334 ChemActivity 18: Aromaticity
6. The following ketone has a large amount of + charge on carbon and – charge on oxygen. This is
because the so-called zwitterionic form of the ketone is much more favorable than you might
expect given that it is charged. (A zwitterion is a compound with both a + and a charge.)
Construct an explanation for why the compound has a large amount of zwitterionic character.
O O
neutral zwitterion
state state preferred
7. The molecule on the left has a lone pair that resides in a p orbital despite the fact that in a p orbital
the lone pair resides closer (90o vs. 109.5o) to N-H and N-C sigma-bonding electrons. Construct
an explanation for why this lone pair resides in a p orbital.
H H
no reason to reside
N N
in a p orbital so it
resides in a sp3
hybrid orbital
8. Indicate the type of orbital holding each lone pair, and label each molecule that is aromatic.
H
H
N O N
N N
pyridine imidazole furan pyrrole cyclopentadienyl anion
(abbreviated "cp")
N
N N
N N
N N N
H
pyrimidine quinoline purine pyrrole anion
9. All of the “heterocycles” in the previous question are commonly encountered in nature or the
laboratory. (A heterocycle is any cyclic molecule containing a noncarbon atom. If you plan to
continue your study of organic chemistry beyond this course you may want to familiarize yourself
with these common heterocycles.) Construct an explanation for why each of the heterocycles
shown above is common.
ChemActivity 18: Aromaticity 335
10. Draw an energy diagram showing both of the following reactions on the same reaction coordinate,
and construct an explanation for why the pKa of cyclopentadiene is much lower than the pKa of
cyclopentane.
H H H H H H
C uphill by C C uphill by C
+50pKa units +16 pKa units
pKa = 50 pKa = 16
11. Explain why carbocation B is formed preferentially when water leaves. Then use a curved
(bouncing) arrow to show the mechanism by which B is formed from A.
OH2 OH2
A B
12. A benzyl carbocation can rearrange to the ion shown below right (called a tropylium ion).
a. Use curved (bouncing) arrows to show the mechanism of this two-step carbocation
rearrangement.
b. What is the driving force for this rearrangement?
13. When an organometallic chemist needs a large anion that will make a strong bond to a metal, a
common choice is the anion of pentamethylcyclopentadiene (pentamethylcyclopentadienyl anion).
a. Draw pentamethylcyclopentadienyl anion, and explain why it is a stable anion.
b. Construct an explanation for why pentamethylcyclopentadienyl anion was nicknamed “cp*.”
14. Read the assigned pages in the text, and do the assigned problems.
336 ChemActivity 18: Aromaticity
Exercises for Part B
15. The anion below left, has two π bonds that contain four π electrons. Ignore the lone pair on the
anionic carbon for now, and place the four electrons from the two π bonds in the MO diagram.
π (anti-bonding)
PE
(non-bonding)
π (bonding)
a. According to your MO diagram with four electrons, does this anion have radical character?
b. NOW assume the lone pair on this anion resides in a p orbital, and add two more electrons
to your MO diagram to reflect that the lone pair electrons are part of the π system.
c. Do you expect the lone pair on this anion to reside in a p orbital as we assumed in part b?
Explain your reasoning.
d. Is this cyclic anion expected to be aromatic?
16. Draw an MO diagram for tropylium ion (structure shown on the previous page), and fill in the π
electrons showing the ground state of this ion.
17. The first half of Hückels' Rule states that a cyclic conjugated π system with 4n+2 π electrons will
be very stable. A corollary to this rule states that a cyclic conjugated π system with 4n
electrons (4, 8, 12, etc.) will be very unstable. Use MO theory to explain this corollary.
18. Consider two stereoisomers of the 10-member ring shown below.
H H
H C C H
C C C
H
H
C C C
H C C H
H H
a. Construct an explanation for why the conformation on the left is very unfavorable.
b. In the conformation on the right, the two H's drawn with wedge-and-dash bonds cause the
carbon backbone to flex out of planarity. Do you expect this molecule to be aromatic, anti-
aromatic or non-aromatic? Explain.
19. Read the assigned pages in the text, and do the assigned problems.
ChemActivity 18: Aromaticity 337
The Big Picture
This ChemActivity is mostly about recognizing aromatic molecules. As a result there are a large
number of exotic aromatic systems shown as examples that you will likely not encounter in other
contexts. Most every aromatic molecule we will encounter in this course contains a six-member ring of
carbons with three double bonds, a benzene ring (also called a phenyl ring).
The next few activities explore reactions involving aromatic rings. Almost all the examples in these
upcoming activities will involve benzene derivatives, but the reactions also apply to larger aromatic
molecules and may work with heterocyclic aromatic molecules.
The reactions in the next few ChemActivities are really quite amazing since the key property of
benzene and other aromatic molecules is their relative nonreactivity. In fact, the reaction showcased in
the next section was discovered accidentally by chemists who were using benzene as a solvent,
assuming it was inert (which it usually is).
Common Points of Confusion
• There are many ways to represent benzene. Unfortunately, the two most common ways (a
hexagon with a circle in it or using only one of the two resonance structures) are both a bit
misleading.
• Look out for the hexagon with a circle in it representation shown in CTQ 1, and remember that the
circle in the middle should really be a dotted-line to properly show that it represents a composite
of both of benzene’s two equivalent resonance structures. The one good thing about this
representation is that it emphasizes the symmetrical nature of benzene.
• If you see benzene represented as one of the two equivalent resonance structures (a six-member
ring with three double bonds), remember that benzene is actually symmetrical. Each of the
carbon-carbon bonds in benzene is halfway between a single bond and a double bond (a 1-½
bond).
• Much student confusion revolves around anti-aromaticity. This is ironic because it is a rarely
encountered phenomenon. One misconception is that an anti-aromatic molecule must violate all
the rules of aromaticity. WRONG. An anti-aromatic molecule must OBEY all the rules of
aromaticity EXCEPT the 4n + 2 rule. (It must instead have 4n π electrons.)
• Students sometimes get confused between the terms anti-aromatic and non-aromatic. They are
very different. Most molecules are non-aromatic, including all noncyclic molecules. Anti-aromatic
molecules turn out to be very rare because it is very easy for most cyclic molecules to violate the
planarity required for anti-aromaticity by adopting a nonplanar conformation. This makes them
non-aromatic instead of anti-aromatic. In fact, most examples of anti-aromatic molecules contain
a cyclobutadiene group. This is because, unlike larger rings, the four-atom-ring of
cyclobutandiene is unable to twist out of a planar conformation. (Model sets show this well if you
are able to make a model of a four-member ring.)
• A lone pair on an aromatic ring resides in a p orbital only if doing so makes the molecule
aromatic. This is because there is an energy “cost” of putting a lone pair in a p orbital vs. a hybrid
orbital due to the fact that p orbitals are closer to other orbitals than hybrid orbitals (which are, by
definition, maximally spread out).
Nomenclature Worksheet 3
BENZENE DERIVATIVES
Model 1: Naming Mono-Substituted Benzene Rings
Simple mono-substituted Cl NO2 CH2CH3 O
benzene rings can be named
by placing the substituent
name in front of benzene chlorobenzene nitrobenzene ethylbenzene ethoxybenzene
Memorization Task NW3.1: Parent Names of Common Benzene Derivatives
A handful of these are so common that they constitute their own parent name. Know the following…
O O
CH3 OH NH2
H OH
toluene phenol aniline benzaldehyde benzoic acid
When a substituent contains an alcohol (OH), amine (NH2), or in some cases a carbonyl, the substituent is
considered the parent chain, and the ring is considered an attached group called a phenyl group.
For other functional groups (e.g., alkenes, halogens, etc.) the benzene ring is often the parent chain.
NH2 Br
OH
3-methyl-1-phenylbutan-2-ol 4-methyl-5-phenylhexan-3-amine (E)-pent-3-en-2-ylbenzene (3-bromo-2-methylpentyl)benzene
Critical Thinking Questions
1. (E) What is the name most often used for aminobenzene?
2. Name each of the following compounds.
Br
OH
3. Draw each of the following compounds from their names.
a. 4-phenylbutan-2-ol b. pent-3-yn-2-ylbenzene c. (E)-4-phenylbut-3-en-2-ol
Nomenclature Worksheet 3 339
Model 2: Naming Multi-Substituted Benzene Rings
Either the ortho/meta/para system or the numbering system may be used for naming benzene rings with
two substituents. When there are three or more substituents the numbering system must be used.
O2N CH3 OH O OH O
H OH
NH2
3-methyl-1-nitrobenzene 2-aminophenol
or or H 3C CH3 H3C CH3
meta-nitrotoluene ortho-aminophenol 2,4-dimethylbenzaldehyde 2-hydroxy-4,6-dimethylbenzoic acid
or or
3-nitrotoluene ortho-hydroxyaniline, etc.
Note that ortho, meta, and para are often abbreviated o, m, and p, respectively.
Critical Thinking Questions
4. Write another name (not appearing in Model 2) for 2-aminophenol.
5. Draw the structure that corresponds to the name 2-phenyl-6-methylphenol.
6. Explain why the following is not a correct name, 4,5-dimethylphenol.
7. Name each of the following compounds.
Br O OH OH
HO OH Br
OH
CH3 HO HO I
8. Draw each of the following compounds from their names.
a. p-benzenediol b. 2,4,6-trinitrotoluene c. (E)-ortho-(prop-1-enyl)phenol
340 Nomenclature Worksheet 3
Exercises
1. Name each of the following compounds.
OH
Br Cl CO2H CHO
Br H3CO
NH2 F NO2
O2N CHO F CO2H
NH2 NO2 F F O2N NO2
2. Draw each of the following compounds from their names.
a. o-nitroaniline
b. 4-aminobenzaldehyde
c. para-hydroxybenzoic acid
d. o-methyltoluene (also called ortho-xylene or o-xylene)
e. meta-xylene
f. p-xylene
g. m-propoxynitrobenzene
h. 2,3-dibromophenol
i. 2,4,5-trimethylaniline
j. 2,6-dimethoxybenzaldehyde
ChemActivity 19: EAS
PART A: ELECTROPHILIC AROMATIC SUBSTITUTION (EAS)
(What products are formed when a strong electrophile is added to benzene?)
Model 1: (review) Electrophilic Addition of HCl
H
Cl
Rxn 1 H Cl
cyclohexene
carbocation intermediate
H
x
Cl
Rxn 2 H Cl
benzene This product
carbocation intermediate DOES NOT form!
Critical Thinking Questions
1. For Rxn 1 (above) draw curved arrows showing the mechanism of electrophilic addition of HCl.
Include an appropriate carbocation intermediate in the box above.
H
Cl
PE PE
carbocation
intermediate
H Cl
H H Cl
carbocation Cl
intermediate
Reaction Progress (Rxn 1) Reaction Progress (Rxn 2)
Figure 19.1: Reaction Diagrams for Electrophilic Addition of HCl
2. Rxn 1 is slightly downhill. Rxn 2 is very uphill (see Figure 19.1). Construct an explanation for
why the reactants in Rxn 2 are much lower in P.E. than the products.
3. Draw the carbocation that would form in Rxn 2, and explain why this carbocation goes back to the
starting material (H–Cl and benzene) instead of forming the product.
342 ChemActivity 19: EAS
Model 2: Electrophilic Aromatic Substitution (EAS)
• Recall that deuterium (D) has nearly identical reactivity as hydrogen (H).
• In the following reaction, assume D–Cl reacts the same way as would H–Cl.
• When benzene is treated with D–Cl, one H is replaced with a D. (With excess D–Cl this
continues until all the H’s have been replaced and the product is C6D6.
H D
D Cl
H C H H C H
C C C C
Rxn 3 H Cl
C C C C
H C H H C H
H H
Critical Thinking Questions
4. Use curved arrows to show a reasonable mechanism for Rxn 3 in Model 2. (Hint: The first step is
formation of a carbocation intermediate, just as in Rxn 2.)
5. Rxns 2 and 3 have the same starting materials and carbocation intermediate, but different
products. The energy diagram for Rxn 2 (using DCl in place of HCl) is shown below using a
dotted line. On this same set of axes, draw a solid line showing the progress of Rxn 3.
D
Cl
carbocation
intermediate
for Rxns 2 & 3
PE
D Cl
Reaction Progress (Rxn 2 with DCl)
Reaction Progress (Rxn 3)
6. Construct an explanation for why Rxn 3 is much more likely to occur than Rxn 2. (Note: Rxn 2
does not occur under normal circumstances.)
ChemActivity 19: EAS 343
7. Draw a generalized mechanism for EAS (Electrophilic Aromatic Substitution) showing the
+
substitution of an electrophile (E ) for one of the H’s of benzene in the presence of a mild base
(:B). (Note: In Rxn 3, E = D , and :B = Cl—)
+ +
H E
E B H B
••
Z Z
Model 3: Lewis Acid Catalysts
Many EAS electrophiles must be made in situ (in the reaction mixture). For example: +NO2 is made when
sulfuric acid protonates (adds H+ to) nitric acid. (The mechanism for this is in your homework exercises.)
EAS reactions including Synthetic Transformations 19.4-19.6 (on the next page) require a Lewis acid
catalyst to generate the electrophile. (Recall that an electron-deficient species can be called a Lewis acid.)
– – – –
Cl Br Cl Br
Cl
–
Fe + Br
–
Fe + Cl
–
Al
+ Br
–
Al +
Cl – Br – Cl – Br –
iron chloride iron bromide aluminum chloride aluminum bromide
Figure 19.2: Lewis acid catalysts used for Synthetic Transformations 19.4-19.6
Critical Thinking Questions
8. Confirm that each atom shown in Figure 19.2 has a zero formal charge.
a. Do the partial charges shown fit the electronegativity data in Model 3 of ChemActivity 4?
b. Based on the partial charges shown, mark the atom on each catalyst that is most Lewis acidic.
9. To the structure of Br2 bound to FeBr3 (below, far right), add a drawing of the electron cloud of Br2
(and appropriate partial charges). DO NOT attempt to draw the electron cloud of FeBr3.
Outline of Undisturbed Outline of Electron Cloud of Br2 Br2 with partial bond to FeBr3
Electron Cloud of Br2 near polar molecule (outline of electron cloud not shown)
partial
bonds Br
Br Br Br Br
Br Br Fe Br
(no dipole) (induced dipole) (permanent dipole) Br
10. Circle the most electrophilic Br atom above. Note the formal charge is misleading in this case.
11. Explain why benzene does not undergo EAS with Br2 unless FeBr3 (or another Lewis acid
catalyst) is present.