Subject Code Chem 3 Reactions and Interactions of Organic and Inorganic

Compounds
Module Code 2.0 Organic Reactions I
Lesson Code 2.10 SN1 Reaction (Energy Diagram and Mechanism)
Time Limit 30 mins.

Components Tasks TAa ATAb

Target By the end of this module, the students will have been able to: 30 s
• Summarize the characteristics of unimolecular
nucleophilic substitution SN1

Hook The occurrence of substitution reactions in nature is quite 2 mins

common. Perhaps, among its very important applications lies
in the biosynthesis of geraniol where two unimolecular
substitution reactions SN1 occur. We will be learning about
the general characteristics of SN1 reactions through this
module.
Geraniol can be extracted from roses and is used in perfumery
and cosmetic products. Moreover, it is also reported to exhibit
antimicrobial, antioxidant, and anti-inflammatory activities
(Chen & Viljoen 2010). If someone in your home is fond of
floral fragrances, it would be interesting to read the list of
ingredients making up the scented products that they use and
identify which ones contain geraniol.

Ignite Nucleophilic Substitution is a polar reaction where a 18 mins

functional group in the electrophilic substrate is replaced by
the nucleophilic reagent. There are two types of nucleophilic
substitution: unimolecular nucleophilic substitution SN1 and
bimolecular nucleophilic substitution SN2. In this module,
the features of the SN1 reaction will be discussed in more
detail.
.
The term unimolecular in SN1 is derived from the observation
that the reaction follows first order kinetics:

rateSn2= k [substrate]

Chemistry 3 SN1 Reaction (Energy Diagram and Mechanism) │ 1 of 5

 The mechanism of an SN1 reaction
involves two steps with a carbocation
formed in between. In the first step, the
leaving group LG (the functional group to
be replaced) detaches from the α-carbon to
form a carbocation intermediate.

In the second step, the nucleophile attacks

the carbocation intermediate, replacing the
LG.

It is worth noting that the carbocation intermediate is planar in

geometry. Hence, the nucleophile may attach to the substrate
from either side of the plane leading to the formation of a
mixture of products comprised by a pair of stereoisomers, if the
α-carbon is chiral.

The energy profile of an SN1 reaction shows that the reaction

proceeds in two steps of varying activation energy and free
energy change. The carbocation intermediate is formed after
the first step.

For a simulation of the changes in the structure of a substrate

corresponding to the various regions of the energy profile,
please follow the link below:

University of Surrey (2011) SN1 Reactions

https://www.youtube.com/watch?v=JmcVgE2WKBE

Several conditions promote the progress of an S N1 reaction and

these mainly arise from the polar nature of the reaction and
from the formation of an intermediate.

The degree of substitution on the α-carbon…

Chemistry 3 SN1 Reaction (Energy Diagram and Mechanism) │ 2 of 5

 The more substituted the α-carbon, the more stable the
carbocation formed will be. A stable carbocation forms
readily, thereby promoting the SN1 reaction.

The nature of the leaving group…

The weaker the Bronsted base that the leaving group
becomes upon detachment, the more favorable the S N2
reaction is.

The nature of the nucleophile…

The progress of an SN1 reaction, a first order reaction, is
dependent on the formation of the carbocation
intermediate. Hence, the rate of an SN1 reaction is
independent of the nature of the nucleophile. However,
the nucleophile must be non-basic to prevent the
competing elimination reaction from occurring.

The nature of the solvent…

Polar protic solvents are polar solvents capable of
hydrogen bonding. Through solvation of the carbocation,
these solvents help stabilize the intermediate formed in
the first step, thereby promoting the SN1 reaction.
Navigate Let’s see how we’re doing so far… 8 mins
For both Levels 1 & 2
CAN WE ALREADY:

2.10.1 Determine whether the following solvents are polar

protic or polar aprotic?

2.10.2 Draw the mechanism for the given reaction? (Lifted

from McMurry 2017, problem no. 10-26 (a, c) p.402)

Chemistry 3 SN1 Reaction (Energy Diagram and Mechanism) │ 3 of 5

 (non-graded)

2.10.3 Explain why hydroxide OH- is NOT a good

leaving group? (graded)
Knot Unimolecular nucleophilic substitution SN1 is a polar reaction 1.5 mins
which follows first order kinetics. The mechanism proceeds (wrap-
in two steps with a carbocation intermediate formed in up)
between. Several conditions promote the S N1 reaction and
these include: i) a more substituted alpha-carbon, ii) a good
leaving group, iii) a non-basic nucleophile, and iv) the use of
a polar protic solvent.
To tie things together even better, let’s work on the following
EXERCISE:

A. Which among the following solvents promotes S N1

reactions and why? (Levels 1 & 2)
O

O OH N
(A1) (A2) (A3)

B. Determine the substrate and the nucleophile in each pair

of reactants. Show the mechanism of the reaction through
curved arrows and draw the final product. (Levels 1 & 2)
(B1)

(B2)

Chemistry 3 SN1 Reaction (Energy Diagram and Mechanism) │ 4 of 5

 C. Draw all isomers of C4H9Br, name them, and arrange
them in the order of increasing reactivity in the S N1
reaction. (Level 2) (adapted from McMurry 2017,
problem no. 10-39, p. 405)

a suggested time allocation set by the teacher

b actual time spent by the student (for information purposes only)

Answer key
NAVIGATE (Formative, for both Levels 1 & 2)

(2.10.1a) polar protic

(2.10.1c) polar aprotic

(2.10.2a)

H H
+ +
OH O O H
H H + Cl- Cl

(2.10.2b)

CH3OH CH3OH H
+
Br O
+
OCH 3 + H3C O
H H

References
Chen W. and Viljoen A.M. (2010) Geraniol- A review of a commercially important
fragrance material. South African Journal of Botany.76:4, 643-651
McMurry, J. (2017) Organic Chemistry. Cengage Learning Asia Pte. Ltd.

Smith, J.G. (2017) 5th Ed. Organic Chemistry. McGraw Hill Education, New York

Solomons, T.W.G., Fryhle, C.B., Snyder, S.A. 11th Ed. Organic Chemistry. John Wiley
& Sons, Inc.

Prepared by: Fiona U. Paredes Reviewed by: Erika Eunice Salvador

Position: Special Science Teacher (SST) II Position: Special Science Teacher (SST) III
Campus: PSHS-CAR Campus: PSHS-WVC
© 2020 Philippine Science High School System. All rights reserved. This document may contain proprietary information and may only be
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Chemistry 3 SN1 Reaction (Energy Diagram and Mechanism) │ 5 of 5