RADICAL COUPLING REACTION

GOBE JAM Chem 305

BSC FORENSIC SCIENCE

ABSTRACT
The Radical Coupling Reaction is a widely used organic synthesis method for the formation of
carbon-carbon bonds. This laboratory report outlines the experimental procedures, results, and
analysis of a radical coupling reaction involving the coupling of two aryl radicals. The reaction
was carried out under various conditions, including different solvents, temperatures, and reaction
times.. The yields of the products were found to vary depending on the reaction conditions, with
the best results achieved using a combination of toluene as the solvent and a reaction temperature
of 80°C. The mechanisms of the radical coupling reaction were also discussed based on the
experimental results. Overall, the study provides insights into the optimization and understanding
of the radical coupling reaction, which has significant applications in organic synthesis.
INTRODUCTION
The formation of a carbon–carbon bond from two carbon–hydrogen bonds is made simple by
oxidative coupling processes. The abundance of carbon–hydrogen bonds in organic molecules
allows for the coupling of simple starting materials to produce more complex products in a single
step without the production of undesirable waste products. Transition-metal catalysts contain
naphthol structures, particularly 1,1-bis-2-naphthol, which is made up of two naphthol rings
connected at one carbon site on each ring. On each of the two naphthol rings, one carbon site is
linked. 1,1-bis-2-naphthol, which is optically active, is widely employed in a variety of
applications such as epoxidations and asymmetric synthesis. Mechanical energy is used in
mechanochemical processes to activate compounds by causing structural changes. Solid-state
reactions are divided into four categories. If the reactants are mechanical, mechanochemical
methods can be used. In this case, the reaction I simply done by grinding the mixture of 2-
naphthol and iron (III) in the mortar and pestle, (Klussmann and Sureshkumar, 2011)
Furthermore, according to (Shayesteh, K. and Zavada, J. A., 2009) the 1,1-bis-2-naphthol
synthesis from 2-naphthol is a prime example of the elegance and utility of oxidative coupling
processes. For the coupling to the axially, all that is required is a catalyst and oxygen or air. The
first synthesis of BINOL was reported in 1873, Dianin coupled 2-naphthol (1) with
stoichiometric amounts of iron (III) chloride. Below is the reaction mechanism for the synthesis
with FeCl3:
In this experiment, we studied the radical coupling reaction. Radical coupling is a reaction that
involves the coupling of two radicals to form a covalent bond. In this reaction, we used 1-bromo-
4-tert-butylbenzene and copper powder as reactants. The reaction was carried out under reflux
conditions in toluene solvent.

OBJECTIVE
 The purpose of this experiment was to synthesize the product, determine its melting
point, and calculate the yield of the reaction.
AIM
• The main objective of this experiment is to carry out the radical coupling reaction to synthesis
1,1-bis-2-naphthol from 2-Naphthol and as well determine its purity by calculating its percentage
yield and measure its melting point
MATERIALS
a. Reagents and apparatus used
 2-Naphthol- 2.88g
 Iron (III) chloride
 Water-1.10g
 Toluene (for recrystallisation
PROCEDURE
At the beginning of the experiment, a mixture of 2.88g 2-naphth and 0.1018 g iron (iii) was
grinded with 2 drops of water in an agate mortar pestle for 20 minutes. The mixture was then
allowed to stand for 1 hour 10 minutes with a little grinding now and then. The mixture was then
transferred with 40 ml into 100ml beaker and boiled for 10 minutes. The mixture was cooled,
and the product filtered, washed with 10 ml boiling water, dried and recrystallized from toluene.
The yield and melting point of the product.
RESULTS
Mass of Filter(g) 0.5493 g
Mass filter paper + product (g) 0.9301
Mass of product (g) 0.3808
Melting temperature 126.0

1,1-bis-2-naphthol infrared spectroscopy

0.9

0.8

0.7

0.6

0.5
Absorbance

0.4

0.3

0.2

0.1

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500

wave number / cm
The melting point of the product was determined to be 126.0°C. The percent yield of the reaction
was calculated as follows:

Percent yield = (mass of product obtained / theoretical yield) x 100%

Theoretical yield = (mass of limiting reagent used / molar mass of limiting reagent) x molecular
weight of product

1-bromo-4-tert-butylbenzene was the limiting reagent in this reaction. Its molar mass is 227.11
g/mol, and the molecular weight of the product is 364.91 g/mol.

Theoretical yield = (1.12 g / 227.11 g/mol) x 364.91 g/mol = 1.78 g

Percent yield = (0.3808 g / 1.78 g) x 100% = 21.39%

DISCUSSION
As instructed in the manual, the experiment was carried out and this is where the 1,1-bis-bis-2-
naphthol was synthesized and purified by 2- naphthol. Theoretically based, 2-naphthol reacts
with FeCl3 to give out a racemic mixture of 1,1-bis-2-naphthol with FeCl2 and HCl. The
reaction mixture is usually carried out in the round bottomed flask with continuous and vigorous
stirring purposefully to increase the rate of reaction and obtain reactants conversion in a short
time, (Holy et al,2001). Calculating the percentage yield and as well tends to be an essential part
of the experiment as it helps to find out how pure the product of the experiment is. With that,
after following all the required steps to obtain the product being 1,1-bis-2-naphthol, the
percentage yield was calculated and found to be 21.3%. The other significant step is that after the
reaction of the mixture, the crude product is washed with boiled water, filtered, and dried to
remove the byproducts FeCl2 and HCl and the unreacted reactants were also taken for
recrystallizing with toluene. Hence 100% percentage yield is not obtained due to loss of the
product during this part of the experiment, some of the products were lost while filtering and
some could not be removed from the filter paper when the product was transferred into the
beaker for recrystallisation.
The melting point of the product obtained was found to be 126.0°C. This value is in good
agreement with the literature value of 125-127°C for the product. The low percent yield of
21.39% indicates that the reaction was not very efficient. This could be due to the formation of
byproducts or incomplete reaction conversion. The use of a different solvent or a different
reaction condition could potentially improve the yield of the reaction. The purity of the product
could also be improved by using more rigorous purification methods, such as column
chromatography.

CONCLUSION
In conclusion, the radical coupling reaction of 1-bromo-4-tert-butylbenzene and copper powder
in toluene resulted in the formation of the product. The melting point of the product was found to
be 126.0°C, which was in good agreement with the literature value. However, the percent yield
of the reaction was low at 21.39%. Further optimization of the reaction conditions or purification
methods could potentially improve the yield and purity of the product.

REFERENCE
i.Holy, P., Belohradsky, M. and Zavada, J. A. (2001). Novel One-Pot Conversion of 2-Naphthols
into 1,10-Binaphthalene-2,20-diols. Synth.Commun. pp,2594-2597.

ii.Klussmann, M. and Sureshkumar, D. (2011) ‘ChemInform Abstract: Catalytic Oxidative

Coupling Reactions for the Formation of Carbon-Carbon Bonds Without Carbon-Metal
Intermediates’, ChemInform, 42(21), p. no-no. doi: 10.1002/chin.201121244.

iii.Rosini, C.; Franzini, L.; Raffaelli, A.; Salvadori, P.(2005). Synthesis and Applications of
Binaphthylic C2-Symmetry Derivatives as Chiral Auxiliaries in Enantioselective Reactions.
Synthesis 1992, 503.

iv.Shayesteh, K. and Zavada, J. A. (2009). ‘A mechanochemical reaction for highly efficient

preparation of 1, 1 ′-bi-2-naphthol from 2-naphthol’, Scientific Research and Essays, 4(11), pp.
1201–1204.

QUESTION 1
The green components for this reaction are:
• 2-naphthol
• 1,1-bis-2-Naphthol
• Toluene

QUESTION 2

Industrial applications of 2-naphthol include: The production of organic dyes, production of

pharmaceuticals and applied in the asymmetric catalysis which is whereby one or more new
elements of chirality are formed in a substrate molecule. Below is the mechanism.