1|Page

DEPARTMENT OF CHEMICAL AND FORENSIC SCIENCES

CHEM 305 LAB TWO: RADICAL COUPLING REACTION
STUDENT NAME: KEALEBOGA AMIE PHIRI
STUDENT NUMBER: 18000352
PROGRAMME: PURE AND APLLIED CHEMISTRY
2|Page

1. 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.

2. 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:
3|Page

3. EXPERIMENTAL
a. Reagents and apparatus used
 2-Naphthol- 2.88g
 Iron (III) chloride
 Water-1.10g
 Toluene (for recrystallisation)

b. Procedure
At the beginning of the experiment, a mixture of 2.8824g 2-naphthol and 0.1018g 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 40ml into 100ml beaker and boiled
for 10-15 minutes. The mixture was cooled and the product filtered, washed with
10ml boiling water, dried and recrystallized from toluene. The yield and melting point
of the product was then recorded and reported.

4. RESULTS
Table 1: mass of 1,1-bis-2-naphthol obtained

Mass of filter paper (g) 0.5165

Mass pf filter paper + product (g) 1.3064
Mass of product (g) 0.7899

CALCULATING THE PERCENTAGE YIELD OF 1,1-Bis-2-NAPHTHOL

Molar mass of 2-naphthol= 144.17g/mol

Mass of 2-naphthol used= 2.8824g
Moles of 2-naphthol= mass/molar mass
Moles of 2-naphthol= 2.8824g/144gmol-1
Moles of 2-naphthol= 0.019993063744190 mols

Molar mass of iron (III) chloride= 162.2g/mol

Mass of iron (III) chloride =1.1018g
Moles of iron (III) chloride= mass/molar mass
Moles of iron (III) chloride= 1.1018g/162.2 gmol-1
Moles of iron (III) chloride= 0.006792848335388mols

Hence iron (III) chloride is the limiting reagent

Chemical reaction equation;

2C10H7OH (aq) + 2FeCl3(aq) ›C20H14O2(aq) + 2FeCl(aq) + 2HCl(aq)

FeCl3 : C20H14O2
2 : 1

 0.006792848335388mols : X
4|Page

X= 0.003396424167694 mols
Mass of C20H14O2= Moles x molar mass
Mass of C20H14O2= 0.003396424167694 mols x 286.32gmol-1
Mass of C20H14O2= 0.972464167694146g

Percentage yield= (Actual yield / theoretical yield) x 100%

Percentage yield= (0.7899g / 0.972464167694146g) x 100%
Percentage yield=81.22%

The measured melting point of the product is 184℃- 190℃.

5. 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
the researchers to get 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 81.22%. 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 by products FeCl 2 and HCl and the unreacted
reactants were also taken for recrystallising 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.

Furthermore, as afore mentioned the purity of the product had to be determined as

well by measuring the melting point of the 1,1-bis-2-naphthol. The melting point was
therefore measured and found to be 184℃- 190℃.Theorically, the melting point of
1,1-bis-2-naphthol is 205℃- 211℃, (Rosini et al,2005). The deviation in the
experimental melting point from the theoretical might be due to the presence of the
reactions by- products FeCl2 and HCl which could not be washed away with boiled
water and dried off the required product These contributions are therefore as well
considered the errors encountered during the experiment not forgetting the unstable
readings that gave the researcher a hard time to take the required masses of the
product. It is therefore recommended to improve the experiment by taking mass
measurements in a well closed room for easy attainment of mass readings as the
analytical balance is atmospheric pressure sensitive. Also, much care and attention
should be put into practice while filtration and recrystallisation to prevent much loss
of the product.
5|Page

6. CONCLUSION
The experiment was successfully carried, radical coupling reaction was carried and in
the process 2- Naphthol was reacted with iron (III) chloride to synthesis 1,1-bis-2-
naphol. The percentage yield of this product was calculated as 81.22% and the
melting point measured was 184℃- 190℃. The purpose of calculating the percentage
purity and measuring the melting point was to determine the purity of the product.

7. REFERENCES
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.

ANWERS TO QUESTIONS
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 also 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.
6|Page