February 4, 2015

Experiment 1: Electrophilic Aromatic Substitution

The purpose of the experiment is to demonstrate electrophilic aromatic substitution using
Friedel-Crafts Alkylation and analyze the relative bromination rates of arene compounds.
Introduction
Since the 1800s, the Friedel-Crafts alkylation is the most useful method for the
introduction of alkyl group.1 From that point, alkylation of arenes was revolutionized. Different
breakthroughs were discovered for the past two centuries to this day. Thomas discovered the use
of FeCl3 instead of the original AlCl3 as the Lewis acid catalyst which is currently used in
modern experiments. 1 A recent breakthrough in alkyl-arene synthesis is the use of solid support
reagents, such as silica gel bound aluminum chloride (Si-AlClx) in conjunction with microwave
chemistry in decreasing synthesis time with increased product yield and decreased waste.2 The
solid support approach was discovered by Merrifield with the successful synthesis of tetrapeptide
in 1963. 2 The biological synthesis of peptide chains in amino acids which is covalently bonded
to solid resins, such as polystyrene was expanded into organic synthesis. 2 These breakthroughs
in Friedel-Crafts method show the significance of the process in modern organic chemistry.
The purpose of this study is to demonstrate the Friedel-Crafts alkylation, synthesize an
alkyl substituted arene by reacting an arene and an alkyl halide in the presence of a Lewis acid
catalyst. In this experiment, biphenyl will be reacted with two counts of tert-butyl chloride in the
presence of catalytic iron (III) chloride to synthesize 4,4-di-tert-butylbiphenyl and two counts of
HCl. The Lewis acid, iron (III) chloride, helps generate the electrophile to attack the aromatic
compound. The chloride from tert-butyl chloride is pulled away by the Lewis acid leaving the

carbocation t-butyl and a negatively charge aluminum bonded to four chlorine atoms. The
positively charged carbocation attacks on the para or carbon 4 of the aromatic ring to minimize
steric hindrance due to its bulky structure. The reaction generates 4,4-di-tert-butylbiphenyl. The
aluminum-chloride anion transfers electron to a chlorine atom which pulls on the hyrdrogen at
carbon 4. The pull on the hydrogen results in an electron transfer to the ring to form pi bond.
Calculations
Limiting reagent = biphenyl
Biphenyl + 2 tert-butyl chloride 4,4-di-tert-butylbiphenyl + 2 HCl
Biphenyl to 4,4-di-tert-butylbiphenyl ratio = 1:1
Biphenyl used = 1.00g = 4,4-di-tert-butylbiphenyl yield

Percent yield=

actual yield
0.79 g
100 =
100 =79
theoretical yield
1.00 g

TLC Rf
Distance travelled by compound A = 3.8 cm;
Distance travelled by compound B = 4.2 cm;
Distance travelled by solvent = 4.8cm
Rf =

distance travelled by compound

distance travelled by solvent

RfA = 3.8 cm / 4.8 cm = 0.81

RfB = 4.2 cm / 4.8 cm = 0.89

TLC
Compound
A = Biphenyl
A+B = Co-spot
B = 4,4-di-tert-butylbiphenyl

Rf

Conditions
0.81 Eluent: hexanes:ethyl acetate;
0.81, 0.89 Plate: silica; Visualization
0.89 method: UV

Melting point
Compound

Experimental Melting
Literature Melting Point
Reference
Point (C)
(C)
4,4-di-tert-butylbiphenyl
~25
126-129
1
1. ChemSpider.com. http://www.chemspider.com/Chemical-Structure.66804.html

Relative reaction rate

Compound

Time (mins)

Anisole
Acetanilide
Diphenyl ether
Toluene
Benzhydrol

0.33
7.0
11
13
91

Experimental Rate
Ranking (Fastest-Slowest)
1
2
3
5
4

Theoretical Rate Ranking

(Fastest-Slowest)
1
2
3
4
5

The purity of the product is poor. The TLC co-spot shows two different spots under UV
light. Spot B (product) is slightly higher than spot A (starting compound) but spot B shows two
different compounds very similar to the co-spot. The product illuminates under UV light just
above the starting material spot observed in spot B. The product obtained is waxy which means
contaminants that are in liquid state at room temperature of 25C are present. The product is to
wet, or waxy, to perform a melting point analysis, therefore, the melting point is assumed to be
around room temperature.
The resulting order of arene reactivity from the experiment from fastest to slowest is
anisole, acetanilide, diphenyl ether, toluene and benzhydrol. The experimental results did not

match with the theoretical order of anisole, acetanilide, diphenyl ether, benzhydrol and toluene.
The toluene appears to have reacted too fast for the experiment compared to the other students
data. This may be due to mishandling of compounds when the bromination of toluene is
performed or the possibility of exposing the mixture to high temperature that increased the rate
of reaction.
The TLC shows three distinct spots under UV light. The co-spot and product spot is
closely similar due to the high amount of starting material in the product. The short wavelength
UV light illuminated the pure product, glowed in blue colour and is more defined in the product
spot compared to the co-spot. The product spot is examined to have two halves, the top is the
product and bottom half is the starting material. Under the conditions used in the experiment,
there is adequate separation between product and starting material if observed in both short and
long wavelength, but not enough separation to distinguish the product form starting material
under long wavelength only. Tert-butyl chloride cannot be used as a co-spot because it is highly
volatile if mixed with acetone.