PREPARATION ACÉTANILIDE

Jonathan R. Cuellar 20131150034

Juan Camilo Figueroa Galindo 20142150081
Juan Sebastián Romero 20141150077
Francisco Jose de Caldas University
Faculty of Science and Education, Degree in Chemistry

1. SUMMARY:
This practice was made with the purpose to synthesize of phenylacetamide or acetanilide was by
acetylation method; the synthesis was carried out in the middle of acetic acid, which acted as a catalyst
for the reaction between the acetic anhydride and aniline, synthesis took place through a Nucleophilic
addition mechanism. Amide formation occurred in a series of important steps (effect of acid medium,
Nucleophilic attack, deprotonation) by this reason it was essential to maintain the conditions of
acidity, temperature (atmosphere and ice bath), agitation, elimination and reflux (10 minutes); finally
retrieved compound is recrysallisation and determined the melting point as a criterion for purity,
yielding a value of (85°C and 105°C) without and with recrystallisation respectively , and an infrared
analysis allowed to corroborate his most important bands, possibly indicating their respective
synthesis.
Keywords: nucleophile, electrophile, amines, amides.

1. INTRODUCTION:
Amines are organic ammonia derivatives
Considered to alcohols and ethers similarly
Considered are organic derivatives of water,
amines Having a nitrogen atom With an
electron pair unbound, This causes the basic
and nucleophilic amines be. Most of the
chemistry of the amine depends on the
unbound electron pair.(McMurry, 2008)
Amines are widely found in nature, mainly in
living organisms, tissues Such as animals,
nicotine and cocaine are examples of snuff
amines, amino acids are the additional
structural basis of all proteins.(McMurry,
2008)
Fig. 1. Structure of nicotine.
Secondary and tertiary amines May be
alkylated by primary reaction with an alkyl
halide primary, these reactions are difficult to
check and give Mixtures of products usually,
unlike tertiary amines are rented to give
quaternary ammonium salts. Primary and
secondary amines can be acylated by a Also
nucleophilic substitution reaction in the acyl
group With an acid chloride or an acid
anhydride to produce an amide. (McMurry,
2008)

Fig. 2. Reaction of Obtaining an amide, in a
common case esta drug acetaminophen.
2. METHODOLOGY:
Reduction of nitrobenzene.
It took 30 mmoles of nitrobenzene and 65
mmoles of mossy tin in a 250 mL round
bottom flask, securely clamped above a stir
motor. Place a Claisen adaptor on top of the
flask; put a water-cooled condenser on one
outlet of the Claisen and a separatory funnel
on the other. Add a spin bar to the flask and
turn on the stir motor. Place 15 mL of
concentrated HCl in the separatory funnel.
Add the HCl to the nitrobenzene/tin mixture a
few mLs at a time. After each addition,
monitor the flask so that it does not get too hot;
if necessary, immerse the reaction flask briefly
in a cold water bath. After the initial reaction
has subsided, add another portion of the acid.
Again, control the temperature of the reaction
in a cold water bath. Continue until all of the
HCl has been added. After all of the acid has
been added let the mixture stir at room
temperature for about 10 min. Remove the
separatory funnel (and rinse it) and place a
ground glass stopper on the open Claisen
outlet (the other outlet still has the water-
cooled condenser). Place a heating mantle
under the reaction mixture and heat and stir for
20 min. Test to see if the reaction has gone to
completion by testing for unreacted
nitrobenzene (below). If nitrobenzene
remains, heat and stir for an additional 10 min
and test again. Test for unreacted
nitrobenzene: Put a few drops of the reaction
mixture in a small amount of water in a test
tube; a clear solution (no oily drops) indicates
that there is no nitrobenzene present. When the
reaction is complete, cool the reaction flask to
room temperature. While stirring, carefully
add 18 mL of 50% NaOH through the Claisen
adaptor. This reaction is exothermic, so have a
cool water bath (not an ice bath) ready in case
the flask gets too warm. The mixture must be
strongly alkaline to ensure complete liberation
of the aniline .Dilute the reaction mixture with
40 mL of water and then steam the heat source.
Collect the distillate in a 100 mL graduated
cylinder: the first 18 mL or so of distillate
should be quite cloudy because you are
distilling over a mixture of aniline and water.
Once the distillate ceases to be turbid, collect
an additional 4 mL. Transfer the entire volume
of distillate to an Erlenmeyer (do not stopper
the flask until the solution is cool!) and save
for use in the acetylation step. Place the pot
residue in the Aqueous Waste carboy in the
main hood.
Preparation of acetanilide.
Dilute the distillate from the previous step with
water to a volume of 65 ml final. Add a spin
bar and place it over a stir motor. Add 2 mL of
Concentrated hydrochloric 5 acid and stir to
homogeneous solution obtener. Dissolve 4, 5
g of sodium acetate trihydrate in 10 mL of
water in a beaker. Measure 3, 5 mL of acetic
anhydride into a graduated cylinder. Warm the
solution of aniline / hydrochloric acid to 50˚C
on a steam bath, add the acetic anhydride, stir,
and add the sodium acetate then a solution all
at once With stirring. Remove the heat source;
Should a white solid begin to precipitate.
Continue to stir the mixture for 20 min Then
cool it in an ice bath to complete
crystallization. Isolate the product by suction
filtration, wash it with cold water, and allow it
to dry.
3. RESULTS AND ANALYSIS:
Melting point before 85 ° C
recrystallizing
Melting point after 108 ° C
recrystallization
Table 1. Data Obtained in the synthesis.
 The reduction of the nitrobenzene can occur by In the second step the electron pair of the
several mechanisms, hydrochloric acid and nitrogen attacks the carbon positively charged
iron is used, this reaction happens while the and binds to this, then the electron of oxygen
necessary hydrogen comes from the water and regenerates the carbon double bond and
the iron passes to Fe3O4-, when the reaction is releases the link with the other oxygen
finished it is necessary to neutralize and stabilized acetate ion form. (McMurry, 2008)
remove the aniline so that it does not A second
product is obtained. It is important that
whenever aniline is synthesized by reduction
of nitrobenzene a neutralization is carried out,
and that the reaction can undergo condition
and different products, in addition the aniline
can react with the medium and give new
products.
Fig. 5. Attack positively charged nitrogen
The reduction reaction can also be given by
carbon.
using tin, which with the nitrobenzene in acid
medium, give the amine product as a
hydrochloride. This reaction occurs by
catalytic hydrogenation of the nitro group, or
reduction thereof. In this reduction the tin state
(0) is oxidized to tin (IV) and the nitrogen is
reduced, the tin (II) chloride likewise reduces
a nitro group, and in the end the amine is found Fig. 6. Formation of the double bond with
as hydrochloride, which in Presence of a oxygen and breaking the link with the other
strong base, releases the aniline. (McMurry, oxygen.
2008)
After that the acetate ion attacks one of the
hydrogen’s bonded to nitrogen is breaking the
link and thus recovering its nitrogen electron
pair and forming the acetic acid as a
byproduct.

Fig. 3. Reaction to obtain aniline.

The reaction mechanism for obtaining
acetanilide is given first by the formation of a
negative charge on one of the oxygens with
double bond anhydride resonance breaks the Fig. 7. Acetate attack one of the hydrogen’s of
double bond and thus the carbon becomes nitrogen.
positively charged as follows:

Fig. 8. Formation of acetanilide and acetic

acid.
Fig. 4. Breaking of the pi link by resonance.
The melting point before recrystallization was
85 ° C, quite apart from pure acetanilide which
is 114 ° C, thus in a first step can be said that
the obtained crystals had a considerable
amount of impurities, this supported the color
crystals taking as an additional factor as these
had a light yellow-green what we could
indicate the presence of aniline, after making
the re crystallization from hexane cycle
melting point was 108 ° C which indicates that
much of the impurities have been removed and
the crystals obtained white have a high purity
level.
Then the IR spectrum found in databases is
presented:
Fig. 8. IR spectrum consulted acetanilide.
The band in the region 3294 cm-1 indicates the
voltages N- H of an amino group, the band in
the region of 1665 cm-1 indicates the presence
of the carbonyl group, in the region of 1436
cm-1se has a characteristic band CH3 voltage
of the band of 754 cm-1 indicates a mono
substitution, the band 1324 cm-1 corresponds
to the voltage CH3. According to the
molecular formula, it acetanilide like structure
that complies with the characteristics that casts
the infrared spectrum is proposed.
Fig. 9. IR spectrum consulted for aniline.
In the spectrum can be observed two bands of
high intensity between 3300 and 3400
indicating the presence of primary amine, a
band of medium intensity above 3000
indicates sp2 hybridized, a doublet at l600
indicating the C = C band of 1500 high
intensity indicating tension CH and finally a
set of bands below 1000 indicating a mono
substitution on the benzene ring.
4. CONCLUSIONS:
- Synthesis was achieved an amide
from an amine and an anhydride by
nucleophilic addition mechanism.
- Reflux keeps the temperature
conditions in the reaction volume and
to ensure that the two contact
substances react in as much as
possible.
- The IR spectrum is a very useful tool
that allows us to corroborate the
compound obtained in addition to the
tests such as boiling or melting point
that are used as purity criteria.
- The re-crystallization allows the
impurities that are soluble to be
removed from the compound
therefore it turns out to be a quite
useful method to purify solid
compounds.
 - Bibliography

McMurry, J. (2008). Química Orgánica .

Belmont: Cengage Learning .

Morrison, B. (1987). Quimica organica .

Boston : Pearson .