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 organic compounds that contain a trivalent nitrogen atom
bonded to one or two or three carbon atoms. When viewed from the structural
formula, amines are derivatives of ammonia in which one or two or three
hydrogen atoms are replaced by alkyl or aryl groups. Thus, if the substitute group
for the hydrogen atom in ammonia is an alkyl group, the possible runus of the
aliphatic amine structure is R2NH or R3N. If the substitute group is aryl, a similar
formula will be found(Rasyid, 2009 : 187).
The acetylation reaction replaces hydroxyl groups in natural starch with
acetyl groups. Replacement with the acetyl group causes reduced bond strength
between starch molecules and changing properties of starch.5 Oxidizing
modification of starch produce starch with clearer gel properties, lower tensile
strength and viscosity. Starch which is oxidized is obtained by oxidizing starch
with pro-oxidant compounds carried on the specified pH, temperature and
reaction time are appropriate(Danimayostu, 2017 : 26).
Amines are considered derivatives of ammonia (NH 3), 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 thethree
methyl groups in trimethylamine replace all the hydrogen atoms
inammonia(Timberlake, 2012 : 495).
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).

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 anilane undergo electrophilic subtitutions
reaction where the amine group acts as a strougly activating group, directing
subtitutions to the ortho and para positions. Furthermore, single the amide group
is bulkier than the orginical amino group, there is more of a proference for pora
subtitution over ortho subtitution. Once the reaction has been carried out, the
amide can be hydrolyzed back to the amino group.
 Synthesis of para bromo aniline
Anilines can be sulfonated and nitrated, but the friedel crafts alkylation and
acylation are not possible since the amino group forms an acide base complex
with the lewis acid required for this reaction. One that the way round this is to
convert amides the aniling to the amides as above before carrying out the
reaction(Patrick, 2005:308 – 309).
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. The nonpolar
hydrocarbon chains of the amine decreases its solubility in water(Timberlake,
2012: 498).
Nucleophilic substitution of an alkyl halide with an azide ion gives an
alkyl azide which can then be reduced with LiAlH 4 to give a primary amine.
Alternatively, nucleophilic substitution of an alkyl halide with a phthalimide ion is
carried out and the N-alkylated phthalimide is then hydrolyzed to the primary
amine. Reductive amination of an aldehyde with ammonia is a third method of
introducing an NH2 group. A fourth possible method is to react an alkyl halide
with ammonia, but this is less satisfactory since overalkylation is possible.
Primary and secondary alkylamines can be alkylated to secondary and tertiary
alkylamines, respectively, by reaction with an alkyl halide. Primary alkylamines
can also be synthesized if ammonia is used instead of an alkylamine. Amino
groups cannot be directly introduced to an aromatic ring. However, nitro groups
can be added directly by electrophilic substitution, then reduced to the amine.
Once the amine is present, reactions such as alkylation, acylation, or reductive
amination can be carried out as described for alkylamine (Patrick, 2004: 295).
Acetanilide is prepared from aniline by acetylating it with acetic anhydride
in the presence of glacial acetic acid. Aniline or phenylamine is a primary amine
with molecular formula C6H5NH2. The reaction between aniline and acetic
anhydride is called acetylation. In this reaction, aniline acts as the nuclepohile and
acyl (CH 3CO-) group from acetic anhydride acts as the electrophile. Here, the
hydrogen atom of –NH2 group is replaced by the acyl group (Aljamali, 2016: 10).
Aromatic amines (arylamines) are weaker bases than alkylamines since the
orbital containing nitrogen’s lone pair of electrons overlaps with the π system of
the aromatic ring. In terms of resonance, the lone pair of electrons can be used to
form a double bond to the aromatic ring, resulting in the possibility of three
zwitterionic resonance structures. (A zwitterion is a molecule containing a
positive and a negative charge.) Since nitrogen’s lone pair of electrons is involved
in this interaction, it is less available to form a bond to a proton and so the amine
is less basic.

(Patrick, 2004: 302).

D. Apparatus and Chemical
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
g. Tissue

E. Work Procedure
1. Added 10 ml of aniline to a 250 ml distillation flask.
 2. Added 14 ml of glacial acetic acid to the distillation flask containing
aniline.
3. Installied statives and clamps to hold the distillation flask and condenser
for distillation.
4. Added boiling stones to the distillation flask.
5. Heated slowly so that the solution vapor does not rise to the column
6. When the distillate starts to come out, wait up to 10 minutes then stop the
distillation
7. Added the residue into cold water until formed crystal
8. The precipitate was filtered and washed using ethanol 2%
9. Aquadest was boiling, added precipitate and norit
10. The solution was filtered and chilled using cold water
11. The filter paper was weight
12. Filtered the solution using buchner funnel
13. Weight the filter paper and the crystal and Calculated the crystal form
F. Observation Result
No. Activity Result
1. 20 mL of C6H11NH2 (brown) + Brown solution
25 mL of CH3COOH (colorless)
2. 45 mL of C6H5NHCOCH. H2O First distillate at 40 minutes at
(solution are destilled) the temperature 104oC
3. C6H5NHCOCH mixed with iod Croudy solution
water (beaker) than (crystal)
4. The crystal are filtered with Brown solution
ordinary filter and then crystal
are transferred to a beaker + H2O
+ heated + stirrer
5. Brown precipitate and clear Croudy solution
solution heated + norit
6. the crystal were washed with White solution
ethanol
 7. Filter paper is weighed and the White crystal a filter
crystal weigh is wighed Paper weight = 0,6 gram
Crystal weight – filter
Paper weight = 8,7 g – 0,6 g
= 8,1 grams

G. Data Analysis
Known : V aniline (C6H5NH2) = 20,4 mL
Mass aniline (C6H5NH2) = 20 gram
Mass asetic acid (CH3COOH) = 26 gram
Mr aniline (C6H5NH2) = 93 g/mol
V asetic acid (CH3COOH) = 27,3 mL
Mr asetic acid (CH3COOH) = 60 g/mol
Mass acetanilide of practicum (C6H5NHCOCH3) = 8,1 gram
Mr acetanilide(C6H5NHCOCH3) = 135,16 g/mol
Asked : % rendement...?
Solution:
mass C 6 H 5 NH 2
Mol C6H5NH2 =
mr C 6 H 5 NH 2
20 g C 6 H 5 NH 2
=
93 g /mol C 6 H 5 NH 2
=0,215 mol
massa CH 3 COOH
Mol CH3COOH =
mr CH 3 COOH
26 g CH 3 COOH
=
60 g /mol CH 3 COOH
= 0, 43 mol
C6H5NH2+ CH3COOH → C6H5NHCOCH3+ H2O
F: 0,215 mol 0,43 mol - -
R: 0,215 mol 0,215 mol 0,215 mol 0,215 mol
R: - 0,215 mol 0,215 mol 0,215 mol
Mass acetanilide (theory) = n acetanilide × Mr acetanilide
 = 0,215 mol × 135 g/mol
= 29,025 gram
Massa of theory = 8,1 gram
mass of acetanilide prakticum
% Rendemen = × 100 %
mass acetanilide theory
8,1 g
= × 100 = 27,9 %
29,025 g

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.
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 orange. 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 1,1 gram dan hasil
perhitungan analisis data diperoleh rendemen sebesar 7,40 %. Ini menandakan
bahwa hasil Kristal asetanilida yang diperoleh belum murni karena rendemen
yang diperoleh sangat rendah. Adapun mekanisme reaksi yang terjadi yaitu:
I. Conclusion and Suggestion
1. Conclusion
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. The
crystals asetanilida obtained by 29,025 grams and the results of data
analysis of obtained rendement 27,9 %.
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
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