MSE245

Organic Materials
Chemistry and Processing
Professor Naomi Matsuura
WB 138
naomi.matsuura@utoronto.ca

February 14, 2022

MSE 245 Course Outline

1. Review: bonding, Lewis structures, hybridization, acids base chemistry
2. Introduction to IUPAC nomenclature (handouts)
3. Alkanes and Cycloalkanes (Ch 3)
4. Alkenes and Alkynes (Ch 4)
5. Reactions of Alkenes/Alkynes (Ch 5)
6. Chirality and the Handedness of Molecules (handouts)
7. Haloalkanes (Ch 7)
8. Alcohols, Ethers, and Thiols (Ch 8)
9. Benzene and its Derivatives (Ch 9)
10. Amines (Ch 10)
11. Aldehydes and Ketones (Ch13)
12. Carboxylic Acids and derivatives (Ch 14 &15)
13. Organic Polymer Chemistry and synthesis (Ch 16 + Brazel & Rosen Ch 1 & 2)
14. Polymer Physical properties (Brazel & Rosen Ch 3, 4, 5 and 6)
15. Polymer processing (Ch17 (Brazel & Rosen Ch-17)
16. Polymer recycling, degradation and environmental impact (handouts)
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 Substitution & Elimination Reactions
• In this chapter, we concentrate on two types of reactions:
• Nucleophilic substitution – any reaction in which one nucleophile is
substituted for another
• b-elimination – removal of atoms/group of atoms from 2 adjacent C atoms
• Because all nucleophiles are also bases, nucleophilic substitution
and base-promoted b-elimination are competing reactions

• In the presence of a strong base, halogen can be removed from

one carbon of a haloalkane and hydrogen from an adjacent
carbon to form a C=C double bond 3

Chapter 7

• Introduction and nomenclature (short review) (7.1)

• Nucleophilic Aliphatic Substitution and β-Elimination
(7.2)
• Nucleophilic Aliphatic Substitution (7.3)
• Mechanisms of Nucleophilic Aliphatic Substitution: SN1
and SN2 mechanisms (7.4)
• SN1 and SN2 dominating factors & experimental
conditions (7.5, 7.6)
• β-Elimination (7.7)
• Mechanism of β-Elimination, E1 or E2? (7.8)
• Substitution vs. Elimination (7.9)

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 HALOALKANES
b-ELIMINATION

Recall: Characteristic Reactions of Alkenes

• Most characteristic reaction of alkenes is addition to the C=C
such that the p bond is broken and, in its place, s bonds are
formed to 2 new atoms/groups of atoms
Hydrochlorination
(hydrohalogenation)

Hydroboration

Hydration

Hydrogenation
(reduction)
Bromination
(halogenation)

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 Recall: Hydrohalogenation (hydrochlorination), a
mechanism of electrophilic addition
• Electrophilic addition happens in many of the reactions
of alkenes, containing carbon-carbon double bonds

b-Elimination
• b-Elimination: removal of atoms or groups of atoms
from adjacent carbons to form a carbon-carbon double
bond
• we study a type of b-elimination called dehydrohalogenation
(the elimination of HX)
b a
C C + CH3 CH2 O-Na+
CH 3 CH 2 OH
H X
Base
An alkyl
halide
C C + CH3 CH2 OH + Na+ X -

An alkene
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 b-Elimination
• Zaitsev’s rule: The major product of a b-elimination
is the more stable (the more highly substituted)
alkene. When cis-trans isomerism is possible, the
trans isomer is favored.

Example (Problem 7.6)

Predict the b-elimination products formed when each
chloroalkane is treated with sodium ethoxide in ethanol:

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 b-Elimination mechanisms
There are two limiting mechanisms for b-elimination
reactions
• E1 mechanism: at one extreme, breaking of the C-X
bond is complete before reaction with base breaks the C-H
bond
• Only R-X is involved in the rate-determining step
• Rate = k[haloalkane]
• E2 mechanism: at the other extreme, breaking of the C-
X and C-H bonds happens at the same time
• Both R-X and base are involved in the rate-determining
step
• Rate = k[haloalkane][base]
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Elimination Reaction Mechanism

• Elimination reaction between a simple haloalkane like 2-
bromopropane and hydroxide ions (from, for example,
sodium hydroxide) to give an alkene.
• In elimination reactions, the hydroxide ion acts as a base -
removing a hydrogen as a hydrogen ion from the carbon
atom next to the C holding the bromine.
• The resulting re-arrangement of the electrons expels the
bromine as a bromide ion and produces propene.

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 E1 Mechanism
• Step 1: Break a bond to give a stable molecule or ion.
Rate-determining ionization of C-X gives a carbocation
intermediate and halide ion.

• Step 2: Take a proton away. Proton transfer from the

carbocation to a base (in this case, the solvent) gives
the alkene.

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Elimination 1 (E1) Mechanism (vs SN1)

• E1 happens at a similar condition as SN1.
• The E1 and SN1 are, in fact, in competition whenever
an alkyl halide is treated in a hydroxylic solvent with a
non-nucleophilic base.
• The best substrate (secondary and tertiary) for E1 is
also the best for SN1, and a mixture of products is
obtained.

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E2 Mechanism
• A one-step mechanism; all bond-breaking and
bond-forming steps are concerted. Simultaneously
(1) take a proton away and (2) break a bond to form
a stable ion or molecule.

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 Elimination Bimolecular (E2) Mechanism
• When a base reacts with an alkyl halide, nucleophile/base can substitute for the
leaving group in an SN(1 or 2) to ELIMINATE HX leading to formation of an
alkene.
• Elimination reaction almost always get mixtures of alkene products
• According to Zaitsev’s rule, In the elimination of HX from an alkyl halide, the
more highly substituted alkene product predominates.
• E2 is the most common occurring mechanism.
• Like SN2, E2 occurs at 1 step without intermediates.
• The leaving group takes 2 electrons from the former C-X bond

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 HALOALKANES
MECHANISMS OF b-ELIMINATION: E1 OR E2

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Summary of E1 versus E2 Reactions for

Haloalkanes

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 Example

What is the major product from an elimination reaction

starting with 2-bromopentane?

a) 1-pentene
b) cis-2-pentene
c) trans-2-pentene
d) a mixture of cis and trans-2-pentene

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Example 7.7
Predict whether each b-elimination reaction proceeds
predominantly by an E1 or E2 mechanism, and write a structural
formula for the major organic product

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 Example
1) Identify the major product(s) for the following reaction
2) State the reaction type

I
NaOCH2CH3

CH3CH2OH

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HALOALKANES
SUBSTITUTION VS b-ELIMINATION

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12
 Substitution & Elimination Reactions
• In Chapter 7, we learned of two types of reactions:
• Nucleophilic substitution – any reaction in which one nucleophile is
substituted for another
• b-elimination – removal of atoms/group of atoms from 2 adjacent C atoms
• Because all nucleophiles are also bases, nucleophilic substitution
and base-promoted b-elimination are competing reactions

• Substitution reactions allows compounds (e.g., haloalkanes) to be converted to

compounds with other functional groups (alcohols, ethers, thiols, sulfides, amines,
nitriles, alkenes, alkynes…) and vice versa
• Elimination reactions allow In the presence of a strong base, functional group (e.g.,
a halogen) can be removed from one C of a haloalkane and hydrogen from an
adjacent C to form a C=C double bond 25

25

Summary of SN1 and SN2 Reactions of Haloalkanes

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13
 Summary of E1 versus E2 Reactions for
Haloalkanes

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Recall (last week): Relative Nucleophilicity

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 Recall (Week 1): Lewis Acids and Bases

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Substitution versus Elimination

• Because many nucleophiles are also strong bases (OH–
and RO–), SN and E reactions often compete.
• The ratio of SN/E products depends on the relative rates of
the two reactions.
• In general, the major barriers for:
• SN2 – Steric hindrance
• SN1/E1 - Carbocation Stability
• E2 - No “big barrier”

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 SN1 versus E1
• Reactions of 2° and 3° haloalkanes in polar protic
solvents give mixtures of substitution and elimination
products. Product ratios are difficult to predict.
• Often the same products with different kinetics

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SN2 versus E2
• It is considerably easier to predict the ratio of SN2 to
E2 products.
• Branching made E2 products (alkenes) more stable

• Strong Nu: favors SN2; Strong base favors E2.

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 Summary of Mechanisms
• We have seen a total of 4 nucleophilic substitution/
elimination reactions. How do you predict what reaction
will take place?
• A primary substrate (RCH2X) reacts by an SN2 mechanism with
good nucleophiles such as I-, Br-, RS-, NH3 or CN-, or E2 attacked
by strong base such as hydroxide ion or an alkoxide ion (RO-, e.g
EtO-)
• A secondary substrate (R2CHX) react by both SN2 and SN1 (or E1
and E2) to give a mixture of substitution and elimination
products
• A tertiary substrate (R3CX) reacts by an E2 pathway if a strong
base is used or by a mixture of SN1 and E1 under neutral or acidic
conditions.

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Summary of SN versus E for methyl and

primary haloalkanes

EtO-

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 Summary of SN versus E for secondary or
tertiary haloalkanes

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S vs E for Haloalkanes: Predict the major product and

the mechanism for each reaction
(Hint: substrate, nucleophile/base, solvent)
Cl 80°C
1. + NaOH
H 2O

30°C
2. + (C2 H5) 3N
Br CH2 Cl2

Br
- +
3. + CH3O Na
methanol

Cl
+ -
4. + Na I
acetone
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