Organic Chemistry
Fourth Edition
David Klein
Chapter 2
Molecular Representations
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Copyright ©2021 John Wiley & Sons, Inc.
2.1 Representing Molecules /
Introduction
• There are many ways to represent molecules.
• Consider what information is necessary to accurately
describe a molecule.
• Which representations are easiest to draw? Which ones
give you more information about the molecule?
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2.1 Representing Molecules /
Limitations
• Notice that the molecular formula would be inadequate
to distinguish between propanol and isopropanol.
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2.1 Representing Molecules / Practice
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SkillBuilder 2.1
Draw a Lewis structure for the following compound:
(CH3)2CC(CH3)OCH2CH(CH3)CHO
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2.2 Bond-Line Structures /
Introduction
• Lewis structures are too impractical to represent a
compound like Amoxicillin, because of its size. But
condensed formulas would tell very little about its
shape.
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2.2 Bond-Line Structures /
Comparison
Lewis structure
• The Bond-line structure (also called a skeletal structure) is easier
to read and to draw
Bond-line structure
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2.2 Bond-Line Structures / Utility
• Bond-line structures are the benchmark representations
for organic compounds.
• It is critical to known how to draw these structures, for
any compound, without difficulty, to succeed in any
organic chemistry course.
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2.2 How to Read Bond-Line
Structures / Introduction
• Each corner or endpoint represents a carbon atom.
There are six carbon atoms in hexane and four in 2-
butene and 2-butyne:
• The zigzag format is fairly accurate in representing the
bond angles for sp3 and sp2 hybridized atoms
o Linear geometry is shown for sp-hybridized atoms
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2.2 How to Read Bond-Line
Structures / Carbon Atoms
• Carbon atoms are not labeled, but a carbon is assumed
to be located at every corner or endpoint on the zigzag.
• H atoms bonded to carbon are not drawn.
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2.2 How to Read Bond-Line
Structures / Hydrogen Atoms
• You must also be able to use the bond-line structure
language to interpret the number and location of H atoms
in a molecule.
• H atoms are not shown, but it’s assumed there are enough
to complete the octet (4 bonds) for each carbon.
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2.2 How to Draw Bond-Line
Structures / Rule One
• If you are given a Lewis structure or condensed structure, you
must also be able to draw the corresponding bond-line structure
Rule 1: sp2 and sp3-hybridized atoms in a straight chain should be
drawn in zigzag format.
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2.2 How to Draw Bond-Line
Structures / Rules Two and Three
Rule 2: When drawing double bonds, draw all bonds as far apart as
possible.
Rule 3: When drawing single bonds, the direction in which the
bonds are drawn is irrelevant.
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2.2 How to Draw Bond-Line
Structures / Rule Four
Rule 4: All heteroatoms (atoms other than carbon and hydrogen)
must be drawn, as well as the H atoms attached to them.
Rule 5: The cardinal rule – Never draw more than four bonds to a
carbon atom (recall the octet rule).
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SkillBuilder 2.2
Draw a bond-line structure for the following compound:
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2.3 Identifying Functional Groups /
Introduction
• Bond-line structures make it easier to see the bonds
made/broken in a chemical reaction
• Compare the condensed formula with the bond-line structure
below for the same reaction
• The bond-line structures make it more obvious to see the
functional group transformation that takes place
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2.3 Identifying Functional Groups /
Definition
• When certain atoms are bonded together in specific
arrangements, they undergo specific chemical
reactions.
• These characteristic groups of atoms/bonds are called
functional groups. Every chemistry student needs to
learn the term for each functional group.
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2.3 Identifying Functional Groups /
List
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2.3 Identifying Functional Groups /
List (continued)
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Conceptual Checkpoint
Atenolol and enalapril are drugs used in the treatment of heart disease. Both of
these drugs lower blood pressure (albeit in different ways) and reduce the risk of
heart attack. Identify and label all functional groups in these two compounds:
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Conceptual Checkpoint
Atenolol and enalapril are drugs used in the treatment of heart disease. Both of
these drugs lower blood pressure (albeit in different ways) and reduce the risk of
heart attack. Identify and label all functional groups in these two compounds:
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2.4 Carbon Atoms with Formal
Charges / Common Scenarios
• A carbon atom will have 4 bonds when it does not have a formal
charge.
• When a carbon has a positive charge (carbocation), it will have a
total of three bonds (and one empty orbital).
• A carbanion will also have
three bonds, but also a lone
pair. (no empty orbitals).
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2.4 Carbon Atoms with Formal
Charges / Practice
• Formal charge (section 1.4) affects the stability and
reactivity of molecules, so you must be able to identify
formal charges in bond-line representations.
• The following structure is incomplete, because it doesn’t
have formal charges correctly indicated.
• Formal charges must always be
drawn. Fix the structure by
adding them.
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2.5 Bond-Line Structures: Identifying
Lone Pairs / Introduction
• Formal charge must be drawn, always, but drawing lone pairs is
optional and they are often not included.
• By knowing the formal charge, the presence (or absence) of lone
pairs is implied.
• Oxygen is in 6th group of PTE, needs 6 valence electrons to be
neutral, so an oxygen anion has 7. The negatively charged
oxygen has one bond, so it must have 6 unshared electrons to
total 7.
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2.5 Bond-Line Structures: Identifying
Lone Pairs / Oxygen
• Oxygen has three possible bonding patterns (the same three
patterns for any 2nd-row atom with 5, 6 or 7 valence electrons
when O has 7 when O has 6 when O has 5
valence e− valence e− valence e−
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SkillBuilder 2.3
Draw all of the lone pairs in the following structure:
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SkillBuilder 2.3
Draw all of the lone pairs in the following structure:
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2.5 Bond-Line Structures: Identifying
Lone Pairs / Nitrogen
• The formal charge on a N atom can be calculated the same way
or by matching its bonding pattern with its formal charge
When N has 6 When N has 5 When N has
valence e− valence e− 4 valence e−
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SkillBuilder 2.4
Draw any lone pairs associated with the nitrogen atoms in
the following structure:
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2.6 Bond-Line Structures in 3-D /
Dashes and Wedges
• All molecules take up spaced in 3 dimensions, but it is difficult
to represent a 3-D molecule on a 2-D piece of paper or
blackboard
• We will use dashed and solid wedges to show groups that point
back into the paper or out of the paper
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2.6 Bond-Line Structures in 3-D /
Other Representations
• Other ways to show 3-D structure
• The shape of a compound governs how it interacts
biologically, and so it is important to accurately depict and
interpret 3-D in bond-line structures.
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2.7 – Introduction to Resonance /
Definition
• Pi bonds and/or formal charges are often more “spread out”
than a bond-line structure can imply.
• Consider the allyl carbocation. In this case, the pi-bond and
the positive are inadequately described by a bond-line
structure.
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2.7 – Introduction to Resonance / p
Orbitals
• If all of the carbons have unhybridized p orbitals, then all 3 of
them overlap side-by-side, and
• All three overlapping p orbitals allow the electrons to move
throughout the overlapping area, and so we say the molecule has
resonance (meaning it has delocalized electrons).
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2.7 – Introduction to Resonance / MO
Viewpoint
• From a molecular orbital point of
view, the three unhybridized p-
orbitals overlap to form three new
MOs
• The two pi electrons occupy the
lowest energy MO, which is the
bonding MO
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2.7 – Introduction to Resonance / MO
Viewpoint (continued)
• The allyl carbocation has a charge
of +1. If it gained an electron it
would go to the nonbonding MO
• The symmetry of the nonbonding
MO suggests the cationic charge is
spread out to both ends of the
three-carbon chain (not just one
carbon atom drawn with the
positive charge)
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2.7 Resonance / Representation
• So how can we use bond-line structures to accurately describe
the positive charge on the allyl carbocation?
• The pi electrons can exist on both sides of the middle carbon, so
we can draw two different resonance structures to represent
the compound
• The resonance arrow, and the brackets, indicate these structures
are describing one compound
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2.7 Resonance / Analogy
• Because neither of the contributors exists (look at M O s), the
average or hybrid is much more appropriate
The resonance structures are not switching back and forth!
• Analogy: a nectarine is a hybrid formed by mixing a peach and a
plum. A nectarine is does not switch back and forth between
being a peach and a plum. It is simply a nectarine, all of the time
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2.7 Resonance / Stabilization
• Delocalized electrons are more spread out, thus lower energy, thus
more stable. So resonance stabilizes a molecule
o Electrons exist in orbitals that span a greater distance giving the
electrons more freedom, minimizing repulsions.
o Electrons spend time close to multiple nuclei all at once, maximizing
attractions.
• Delocalization of charge
o The charge is spread out over more than one atom. The resulting partial
charges are more stable than a full +1 charge.
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2.8 Curved Arrows / Introduction
• Throughout Organic Chemistry, we will be using curved arrows
to show electron movement
• The sooner you master this skill, the easier the course will be
o The arrow starts where the electrons are currently located
o The arrow ends where the electrons will end up after the electron
movement
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2.8 Curved Arrows / Rule One
• There are specific rules for using curved arrows to describe
electron delocalization (i.e. resonance).
Rule 1: Never show a single (sigma) bond as being delocalized.
• Single bonds break in a chemical reaction, not resonance.
• Resonance occurs for electrons existing in overlapping p orbitals
(pi-bonds and lone pairs… not sigma bonds).
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2.8 Curved Arrows / Rule Two
Rule 2: Never exceed an octet for 2nd row elements (B, C, N, O, F).
• The valence shell of an atom in the 2nd row has only 4 orbitals,
holding a max. of 8 electrons.
• These curved arrows violate rule 2.
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2.8 Curved Arrows / Second Row
Elements
• 2nd row elements (B, C, N, O, F) will sometimes have less than
an octet, just never more than an octet.
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SkillBuilder 2.5
Inspect the arrow drawn on the following structure and
determine whether it violates either of the two rules for
drawing curved arrows.
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2.9 Formal Charges in Resonance /
Importance
• When using curved arrows to derive resonance structures, you
will often have one or more formal charges to contend with.
• You have to be able to indicate formal charge to draw a valid
structure.
• Consider the resonance structure derived from the curved arrows
shown below:
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2.9 Formal Charges in Resonance /
Must Be Shown
• We can draw the other resonance structure by following the
instructions provided by the curved arrows…
… but we have to show the formal charges to draw it correctly:
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SkillBuilder 2.6
Draw the resonance structure below. Be sure to include
formal charges.
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SkillBuilder 2.6
Draw the resonance structure that is indicated by the
curved arrows. Be sure to include formal charges.
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2.10 Resonance Pattern Recognition /
Five Patterns
• There are five general bonding patterns in which resonance
occurs. Recognize these patterns to predict when resonance will
occur
1. Allylic lone pair
2. Allylic carbocation
3. Lone pair of electrons adjacent to a carbocation
4. A pi bond between two atoms with different electronegativities
5. Conjugated pi bonds in a ring
• The only way to recognize these patterns is to do lots
and lots of practice problems and examples.
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2.10 Resonance Pattern Recognition /
Pattern One
Pattern #1
• Vinyl and allyl refer to the atoms of the pi bond and next door to
the C=C double bond, respectively
• We look for allylic lone pairs
because they will be
resonance delocalized
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2.10 Resonance Pattern Recognition /
Pattern One, Examples
Pattern #1
• All of the lone pairs drawn in these examples are allylic
• Two curved arrows must be used to show the delocalization of
an allylic lone pair.
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2.10 Resonance Pattern Recognition /
Pattern One, Practice
Pattern #1
• When the atom with the allylic lone pair has a negative charge, the
charge is delocalized with the lone pair, shown here.
• If the allylic atom is neutral, then it will become positive, and the
atom receiving the lone pair will become negative.
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Conceptual Checkpoint
For each of the compounds, locate the pattern we just
learned (lone pair next to a 𝜋 bond) and draw the
appropriate resonance structure.
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2.10 Resonance Pattern Recognition /
Pattern Two
Pattern #2
2. Allylic carbocations
Only one curved arrow is needed to show resonance
• If there are multiple double bonds (conjugated), then multiple
contributors are possible. They are drawn by moving one electron pair
at a time
A total of three resonance structure for this allylic carbocation
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Conceptual Checkpoint
Draw the resonance structure(s) for each of the
compounds below.
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2.10 Resonance Pattern Recognition /
Pattern Three
Pattern #3
3. A lone pair adjacent to a
carbocation
• Only one arrow is needed
• Recognize how the formal charges are affected by the electron
movement in these two examples
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Conceptual Checkpoint
For each of the compounds below, locate the lone pair
adjacent to C+ and draw the resonance structure:
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2.10 Resonance Pattern Recognition /
Pattern Four
Pattern #4
4. A pi bond between atoms of different electronegativity
• The pi electrons will be more attracted to the more electronegative
atom, causing the pi bond to be unequally shared.
• These two structure represent the “extreme” descriptions of the pi-
bonded electrons (equally shared versus not shared). The actual
compound is a hybrid of the two (unequally shared).
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Conceptual Checkpoint
Draw a resonance structure for each of the compounds
below.
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2.10 Resonance Pattern Recognition /
Pattern Five
Pattern #5
5. Conjugated pi bonds in a ring
• Each atom in the ring has an unhybridized p orbital that can overlap
with its neighbors
• The pi bonds can be pushed over by one position (clockwise or
counterclockwise, doesn’t matter, the result is the same).
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2.10 Resonance Pattern Recognition /
Summary
Summary of the five main patterns
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Conceptual Checkpoint
Draw resonance structures for each of the following.
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2.10 Resonance Pattern Recognition /
Practice
• Practice the act of recognizing the patterns of resonance
and using curved arrows to push electrons and show their
delocalization.
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2.11 Assessing Resonance Structures /
Introduction
• When multiple resonance structures can be drawn, we
know a blend of all of them, the hybrid structure, is the
actual structure of the compound.
• Typically, not all of the resonance structures will
contribute equally to the hybrid.
• The following rules, listed in order of importance,
allow us to determine the most significant resonance
form(s) for a given compound (i.e. the major resonance
form).
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2.11 Assessing Resonance Structures /
Rule One
Rule 1: The most significant resonance forms have the greatest
number of filled octets.
Carbocation doesn’t In this structure, all atoms have
have a full octet an octet, so it is the major
resonance contributor
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2.11 Stability of Contributors / Rule
Two
Rule 2: The structure with fewer formal charges is more
significant.
The first two structures both have full octets, but the first
one has fewer formal charges, so it is the most significant
resonance contributor.
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2.11 Stability of Contributors / Rule
Two, Example
If the compound has an overall formal charge, focus only on
drawing resonance forms that show the delocalization of the
charge
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2.11 Stability of Contributors / Rule
Three
Rule 3: a structure with a negative charge on the more
electronegative atom will be more significant, and vice versa.
We default to Rule 3 here
because more than one
structure has all atoms with a
full octet, and the same
number of formal charges.
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2.11 Stability of Contributors / Rule
Four
Rule 4: Resonance forms that have equally good Lewis structures
are described as equivalent and contribute equally to the resonance
hybrid.
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SkillBuilder 2.7
Rank the following resonance forms, from most
significant to least significant, and briefly explain the
rankings.
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2.12 The Resonance Hybrid
• The resonance hybrid represents the pi bond of an allylic
carbocation as being delocalized over all three carbon atoms.
• This is consistent with MO theory, in that the pi electrons
occupy the bonding MO, which has no nodes and is spread out
across all three atoms.
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SkillBuilder 2.8
Draw a resonance hybrid for the following anion:
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2.13 Delocalized Lone Pairs
• Localized electrons are not in resonance.
• Delocalized electrons are in resonance (and are more stable).
• To be delocalized, a lone pair of electrons must be adjacent to an
atom with an unhybridized p orbital.
The lone pair on the nitrogen
is delocalized because it is
next door to a carbon atom
with a p-orbital.
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2.13 Delocalized Lone Pairs
• In one structure, the N is sp3 hybridized, and the other indicates
the N atom is sp2 hybridized. So which is it?
If a lone pair
participates in
resonance, then it
occupies a p-orbital.
• The lone pair is delocalized, which is only possible through
overlapping p-orbitals. So, the nitrogen must be sp2 hybridized.
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2.13 Localized Lone Pairs / Definition
• A lone pair does not participate in resonance if it cannot overlap
with an adjacent p-orbital… it is a localized lone pair.
The lone pair in pyridine
cannot overlap with p-
orbital on the adjacent atom.
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2.13 Localized Lone Pairs / General
Guidelines
• Don’t assume a lone pair is delocalized just because it is next
door to a pi bond.
• As a general rule, you can assume that when an atom possesses
a pi bond and a lone pair, they both will not participate in
resonance.
• And, as always, if there is no p-orbital next door to the lone pair,
then it will be localized.
Copyright ©2021 John Wiley & Sons, Inc. 75
SkillBuilder 2.9
Histamine is a compound that plays a key role in many biological
functions. Most notably, it is involved in immune responses, where
it triggers the symptoms of allergic reactions:
Each nitrogen atom exhibits a lone pair. In each case, identify
whether the lone pair is localized or delocalized and then use that
information to predict the geometry for each nitrogen atom in
histamine.
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