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The Complete Report of Organic Chemistry I with title “Synthesis of

Nitrobenzene” Was made by:
name : Hasrilia Beskara
ID : 1713441008
group : V (five)
class : ICP of Chemistry Education
After checked and consulted by assistant and assistant coordinator, so this report
was accepted
Makassar, May 2018
Assistant Coordinator, Assistant,

Imranah, S.Pd Anugrah Alam

Known by
Reaponsibility Lecturer,

Hardin S.Si, S.Pd, M.Pd

ID 19870807 2015 04 1 004
A. TITLE OF EXPERIMENT
Synthesis of Nitrobenzene
B. OBJECTIVE OF EXPERIMENT
At the last of this practicum, college student could knows about this:
1. How to prepare and use the tools that need in preparation organic
compound of liquid such as reflux, the reaction solvent, using separation
funnel, drying filtration and distillation.
2. Principle of electrophilic aromatic substitution.
3. Difference typical between the reaction of aliphatic and aromatic
compounds.
C. LITERATURE REVIEW
Functional groups can be classed as aliphatic or aromatic. An aliphatic
functional group is one where there is no aromatic ring directly attached to the
functional group. An aromatic functional group is one where an aromatic ring is
directly attached to the functional group. There is one complication involving
esters and amides. The aromatic ring must be attached to the carbonyl side of the
functional group. These functional groups are defined as aromatic or aliphatic
depending on whether the aryl group is directly attached to the carbonyl end of the
functional group. There is one complication involving esters and amides. These
functional groups are defined as aromatic or aliphatic depending on whether the
aryl group is directly attached to the carbonyl end of the functional group, that is,
Ar–CO–X. If the aromatic ring is attached to the heteroatom instead, then the ester
or amide is classed as an aliphatic amide (Patrick, 2005: 29).
Organic chemistry has two main divisions. One division deals with aliphatic
(fatty) compounds. Methane is a typical example of this type of compound. The
second division includes the aromatic (fragrant) compounds, of which benzene is
a typical example. Compounds in the two groups differ in a number of ways. The
two differ chemically in that the aliphatic undergo free-radical substitution
reactions and the aromatic undergo ionic substitution reactions. In this chapter you
examine the basics of both aromatic and heterocyclic aromatic compounds,
concentrating on benzene and related compounds (Moore, 2011: 94).
One type of reaction that can involve aromatic systems is an electrophilic
substitution reaction. Like the substitution reactions you learned in your first
semester of Organic Chemistry, this process involves the substitution of
something for a hydrogen atom. In this reaction, a nucleophile (the aromatic
system) attacks the electrophile. The stability of the aromatic system makes it a
poor nucleophile, though, so a very strong electrophile is needed to force the
reaction to occur. For example, the electrophile bromine (Br2) is strong enough to
attack the double bond in an alkene, but it’s not strong enough to attack an
aromatic system. However, the Br+ ion works because it’s a much stronger
electrophile (Moore, 2011: 94).
The most common reaction of aromatic compounds is electrophilic aromatic
substitution, a process in which an electrophile (E+) reacts with an aromatic ring
and substitutes for one of the hydrogens. Many different substituents can be
introduced onto the aromatic ring by electrophilic substitution. To list some
possibilities, an aromatic ring can be substituted by a halogen (-Cl, -Br, -I), a nitro
group (-NO2), a sulfonic acid group (-SO3H), an alkyl group (-R), or an acyl group
(-COR). Starting from only a few simple materials, it’s possible to prepare many
thousands of substituted aromatic compounds. Monosubstituted benzenes are
systematically named in the same manner as other hydrocarbons, with -benzene as
the parent name. Thus, C6H5Br is bromobenzene, C6H5NO2 is nitrobenzene, and
C6H5CH2CH3 is ethylbenzene. The name phenyl, pronounced fenil and sometimes
abbreviated as Ph, is used for the -C6H5 unit when the benzene ring is considered
as a substituent. In addition, a generalized aromatic substituent is called an aryl
group, abbreviated as Ar, and the name benzyl is used for the C6H5CH2-group

(McMurry, 2011: 157-160).

In this section we use benzene as a typical aromatic compound to study three
basic reactions: halogenation, sulfonation, and nitration. In the case of
halogenations, the electrophile is the X+ ion (X = Cl or Br). In sulfonation and
nitration, the electrophiles are SO3 and NO2+, respectively. In each case, part of
the mechanism involves the generation of the electrophile (Moore, 2011: 95).
According to Patrick (2005: 145-146) nitration are electrophilic substitutions
which involve strong nitration electrophiles and do not need the presence of a
Lewis acid. In nitration, sulfuric acid serves as an acid catalyst for the formation
of a nitronium ion (NO2+) which is generated from nitric acid by a very similar
mechanism to that used in the generation of sulfur trioxide from sulfuric acid. The
mechanism for the nitration of benzene is very similar to sulfonation. As the
aromatic ring forms a bond to the electrophilic nitrogen atom, a π bond between N
and O breaks and both electrons move onto the oxygen atom. Unlike sulfonation,
this oxygen keeps its negative charge and does not pick up a proton. This is
because it acts as a counterion to the neighboring positive charge on nitrogen.

The potential energy surface for addition of NO2+ to benzene is rather

complex. When unsymmetrical aromatic systems are considered, this complexity
becomes even greater as compared to the symmetric benzene molecule. A wide
set of minimum energy structures may be located, from which at least three are of
primary relevance to the nitration mechanism. The first minimum is a weak π
complex that represents a preorganized weakly bonded state, where low energy,
nonspecific, and attractive interaction between NO2+ and the aromatic π system
as a whole occurs. Ring substituents should have therefore strong effects on the
relative stability of the relevant intermediates. A major substituent effect is on the
energy and structure of the unoriented π complex. For benzene (the parent
aromatic compound), NO2+ is found to lay in the axis normal to the molecular
plane of the aromatic ring (Queiroz et al, 2006: 6194-6195)
The generation of the electrophile for a nitration reaction begins with the
reaction of nitric acid with sulfuric acid. Even though nitric acid is a strong acid,
it’s weaker than sulfuric acid and therefore more baselike, so nitric acid acts as a
base and donates an OH–. This process forms the nitronium ion (NO2+) and water
(H+ from the sulfuric acid and OH– from the nitric acid). Nitroaromatic
compounds are useful in synthesis because converting the nitro (-NO2) group to
an amino (-NH2) group is relatively easy. For example, the reaction of
nitrobenzene with acidic tin(II) chloride (SnCl2) converts nitrobenzene to aniline,
an important industrial chemical used in the production of medicines, plastics, and
dyes, to name but a few (Moore, 2011: 96-97).
Aromatic rings are nitrated by reaction with a mixture of concentrated nitric
and sulfuric acids. The electrophile is the nitronium ion, NO2+, which is formed
from HNO3 by protonation and loss of water and which reacts with benzene in
much the same way Br+ does. Aromatic nitration does not occur in nature but is
particularly important because the nitro-substituted product can be reduced by
reagents such as iron, tin, or SnCl2 to yield an amino-substituted product, or
arylamine, ArNH2. Attachment of an amino group to an aromatic ring by the two-
step nitration/reduction sequence is a key part of the industrial synthesis of many
dyes and pharmaceutical agents

(McMurry, 2011: 163).

The ratio of very mixed acids effect on deep nitrogen content product, where
H2SO4 is other than as a catalyst as well as a functioning dehydrating agent as the
water binder formed in the reaction nitration. At the moment the number of H2SO4
is small then the more water that is not bound so it will inhibit substitution of OH
group by NO2 group. Conversely, if the amount of H2SO4 the greater the H2SO4 as
the catalyst can be decrease the activation energy directly can accelerate the rate
of reaction, so the levels nitrogen will be higher up optimum comparison is
achieved if H2SO4 is excessive then H2SO4 will destabilize some of the cellulose
so that the reacting cellulose becomes more small, as well as the greater the
amount of HNO3 then the reaction will shift in the direction product formation.
Than the type of acid in a mixed acidvery different to nitrogen levels in the
product. The greater the number of H2SO4 Then the higher nitrogen content up 1:
4 ratio, it shows that H2SO4 other than as a catalyst which can decrease the
activation energy such that speed up the reaction rate. Besides H2SO4 as well as a
functioning dehydrating agent as a water binder formed during nitration process in
which the OH group is on cellulose substituted with NO2 groups. Comparison of
HNO3 in mixed acid very influential on nitrogen levels. Once the optimum
conditions are reached lower comparison of HNO3 to H2SO4, levels nitrogen is
getting smaller (Purnawan, 2010: 32-33).
 BIBLIOGRAPHY

McMurry John. 2010. Fundamental of Organic Chemistry. United States: Prentice

Hall.

Moore John T. and Langley Richard H. 2010. Organic Chemistry II for Dummies.
Canada: Wiley Publishing, Inc.

Patrick G. L. 2005. Instant Note Organic Chemistry 2nd Edition. United States:
BIOS Scientific Publisher.

Purnawan. 2010. Optimasi Proses Nitrasi pada Pembuatan Nitro Selulosa dari
Serat Limbah Industri Sagu. Yogyakarta: Jurusan Teknik Lingkungan,
Fakultas Sains dan Terapan Institut Sains dan Teknologi AKPRIND.

Queiroz Freire de Jorge, et al. 2006. Electrophilic Aromatic Nitration:

Understanding Its Mechanism and Substituent Effects. United States:
American Chemical Society Published.