Nitration of bromobenzene

Dr.Galina Melman
Ledina Banushllari
04/02/2024

Introduction:
Nitration of bromobenzene occurs under acidic conditions where a concentrated mixture of
sulfuric and nitric acid allows attachment of the nitro group on the ring. In this experiment the
Lewis base, bromobenzene, attacks the Lewis acid, nitronium ion and it forms a sigma complex.
This is the rate determining step of the reaction. Here, bromobenzene serves as the
nucleophile, while nitronium ion serves as the electrophile. A base such as water or bisulfate will
deprotonate the complex and produce three different products due to the presence of the
bromine atom on the ring, while the nitro group will attach ortho, para or meta on the ring. In this
reaction, bromobenzene serves as the nucleophile while the nitro group is the electrophile.

Source: Experimental Organic Chemistry

Source: Experimental Organic Chemistry

Source: Experimental Organic Chemistry

Depending on where the nitro group attaches, the activation enthalpies will also change. When
NO2 attaches at the ortho and para position, the activation enthalpies are lower than in meta
position due to the stability of the ortho and para attachment. The free electrons of the bromine
atom increase the stability of the benzene ring when the NO2 is attached in ortho and meta
position and bromine is considered an ortho-para director because it favors formation of these
isomers. The desired nitration ratio is found to be 100:1 and on a purely statistical basis the ratio
is predicted to be 2:1. When bromine forms a positive ion, the nitro group attaches to ortho and
para position.

Materials and methods:

Refer to the attached pages.

Data and observations:

When bromobenzene was added in the mixture of the acids, the mixture turned a little bit
yellowish and some precipitate in the form of small solid “crumbs” formed, which looked like
butter. When hot ethanol was added, the product fully dissolved and the crystals formed looked
like white powder, not fully dried.
Mass of the product from the first crop was 7.74 g and from the second crop it was 4.28 g. The
melting temperature of the product obtained was 117-118 C which shows that the addition could
be in position 4.

Discussion:
Activating groups increase the rate of an electrophilic aromatic substitution reaction relative to
hydrogen, while deactivating groups decrease the rate. Halogens, in this reaction Bromine,
behave as deactivators due to the stronger electron withdrawing effect and weaker electron
donating resonance effect. In a monosubstituted benzene ring, one of the positions of the ring
has been substituted with another atom or group of atoms. Due to 2 equivalent ortho sites, 2
equivalent meta sites and one para site, three constitutional isomers can be formed (40% ortho,
40% meta and 20% para). In this reaction, 2-bromonitrobenzene and 4-bromonitrobenzene are
obtained.
The nitro group in the benzene ring is an electron withdrawing group which causes weakening
of the C-Br bond, which makes it easier to replace the Br group. Since the NO2 group is a
highly-electron withdrawing group, it withdraws electron density from the ring and makes the
ring less nucleophilic.
The reaction must be maintained at a temperature between 30-35 C in order to avoid dinitration.
By controlling the temperature, suppression of dinitration can be achieved due to deactivating
nitro substituents. If di-nitration product is obtained, the second nitro group will be attached in
position 6 and the product formed would be 1-Bromo-2,6-dinitrobenzene. Isolating
4-bromonitrobenzene from 2-bromonitrobenzene can be performed based on the polarities of
the two compounds by using hot ethanol. At room temperature, 2-bromonitrobenzene is very
soluble while 4-bromonitrobenzene is slightly soluble. This difference allows isolation of the less
soluble product in the first crop and the more soluble product in the second crop of
recrystallization from ethanol.
The melting temperature range obtained was 117-118C which indicates isolation of
4-bromonitrobenzene. The temperature varies by a few degrees from the accepted value
(125C) which indicates some impurities still present or maybe crystals from
2-bromonitrobenzene since this last one has a lower melting point.

Conclusions:

Electrophilic aromatic substitution (EAS) is a powerful tool in organic synthesis to construct

substituted aromatic compounds. This method involves substitution of an atom or group of
atoms on an aromatic ring with an electrophile. Some common uses of EAS include introduction
of functional groups, building blocks for more complex molecules, medicinal chemistry, dye
synthesis, natural product synthesis, materials science etc.