Experiment 15:
SUBSTITUENT EFFECTS ON
THE RATE OF
ELECTROPHILIC AROMATIC
SUBSTITUTION
Objectives:


To explore how different substituent
groups on an aromatic ring affect the rate
and orientation of electrophilic aromatic
substitution using a qualitative bromine
test.
To determine directing ability of acetamide
group using TLC analysis.
Before coming to lab…

Review these techniques:

TLC Analysis

Acid-base Extraction
CHEMICAL EQUATION
• The progress of the bromination of an aromatic
ring can be followed easily by a color change.
• The more reactive the aromatic ring is, the
faster the color will disappear.
G
G
+
colorless
Br2
red
+
HBr
Br
colorless
colorless
MECHANISM
CH2CH2CH3
+
Br
H
CH2CH2CH3
CH2CH2CH3
Br
Br
An electron pair from
the aromatic ring
attacks Br2, forming a
new C-Br bond…
HBr
H
H
H
+
H
Br
…and leaving a
nonaromatic, carbocation
intermediate.
Br
The carbocation intermediate
loses H+, and the neutral
substitution product forms as
two electrons from the C-H
bond move to regenerate the
aromatic ring. HBr forms as a
byproduct.
REACTIVITY OF AROMATIC
RINGS


The substituent ALREADY ON the
aromatic ring determines the position
and rate of substitution of the second
(INCOMING) electrophile.
We use the reactivity of BENZENE
(no substituent) as a reference point.
REACTIVITY OF AROMATIC
RINGS

If we use the reactivity of benzene (substituent =
H) as a reference point, activating substituents
are all electron donating groups, and their relative
activation strengths are:
H < Phenyl < CH3 < NHCOCH3 < OCH3 < OH < NH2

Deactivating groups are electron withdrawing
groups and their activities relative to hydrogen
are:
NO2 < COR < CHO < I < Br < Cl < F < H
SUBSTITUENT EFFECTS
GENERALIZATIONS




Substituents in which the atom bonded to
the ring has an unshared pair of electrons,
with the exception of alkyl and phenyl
groups, are ortho-para directing. All
other substituents are meta directing.
All ortho/para directors are activators,
with the exception of halogens. Halogens
are ortho-para deactivators.
All meta directors are deactivators.
Alkyl and Phenyl groups are also orthopara directing.
OVERVIEW




React bromine solution with six
monosubstituted aromatic compounds.
Follow rate of reaction based on color
change.
Neutralize and extract acetanilide
product to purify compound for
further analysis.
To analyze the bromoacetanilide
product to identify product
substitution.
SYNTHESIS

Place small amount of
monosubstituted aromatic
compound in small test tube.

Place test tubes in water bath.

Add Bromine solution to each.



Record the approximate amount of
time it takes for the solution to
lose color.
Place in hot water bath if
necessary to complete reaction.
After 1 hour, estimate the reaction
order based on the relative amount
of color lost.
Table 15.1
Compound
Structure
OPA,
OPD,
or MD
Reaction
Order
ethyl
benzene
anisole
acetanilide
phenol
benzaldehyde nitrobenzene
***Aromatic ring is given for each compound…remember to
complete structure with appropriate substituent!***
***Identify each substituent as an ortho/para activator (OPA),
ortho/para deactivator (OPD), or a meta deactivator (MD).***
***Simply record the order that the reactions occurred. Actual
reaction times are not required. 1=fastest  6=slowest! ***
PURIFICATION/ISOLATION






Once pale yellow, remove acetanilide
tube.
Add deionized water to tube.
Add 5 drops of NaOH. Test pH using
glass rod.
Repeat until the solution is basic.
Add ethyl acetate. Place small cork in
top of test tube, and shake to mix.
Allow layers to separate.
ANALYSIS
• Prepare TLC plate and chamber.
• Apply provided standards to TLC
plate.
• Apply TOP layer from test tube to
TLC plate ( sample solution).
A
B U C D
• Develop plate and visualize spots
using UV lamp.
filter paper
• Calculate Rf value of all spots and
identify product in sample solution.
A
B U C D
Tables 15.2 and 15.3
Rf Values
Identification
Standard
o-bromoacetanilide
***Rf values are 2 decimal
places, never more, never less.
And unitless.***
Sample
m-bromoacetanilide
p-bromoacetanilide
MAJOR
Product
Name
MAJOR
Product
Structure
***Write in name of product formed from bromination of
acetanilide.***
***Draw structure of major product formed.***
HINTS…


Be sure that your test tubes do NOT
contain any acetone. It reacts very
quickly with bromine and can give
inaccurate test results.
If after the one hour period of heating in
the water bath the solutions have not
completely lost their color, estimate by
the relative amount of color lost.
SAFETY CONCERNS


CAUTION: In this experiment you
are using bromine, which is poisonous
and can cause severe burns!
All aromatic solutions are prepared in
glacial acetic acid which can cause
severe burns!
WASTE MANAGEMENT



Place ALL liquid waste in container labeled
“LIQUID ORGANIC WASTE”.
Place used TLC plates and filter papers in
yellow trash can.
Place used TLC spotters broken glass box
(NOT TRASHCAN!!!!!!!!!!!).
CLEANING UP…

TEST TUBES: clean all test tubes with
soap/water/brush and rinse with wash acetone.
Leave inverted in test tube rack to dry.

TLC CHAMBER: remove filter paper and leave
in drawer with cap off.

BEAKER: if only used for water, simply dry out
with a paper towel.

GRADUATED CYLINDER: rinse any excess
bromine solution into wash acetone container.
Clean with soap/water/brush and rinse with
wash acetone.
LABORATORY NOTEBOOK
(Pre-lab)
• OBJECTIVE
(Must clearly state…)
• What you will be doing
• How you are going to do it
• How you will determine if it worked
• CHEMICAL EQUATION
• Include the chemical equation from the top of page 131 of the lab manual.
• TABLE OF PHYSICAL DATA
(Complete the following table using a
site listed on WWW Links ONLY. Wikipedia is unacceptable!)
Compound
Ethylbenzene
MW (g/mol)
bp(oC)
d (g/mL)
HAZARDS
Anisole
Acetanilide
Phenol
Benzaldehyde
Nitrobenzene
Acetic acid
Ethyl acetate
Hexane
• REFERENCE TO PROCEDURE
bromine
(Must include…)
•full title including edition and authors
•page numbers where actual procedure can be found
LABORATORY NOTEBOOK
(In-lab)
• DATA/CALCULATIONS
•
•
•
•
Reaction rates of aromatic compounds with bromine solution.
Sketch TLC diagram, including all cm measurements
TLC developing solvent system
Show at least one TLC Rf calculation
• EXPERIMENTAL PROCEDURE
•
•
•
•
In paragraph form, describe the procedure that you actually followed
during the lab.
Paragraph must be written in PAST TENSE, PASSIVE VOICE.
Include any volumes or weights of chemicals used during the
experiment.
Include any mistakes, accidents, or observations if applicable.
For next lab…


Pre-lab notebook entry for
Experiment 17 will be due at the
beginning of lab!
Final lab report for Experiment 15,
along with completed lab notebook
pages, will be due at the beginning of
lab!