
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.


Review these techniques:

TLC Analysis

Acid-base Extraction

• 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
+
Br
2 red
G
Br colorless
+ HBr colorless

CH
2
CH
2
CH
3
CH
2
CH
2
CH
3
CH
2
CH
2
CH
3
+ Br Br
H
H
An electron pair from the aromatic ring attacks Br
2
, forming a new C-Br bond…
H
H Br
Br
…and leaving a nonaromatic, carbocation intermediate.
+ HBr
H
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.


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.


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 < CH
3
< NHCOCH
3
< OCH
3
< OH < NH
2

Deactivating groups are electron withdrawing groups and their activities relative to hydrogen are:
NO
2
< COR < CHO < I < Br < Cl < F < H




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.







Place small amount of monosusbtituted aromatic compound in small test tube.
Place test tubes in water bath.
Add Bromine solution to each.
Record the 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.

Aromatic
Compound ethyl benzene anisole acetanilide phenol benzaldehyde nitrobenzene
Structure
(fill in appropriate substituent)
Reaction Order


Rank in order 1-6.
Record reaction time in lab notebook.


Once colorless, 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.

• Prepare TLC plate and chamber.
• Apply provided standards to TLC plate.
• Apply TOP layer from test tube to
TLC plate ( sample solution).
• Develop plate and visualize spots using UV lamp.
• Calculate R f value of all spots and identify product in sample solution.
A B U C D filter paper
A B U C D

Identification
R f
Values
Standard
o-bromoacetanilide

Rf values are UNITLESS

Rf values are 2 decimal places
ONLY!
m-bromoacetanilide NOT AVAILABLE (n/a)
p-bromoacetanilide
Product
Name
Product
Structure
Sample

Write in name of product formed from bromination of acetanilide.

Draw structure of major product formed.


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.


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!


Place aqueous waste from extraction in bottle labeled “ Aqueous Waste (EAS)”

Place all other waste from experiment in bottle labeled “Organic Waste (EAS)”

Place used TLC plates and filter papers in yellow trash can.

Place used TLC spotters broken glass box .


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.