Experiment 3

CHEM 613
Experimental Organic Chemistry
2013
Anastazija Ristovska

Post-Lab
Nitrating Aromatic Compounds

The purpose of this experiment was to obtain o-nitroaniline and p-nitroaniline by

preparing acetanilide, adding sulfuric acid to it in order to prepare it for a nitro-group addition,
and then adding nitric acid which gives the final desired product.
The benzene ring of aniline is strongly activated by the amino group (an electron-donor
froup) allowing for easy dinitration. In order to achieve mononitration we need to decrease the
NH2 activity by acetylation of the amine. The acetyl group, which acts as a protective group, is
subsequently removed by acid hydrolysis. The speed of reaction is determined by the act of
nitronium ion attacking the aromatic ring. We chose to perform our aniline nitration reaction is a
mixture of concentrated nitric and sulfuric acids, but it can also be performed in a mixture of
nitric acid in glacial acetic acid or simply concentrated nitric acid. In the nitration mixture the
electrophile is the nitronium ion formed when the nitric acid is protonated by the sulfuric acid,
and then an H2O molecule leaves from the protonated nitric acid, leaving behind an NO2+ ion.
This nitronium ion attacks the benzene ring, slowly or fast depending on how
deactivated or activated the benzene ring is. Once attached to the benzene ring, it shares a
carbon atom together with a hydrogen atom, but then the hydrogen atom leaves, most likely
pulled out of the intermediate by the deprotonated sulfuric acid anion. Since the amino group
activates the benzene ring in the ortho and para positions, these are the positions protonation is
most likely to occur. Percentagewise the para nitration product predominated based on our
rough melting-point analysis estimates of the final product. The acetanilide reagent was prepared
by the TAs and we used a ready product. As already stated, the acetyl group was only added as a
protective measure against dinitration by decreasing the reactivity of the benzene ring, and was
removed in the end. 2.70g acetanilide was used and the expected theoretical yield of nitroaniline
was 2.759g. The actual yielded amount was 0.70g, giving a percent yield of 25.37%.
The experimental procedure consisted of adding 2.70g acetanilide (pre-prepared by the
TAs) and 4.5ml 96% concentrated sulfuric acid to an Erlenmeyer flask, swirling it till dissolved,
and placed in an ice bath. We mixed 4.5ml 96% sulfuric acid with 1.5ml 65% nitric acid, and
started adding this mixture very slowly to the acetanilide solution, 0.5ml at a time. Since the
reaction was exothermic and the Erlenmeyer flask tended to overheat, the flask was kept in the
ice bath for most of the acid addition. At one point the solution in the flask turned solid, and in
1

order to bring it to liquid state it was placed on the bench at room temperature. Eventually 25 ml
ice-col water was added to the Erlenmeyer flask. A strong yellow precipitate formed. The flask
was placed on a heat plate and was brought to boiling. The yellow precipitate dissolved and the
solution turned translucent, but soon afterwards, as the yellow slur was disappearing a dark red
liquid began appearing underneath. When all yellow precipitate has vanished, the flask was
cooled on the bench. Next 25ml 25% ammonium hydroxide was added in portions and during
these additions mostly yellow, but also brown/red/etc. precipitate was forming in a vigorous
exothermic reaction with the similitude of boiling. The precipitate was isolated by vacuum
filtering. The isolated crystals were washed using 95% ethanol through recrystallization.

50

697
632
753
840

1182

1505

3362

30

999

1135

3482

Transmittance

1395

3220
3242

40

1446
1113

1481 1471

1588
1598
1632

20

1297

4000

3000

2000

1000

Wav enumber (cm-1)

Figure 1: 4-Nitroaniline FTIR (KBr) Spectrum Obtained in Our Labs

At 1297cm-1 (in the 1250-1335cm-1 range) there is an aromatic amine stretch,
accompanied by an N-H primary amine wag between 632cm-1 and 840cm-1. The 3362cm-1 stretch
comes from the primary amine N-H symmetric bond vibrations and it is the longest stretch in
the non-fingerprint region. The stretch at 1297cm-1 can as well be described as a symmetric N-O
stretch. The stretches between 1446cm-1 and 1505cm-1, as well as those between 1588cm-1 and
1632cm-1 are all in-ring aromatic C-C stretches. Perhaps the stretches around 1481cm-1 can also
be characterized as an N-O asymmetric vibration stretch. Theres a very short aromatic C-H
stretch in the 3000-3100cm-1 area. In all primary aromatic amines, the N-H stretching frequencies
occur in the 3300-3500cm-1 range. The 3482cm-1 stretch is caused by the N-H asymmetric
vibrations.

65

100
O

138
O

NH2

50

14

10
20
(mainlib) p-Nitroaniline

27

30
32
30

44

71 74

57
50

80

63

52

41

40

108

92

39

60

70

86
80

122

105
90

100

110

120

130

140

150

Figure 2: 4-Nitroaniline Mass Spectrum (from lab)

The molecular weight peak is given at m/z=138, the peak at m/z=92 represents the
molecular charged fragment of just aniline without the nitro group, theres a small peak at
m/z=122 for the charged molecular fragment of nitrobenzene without the amine functional
group. The peak at m/z must represent nothing other than a C-C-NH fragment resulting from
the breaking up of the benzene ring. The largest peak, that at m/z=65, can most likely be
resolved by supposing that it likewise resulted from fragmenting the benzene ring, i.e. of a
fragment C-NH-C-CH-CH of +1 charge. The m/z=80 peak must be representing that fragment
of the benzene ring after the entire (neutral) -C-NO2 group has been removed. The m/z=108
peak represents that fragment that occurs when the C-NH2 group is removed from the
compound.

Figure 3: 4-Nitroaniline IR (KBr) Spectrum (obtained from literature)

The activated or deactivated reactivity state of monosubstituted benzenes as a function

of the type of substituent can be theoretically quantized by calculating the energy of HOMO
orbitals that are an indicator of the electrophilic substitution ability. We are interested in learning
why aniline is activated.
The energy of the HOMO of aniline is -8.155 eV.
The energy of HOMO of benzene is -10.079 eV.
The difference between the two values is (-10.079 eV) - (-8.155 eV) = -1.924 eV. The
difference is smaller than zero, and therefore aniline is activated, i.e. adding the NH2 amino
group activated the benzene ring in the ortho-para positions.
All calculations and molecular modeling were done using HyperChem 8.04.

Figure 2: Aniline Structural Formula and 3D geometry

Figure 3: Plot of HOMO of Aniline, Energy = -8.155 eV

Plot of HOMO of Benzene, Energy = -10.079 eV