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
+

colorless

Br2
red

HBr

Br
colorless

colorless

MECHANISM

CH2CH2CH3

Br

CH2CH2CH3

CH2CH2CH3

Br

Br

An electron pair from

the aromatic ring
attacks Br2, forming a
new C-Br bond

HBr

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.

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 compoundremember 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.

!
Im LIDE
I
N
TA
E
AC

ANALYSIS

Prepare TLC plate and chamber.

Apply provided standards to TLC

plate.
Apply TOP layer from test tube to
TLC plate ( sample solution).

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

o-bromoacetanilide

m-bromoacetanilide

Standard

Sample

***Rf values are 2 decimal

places, never more, never less.
And unitless.***

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.