for the reaction.

Fluorine is the most electronegative element. This means it is an electron withdrawing group.
It is deactivating. And it is meta-directing. So the product will be:

F F Br
FeBr3
+ Br Br + H Br
The second part of the question asks you to explain the regiochemistry using the curly arrow
notation. This means it wants you to inspect the various resonance structures and use these to
justify the meta-substitution.

If we look at the reaction at the para position first we see that one of the resonance structures
puts the carbocation next to the most electronegative element, the fluorine. This is
disfavoured. Molecules shouldn’t make an electron deficient cation more electron deficient by
withdrawing the electrons. So, this is disfavoured.

F F Br
Br
Br Br + Fe Br
Fe Br
Br Br Br
H Br

F F

Br Br
H H

The same occurs if the bromine adds to the ortho-position. One of the resonance structures
has the carbocation next to the fluorine atom. The only substitution pattern that doesn’t lead
to this kind of disfavoured resonance structure is addition to the meta position.

F Br F Br
F
Br Br H + Fe Br
Fe
Br Br Br
Br

F F
F Br F
H H

F Br

And hence, reaction occurs here.

Question 9
Give the products of this reaction scheme.

? ?
SO3 HNO3 H2SO4
HO H2SO4 H2SO4 Heat HO NO2

C8H10O4S C8H9NO6S
Answer
Both the reactions are examples of electrophilic aromatic substitution. The beauty of this
reaction scheme is that we are controlling the position of the nitro group in the final
compound. If we simply performed nitration of the first compound the nitro group would be
para-to the phenol. Instead, we perform a sulfonation reaction. This adds a sulfonic acid in the
para position. The reaction is identical to all the ones before it. The sulfuric acid activation
sulfur trioxide, making it into a more powerful electrophile. We then get our standard
substitution reaction.

O O O O O
H OH
S H S S H
O O O OH O O S
O O O
HO HO
S
O OH

HO

OH
S
O O

Nitration occurs as normal but it only has one position that it can add to (why do you think I say
“only one position”?).

The clever bit is sulfonation is reversible. Heat a sulfonic acid in the presence of acid and it will
eliminate. This means it effectively acts as a removable ‘blocking group’ or protecting group
and permits us to add a group in a position electronics normally would not permit. The
elimination, or desulfonation, is effectively the reverse reaction of sulfonation.

O O
S
O OH
HO NO2 HO NO2
O H HO NO2
OH S
S O
HO
O O
O OH
H S
O O

The actual answer to the question was just:

SO3 HNO3 H2SO4

HO H2SO4 HO H2SO4 HO NO2 Heat HO NO2

SO3H SO3H
Question 10
Draw the expected azo dye products formed when 3,5-dimethylaniline (below) is diazotized
and then reacted with the following aromatic compounds.

O N
O HO NO2
S O

NH2

3,5-dimethylaniline

Answers
Guess what? This is an example of azo dye formation through electrophilic aromatic
substitution. The only ‘fly in the ointment’ is that the different aromatic rings will direct the
reaction to occur at different positions on the ring.

The first one, anisole, is an ether. It is electron donating so activates the ring and leads to ortho
and para substituents. The major product will be the para -derivative (shown below) on steric
grounds.

O N
N

The second is a sulfonic acid. These are electron withdrawing groups. This means they are
deactivating and direct to the meta position.

OH
O
S
O

N
N

Nitrobenzene is the same. It is meta-directing:

O2N

N
N

Finally, the dimethylaniline derivative is highly activating and ortho, para directing. The para
position is blocked so the reaction must occur at an ortho position.
 N
N
N

Question 11
In theory, the dye below can be synthesized in one of two ways, breaking either bond ‘a’ or
bond ‘b’. Only one route leads to good yields. State which one and explain your choice.

a N

N
N

O2N b

Answer
This question is asking you to inspect the two aromatic rings and determine which wll be the
better nucleophile and which will direct substitution at the correct position of the ring. If we
look at bond ‘a’ first. Breaking this bond will lead to the two compounds below. Nitrobenzene
contains an electron withdrawing group. This means it will be a poor nucleophile, but, more
importantly, electron withdrawing groups direct electrophilic aromatic substitution to occur at
the meta position. The wrong position. This would be a bad choice.

a N
N
N +
N O2N N
N
O2N nucleophile electrophile

Breaking bond ‘b’ makes much more sense. This leaves an aniline derivative as nucleophile.
These are electron rich nucleophiles that attack at either the ortho or para positions as
required.

N N
N N
N +
N
O2N
O2N b
electrophile nucleophile
Molecules to Materials
The Organic Chemistry of Materials
Part 2: Radicals, hydrolysis, oxidation & the Maillard reaction

Question 1
Three compounds were isolated from the radical bromination shown below. Which was the
major product, and which was the minor? Give a brief explanation of your answer.

Br
Br2 Br
light Br
+ +

A B C
Answer
This is standard radical halogenation reaction. The reaction proceeds through the mechanism
described below:

initiation

Br Br 2 x Br

propagation

Br + H R Br H + R

R + Br Br R Br + Br

The key to the selectivity is the stability of the radical R•. Radicals are electron deficient
species (only 7 valence electrons). This means they are stabilized by electron donating groups
(or resonance). In this question it means the tertiary bromide B, made from a tertiary radical
will be favoured as it is the more stable radical (three electron donating group).

The least favoured will be A, as it has the least stable radical intermediate, a primary radical.

Question 2
Show two possible products for the addition of a methyl radical to 1-pentene.

H3C +
?
Answer
This question is about radical stability. Addition of the methyl radical could occur at either end
of the alkene and would give the following two compounds:

The secondary radical, the product on the left, is more stable as it has two ‘electron donating’
alkyl groups. The primary radical on the right is less stable as it has only one ‘electron
donating’ alkyl group.

H3C + +
It is possible we could have formed different radicals if the methyl radical abstract a hydrogen
atom from 1-pentene to give a carbon radical (and methane gas). Possible radicals are shown
below. The first is the most stable is it is delocalized over the double bond.

The second two are less stable as they are localized on a single atom. The one on the far right
is the least stable as it is a primary radical.

H3C + + +

H C H
H

Finally, I haven’t drawn the radical on the alkene itself (it has three C–H bonds). This is because
vinyl radicals are unstable and the vinyl C–H bonds are much stronger than alkyl C–H bonds.

Question 3
Radicals are useful reagents in organic chemistry. They can be used to prepare cyclic
molecules in good yields. The following reaction uses only chemistry that we have covered.
Draw a reaction mechanism and explain the observed selectivity (why does this bromine
radical add to one alkene and not the other?).

Br
(t-BuO)2
H Br + Ph Ph

Answer
This question is looking at a number of factors. It is making you think about chemistry. How do
I form this compound? Which bonds are being made? What is the most likely order of events?
How can it all be achieved with radicals?

So, let’s look at the product molecule and highlight the bonds that have been made:

Br H H

Ph

There are three new bonds. How can we make these using the chemistry we have covered?
First, we have studied the addition of a bromine radical to an alkene. This should give us an
idea of how the C–Br bond. Secondly, we saw that this reaction also makes a C–H bond during
propagation. So the only bond we haven’t really seen how we could make is the C–C bond.
But to certain extent we have. We introduced polymerization. This showed you that it is
possible to make C–C bonds from a radical. Putting this all together you should be able to
come up with an answer. It isn’t about memorizing a reaction. It is about applying the same
principles to new systems. It is problem solving.
initiation

t-Bu
O O 2x t-Bu O
t-Bu

t-Bu O + H Br t-Bu OH + Br

propagation

Br + Ph Br Ph

Br H

Br Ph Ph

Br H Br H H
+ H Br + Br
Ph Ph

The initiation steps are identical to before. The first addition of the bromine radical occurs to
give a tertiary radical. This is a relatively stable radical. It could have added to the other alkene
to give a resonance stabilized benzylic radical. It doesn’t for two reasons. First, and most
importantly, that wouldn’t give us the product drawn! Secondly, it had the choice of adding to
a terminal alkene (a small CH2) position or an internal alkene, with a substituent. It chose the
less sterically demanding target.

The tertiary radical then cyclises onto the second alkene to give a resonance stabilized
benzylic radical. This then propagates the chain.

Question 4
BHT (A) is a synthetic antioxidant. If the tert-butyl substituents [R–C(CH3)3] were moved to the
meta position on the benzene ring (compound B), would the isomer be a better or worse
antioxidant. If it is worse, why?

OH OH

A B
Answer
Compound B is a worse antioxidant. Compare the resonance structures. In A (BHT), all the
carbon radicals are found on tertiary carbon atoms. In compound B only one is tertiary, the
others are secondary:
 O O O O

A
OH O O O

B
Question 5
Which of these compounds is unlikely to be a good antioxidant?

OH
OH N N
OH
HO OH CHO OH N NH
N
HO
OH
N
OH CHO
HO
O O

propyl gallate gossylpol losartan

Answer
The first two are both phenols. They can readily stabilize a radical over at least one ring. They
should be good antioxidants. The final compound does not contain a phenol group. It is
unlikely to be a good antioxidant.

Question 6
What are the products of base-mediated hydrolysis using sodium hydroxide of the following
triglyceride? Give a mechanism for the base-mediated hydrolysis reaction.

O O

O O

Answer
In this example, we will get three different fatty acids and glycerol. The only trick is to
remember that you form the carboxylate anion and not the actual acid.
 O

Na+–O
O

Na+–O
O

Na+–O

The mechanism for base-mediated hydrolysis is:

O OH O OH O O
R R
R R H + O
+
HO
O O O O
nucleophilic elimination irreversible
attack deprotonation
ester tetrahedral carboxylate alcohol
intermediate

Question 7
What is the product of the following condensation reaction?

H+
NH2 O OH (–H2O)
+
?
Answer
This is an example of imine formation. We would accept either the imine product or the cyclic
aminal.

OH
N H
or O N

Question 8
Using the curly arrow notation, draw a reaction mechanism for the hydrolysis of the imine
shown below. Give the products of this reaction.

H+
H2O

HO2C N
?
Answer
Hydrolysis of an imine is the reverse of its formation (and is the same as the hydrolysis of an
acetal as found in the lecture 5). The mechanism is given below:
 HO2C
HN
HO2C N HO2C N H O
H H
H+
O
H H O
H H

HO2C HO2C
H N HN
O
H O H+ O
H H
H
O HO2C NH2
H H

The products are glycine (and to be strictly correct this should be drawn in its zwitterionic
form; but we’re nice) and cyclohexanone.

HO2C NH2 or &

O2C NH3
O
Molecules to Materials
The Organic Chemistry of Materials
Extra questions about flavour

Question 1
What are three important factors which allow us to sense odours?

Answer
To be able to smell a compound some percentage of it must be in the gas or vapour phase
(i.e. it must be volatile), this also means it must have a low molecular weight, and be non-
ionic. Extra: we can sense smells in relatively low concentrations (again, think durian)

Question 2
What are three important factors which allow us to taste fl avours?

Answer
Strictly speaking there are only two criteria we discussed: the compound must be water
soluble (almost all liquid that we eat/ drink is water based), and it must be present in high
concentrations. The third factor we discussed was simply that there is no limit to the
molecular weight of a fl avour compound (but that’s not really a restricting factor)

Question 3
Describe (in detail) what theory the fi gure below is showing and label each part of the
diagram
Answer
The fi gure shows a schematic for the AH/ B-𝛄 model of sweetness. It states that a
glycophore (sweet compound) must have three complementary contact points with the
receptor in order for a molecule to be “ sweet”. All sweet compounds must obey the AH/ B-
𝛄 model but not all compounds that obey t he model are necessarily sweet.
The glycophore and receptor each have:
AH – a hydrogen bond donating group (like an OH or NH group)
B – a hydrogen bond accepting group (typically something with a lone pair of e- like an O or
N)
𝛄 – an additional group with a hydrophobic interaction or van der Waals interaction (could
be non-polar CH or even an aryl ring)
AH pairs with B, B pairs with AH, and 𝛄 pairs with 𝛄

Glycophore
(sweet compound)

Complementary
hydrogen bond Complementary
interactions hydrophobic
interactions

Receptor
(tongue)