CHEM 2213 Final Exam Booklet Solutions

Contents
Section 1: Structural Representations (Anatomy of a Molecule) ....................................... 5
Molecular Representations............................................................................................. 5
Wedge/Dash Notation .................................................................................................... 5
Line Notation................................................................................................................... 5
Condensed Notation ....................................................................................................... 6
Newman Projections ....................................................................................................... 6
Fischer Projections .......................................................................................................... 6
Cyclic Chair Representations........................................................................................... 7
Practice Problem: Steric Factors in Cyclohexanes ...................................................... 8
Section 2: Intermolecular Forces ........................................................................................ 9
London Dispersion Forces ............................................................................................... 9
Dipole-Dipole Forces ....................................................................................................... 9
Hydrogen Bonding .......................................................................................................... 9
Boiling Point Determination ........................................................................................ 10
Key Concept – Breaking a “Tie” .................................................................................... 11
Practice Problem: Ranking Boiling Points ................................................................. 12
Section 3: IUPAC Systematic Naming ............................................................................. 13
Wize’s General Naming Rules: ...................................................................................... 13
Wize’s Things to Consider: ............................................................................................ 13
The Carbon Chain .......................................................................................................... 13
The Substituents ........................................................................................................... 14
Functional Groups ......................................................................................................... 15
Practice Problem: IUPAC Naming ............................................................................. 16
Section 4: Isomers ............................................................................................................. 17
Structural Isomers (aka Constitutional Isomers) .......................................................... 17
Geometric Isomers........................................................................................................ 17
Conformational Isomers ............................................................................................... 18
Section 5: Stereochemistry and Stereoisomerism ............................................................. 19
R/S Nomenclature ......................................................................................................... 19
Practice Problem: ...................................................................................................... 19
Practice Problem: Naming Chiral Compounds.......................................................... 20
Molecules with more than one asymmetric carbon .................................................... 21

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Enantiomers and Diastereomers .................................................................................. 21

Meso Compounds ......................................................................................................... 21
Example Problem: Other meso compounds ............................................................. 23
Stereoisomers in Alkenes.............................................................................................. 23
Isomer Flow Chart ......................................................................................................... 24
Practice Problems.............................................................................................................. 25
Section 6: Acid/Base Equilibria ........................................................................................ 28
Equilibrium Constants and Le Chatelier’s Principle ...................................................... 28
Acid/Base Definitions .................................................................................................... 28
pKas of Common Molecules .......................................................................................... 30
Acid/Base Equilibriums ................................................................................................. 32
Species in Solution of Various pH ................................................................................. 35
Practice Problems.............................................................................................................. 37
Section 7: Mechanisms of Chemical Reactions ................................................................ 39
SN2 Reactions ................................................................................................................ 39
Tips for a successful SN2 reaction ................................................................................. 39
SN1 Reactions ................................................................................................................ 47
Tips for a successful SN1 reaction ................................................................................. 47
E1/E2 Eliminations ........................................................................................................ 52
Tips for a successful E2 or E1 reactions ........................................................................ 53
Practice Problems.............................................................................................................. 58
Chapter 8. Addition to Alkenes ........................................................................................ 62
8.1 Carbocation Stability and Rearrangements ............................................................ 62
Carbocation Rearrangements ................................................................................... 62
8.2 Hydrohalogenation ................................................................................................. 63
Steps of a hydrohalogenation ................................................................................... 64
Mechanism................................................................................................................ 64
8.3 Acid-catalyzed Hydration ........................................................................................ 66
Steps of a hydrohalogenation ................................................................................... 66
Mechanism................................................................................................................ 67
8.4 – Terpene Biosynthesis ........................................................................................... 68
Carbocation Rearrangements ................................................................................... 68
Chapter 9. Aromaticity and Electrophilic Aromatic Substitution..................................... 69

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9.1 Aromaticity.............................................................................................................. 69
9.2 Aromaticity and Lone Pairs ..................................................................................... 70
9.3 Electrophilic Aromatic Substitution Reactions ....................................................... 70
Mechanism................................................................................................................ 70
Reactions of Aromatic Rings ..................................................................................... 71
9.4 Considerations for Electrophilic Aromatic Substitutions ........................................ 72
Chapter 10. Oxidation and Reduction ............................................................................... 73
10.1 Oxidation and Reduction Definitions .................................................................... 73
10.2 Assigning Oxidation States .................................................................................... 73
10.3 Hydrogenation ...................................................................................................... 74
Full Hydrogenation Reactions ................................................................................... 74
Mechanism................................................................................................................ 75
Partial Hydrogenation Reactions .............................................................................. 75
10.4 Reduction Reactions ............................................................................................. 77
Reduction using NaBH4 ............................................................................................. 77
Reduction using LiAlH4 .............................................................................................. 77
Practice Problems.............................................................................................................. 79
Chapter 11. Chemistry of Carbonyls (Ketones and Aldehydes) ....................................... 81
11.1 Reactions of Carbonyl Compounds (Oxidations and Reductions) ........................ 81
Oxidations ................................................................................................................. 81
Reductions ................................................................................................................ 82
11.2 Keto/Enol Tautomerization ................................................................................... 83
Reactions of Ketones in Water (and D2O)................................................................. 84
11.3 Additions to Carbonyls .......................................................................................... 85
11.4 Synthesis and Applications of Acetals and Ketals ................................................. 86
Acetal/Ketal Formation ............................................................................................. 86
11.5 Synthesis and Applications of Imines ................................................................... 89
Choice of Amine ........................................................................................................ 90
Reductive Amination................................................................................................. 91
11.6 – Aldol Reaction .................................................................................................... 92
Retro-aldol and Deuterium Incorporation ................................................................ 93
Mixed Aldol Reactions .............................................................................................. 94
Practice Problems.............................................................................................................. 95

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Chapter 12. Nucleophilic Acyl Substitution ..................................................................... 98

12.1 Reactivity and General Trends .............................................................................. 98
12.2 Carboxylic Acids .................................................................................................... 99
Additional Important Carboxylic Acid Reactions .................................................... 101
12.3 Acid Chlorides ..................................................................................................... 102
12.4 Anhydrides/Esters/Amides ................................................................................. 104
Overviews of Reactions You Need to Know............................................................ 108
12.5 Acyl Phosphates .................................................................................................. 109
12.6 Claisen Condensation.......................................................................................... 110
Special Considerations ............................................................................................ 111
Practice Problems............................................................................................................ 113
Chapter 13. Spectroscopy ............................................................................................... 117
13.1 IR Spectroscopy ................................................................................................... 117
Stretching Vibrations: ............................................................................................. 118
Bending Vibrations: ................................................................................................. 118
Steps for Analyzing an IR Spectrum ............................................................................ 121
Example of IR Spectra of common molecules ........................................................ 122
13.2 Degrees of Unsaturation ..................................................................................... 126
13.3 Carbon NMR ........................................................................................................ 126
Understanding Number of Types of Carbon in a Molecule .................................... 126
Understanding Chemical Environment and effect on chemical shift ..................... 127
Carbon-13 DEPT-135 NMR .......................................................................................... 128
13.4 Proton NMR ........................................................................................................ 133
Practice Problems ....................................................................................................... 140
Review Section ............................................................................................................... 147
Substitution and Elimination ‘simplified’ .................................................................... 147
Functional Group Quick Reference ............................................................................. 148
Extra Pages...................................................................................................................... 150

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Section 1: Structural Representations (Anatomy

of a Molecule)

Molecular Representations
There are many different ways to represent organic molecules. Depending on the exact
problem you are dealing with, some representations may be more helpful than others.

Wedge/Dash Notation
This notation uses solid wedge bonds and dashed bonds to specify whether a bond is
going into the page, or out of the page:

Example:

Note that:

• Bonds coming out of the page are shown as a wedge bond ( )

• Bonds going into the page are shown as a dashed bond ( )

Line Notation
With line notation, carbon atoms denoted at the end of each bond ‘line’ and at the
vertices of multiple lines.

Hydrogen atoms are implied, and atoms other than carbon are written in.

Example:

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Condensed Notation
In condensed notation, no bonds are actually shown. Instead, the molecule is listed as a
molecular formula with structural information embedded in it.

Example:

Newman Projections
Newman projections allow us to visualize conformational changes based on the concept
of looking “down” a C-C bond. By doing this, we observe a front carbon and its
substituents and a back carbon with its substituents
.
This is very useful for looking at single bonds and rotation about them.

Example:

The front carbon atom is represented by the meeting of the 3 groups at the centre
(looking like it forms 3 pie pieces). The back carbon is represented by the large circle, with
its 3 groups also attached.

Fischer Projections
Fischer Projections use horizontal and vertical lines in order to depict whether atoms are
going into the page or out of the page.

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Example:

In a Fischer Projection the horizontal lines depict atoms coming out of the page, while the
vertical lines depict atoms going into the page.

Wize Tip

In order to remember that the arms come forward in the Fischer projection, people
often think about the molecule giving you a hug or being a turtle being stuck on its back.

This notation is commonly used in determining stereochemistry, particularly in

compounds with more than one. Also, acyclic carbohydrates/sugars are most commonly
depicted as Fischer Projections.

Wize Tip

You can easily redraw in Fischer projections to compare stereochemistry – this will be
useful later!

Cyclic Chair Representations

Often 6-membered rings containing only single bonds (cyclohexane rings) are
represented in their chair conformation. As these molecules only have single bonds, they
are free to rotate.

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This gives them many different conformations or shapes, that they can adopt. In the case
of 6-membered rings, the most stable of these conformations is the chair.

It is also important to note that if there are any bulky substituents on the ring, they will
prefer to be observed in the equatorial position.

Practice Problem: Steric Factors in Cyclohexanes

Draw any possible conformations of the following compound and comment on the
stability (ignore enantiomers):

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Section 2: Intermolecular Forces

London Dispersion Forces

London Dispersion Forces (LDF) are observed by ALL discrete molecules. These arise from
the ability of molecules to polarize. Polarization occurs because the electrons that are
held around atoms (and hence molecules) are able to move within ‘electron clouds’ or
orbitals. This movement can allow for charges to align instantaneously and induce a
dipole. Once a dipole is achieved there is a moment of attraction between the molecules
as their dipoles align.

Wize Concept

Larger molecules have stronger London Dispersion Forces

Dipole-Dipole Forces
Dipole-Dipole Forces are only observed between molecules with a permanent dipole (i.e.,
polar molecules). Once again, in this case we see alignment of these dipoles in order to
cause an attractive force. Until LDF, these dipoles are permanent so the attraction
between these molecules are stronger than with LDF only.

Hydrogen Bonding
Hydrogen bonding is an extreme case of Dipole-Dipole forces. This arises from the
significantly large different in electronegativity different between:

Hydrogen (H) and Oxygen (O): H-O bonds

Hydrogen (H) and Nitrogen (N): H-N bonds

This causes a significantly large dipole that undergoes an incredibly large attractive force.
This force is so large, that it is on the magnitude of an actual bond! Therefore, this is
exhibited in polar molecules with H-O, and/or H-N bonds.

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Example: The hydrogen-bonds are labeled in the structures below

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Boiling Point Determination

We can use the type(s) of intermolecular forces exerted on a molecule to predict the
relative boiling and melting points of a set of compounds:

Key Concept – Breaking a “Tie”

Sometimes, you may find that you have two molecules that are sufficiently similar,
therefore resulting in a “tie” for the melting/boiling point analysis rules we have already
laid out. Therefore, we must define a few more rules to help in these situations.

1) Count the number of electrons

Imagine the following situations:

More electrons cause the molecule as a whole to be more polarizable, therefore the
instantaneously induced dipole in LDF will be greater causing a stronger attraction.

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2) Molecule Shape – ‘Branching’

Imagine the following situation:

Because pentane is a straight chain, it can line up better with other pentane molecules,
and therefore have a greater area of polarized contact. This increases the attraction
observed between the molecules, and therefore increases its melting point.

3) Long-chain Multiple Bonds

When considering fatty acids, we must be careful of whether they are saturated (contains
all C-C single bonds) or unsaturated (contains one or more C=C double bond).

Putting this all together you get the rules for assigning relative melting and boiling points

Practice Problem: Ranking Boiling Points

List the following molecules in order of increasing boiling point and explain why.

EtOH, EtSH, EtF, C2H6

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Section 3: IUPAC Systematic Naming

Wize’s General Naming Rules:

1. Identify and name the longest carbon chain

2. Identify and name any substituents on the carbon chain
3. Give these substituents the appropriate ‘address’
4. Add substituent names as a prefix to the carbon chain
5. Change suffix of the carbon chain if necessary (for functional groups)

Wize’s Things to Consider:

• The length of the longest carbon chain

• The types of C-C bonds in that chain
• The functional groups incorporated in the chain
• The priority of each of those functional groups.

The Carbon Chain

The root of the name will always identify as number corresponding to the longest
continuous chain of carbon atoms.

# carbon atoms = root

1 = meth- 6 = hex-

2 = eth- 7 = hept-

3 = prop- 8 = oct-

4 = but- 9 = non-

5 = pent- 10 = dec-

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This carbon chain must include any C-C multiple bonds present in the molecule, as this
will complete the name of the carbon chain.

The Substituents
These are generally low priority ‘functional groups’ that are attached to the carbon chain.
They will be listed before the name of the carbon chain. They include alkyl groups, alkoxy
groups and halides.

Substituents that have similar priority as the ones listed above must be listed with the
lowest possible numbering system, or ‘address’. For example:

Going from left to right, the Cl has an address of 2. Going from right to
left, the Cl has an address of 4. Since 2 < 4, we have a 2-chloro
substituent. The name is 2-chloropentane.

WATCH OUT!

Note that each number and letter is separated by a hyphen (-)

If there is more than one substituent, then the two numbers combined must give the
lowest possible numbers. For example:

Going from left to right, the Cl is on C4 and the Br is on C3. Going

from right to left, the Cl is on C2 and the Br is on C3. Since 2,3 <

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3,4, we have 3-bromo-2-chloro. The name is 3-bromo-2-chloropentane.

WATCH OUT!

Note that the substituents are listed in alphabetical order

If there is more than one substituent of the same type, then we don’t list them separately,
instead we combine them with a prefix. Each number is separated by a comma (,). Also
notice that the prefixes used are as follows:

# = prefix

1 = no prefix 6 = hexa-

2 = di- 7 = hepta-

3 = tri- 8 = octa-

4 = tetra- 9 = nona-

5 = penta- 10 = deca-

Functional Groups
These are higher priority groups that occur along the carbon chain. These often result in
a modification of the suffix of the carbon chain. These also effect the ‘addressing’ of the
chain, as many of these groups are terminal and must start on Carbon-1. The priorities of
these functional groups are listed below:

(Highest priority) Carboxylic Acids, Esters, Amides, Aldehydes, Ketones, Alcohols, Thiols,
Alkenes, Alkynes, Alkyl Halides, Alkanes (Lowest priority)

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Practice Problem: IUPAC Naming

Provide the IUPAC names for the following compounds:

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Section 4: Isomers
Chemical isomers are molecules that have the same molecular formula, but a different
chemical structure.

There are many different types of isomers from those with different bond connectivity to
those with different three-dimensional space occupation.

Structural Isomers (aka Constitutional Isomers)

Structural (or constitutional) isomers are molecules that have the same molecular
formula, but the bonding in the two molecules is different.

Both of these molecules have a molecular formula of C5H12, but have very different
structures. They are constitutional isomers.

Geometric Isomers
Geometric isomers are generally seen in strained systems such as alkenes and
cyclohexane rings. Because of restricted rotation about a double bond (or in a ring system)
we must specify the direction in which the substituents are pointing.

Pictured above is 2-iodo-2-butene. It is very obvious looking at the two structures that
they are different from one another. However, because of the -bond in the double bond,
this structure cannot rotate freely. Therefore, these are two different geometric isomers.
On the left, the double bond is cis or (Z) and on the right, the double bond is trans or (E).
So they would be named (Z)-2-iodo-2-butene and (E)-2-iodo-2-butene.

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Cis/trans Isomerism (Geometric) is also observed in cyclohexane rings.

Example: Compare the two cyclohexane rings below.

Conformational Isomers
Conformational isomers are seen in molecules that have single bonds and can therefore
rotate around them. Because of steric hindrance, some conformations of a molecule are
more stable than the other. But in the end conformational isomers are observed in
identical molecules.

Example: All of the below molecules are conformations of butane, just in different
conformations:

Cyclohexane rings also show conformational isomerization. There are several

conformational changes involved between chair-chair conformational changes (or “chair
flips”).

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Section 5: Stereochemistry and

Stereoisomerism

R/S Nomenclature

Note: the above molecules are chiral and are not equivalent

Origin of the R/S nomenclature

Practice Problem:
Assign R/S to the following compounds.

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Practice Problem: Naming Chiral Compounds

Name the following compound.

The physical properties of a pair of enantiomers are identical (ie. Boiling point, retention
factor).

However, chiral compounds have the ability to rotate plane-polarized light some angle to
the right (+) or left (-). This phenomenon does not correspond to the R/S configuration.
This means a compound that structurally is R (right) does not necessarily rotate plane
polarized light to the right (+) as well. You cannot predict the optical activity of a chiral
molecule based on the structure! You must do an experiment.

This property is very useful in determining how enantiomerically pure a compound is. For
example the optical rotation of S-carvone is +61°. As a result the optical rotation of R-
carvone is -61°. If we have a 50:50 mixture of this compound, the optical rotation is
observed to be 0°. This is called a racemic mixture (50/50 mixture of 2 enantiomers).
Furthermore, if we had a mixture where there was more R-carvone then S-carvone then
the optical rotation of that mixture would be between -61° and 0°. The exact value would
depend on the ratio of R/S in the mixture.

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Molecules with more than one asymmetric carbon

It is very possible for organic compounds to have more than one chiral centre. Once you
increase the number of chiral carbons you increase the number of possible stereoisomers
significantly.

Wize Concept

# of stereoisomers = 2n
Where n = the number of stereocentres

Therefore, for a molecule with 2 stereocenters, there are 4 possible configurations:

(R,R) (S,S) (R,S) (S,R)

Enantiomers and Diastereomers

Enantiomers will have directly opposite stereochemical assignment. Therefore in the case
of 2 stereocentrers the molecules corresponding to (R,R) and (S,S) are enantiomers (as
are those corresponding to (R,S) and (S,R). However, those molecules where there is a
change in one or more of the stereocenters (but not all) are also related. These
stereoisomers are diastereomers. So in the above example (R,R) and (R,S) are one
example of diastereomers.

Meso Compounds
When you have more than one stereocenter you must be wary of mirror planes within
the molecule.

This gives rise to a meso compound. A meso compound is when two stereoisomers are
identical despite the presence of stereocenters. This means that meso compounds will
not exhibit any optical rotation. Take 2,3-dibutanol as an example:

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Example Problem: Other meso compounds

Stereoisomers in Alkenes
We have already explored conformational isomers of alkenes using cis- and trans-
notation. This notation however is only for compounds where one of the groups on each
of the carbon is a hydrogen.

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Isomer Flow Chart

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Practice Problems
1) Assign R/S to the following compounds.

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2) Assign the isomeric relationship between the following compounds (conformers,

enantiomers, diastereomers, constitutional isomers, identical compound).

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3) How many possible stereoisomers are possible for the following compounds:

4) Rank the following compounds in order of increasing boiling point:

a)

b)

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Section 6: Acid/Base Equilibria

Equilibrium Constants and Le Chatelier’s Principle

An equilibrium is achieved when both the forward and reverse reactions are occurring at
the same rate. To define the extent to which equilibrium favours one side of the reaction
over the other, we can use the Equilibrium Expression or Equilibrium Constant.

Given the model reaction:

Where A/B are reactants, C/D are products and a,b,c,d are their stoichiometric
coefficient, the Equilibrium Expression (in terms of concentration) can be written as:

Wize Tip

Large values of K mean the product side of the reaction is favoured.

Acid/Base Definitions

pH/pOH: The negative log of the concentration of H+ in solution. pH is an indicator of

acidity, where pH values of less than 7 is considered acidic, pH values of greater than 7 is
considered basic, and a pH of 7 is considered neutral.

Ka/Kb: The Kc value specifically referring to a reaction where H+ (or H3O+) is a product (Ka)
or where OH- is a product (Kb). If Ka is large = good acid/ if Kb is large = good base.

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pKa/pKb: The negative log of the Ka/Kb value for a species. It is used as an indicator of how
acidic various protons in organic molecules are.

Wize Tip

The lower the value of pKa/pKb the more acidic/basic the molecule!

Arrhenius Acid: A species that causes the concentration of H+ to increase when added to
water (e.g. HCl or H2SO4).

Arrhenius Base: A species that causes the concentration of OH- to increase when added
to water (e.g. NaOH or KOH).

Brønsted-Lowry Acid: A species that acts as an H+ donor (e.g. HCl or H2SO4).

Brønsted-Lowry Base: A species that acts as an H+ acceptor (e.g. CO32-, NaOMe).

Lewis Acid: A species that is an electron acceptor (generally these species have empty
orbitals to accept an electron pair with) (e.g. BF3). “Lewis ‘lectrons”

Lewis Base: A species that is an electron donor (generally these species have lone pairs
to donate to another species) (e.g. NMe3).

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pKas of Common Molecules

Quick Reference: Approximate pKa Values for Common Organic Molecules

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Acid Structure Type pKa Conjugate Base

Structure

Sulfonic Acid -9

Mineral Acid -7

Hydronium Ion -1

Acetic Acid (Carboxylic 5

Acid)

Acetylacetone 10

Phenol 10

Water (alcohol) 16

Acetone (Ketone) 20

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Acetylene (Alkyne) 25

Ammonia (Amine) 38

Ethylene (Alkene) 44

Ethane (Alkane) 50

Acid/Base Equilibriums
Knowing which species exhibit acidic protons and which species are strong bases proves
to be very useful in organic chemistry due to deprotonation reactions.
An acidic proton can be deprotonated if it is attacked by a base that possesses a conjugate
acid with a far higher pKa.

1. Size: If you are dealing with atoms in the same group of the periodic table, the
larger the atom is, the weaker the H-X bond and the more stable the conjugate
base will be. This comes from a lower charge density on the conjugate base/anion.

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For example: pKa HI < HBr < HCl < HF because the ionic radius is I- > Br- > Cl- > F- (HI
is the most acidic, HF is the least acidic).

2. Electronegativity: If you are dealing with atoms in the same period/row of the
periodic table, the more electronegative the anion is the more stable of a
conjugate base it will be. This is because being more electronegative means the
ion can hold the negative charge better.

For example: pKa HF < H2O < NH3 < CH4 because the electronegativity of the anionic
atom in the conjugate base is F > O > N > C (HF is the most acidic, CH4 is the least acidic).

3. Resonance: Any conjugate base that exhibits resonance will be more stable than
one that does not. For example:

pKa:

because the carboxylate ion exhibits resonance and the alkoxide ion does not.
(CH3COOH is more acidic than CH3OH)

4. Induction: Similar to resonance, the other groups attached to the atom being
deprotonated can also affect the acidity of the species. In this case we are
referring to induction.

Here we will see electron withdrawing groups will cause increase in acidity, while
electron donating groups will cause a decrease in acidity.

pKa:

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In this example, the electron withdrawing effects of the electronegative fluorine pull
electron density away from the carbonyl group (this stabilizes the conjugate base).
Furthermore, the closer that fluorine group is to the carbonyl, the more inductive effect
(better stabilization).

Fluorine works better than Cl, Br, I because it is the most electronegative, but all halogens
create inductive stabilization (in addition to other electron withdrawing groups like O, and
NO2).

5. Hybridization and aromaticity: The hybridization of the atom can play a role on
acid and base strength.

The energy of the orbital that carries the negative charge (or is getting protonated) can
have a large effect on reactivity. With hybrid orbitals it’s important to remember their
relative energies – (most stable) s < sp < sp2 < sp3 < p (less stable).

If an anion is put in an orbital with more s-character it is more stable. Conversely, a

lone pair sitting in an orbital with more s-character is less reactive.
pKa:

pKb:

The availability of the lone pair also contributes to base strength. In certain
aromatic compounds, the lone pair is involved in stabilizing the aromatic molecule,
and is more difficult to protonate. Additionally, if deprotonation can create an
aromatic compound, that is good!

pKb:

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pKa:

Species in Solution of Various pH

Wize Tip

The pH of a solution dictates if a functional group is protonated

If the pH > pKa – The predominant form is the A- or deprotonated species (note: not always
negatively charged!)

If the pH < pKa –The predominant form is the HA or protonated species

If the pH = pKa – The species is 50:50 HA and A-

Example: Take the following:

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Practice Problems
1) Predict the side of the equilibrium that is favoured.

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2) Circle the most acidic protons of each compound. For each pair of compounds choose
the best acid (in cases with one compound, which is the most acidic proton). Justify your
choice.

3) Given the amino acid predict its predominant structure in the following pHs:

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Section 7: Mechanisms of Chemical Reactions

SN2 Reactions
Mechanism:

SN2 reactions are bimolecular substitution reactions, meaning two species come
together in the transition state (Nu- and H3C–X in the above picture). Since the transition
state involves both species, the rate = k[Nu-][CH3X]. This means the reaction rate is
dependent on both the nucleophile and the electrophile.

Tips for a successful SN2 reaction

Good Nucleophile

Because the rate is dependent on the nucleophile, having a strong nucleophile is ideal.
These are most commonly anionic compounds.

Wize Tip

Good nucleophiles are just unstable conjugate bases!

Often, these nucleophiles are generated and then added to a good electrophile for S N2
reactions. Remember: acid base reactions are faster than SN2 reactions!!

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Good Electrophiles

Because the rate is also dependent on the electrophile, having a good electrophile is ideal.
This involves two factors: Sterics and the Leaving Group:

1) Sterics: Bulkier electrophiles are more difficult to attack for a SN2 substitution. As a
result, the rate can be dictated by the substituents around a carbon centre:

2) Leaving Group: If we can make the leaving group very stable, the reaction will proceed
easier. The same factors that influence conjugate base stability can be applied to leaving
group stability.

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Orbital Considerations

We break a bond by donating electron density into the antibonding orbitals (determined
using MO theory).

For a carbon-halogen bond, these antibonding orbitals are largest on the carbon, and
point in an opposite direction from the bonding orbitals. This is the origin of the backside
attack. The stereochemical outcomes of this property are an inversion of
stereochemistry:

Reaction Diagram

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Solvent Effects

Solvent can play an important role in facilitating SN2 reactions, so it is important to be

aware of the reaction solvent.

Exam Tip

Often, your professors will give you a big tip by using a particular solvent (especially
when asking you to decide between SN1 and SN2 reactions).

Wize Tip

The SN2 reaction will occur best in polar, aprotic solvents

Solvent such as: DMSO, Acetone, and DMF

vs.

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Polar solvents will help stabilize the transition state (lowering activation energy).

Additionally, by not containing acidic protons, they allow you to use strong nucleophiles.

Important considerations
-OH is a terrible leaving group!!! The following reaction will never occur:

But we have some tricks available to us, to convert OH groups into good leaving groups
(typically halogens):

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Example of Alcohol Conversion

Remember: PBr3 and SOCl2 work via an SN2 mechanism. This has two important results:

1) You cannot convert a tertiary alcohol to a halide this way

2) You invert the stereochemistry

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Intramolecular SN2 Reactions

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SN1 Reactions

Mechanism

SN1 reactions are unimolecular substitution reactions, meaning only one species is
present in the transition state. In the above example, the slow step is the breaking of the
C–X bond, and this is called the rate determining step.

Since the rate is completely dictated by the formation of the carbocation, the rate =
k[R3CX]. This means the reaction rate is completely independent of the nucleophile.

Tips for a successful SN1 reaction

Since we don’t need to worry about the nucleophile, we can just focus on what makes a
good electrophile.

Carbocation stability

Remember that the reaction intermediate in a SN1 reaction is a carbocation, and having
more alkyl groups around a carbocation will stabilize it greatly.

As a result of increased stabilization, we lower the intermediate energy and get a much
faster reaction.

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Special cases for carbocation stability

A very important stabilization method for carbocations comes as a result of resonance.

When multiple resonance forms are possible, the stability of a carbocation increases
greatly.

So, even though these alkyl-iodides look like primary alkylhalides (and thus should only
go via SN2), they can undergo SN1 reactions:

Leaving Group stability

Similar to SN2 reaction, having a good leaving group will increase the rate of the reaction.
This is again due to the lower energy of a more stabilized leaving group, causing a
decrease in the energy required to break the bond.

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Orbitals and Geometry

Remember, carbocations are planar! This can have important stereochemical outcomes.
Predict the product of the following reaction:

Reaction Diagram

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SN1 reactions have a characteristic reaction diagram. The initial rate determining step,
(the C–I bond breakage) requires a lot of energy and forms a high energy carbocation
intermediate.
This intermediate quickly reacts with whatever nucleophile is present (in this case EtOH)
to form the final product.

Solvent Effects

Solvent can play an important role in facilitating SN1 reactions. In most cases, the
nucleophile is often the solvent.

Wize Tip

The SN1 reaction will occur best in polar, protic solvents

Solvent such as: H2O, ROH (alcohols), RCO2H (carboxylic acids).

The polarity will help stabilize the charged carbocation intermediate,

The protic solvent is also useful for solubilizing the leaving group.

Special Considerations
Once again, -OH is a terrible leaving group!! But we can take advantage of its basicity to
convert it into a good leaving group.

For example:

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E1/E2 Eliminations
Overview

Like their analogous substitution reaction, E2 and E1 eliminations are named according to
their rate determining step, or how many species are present in the transition state.

For E2 eliminations, the transitions state contains both the substrate and the base, so the
rate depends on both species.

For E1 eliminations, a carbocation must form first, so the rate depends only on the
substrate (and not on the base).

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Tips for a successful E2 or E1 reactions

Choice of Base

Strong bases are ideal for E2 reactions.

These are typically alkoxides (NaOEt for example), because they are too reactive for SN2
reactions (unless the alkyl halide is primary).

In addition, since E1 reactions do not depend on the base at all, the presence of a strong
base almost always means an E2 will take place.

In addition, bulky, strong bases are ideal for E2 reactions, as they will reduce any
substitution side-products.

Substrates for E1

Anytime you are able to stabilize a carbocation, you should be aware that an E1
elimination may occur.

WATCH OUT!

It is very likely that when the E1 reaction is occurring, the SN1 reaction is also occurring

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Additional Ways to Stabilize a Carbocation

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Orbitals and Geometry

E2 eliminations rely on donating electron density into the same antibonding orbital that
was discussed for SN2 reaction. This means the leaving group and the proton need to be
aligned antiperiplanar to one another.

Wize Tip

To get the correct geometry for E2 eliminations, use Newman projections!

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E1 eliminations proceed via a planar carbocation intermediate, so eliminations can occur

from the top or bottom face.

Special Considerations

For E2 eliminations (if you have the option) the most common product will have the
double bond with the most substitution. This is called Zaitsev’s Rule.

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In addition, you should pay special attention to the 3D geometry of the substrate:

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Practice Problems
1) Answer the following true or false questions:

i) The reaction between 3-chloro-3-methylpropane and NaSMe will proceed faster with
increased NaSMe concentration. _____

ii) E1 and SN1 reactions share a common carbocation intermediate. _____

iii) (S)-2-chlorobutane reacts with sodium acetate (CH3CO2Na) in DMF to give an optically
pure product. _____

iv) Methyl halides readily undergo E2 reactions. _____

v) SN2 reactions of secondary alkyl bromides with NaI proceed slower in H2O than in
DMSO. _____

vi) 2-Bromopropane reacts with sodium hydroxide (NaOH) to give 2-propanol as the major
product. _____

vii) Sodium fluoride is a better nucleophile that sodium iodide. _____

viii) The major product between 2-iodo-3-methylbutane and KOtBu is 2-methyl-2-butene.

_____

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2) Predict the products of the following reactions:

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3) Draw the mechanism for the following reaction:

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4) Predict the product and draw the mechanism for the following reaction. Justify any
observed regioselectivity (reaction at one molecule site over another).

5) Predict the product and draw the mechanism for the following reaction. Draw a
reaction profile and label any important features.

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Chapter 8. Addition to Alkenes

8.1 Carbocation Stability and Rearrangements

Carbocations are carbon atoms that carry a positive charge. They are formed when a
leaving group departs (see the SN1, SN2, E1 and E2 reaction!) or when an alkene acts as a
nucleophile.

• carbocations that are more substituted are more stable (tertiary > secondary
> primary >>> methyl)
• carbocations can also be stabilized by resonance (i.e. vinylic and allylic)

Carbocation Rearrangements
Sometimes, carbocations will rearrange in order to produce a more stable form. This can
happen a few different ways with two being the most common:

1. a 1,2-hydride shift
2. a 1,2-methyl shift

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The important thing to know about these rearrangements is that they lead to the
production of multiple products! This is important to know when you are asked to
draw the products of reactions and need to be accounted for when drawing
mechanisms.

Whenever you have a reaction that generates a carbocation, stop and ask yourself "is
this the best carbocation, or can it be better?". If the answer is "no" - keep going! If
the answer is "yes", draw the rearrangement and then predict the products from both
the rearranged and non-rearranged carbocation!

Don't try and draw too many rearrangements! You will only have one 1,2-hydride shift
or 1,2-methyl shift in any given reaction! This can save you from drawing too much
side pathways.

8.2 Hydrohalogenation
Hydrohalogenation reactions:

1. occur in multiple steps and are classified as an "ionic" reactions

2. proceed via a carbocation intermediate
3. have Markovnikov addition for a regiochemical outcome (Markovnikov
addition has the higher priority group added to the more substituted carbon
atom)
4. have addition at the carbocation intermediate from top and bottom face
with 50/50 distribution to give mixed stereochemical distribution (a racemic
mixture if there is only one stereocentre)

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Steps of a hydrohalogenation

1. addition of the hydrogen atom to the alkene to generate a carbocation

2. there may be carbocation rearrangement
3. nucleophilic attack of the halogen anion onto the carbocation

Mechanism

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Example: predict the product of the following hydrohalogenation reactions below.

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8.3 Acid-catalyzed Hydration

Acid-catalyzed hydrations reactions:

1. occur in multiple steps and are classified as an "ionic" reactions

2. proceed via a carbocation intermediate
3. have Markovnikov addition for a regiochemical outcome (Markovnikov
addition has the higher priority group added to the more substituted carbon
atom)
4. have addition at the carbocation intermediate from top and bottom face
with 50/50 distribution to give mixed sterechemical distribution (a racemic
mixture if there is only one stereocentre)

Steps of a hydrohalogenation

1. addition of the hydrogen atom from the acid to the alkene to generate a
carbocation
2. there may be carbocation rearrangement
3. nucleophilic attack of the water nucleophile onto the carbocation
4. deprotonation of the OH2+ group to regenerate the catalyst and generate the
OH group

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Mechanism

Example: predict the product of the following acid-catalyzed hydration reaction below.

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8.4 – Terpene Biosynthesis

Alkenes are useful building blocks in our body, they make a number of very important
compounds. A small emphasis is placed on this in Chem 233 by demonstrating terpene
biosynthesis.

Terpenes are aliphatic compounds that are made up of 5-carbon units, with varying
numbers of double bonds or cycles. They are formed in the body via a number of
carbocation rearrangements.

The way these compounds are tested is via ‘roadmap’ type questions, which ask you to
put in the appropriate charges and arrow-pushing to make a product.

Carbocation Rearrangements

For the following terpene, show the charges and double bonds present en route to
forming the final product

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Chapter 9. Aromaticity and Electrophilic

Aromatic Substitution

9.1 Aromaticity
Aromatic molecules (compounds) are special molecules that meet a particular set of
criteria and are especially stable.

In order to be aromatic, a molecule must be:

1. The compound must obey Hückel's Rule (# of π-electrons = 4n + 2)

2. The compound must contain a 'concentric ring of aligned p orbitals.'
Resonance!
3. The compound must be planar (big rings are not planar)
4. The molecule must be cyclic

Example: some carbon-carbon containing organic and not-aromatic molecules

The "n" in Huckel's Rule (4n + 2) is an integer! This means that you should solve for
how many pi electrons make something aromatic (2, 6, 10, 14, etc.) and then see if the
structure has that many electrons!

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9.2 Aromaticity and Lone Pairs

Sometimes, cyclic molecules with heteroatoms (non-carbon and hydrogen atoms) can
also be aromatic. There are three common heteroatoms that you should be on the look-
out for:

1. nitrogen: when sp3 hybridized, donates 2 pi electrons; when sp2 hybridized,

donates zero pi electrons
2. oxygen: sp3 hybridized, donates 2 pi electrons
3. sulphur: sp3 hybridized, donates 2 pi electrons

9.3 Electrophilic Aromatic Substitution Reactions

Electrophilic Aromatic Substitution (EAS) reactions are a vital tool for functionalizing
aromatic rings and are useful to make complex molecules. They rely on the fact that most
aromatic rings are relatively electron-rich and will attack a suitable electrophile via a
standard addition-type mechanism. However, since benzene is aromatic and very stable
(i.e. unreactive!) we use a catalyst to activate the benzene ring to force it to do chemistry!

Mechanism

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Reactions of Aromatic Rings

Example: Provide product(s) and suitable mechanism for the following reaction:

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9.4 Considerations for Electrophilic Aromatic Substitutions

The rate of an electrophilic aromatic substitution (EAS) reaction is greatly impacted by
substituents on the aromatic ring. Electron-donating groups (have lone pairs) will
activate the benzene ring and accelerate the reaction. Electron-withdrawing groups
(have multiple bonds) will activate the benzene ring and decelerate the reaction. Some
examples are below.

The substituents play a role in the regioselectivity of an EAS reaction. Electron-donating

groups (EDG) will favour EAS reactions in the ortho and para positions. Stronger directors
(amines, alcohols, ethers) will have the strongest directing effect. Electron-withdrawing
groups (EWG) will favour EAS reactions in the meta position.

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Chapter 10. Oxidation and Reduction

10.1 Oxidation and Reduction Definitions

Reduction: gain of electrons; more bonds to hydrogen/less bonds to oxygen

Oxidation: loss of electrons; more bonds to oxygen/less bonds to hydrogen

10.2 Assigning Oxidation States

How to assign oxidation states:

1. treat all bonds as if they were ionic

2. Electrons go to the more electronegative atom
3. C is more electronegative than H
4. Carbon-carbon bonds are broken homolytically
5. Oxidation state = how many valence electrons it SHOULD have – how many it has
currently

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10.3 Hydrogenation

Hydrogenation reactions add hydrogen atoms across multiple bonds (both alkenes and
alkenes) to reduce them (i.e. make more bonds to hydrogen).

• alkenes can be hydrogenated to make alkanes

• alkynes can be hydrogenated to make both alkanes or alkenes (both cis and
trans!)

There are three kinds of hydrogenation reactions you should know:

1. reduction of alkenes and alkynes to make alkanes with H2 and Pd/C

2. reduction of alkynes to make cis alkenes with H2 and Lindlar's catalyst
3. reduction of alkynes to make trans alkenes with metal/liquid ammonia (NH3)

Full Hydrogenation Reactions

The reactions with hydrogen gas (H2) and a metal catalyst (usually Pd/C or Pt or Ni) leads
to syn (i.e. the same side) addition of the hydrogen atoms for the stereochemical
outcome.

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Mechanism

Partial Hydrogenation Reactions

In order to pause at the alkene there are reactions you should know:

1. reduction of alkynes to make cis alkenes with H2 and Lindlar's catalyst

2. reduction of alkynes to make trans alkenes with metal/liquid ammonia (NH3)

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Example: Predict the product of the following hydrogenation reactions

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10.4 Reduction Reactions

Reduction using NaBH4

Sodium borohydride (NaBH4) is a weak reducing agent and therefore only reacts with
aldehydes and ketones. A reduction reaction leads to less bonds to an oxygen atoms and
more bonds to hydrogen atoms.

• Reduction of an aldehyde gives a primary alcohol.

• Reduction of a ketone gives a secondary alcohol.

Reduction using LiAlH4

Lithium aluminum hydride (LiAlH4) is a strong reducing agent and therefore only reacts
with all carbonyls. A reduction reaction leads to less bonds to an oxygen atoms and more
bonds to hydrogen atoms.

• Reduction of an aldehyde gives a primary alcohol.

• Reduction of a ketone gives a secondary alcohol.
• Reduction of esters and acids gives a primary alcohol.
• Reduction of amides gives amines.

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Since LiAlH4 is so much more reactive than NaBH4, the reaction is done at low
temperatures and in non-protic solvents (Et2O).

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Practice Problems
1) Predict the product/reactants/reagents of the reactions below.

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2) Predict the product of the reaction below.

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Chapter 11. Chemistry of Carbonyls (Ketones

and Aldehydes)
11.1 Reactions of Carbonyl Compounds (Oxidations and
Reductions)

Oxidations

Carbonyl compounds are often made from alcohols via oxidation reactions. There are only
two different alcohol/aldehyde oxidants needed for Chem233: Jones’ Reagent and PCC

Jones Reagent: CrO3 + H2SO4 + H2O (H2Cr2O7)

PCC: Pyridinium chlorochromate

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Reductions

There are only two different reductants (for carbonyl compounds) needed for Chem233:
NaBH4 and LiAlH4

Sodium Borohydride – NaBH4

Lithium Aluminum Hydride – LiAlH4

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General Mechanism for Hydride Reductions:

11.2 Keto/Enol Tautomerization

If a ketone (or aldehyde) is dissolved in solution, it can exist in two forms: the Keto and
Enol form (however the Keto form is greatly favoured). These two compounds are
tautomers of one another. A tautomer is another relationship, which is formally a type of
structural isomerism, that gets its own special name! It is not resonance! Bonds have to
break in order to convert between two tautomeric forms.

Example: Provide a Mechanism for the following reaction:

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Example: Provide a Mechanism for the following reaction:

Reactions of Ketones in Water (and D2O)

A common question that will appear on a midterm is something like the following:

Example: What is the maximum number of Deuterium atoms that can be incorporated
under these conditions into the following compounds?

It’s important to remember that even though the equilibrium lies in favour of the keto-
form, the enol form can form occasionally. This means that the protons alpha (beside) the
carbonyl group are rapidly exchanging. If the compound is in D2O instead of H2O,
deuterium will replace the acidic hydrogens.

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11.3 Additions to Carbonyls

Additions to carbonyls are very common in organic chemistry, especially because they
provide a route to functionalized alcohols. At this point in your chemistry career, the only
anionic nucleophiles you need to concern yourself with are acetylides and hydrides (such
as NaBH4 or LiAlH4)

Example: Predict the products of the following reactions:

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11.4 Synthesis and Applications of Acetals and Ketals

Acetal Formation

Ketal Hydrolysis

Acetal/Ketal Formation

Ketals and Acetals only form under acidic conditions(!), and we can prove why when we
look at the mechanism for their formation.

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Example: Predict the products and provide mechanisms for the following reactions:

Hemiacetal/hemiketals are not stable!! It’s rare to see an example of one, but examples
do exist:

Above are two examples of stable hemiacetal/hemiketals.

When they form cyclic hemi-compounds, they are stable.
This is not the same for acyclic compounds!

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Example: Provide the product(s) of the following reactions

Example: Provide the reagents for this transformation

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11.5 Synthesis and Applications of Imines

Imines and enamines are synthesized and hydrolyzed in a similar fashion to acetals and
ketals. Similarly, they require a catalytic amount of acid to proceed to the product.

Example: Predict the products and provide mechanisms for the following reactions:

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Choice of Amine

It is common to see strange amines as reagents on your chemistry exam. Professors will
use these compounds to test your ability to recognize the most basic nitrogen on an
amine (or related compound).

Example: Circle the most basic (and nucleophilic) atom

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Reductive Amination

One of the most popular synthetic routes to amines is using the ‘Reductive Amination’
reaction. This reaction utilizes the hydrogenation reaction learned in the previous section
to reduce the imine to an amine:

This route was developed and provides a much easier route to secondary amines than
SN2 reaction:

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11.6 – Aldol Reaction

The Aldol reaction is classic carbon-carbon bond forming reaction and very popular
component of organic chemistry.

Example: Predict the products and draw a mechanism for the following reaction

Example: Provide the starting material for the following reaction

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Retro-aldol and Deuterium Incorporation

Aldol reactions are reversible in water:

As a result, in deuterium-labelled water, Aldol products can begin incorporating

deuterium.

Example: Pure, proteum-product A, was dissolved in sodium deutroxide and deuterium

oxide. What is the greatest number of deuteriums that can be incorporated into structure
B?

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Mixed Aldol Reactions

Remember the relative reactivity of aldehydes and ketones. This can help you predict the
minor and major products in ‘Mixed Aldol’ reactions (reactions containing 2 different
carbonyls).

Example: Predict the products of the following reactions:

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Practice Problems
1) Predict the products of the following reactions:

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2) Provide the reagents:

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3) Provide a mechanism for the following reaction and explain why it is favoured.

4) Propose a synthesis of the following compound using the provided chemicals as the
only carbon sources (in the product – protecting groups are fine).

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Chapter 12. Nucleophilic Acyl Substitution

12.1 Reactivity and General Trends

Above are the five key functional groups that you need to be familiar with for Nucleophilic
Acyl Substitution. Most of the reactions and mechanism you’ll need to know will deal with
converting between these groups.

Example: Reactivity of Carboxylic Acid Derivatives

Rank the following in electrophilicity. Use diagrams in your answer.

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12.2 Carboxylic Acids

Reactions of Carboxylic Acids

Example: Provide a mechanism for the following reaction:

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Example: Predict the products and provide mechanisms for the following reactions:

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Additional Important Carboxylic Acid Reactions

Above are two reactions that are very important, however their mechanism is not
discussed in this course. Nevertheless, you should be familiar with these reactions and
some potential applications for these reagents!!

Example: Predict the product(s) of the following reactions:

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12.3 Acid Chlorides

Reactions of Acid Chlorides

Example: Provide mechanisms for the following reactions:

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Example: Provide a mechanism for the following reaction:

Example: Predict the products of the following reaction:

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12.4 Anhydrides/Esters/Amides
Reactions of Anhydrides

Reactions of Esters

Reactions of Amides

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Example: Provide mechanisms for the following reactions:

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Example: Provide mechanisms for the following reactions:

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Example: Provide mechanisms for the following reactions:

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Example: Predict the product and provide a mechanism for the reaction below:

Overviews of Reactions You Need to Know

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12.5 Acyl Phosphates

The human body doesn’t use ‘acid chlorides,’ mainly because you’d die if you had them
in your body. But we can make similar electrophilic acyl groups using ATP (adenosine
triphosphate).

Example: Predict the product of the following reactions:

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12.6 Claisen Condensation

Example: Predict the product and draw a mechanism for the following reaction:

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Special Considerations

Choice of ester
A relatively weak base is used in the Claisen Condensation. Remember, the pK a of an
alcohol is around 15, while the pKa of an ester is around 25, so this reaction should not be
very favourable. However, the reaction does proceed due to the formation of a stable
intermediate.

Example: Explain why the top reaction proceeds, but the bottom reaction does not.

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Choice of Base
The choice of alkoxide is important in the Claisen reaction. The wrong base can lead to
unwanted byproducts. Remember, nucleophilic acyl substitution of the ester is also
possible.

Example: Predict the products of the below reactions, as well as any potential
byproducts:

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Practice Problems
1) Predict the Products

2) Provide the reagents to complete the reactions.

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3) Provide a mechanism for the following reactions.

*Rationalize the product of this reaction using diagrams. Why does it form?

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4) Propose a synthesis of the following product using the provided starting materials:

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Chapter 13. Spectroscopy

13.1 IR Spectroscopy
Area of spectroscopy corresponding to the infrared (IR) region of the electromagnetic
spectrum

Typical range is 4000 – 400 cm-1 (wavenumber)

Note: Wavenumbers are a frequency unit such that wavenumber = 1/(wavelength in cm)

Infrared spectroscopy can only give information about polar bonds.

The stronger the dipole the stronger the IR absorption (think polar bonds, O-H, C=O etc.)

IR Spectroscopy is a useful tool for determining presence of specific FUNCTIONAL

GROUPS

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Stretching Vibrations:

Bending Vibrations:

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Here’s a sample IR spectrum of cyclohexanol

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Steps for Analyzing an IR Spectrum

1) Examine the region >3300cm-1
>3400cm-1 are indicative of OH or NH stretches, these bands will be intense and
broad. OH will be more intense than NH
Side note: If you have a primary amine there will be 2 N-H bands (one for each N-
H bond)

2) Examine the bands ~3000cm-1

If there are bands a little less than 3000cm-1 sp3 C-H present
If there are bands a little more than 3000cm-1 likely C=C-H present (aromatic or
alkene)
If there’s a band ~3300cm-1 likely C≡C-H (terminal alkyne)
Note this band must be relatively sharp (or else could be OH or NH stretch)

3) Examine the triple bond region (~2200 cm-1)

Presence of a small to medium intensity peak in this region is indicative of a triple
bond, either an alkyne ( ) or a nitrile ( ). It can sometimes be quite
difficult to distinguish between the two, but a more polar functional group (or
molecule) will have a sharper, more intense, peak.

4) Examine the carbonyl region (~1700 cm-1)

Presence of an intense band in this region is indicative of a carbonyl function
group, use the table and relative wavenumber of the band to determine what type
of carbonyl compound it is (amide, carboxylic acid, ester, aldehyde etc)

There’s no real one way to analyze an IR spectrum, it takes time and practice. You’ll always
have access to an IR table so don’t be afraid to use it! (But don’t over-analyze)

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Example of IR Spectra of common molecules

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Examples:

Examine the following IR spectra, labels any indicative peaks and correspond them to a
specific functional group. If possible propose a structure

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A few last notes:

Other factors that can affect IR stretching frequency include ring strain and resonance
contributors

The greater the ring strain the larger the stretching frequency (takes more energy to
vibrate)

Also, the larger the S character in a bond the higher the stretching frequency, this is
especially important to consider in molecules that have resonance contributors

Example:
Stretching frequency of acetone is 1715cm-1 while acetophenone is 1695cm-1

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13.2 Degrees of Unsaturation

A saturated molecule is one with the full number of hydrogen atoms it can have. The
general formula for this CnH2n+2. A degree of unsaturation “uses” up some of these
hydrogen atoms. They can come in the form of multiple bonds or rings.

Double bond = 1 degree of unsaturation

Triple bond = 2 degrees of unsaturation
Ring = 1 degree of unsaturation

You need to be able to calculate the degrees of unsaturation. The calculation is shown
below:

[(𝟐𝑪 + 𝟐) + 𝑵] − 𝑯 − 𝑿
𝑫𝑼 =
𝟐

C = carbon
N = nitrogen
H = hydrogen
X = halogen (F, Cl, Br, I)

13.3 Carbon NMR

Nuclear Magnetic Resonance (NMR) is one of the most powerful ways of getting
structural information from a molecule of interest.

It is a method exploiting the inherent property of same atomic nuclei spin.

Because nuclei are charged particles if they are also spinning they create a magnetic field,
and are hence magnetically active.

Carbon NMR is a useful tool for identifying the number of types of carbon in a molecule
as well as information about its direct chemical environment (in other words it’s electron
density, this will be affected by presence of electron donating or withdrawing groups)

Understanding Number of Types of Carbon in a Molecule

First let’s review the concept of number of types of carbon. Understanding symmetry here
is extremely important!

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Examples: Determine the number of types of carbon in the following molecules

a) Benzene

b) Butane

c) 2-bromopentane

d) Toluene

Now that you have an understanding of how to determine number of types of carbon, we
can apply it to the method of 13C NMR (sidenote the 13 always come before the letter C,
never after)

Each different type of carbon in a molecule will have its own specific peak on a 13C
spectrum. Therefore in the example of benzene, although there are 6 total carbons in the
molecule there exists only one type of carbon based on symmetry so there will only be
one peak in the carbon NMR!

Understanding Chemical Environment and effect on chemical shift

The chemical shift (ppm value) of a typical 13C NMR spectrum ranges from 0-200ppm.

High Electron Density = Low ppm Value (upfield)

Low Electron Density = High ppm Value (downfield)

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When considering electron density around a nucleus the two main factors are inductive
and resonance effects. Also note that any carbon that’s part of an aromatic ring has a
relatively high chemical shift due to magnetic anisotropy.

The following page is a reference guide for approximate chemical shifts based on
connectivity at that carbon. You will also be provided a guide like this

Carbon-13 DEPT-135 NMR

Since you cannot tell C’s, CH’s, CH2’s, CH3’s apart in the carbon NMR from multiplicity due
to decoupling, we sometimes use a technique called DEPT-135 NMR. This technique
“phases” the carbon signals differently depending on what kind they are. A typical DEPT-
135 spectrum has:

Quaternary carbons = disappear

CH’s = point up
CH2’s = point down
CH3’s = point up

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Now that we have the basics down let’s look at some spectra!

1) cyclohexanone

# of peaks =

Notes on peak location

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2) ethyl acetate

# of peaks =

Notes on peak location

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3) phenol

# of peaks =

Notes on peak location

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13.4 Proton NMR

Proton NMR is one of the most common and most powerful tools for providing
structural information of a molecule, it’s invaluable!!

Proton NMR works on the same principles as carbon NMR where it exploits the inherent
property of nuclei that is spin

Also like carbon NMR it provides the number of types of protons in the molecule, but it
also provides much more information.

Proton NMR provides the following information:

1) Number of types of hydrogen

2) Number of equivalent hydrogens contained in a type
3) Chemical environment
4) Magnetic environment

1) Number of types of hydrogen

This is a familiar concept that was explored again in 13C NMR. Let’s go over a few examples
as a refresher.

Examples: Determine the number of different types of hydrogen in each of the following
molecules

a) Ethyl benzene

b) 3-hexyne

c) 6-methylheptan-2-ol

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2) Number of equivalent hydrogens contained in a type

This point is pretty self-explanatory. The area under each peak is proportional to the
amount of hydrogens that represent the peak. As an example determine the amount of
each hydrogen type in examples a-c of the previous section

3) Chemical Environment (electron density)

Also similarly to 13C NMR the ppm value of each peak is indicative of the amount of
electron density surrounding the nucleus. As with before:

High Electron Density = Low ppm Value (downfield)

Low Electron Density = High ppm Value (upfield)

Again the factors to consider are inductive and resonance effects, as well as presence of
aromatic rings.

The following page provides a useful figure as a reference guide for approximating
chemical shift based on the nearby functional groups. You will be allowed to use one of
these on the final so don’t spend time memorizing it but it’s important to at least be
familiar with it.

Examples: Estimate the chemical shift for the different types of hydrogen in each of the
following molecules

a) 2-Butanone

b) Ethyl Benzene

c) Ethyl Benzoate

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4) Magnetic environment(Connectivity)
Probably the biggest difference between carbon and proton NMR is that proton NMR
gives direct information in terms of connectivity of the molecule. For reasons that we
won’t go into much detail here for the essence of time, each neighboring hydrogen will
split the parent peak into one more peak. According to the n+1 rule

# peaks = n + 1

where n = # of non-equivalent proton neighbors

Parent peak # # of neighbouring H Resulting peak# / name

1
2

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Now that we’ve covered why proton NMR is useful let’s get to some spectra

a) Propanal

# of types of H =

Total Number of H =

Multiplicity of Each

b) Ethyl acetate

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# of types of H =

Total Number of H =

Multiplicity of Each

c) Benzyl methyl ether

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# of types of H =

Total Number of H =

Multiplicity of Each

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Practice Problems
Propose a structure of a molecule given the following spectra. The Molecular formula is
C2H3N.

Key function groups present?

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# of Carbon =

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# of types of H =

Total Number of H =

Multiplicity of Each

Structure?

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Propose a structure of a molecule given the following spectra. The Molecular formula is
C4H8O.

Key function groups present?

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# of Carbon =

# of types of H =

Total Number of H =

Multiplicity of Each

Structure?

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Propose a structure of a molecule given the following spectra. The Molecular formula is
C9H10O2.

Key function groups present?

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# of Carbon =

# of types of H =

Total Number of H =

Multiplicity of Each

Structure?

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Review Section

Substitution and Elimination ‘simplified’

Reactivity of Alkyl Halides (AH)/molecules with good leaving groups

SN1 SN2 E1 E2

X X X
Primary
AH

Secondary Only
AH with
strong
bases

X
Tertiary Any
AH base
• Remember – SN2 reactions depend on the nucleophile! Better nucleophiles make
the reaction quicker.
• SN1 reactions only depend on the electrophile!
• Often, if a substrate can undergo SN1 it can undergo E1. Look out for reaction
conditions and the presence on a bulky conjugate base.

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Functional Group Quick Reference

Functional Group Name Suffix

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Extra Pages

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