Scribd
Upload
157 views

KLEIN Chap 2 Handout

The document discusses ways to represent molecules including Lewis structures, bond-line structures, and showing 3D representations. It also covers identifying functional groups and using curved arrows and formal charges to depict resonance in organic structures.

Uploaded by

Jeriz Marie Gamboa
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
157 views

KLEIN Chap 2 Handout

The document discusses ways to represent molecules including Lewis structures, bond-line structures, and showing 3D representations. It also covers identifying functional groups and using curved arrows and formal charges to depict resonance in organic structures.

Uploaded by

Jeriz Marie Gamboa
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 10

1/9/2015

2.1 Representing Molecules

2.1 Representing Molecules

There are many ways to represent molecules:


Given that there are three isomers of propanol (below),
which structures above are adequate to represent only
isopropanol and not its isomers?
If you were representing a large molecule with 20 or
more atoms, which structure would be most time
consuming to draw?
Which structures give you the most information about
the structure?
Copyright 2012 John Wiley & Sons, Inc.

2-1

Klein, Organic Chemistry 1e

2.1 Representing Molecules


To draw large molecules quickly, a different type of
representation is needed.
Consider the antibiotic amoxicillin. Its Lewis structure
looks cluttered, and it would be very time consuming to
draw.

Practice with SKILLBUILDER 2.1.


Copyright 2012 John Wiley & Sons, Inc.

2-2

Klein, Organic Chemistry 1e

2.2 Bond-line Structures


The bond-line structure is easier to read and to draw:

vs.

Copyright 2012 John Wiley & Sons, Inc.

2-3

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

2-4

Klein, Organic Chemistry 1e

1/9/2015

2.2 Bond-line Structures


Practice identifying the location of the carbon atoms
and counting the number of carbon atoms in the
structures below.

2.2 Bond-line Structures


Double bonds and triple bonds are represented as you
might expect:

Why is a triple bond written without zigzagging?

Copyright 2012 John Wiley & Sons, Inc.

2-5

Klein, Organic Chemistry 1e

2.2 Bond-line Structures


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 we can assume there are
enough to complete the octet (four bonds) for each
carbon:

Copyright 2012 John Wiley & Sons, Inc.

2-6

Klein, Organic Chemistry 1e

2.2 Bond-line Structures


If you are given a Lewis structure or condensed
structure, you must also be able to draw the
corresponding bond-line structure:
Heteroatoms (atoms other than C and H) should be labeled
with all hydrogen atoms and lone pairs attached.

NEVER draw a carbon with more than FOUR bonds!


H atom locations
interpreted
Copyright 2012 John Wiley & Sons, Inc.

2-7

Practice with SKILLBUILDER 2.3.


Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

2-8

Klein, Organic Chemistry 1e

1/9/2015

2.2 Bond-line Structures


Draw bond-line representations for the following Lewis
structures:

Copyright 2012 John Wiley & Sons, Inc.

2-9

Klein, Organic Chemistry 1e

2.3 Indentifying Functional Groups


More functional groups are listed in table 2.1

2.3 Indentifying Functional Groups


When certain atoms are bonded together in specific
arrangements, they undergo specific chemical reactions.

Such arrangements of atoms are called functional


groups. WHY are such groups called FUNCTIONAL?
Copyright 2012 John Wiley & Sons, Inc.
2-10

Klein, Organic Chemistry 1e

2.4 Bond-line Structures With


Formal Charge
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.
Label all of the formal charges in the following
molecule.

Practice with CONCEPTUAL


CHECKPOINT 2.11.
Practice with CONCEPTUAL CHECKPOINTS 2.12
and 2.13.
Copyright 2012 John Wiley & Sons, Inc.

2-11

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

2-12

Klein, Organic Chemistry 1e

1/9/2015

2.4 Bond-line Structures With


Formal Charge

2.4 Bond-line Structures With


Formal Charge

Most carbon atoms will have FOUR covalent bonds and


no lone pairs to avoid carrying a formal charge.

Most carbon atoms will have FOUR covalent bonds and


no lone pairs to avoid carrying a formal charge.

Sometimes carbon will have a +1 charge. In such cases, the


carbon will only have THREE bonds.

Sometimes carbon will have a -1 charge.

Is there anything especially unstable about CARBANIONS?

Is there anything especially unstable about CARBOCATIONS?

Copyright 2012 John Wiley & Sons, Inc.

2-13

Klein, Organic Chemistry 1e

2.5 Bond-line Structures and Lone


Pair Electrons
Sometimes lone pairs are omitted from bond-line
structures. For example:
You cant determine the formal charge on the N atom unless
you know how many electrons there are on the N.
It could be:

If carbon carries a charge in a molecule, the charge


MUST be shown on the bond-line structure.
Copyright 2012 John Wiley & Sons, Inc.

2-14

Klein, Organic Chemistry 1e

2.6 3D Bond-line Structures


The vast majority of molecules are 3-dimensional (3D),
but it is difficult to represent a 3D molecule on a 2dimensional (2D) 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.

You must ALWAYS draw formal charges on a bond-line


structure to eliminate confusion.
Copyright 2012 John Wiley & Sons, Inc.

2-15

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

2-16

Klein, Organic Chemistry 1e

1/9/2015

2.6 3D Bond-line Structures


Imagine the thin lines as being flat in the plane of the
board/paper:

2.6 3D Bond-line Structures


Here are some other ways to show 3D structure:

Dashed and solid wedges to show groups that point back into
the paper or out of the paper.

We will focus on this type of representation


in Chapter 5.
Copyright 2012 John Wiley & Sons, Inc.

2-17

Klein, Organic Chemistry 1e

Read the MEDICALLY SPEAKING section of Chapter 2 to


see one example of how 3D structure is
important.
Copyright 2012 John Wiley & Sons, Inc.

2-18

Klein, Organic Chemistry 1e

2.7 Resonance

2.7 Resonance
Lets look at the hybridization of
the carbons in the allyl
carbocation:

How do we represent the complete picture of the allyl


carbocation provided by valence orbital and MO
theories using a bond-line structure?

Calculate the steric number (# of


bonds + lone pairs).

The pi electrons can move freely to both sides of the


molecule, so we can use two resonance contributors to
represent the structure.

When the steric number is 3, it is


sp2 hybridized.
The square brackets indicate that both resonance
contributors exist simultaneously.
Copyright 2012 John Wiley & Sons, Inc.

2-19

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

2-20

Klein, Organic Chemistry 1e

1/9/2015

2.7 Resonance

2.8 Curved Arrows in Resonance

Resonance makes a molecule MORE stable through:


Delocalization of electrons:

Electrons in resonance exist in orbitals that span a greater distance


giving the electrons more freedom.

Delocalization of charge:

The charge is spread out over more than one atom. The resulting
partial charges are more stable than a full +1 charge.

+
+
resonance hybrid

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.

Curved arrows generally show electron movement for


PAIRS of electrons:
The arrow starts where the electrons are currently located.
The arrow ends where the electrons will end up after the
electron movement.

We will explore curved arrows to show other


reactions in Chapter 3.
Copyright 2012 John Wiley & Sons, Inc.

2-21

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

2-22

Klein, Organic Chemistry 1e

2.8 Curved Arrows in Resonance

2.8 Curved Arrows in Resonance

Rules for using curved arrows to show RESONANCE:

Rules for using curved arrows to show RESONANCE:


2. Never exceed an octet for 2nd row elements (B, C, N, O, F)
Atoms in the 2nd row can only have four 2nd energy level
orbitals holding a max. of 8 electrons.
Examples of arrows that violate rule 2.

1. Avoid breaking a single bond.

Single bonds can break, but NOT in RESONANCE.


Resonance occurs for electrons existing in overlapping p
orbitals, while electrons in single bonds are overlapping sp,
sp2, or sp3 (sigma) orbitals.
How does this arrow look?
Copyright 2012 John Wiley & Sons, Inc.

2-23

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

2-24

Klein, Organic Chemistry 1e

1/9/2015

2.8 Curved Arrows in Resonance


Rules for using curved arrows to show RESONANCE:
3. 2nd row elements (B, C, N, O, F) will rarely, but sometimes,
have LESS than an octet.

What will the resonance hybrid look like for this


structure?
Practice with SKILLBUILDER 2.6.
Klein, Organic Chemistry 1e
Copyright 2012 John Wiley & Sons, Inc.

2-25

2.9 Formal Charge in Resonance


When using curved arrows to show RESONANCE,
structures will often carry a formal charge that must be
shown.
Draw the resonance contributor indicated by the arrows
below.

Are any of the rules violated?


Show any formal charges on the contributors.
Copyright 2012 John Wiley & Sons, Inc.

2.9 Formal Charge in Resonance


In the resonance, the arrows tell us how to move the
electrons to obtain the other contributor.

Draw arrows showing the resonance in the reverse


direction.
You can also think of the arrows as showing the
direction that charge will flow.
Practice with SKILLBUILDER 2.7.
Copyright 2012 John Wiley & Sons, Inc.

2-27

Klein, Organic Chemistry 1e

2-26

Klein, Organic Chemistry 1e

2.10 Patterns in Resonance


There are 5 main bonding patterns in which resonance
occurs. Recognize these patterns to predict when
resonance will occur:
1.
2.
3.
4.

Allylic lone pairs


Allylic positive charge
Lone pair of electrons adjacent to a positive charge
A pi bond between two atoms with different
electronegativities
5. Conjugated pi bonds in a ring

We will see many examples in the next few


slides.
Copyright 2012 John Wiley & Sons, Inc.

2-28

Klein, Organic Chemistry 1e

1/9/2015

2.10 Patterns in Resonance


VINYL and ALLYL refer to positions directly bonded to
or one atom away from a C=C double bond.

2.10 Patterns in Resonance


1. Identifying allylic lone pairs:

Circle all of the allylic lone pairs.

Draw arrows on each structure to show resonance.

Label the vinylic chlorides and the allylic chlorides.

Copyright 2012 John Wiley & Sons, Inc.

2-29

Copyright 2012 John Wiley & Sons, Inc.

Klein, Organic Chemistry 1e

2.10 Patterns in Resonance


1. Identifying allylic lone pairs:

2. Dealing with allylic positive charge:

Practice with CONCEPTUAL CHECKPOINT 2.25.

2-31

Klein, Organic Chemistry 1e

2.10 Patterns in Resonance

For each of the following, show the resulting resonance


contributor and all formal charges.

Copyright 2012 John Wiley & Sons, Inc.

2-30

Klein, Organic Chemistry 1e

Only one curved arrow is needed.

If there are multiple conjugated double bonds, then multiple


contributors are possible. Show the resonance contributors
and curved arrows below.

Draw a resonance hybrid.

Practice with CONCEPTUAL CHECKPOINT


2.26.
Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

2-32

1/9/2015

2.10 Patterns in Resonance


3. A lone pair adjacent to a positive charge:

2.10 Patterns in Resonance


3. A lone pair adjacent to a positive charge:

Only one arrow is needed.


Explain how the formal charges are affected by the electron
movement in the following examples.

Copyright 2012 John Wiley & Sons, Inc.

2-33

Draw all possible resonance contributors

Practice with CONCEPTUAL CHECKPOINT 2.27.


Copyright 2012 John Wiley & Sons, Inc.

Klein, Organic Chemistry 1e

2-34

Klein, Organic Chemistry 1e

2.10 Patterns in Resonance

2.10 Patterns in Resonance


4. A pi bond between atoms of different
electronegativity:

Consider the resonance in the NITRO group.


Why cant ONE arrow be used to cancel out the formal
charge and create a resonance contributor?

5. Conjugated pi bonds in a ring:

Each atom in the ring MUST have an unhybridized p orbital


that can overlap with its neighbors.

Electrons can be shown to move clockwise or


counterclockwise.
What type of motion do the electrons actually have?

The pi electrons will be more attracted to the more


electronegative atom.

Explain how the formal charges are created by the


electron movement in the following examples.

Practice with CONCEPTUAL CHECKPOINT 2.28.


Copyright 2012 John Wiley & Sons, Inc.

2-35

Klein, Organic Chemistry 1e

Practice with CONCEPTUAL CHECKPOINT


2.31.

Copyright 2012 John Wiley & Sons, Inc.

2-36

Klein, Organic Chemistry 1e

1/9/2015

2.10 Patterns in Resonance

2.10 Patterns in Resonance

Summary Figure 2.5:

Show all of the resonance contributors for the following


molecule.

Practice with CONCEPTUAL CHECKPOINT 2.32.

Copyright 2012 John Wiley & Sons, Inc.

2-37

Klein, Organic Chemistry 1e

2.12 Delocalized vs. Localized

Generally, lone pars adjacent to a C=C double bond


are capable of resonance, but not in this case.

2-38

Klein, Organic Chemistry 1e

2.12 Delocalized vs. Localized

The electron movement above does not violate any of our


rules, so why cant the nitrogens lone pair be delocalized?

Notice that carbons with 4 bonds (sp3) isolate areas of


resonance from one another.

Copyright 2012 John Wiley & Sons, Inc.

Recall that delocalized electrons must exist in an unhybridized p orbital


overlapping with p orbitals on neighboring atom.
The nitrogens lone pair is positioned perpendicular to the plane, where
the other pi electrons reside.
Practice with SKILLBUILDER 2.9.

The electron movement above does not violate any of


our rules, so why cant the nitrogens lone pair be
delocalized?
Copyright 2012 John Wiley & Sons, Inc.

2-39

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

2-40

Klein, Organic Chemistry 1e

10

You might also like