Organic Chemistry Laboratory Formal Report

CHEMISTR
Synthesis of 3-nitrobenzaldehyde Y

using nitration reaction to 20

benzaldehyde 2L
Dave Gabriel E. Cadungog*, Ronald Roie Bernadas, Chesler Ramirez,
Patrick Malcolm Santos
Department of Chemistry, College of Science

*Corresponding author; e-mail: Cadungogdave@yahoo.com

Abstract

In this experiment, the researchers wanted to synthesize 3-

nitrobenzaldehyde. 0.85 mol conc. H2SO4 and 0.475 mol HNO3 was used to
produce the nitronium ion which is the electrophile. This experiment used
an aromatic substitution reaction using an electrophile, particularly
nitration process. The synthesis reaction produced 3.0652 g 3-
nitrobenzaldehyde with a percent yield of 40.6%.

Keywords: Electrophilic addition, Nitration, Synthesis, Aromatic compound

Introduction

A lot of derivatives of benzene were originally isolated from the fragrant balsams

obtained from trees and plants. These compounds were described as aromatic due to

its pleasant odors. However, it was discovered that many derivatives of benzene are

odorless. Yet, they are still called aromatic to describe all derivatives of benzene

regardless of their fragrance (Solomons, et al., 2014)

Electrophilic aromatic substitution reaction is a reaction where one of the

aromatic protons is replaced by an electrophile where the aromatic moiety is preserved.

Examples of this are bromination, chlorination, nitration, sulfonation/desulfonation,

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 Organic Chemistry Laboratory Formal Report

Friedel-Crafts alkylation and acylation, reduction, benzylic formation, oxidation, and

Clemmensen reduction (Klein, 2012).

Nitration happens when benzene is treated with a mixture of nitric acid and

sulfuric acid which results to formation of nitrobenzene. It can also be done by using

HNO3 alone, or a mixture with organic acids like sulfuric acid, selenic acid, or acetic

anhydride (Norman and Taylor, 1965). This reaction proceeds via an electrophilic

aromatic substitution where nitronium ion is formed and believed to be the electrophile.

This electrophile forms when the acid-base reaction between HNO 3 and H2SO4

happens. The nitric acid in this situation, must be completely ionized into the nitronium

ion. The figure 1 below represents the nitration reaction to produce a nitrobenze using

the reagents needed.

Figure 1

In this experiment, the objective is to synthesize a compound which is 3-

nitrobenzaldehyde. It was done by doing the said type of reaction above. Figure 2

shows the structure of the said compound. It can be seen that the compound contains

an aldehyde, phenyl group and a nitronium ion.

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Figure 2

Experimental methodology

A 45 mL of concentrated H2SO4 was filled on a 50 mL flask. 45 mL of fuming HNO 3 was

carefully added while stirring and cooling with an ice bath. Temperature of the mixture

did not exceed 10OC. 5.3 g of benzaldehyde was added in the mixture and the

temperature was kept constant at 15 OC for about 1 hour. Ice bath was removed and the

reaction mixture was stored overnight in room temperature. On a 500 mL beaker, the

reaction mixture was poured with 250 g crushed ice. The yellow precipitate formed was

sucked off over a Buchner funnel and washed with 100 mL cold water. It was then

dissolved in 65 mL diethyl ether and then shaken out with 65 mL of 5% NaHCO 3

solution. The organic phase was dried over sodium sulfate, filtered and solvent was

subjected to rotary evaporator. Amount of 3-nitrobenzaldehyde produced was measured

and percent yield was calculated.

Results and discussion

In the experiment, the mixture of the concentrated sulfuric acid and nitric acid is
necessary to produce the nitronium ion which will react with the benzene resulting to a
nitrobenzene. Instead of using pure benzene, benzaldehyde was used instead to get
the wanted compound.

The reaction mixture used crushed ice for the resulting product to precipitate and
be collected. Since the compound being synthesized is insoluble to water, water was

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used to collect it. Then, the crude was dissolved in diethyl ether and 5% NaHCO 3 was
added. The addition of 5% NaHCO 3 was done so the excess acids in the reaction which
were not used will be dissolved by it. It might affect the yield of synthesis if the excess
acids will not be removed. The organic phase then was dried over sodium sulfate. In
this experiment, instead of using sodium sulfate, magnesium sulfate was used instead.
This procedure will remove excess water in the product.

The table below shows the result of the experiment. It can be seen that the
synthesis of 3-nitrobenzaldehyde produced only 3.0652g. The theoretical yield which is
7.55g was calculated using stoichiometry and the values or amount of reactants used
resulting to the production of the said compound.

Mass of Beaker 65.2992

Mass of Beaker with Sample 62.2340
Theoretical Yield 7.55 g
Experimental Yield 3.0652
Percent Yield 40.6%
The overall reaction has a percent yield of 40.6%. It was calculated using the

Experimental Yield
100
theoretical and experimental yield value using the equation Theoretical Yield .

A total of 3.0652 g 3-nitrobenzaldehyde was synthesized in this experiment. This

leads to a 40.6% yield of the desired compound. One of the things that may affect the

yield is the preparation of the nitration mixture. The temperature might not be

maintained below 10OC.

References

Fryhle, C.; Snyder, S.; Solomons, G. Organic Chemistry 11th Edition. John Wiley & Sons
Singapore Pte. Ltd.: Asia. 2014; p.674

Klein, D. Organic Chemistry 2nd Edition. John Wiley & Sons, Inc.: USA. 2012; pp. 882-
884

Norman, R.; Taylor, R. Electrophilic Substitution in Benzenoid Compounds; Elsevier

Publishing Company: Netherlands, 1965; p. 61, 64