APPROVAL SHEET

The complete report of Organic Chemistry II Experiment with the title

“Synthesis of Acetanilide” was made by:
Name : Helny Lydarisbo
ID : 1513442002
Class : Chemistry Education of ICP
Group : II
After checked and consulted by Assistant and Assistant Coordinator, so this report
was accepted.

Makassar, November 2016

Assistant Coordinator Assistant

Rizwan Dwi Antoro Arnan Arkhilaus

Known by,
Responsibility Lecturer

Iwan Dini S.Si, M.Si

ID. 19720317 2005501 2 002
A. TITLE OF EXPERIMENT
Synthesis of Acetanilide

B. OBJECTIVE OF EXPERIMENT
In the end of experiment, the apprentice should be understood about:
1. Skilled arrange and use the tools in synthesis of organic substance.
2. Explain the high refining technique.
3. Explain basic principle of chemistry in amine compound.

C. LITERATURE REVIEW
Amines are considered derivatives of ammonia (NH3), in which one or
more hydrogen atoms attached to the nitrogen atom are replaced with alkyl or
aromatic groups. In methylamine, a methyl group replaces one hydrogen atom in
ammonia. The bonding of two methyl groups gives dimethylamine, and the
three methyl groups in trimethylamine replace all the hydrogen atoms in
ammonia (Timberlake, 2012: 495).
Amines and amides can be defined as being primary, secondary, tertiary,
or quaternary depending on the number of bonds from nitrogen to carbon (picture
1). Note that a quaternary amine is positively charged and is therefore called a
quaternary ammonium ion. Note also that it is not possible to get a quaternary
amide.

Picture 1. (a). Amines; (b). Amides

(Patrick, 2004: 44).
 Amides with an unsubstituted –NH2 group are named by replacing th –oic
acid or –ic acid ending with –amide, or by replacing the –carboxylic acid ending
with –carboxamide.

Acetamide Hexanamide Cyclopentane-

Carboxamide
If the nitrogen atom is further substituted, the compound is named by first
identifying the substituent groups and then the parent amide.the substituents are
preceded by the letter N to identify them as being direcly attached to nitrogen.

(McMurry, 2008: 787).

Because amines contain a polar N-H bond, they form hydrogen bonds with water.
In primary (1°) amines, -NH2 can form more hydrogen bonds than the secondary
(2°) amines. A tertiary (3°) amine, which has no hydrogen on the nitrogen atom,
can form only hydrogen bonds with water from the N atom in the amine to the H
of a water molecule. The aromatic amines use the name aniline. Alkyl groups
attached to the nitrogen of aniline are named with the prefix N- followed by the
alkyl name.

Like alcohols, the smaller amines, including tertiary ones, are soluble because
they form hydrogen bonds with water. However, in amines with more than six
carbon atoms, the effect of hydrogen bonding is diminished. Then the
nonpolar hydrocarbon chains of the amine decreases its solubility in
water (Timberlake, 2012: 498).
Acetic acid is a bulk chemical which is produced today in an amount
exceeding 10 million tons per year world wide. It is one of the most used organic
acids in the chemical industry. The largest consumption of acetic acid is for the
production of vinyl acetate which is a monomer building block. About 33% of the
world production of acetic acid in 2008 was used for the manufacture of vinyl
acetate. Acetic acid is furthermore employed in the synthesis of cellulose acetate,
which is used to produce acetate fibres. Finally, acetic acid also finds application
as food additives due to its role as acidity regulator (Lomate, 2015: 1).
Aromatic amines such as aniline undergo electrophilic substitution
reactions where the amino group acts as a strongly activating group, directing
substitution to the ortho and para positions. Like phenols, the amino group is such
a strong activating group that more than one substitution may take place. For
example, reaction of aniline with bromine results in a tribrominated structure as
the only product. This problem can be overcome by converting the amine to a less
activating group. Typically, this involves acylating the group to produce an amide.
This group is a weaker activating group and so mono-substitution takes place.
Furthermore, since the amide group is bulkier than the original amino group, there
is more of a preference for para substitution over ortho substitution. Once the
reaction has been carried out, the amide can be hydrolyzed back to the amino
group.

(Patrick, 2004: 308).

Acetanilide is a white solid organic compound mainly used in organic
synthesis. Other names of this compound include N-phenylacetamide, acetanilide
and acetanil. It was formerly used for treating fever and headache and was known
by its brand name Antifebrin

(Bhattacharya, 2011).
Anilines can be sulfonated and nitrated, but the Friedel–Crafts alkylation
and acylation are not possible since the amino group forms an acid base complex
with the Lewis acid required for this reaction. One way round this is to convert the
aniline to the amide as above before carrying out the reaction (Patrick, 2004: 309).
This organic compound can be synthesized by the reaction of acetic
anhydride with aniline. It happens in the following way:
C6H5NH2 + (CH3CO)2O → C6H5NHCOCH3 + CH3COOH
This production method of Acetanilide used to be a traditional experiment in
introductory lab classes of organic chemistry. However, it was replaced by the
preparation process of other compounds (aspirin or paracetamol) to avoid using
aniline which is a suspected carcinogen (Bhattacharya, 2011).
Reaction of an aniline with nitrous acid results in the formation of the
stable diazonium salt in a process called diazotization. In the strong acid
conditions used, the nitrous acid dissociates to form an NO ion which can then act
as an electrophile. The aromatic amine uses its lone pair of electrons to form a
bond to this NO ion. Loss of a proton from the intermediate formed, followed by a
proton shift leads to the formation of a diazohydroxide. The hydroxide group is
now protonated turning it into a good leaving group, and a lone pair from the aryl
nitrogen forms a second π bond between the two nitrogen atoms and expels
water (Patrick, 2004: 309).
Acetanilide, which contains 10.4 wt percent nitrogen , has been proposed
as a secondary standard for compounds which do not require any auxiliary
material. It is available in high purity, is nonhygroscopic, has a very low vapor
pressure, can be pressed into reasonably good pellets, can be ignited with any type
of fuse and burns completely without an auxiliary substance. It is available
through the Office of Standard Reference Materials (OSRM) as a microanalytical
standard for nitrogen compounds (Johnson, 1975: 487).
Secondary and tertiary amines can also be exhaustively methylated then
treated with silver oxide. However, mixtures of different alkenes may be obtained
if the N-substituents are different alkyl groups (Patrick, 2004: 308).
The reader is reminded that the word distillation can be translated as
“separation drop by drop”. It can therefore he used as a collective term for
processes in which mixtures of ilrntually soluble liquids can be separated by
evaporation and condensation of the liquid, the condensed part becoming richer in
the niost volatile component. The word gives no indication of the technique
adopted in the separating process. The ternis “simple distillation” and
“countercurrent distillat ion” (Krell, 1982: 44).
A nitro group substitutes a hydrogen atom in the aromatic ring of
Acetanilide in this electrophilic aromatic substitution reaction. In this reaction, the
aromatic ring functions as the nucleophile while the nitronium ion functions as the
electrophile. It can be considered as a reaction of a Lewis base with a Lewis
acid (Bhattacharya, 2011).
In simple distillation the molecules emerging from the evaporating surface
move uniformly until they reach the condensing surface. In countercurrent
distillation part of the condensed vapour, termed “reflux”, returns to the boiler,
meeting in its passage the rising vapour. Provision is made for intimate contact
between the liquid and vapour in a tube, or “column”, between the boiler and
condenser. Thus, while simple distillation consist merely of evaporation and
condensation, in countercurrent distillation there is an exchange of material and
heat between the two phases in the column. This exchange tends towards an
equalization of temperature between the phases and to an alteration in the
composition of the phases so that equilibrium is approached (Krell, 1982: 45).
From explain can be concluded that asetanilida is a compound derivative
acetyl amines aromatic who are categorized as amide primary, where one atom of
hydrogen who in aniline used or replaced with one an acetyl group. Asetanilida in
shape smooth white soluble in water but not dissolve in oil paraffin. As for the
basic principle of the separation of distillation namely a mixture based on boiling
points differences.

D. APPARATUS AND CHEMICALS

1. Apparatus
a. Destillation flask 1 piece
b. Libik condenser 1 piece
c. Hot plate 1 piece
d. Analytical balance 1 piece
e. Thermometer 110ᵒ 1 piece
f. Stative and clamp 1 piece
g. Spray bottle 1 piece
h. Drop pipette 1 piece
i. Buncher funnel 1 piece
j. Beaker glass 1000 ml 1 piece
k. Beaker glass 250 ml 1 piece
l. Beaker glass 100 ml 1 piece
m. Beaker glass 500 ml 1 piece
n. Graduated cylinder 50 ml 1 piece
o. Smooth cloth 1 piece
p. Rought cloth 1 piece
q. Boiling stone 3 piece
r. Stir bar 1 piece
2. Chemicals
a. Aniline (C6H5NH2)
b. Glacial acetic acid (CH3COOH)
c. Aquadest (H2O)
d. Ethanol 95%
e. Norit
f. Filter paper whatmen
g. Tissue
E. WORK PROCEDURE
1. In the round flask, put 20 mL of Aniline and 25 mL of Acetate acid
glacial
2. After that, set distillation tools and put thermometer in the top of round
flask
3. After distillation, put the solution into cooled water
4. Then, filtered the solution with filter paper whatman
5. Next, washed the crystal used water, after that washed with ethanol 95%
6. After that, added norit to the crystal
7. Then, filtered with filter paper whatman
8. Weighed the crystal used analytical balance
9. Calculated the rendement of crystal (Acetanilide)

F. OBSERVATION RESULT
No Activity Observation
20 ml of aniline C6H5NH2 (brown) The color of solution is brown
1. + 25 ml of acetic acid glacial
CH3COOH (colorless) →
The solution was distillated until 30 There is not destilate
2. 104ᵒ−105ᵒC
minutes →
The solution was put into cold water Formed two layer:
(160 ml)→ - In top : white crystal
3.
- In bottom : brown
precipitate
4. The mixture was filtered→ Brown crystal with precipitate
The solution was washed with H2O the color of precipitate
5.
and ethanol 95 % (crystal) become light brown
Norit was added into precipitate The color of precipitate
6. (crystal)→ (crystal) still light brown but
there is crystal in precipitate
7. The precipitate (crystal) was The precipitate (crystal) is light
 filtered→ brown
The precipitate (crystal) was weight Mass of precipitate (crystal) is
8.
3.2881 g

G. DATA ANALYSIS
Known: Mass of C6H5NH2 = 20 grams
Mass of CH3COOH = 26 grams
V C6H5NH2 = 20 mL
V CH3COOH = 25 mL
Mr C6H5NH2 = 93 g/mole
Mr CH3COOH = 60 g/mole
Mr C6H5NHCOCH3 = 135 g/mole
Asked : % rendement = …?
Solution:
mass of CH3 COOH 26 g
n CH3COOH = = = 0.4333 mole
Mr CH3 COOH 60 g⁄mole
mass of C6 H5 NH2 20 g
n C6H5NH2 = = = 0.2150 mole
Mr C6 H5 NH2 93 g⁄mole

C6H5NH2 + CH3COOH C6H5NHCOCH3 + H2O

Initially : 0.2150 mole 0.4333 mole - -
React : 0.2150 mole 0.2150 mole 0.2150 mole 0.2150 mole
Eq : - 0.2183 mole 0.2150 mole 0.2150 mole

m C6H5NHCOCH3 = (n x Mr) C6H5NHCOCH3

= 0.2150 mole x 135 g/mole
= 29.0250 grams (mass of theory)

mass of experiment
% rendement = x 100%
mass of theory
3.2881 g
= x 100%
29.0250 g

= 11.33 %
H. DISCUSSION
Asetanilida merupakan senyawa turunan asetil amina aromatik yang
digolongkan sebagai amida primer, dimana satu atom hidrogen yang pada anilin
digunakan atau digantikan dengan satu gugus asetil. Asetanilida berbentuk butiran
halis berwarna putih yang larut dalam air namun tidak larut dalam minyak parafin.
Adapun manfaat asetanilida banyak digunakan dalam industri kimia. Beberapa
diantaranya yaitu sebagai bahan baku pembuatan obat-obatan, sebagai zat awal
pembuatan penisilium, sebagai bahan pembantu dalam industri cat dan karet, dan
masih banyak lagi (Diah, 2010).
Terdapat beberapa cara dalam pembuatan asetanilida yaitu: (a) Pembuatan
asetanilida dari asam asetat anhidrid dan anilin, (b) Pembuatan asetanilida dari
asam asetat dan anilin, (c) Pembuatan asetanilida dari keton dan anilin, (d)
Pembuatan asetanilida dari tioasetat dan anilin. Dan yang digunakan pada
percobaan ini yaitu pembuatan asetanilida dari asam asetat dan anilin. Mekanisme
reaksi pembuatan asetanilida disebut juga dengan reaksi asilasi amida yang mula-
mula anilin bereaksi dengan asam asetat membentuk suatu amida dalam keadaan
transisi. Kemudian diikuti dengan reduksi H2O membentuk asetanilida yang
belum murni (Braday, 1999). Pada percobaan ini dilakukan dengan cara
mereaksikan anilin (C6H5NH2) dengan asam asetat glacial (CH3COOH). Anilin
berfungsi sebagai nukleofilik atau sebagai bahan dasar yang akan disubtitusi oleh
atom H, yang menyumbangkan pasangan elektron bebas, sedangkan asam asetat
glacial berfungsi sebagai elektrofilik pada atom C, dimana keelektronegatifan C
lebih kecil daripada N sehingga dapat diikat oleh atom C. Pada saat pengambilan
asam asetat glacial, larutan tersebut harus ditutup untuk mencegah terjadinya
penguapan, akibat dari sifat asam asetat glacial yang mudah menguap. Sama
halnya dengan pengambilan anilin, larutan tersebut harus ditutup untuk mencegah
terjadinya oksidasi, akibat sifat dari anilin yang mudah teoksidasi, jika kontak
dengan cahaya anilin akan mengalami reaksi oksidasi. Adapun titik didih dari
asam asetat glacial yaitu 118oC dan titik didih anilin yaitu 184,4oC.
Kedua larutan tersebut direaksikan sehingga menghasilkan larutan yang
berwarna coklat. Campuran kemudian di destilasi untuk memisahkan asetanilida
dengan hasil samping reaksi yang terbentuk yaitu air, dan juga tidak terbentuk lagi
anilin dan asam asetat. Pada saat proses destilasi tidak ada destilat yang keluar
(dihasilkan), hal ini disebabkan pada proses destilasi hot plate yang digunakan
rusak dengan kata lain suhunya terkadang naik dan terkadang turun dengan
sendirinya. Suhu optimal pemanasan yaitu 114-183oC, jika pemanasan dibawah
suhu 114oC maka kristal asetanilida yang terbentuk sedikit dan jika pemanasan
melewati suhu 183oC maka tidak terbentuk kristal asetanilida. Dimana titik didih
asetanilida yaitu 304-305oC. Adapun prinsip kerja dari proses destilasi yaitu
pemanasan, penguapan, dan pendinginan. Prinsip dasar destilasi yaitu pemisahan
suatu campuran berdasarkan perbedaan titik didihnya. Sebelum proses destilasi,
kedalam labu ditambahkan batu didih yang berfungsi untuk mengurangi letupan-
letupan gas pada pemanasan karena batu didih memiliki pori-pori yang dapat
menyerap panas. Fungsi dari pemanasan yaitu untuk mempercepat reaksi agar
asetanilida yang terbentuk banyak. Lama pemanasan juga dapat mempengaruhi
hasil asetanilida dikarenakan semakin lama pemanasan, semakin banyak hasil
asetanilida yang diperoleh.
Residu yang tinggal didalam labu dimasukkan kedalam air dingin untuk
mempercepat terbentuknya kristal serta untuk menghidrolisis asam. Hal ini
dikarenakan suhu yang rendah mengakibatkan pergerakan atom melambat dan
ikatan antar molekulnya semakin kuat dan akhirnya merapat membentuk kristal
berwarna putih. Larutan kemudian disaring dengan menggunakan corong Buchner
dan kertas saring whatman untuk memisahkan Kristal dan pengotornya kemudian
dicuci dengan air dan etanol, etanol berfungsi untuk mengikat zat pengotor dan air
berfungsi untuk melarutkan Kristal. Oleh karena endapan yang terbentuk
berwarna cokelat maka ditambahkan norit untuk mengikat zat warna pengotor
yang berukuran besar yang terdapat pada kristal, karena norit memiliki pori-pori
yang besar. Norit (karbon aktif) merupakan suatu jenis karbon yang diaktifkan
dengan tujuan memperluas permukaannya dan meningkatkan kemampuan
adsorpsi karbon aktif itu sendiri. Norit yang digunakan dalam percobaan ini ialah
norit yang memiliki tekstur yang lebih halus, hal ini berfungsi untuk memperluas
permukaan sehingga proses pemurnian dapat berlangsung lebih baik.
 Setelah penambahan norit warna dari kristal masih berwarna coklat,
kemudian disaring lagi dan didapatkan Kristal yang masih berwarna coklat.
Campuran dari air dan etanol merupan campuran biner, yaitu campuran antara zat
terlarut dan zat pelarut dimana keduanya berfase cair dan berfungsi sebagai
pelarut. Proses kristalisasi bertujuan untuk memperoleh Kristal asetanilida murni,
karena prinsip kristalisasi adalah pemurnian suatu zat padat dari campuran atau
pengotornya yang dilakukan dengan cara kristalisasi kembali (rekristalisasi)
dalam pelarut yang cocok. Hasil kristalisasi asetanilida yang diperoleh berwarna
coklat, hal ini tidak sesuai dengan teori yang mengatakan bahwa Kristal dari
asetanilida yaitu berwarna putih. Hal ini di karenakan pada saat pencucian tidak
berulang ulang dilakukan sehingga zat pengotornya masih ada. Hasil Kristal
asetanilida yang diperoleh sebesar 3,2881 gram dan hasil perhitungan analisis data
diperoleh rendemen sebesar 11.33%. Ini menandakan bahwa hasil Kristal
asetanilida yang diperoleh belum murni karena rendemen yang diperoleh sangat
rendah. Adapun mekanisme reaksi yang terjadi yaitu:
H H

N H N H -
O O
+
+ H3C C + H3C C
OH OH

- -
N H O H O
+ +
+ H3C C N C CH3
OH H OH
- -
H O H O
+ +
N C CH3 N C CH3 + H

H OH OH

- -
H O H O
+ + -
N C CH3 + H
+
N C CH3 + H + OH
OH

-
H O H O
+ + -
N C CH3 + H + OH N C CH3 + H2O
I. CONCLUSSION AND SUGGESTION
1. Conclusion
a. A manner used in synthesis asetanilida that is synthesis asetanilida
from aniline and acetic acid with distillation method.
b. The basic principle distillation the separation a mixture of based on
boiling points differences.
c. Asetanilida is a compound of derivative acetyl aromatic amines who
are categorized as amides primary, where one atom of hydrogen which
on aniline used or replaced with one of an acetyl group.
d. The crystals asetanilida obtained by 3.2881 grams and the results of
data analysis of obtained rendement 11.33 %.
2. Suggestion
For practicum in the future should the work procedure must be clear in
doing that the apprentice not wrong in doing the practicum because it will
impact on the outcome of which was obtained.
 BIBLIOGRAPHY

Johnson, Warter H. 1975. The Enthalpies of Combustion and Formation of

Acetanilide and Urea. Journal of Research of the National Bureau of
Standards-A Physics and Chemistry. Volume.79A, Issue. 3.

Krell, Erich. 1982. Handbook of Laboratory Distillation volume 2. New York:

Elsevier Scientific Publishing Company.

Lomate, Samadhan, et al. 2015. High yield lactic acid selective oxidation into
acetic acid over a Mo-V-Nb mixed oxide catalyst. Sustainable Chemical
Processes. Volume.3, Issue.5.

McMurry, John. 2008. Organic Chemistry. United State: Thomson Learning.Inc.

Patrick, G. 2004. OrganicChemistry second edition. USA: BIOS Scientific

Publishers.

Timberlake, Karen C. 2012. Chemistry. USA: Prentice Hall.

http://www.chemistrylearner.com/organic-chemistry1 accessed on 11 November

2016