Praktikum#5 Dan 6
Praktikum#5 Dan 6
Praktikum#5 Dan 6
Ketones
Standards
Cyclohexanone, Benzophenone, and
Benzaldehyde
Procedure
Add a solution of 1 or 2 drops or 30 mg of
unknown in 2 mL of 95% ethanol to 3 mL of 2,4-
dinitrophenylhydrazine reagent. Shake
vigorously, and, if no precipitate forms
immediately, allow the solution to stand for 15
minutes. The 2,4-dinitrophenylhydrazine
reagent will already be prepared for you.
Positive test
Formation of a precipitate is a positive test.
Complications
• Some ketones give oils which will not solidify.
• Some allylic alcohols are oxidized by the
reagent to aldehydes and give a positive test.
• Some alcohols, if not purified, may contain
aldehyde or ketone impurities.
Tollen’s Test for Aldehydes
Aldehyde
Standards
Cyclohexanone and Benzaldehyde
Procedure
Add one drop or a few crystals of unknown to 1
mL of the freshly prepared Tollens reagent.
Gentle heating can be employed if no reaction is
immediately observed.
Tollens reagent: Into a test tube which has been
cleaned with 3M sodium hydroxide, place 2 mL
of 0.2 M silver nitrate solution, and add a drop
of 3M sodium hydroxide. Add 2.8% ammonia
solution, drop by drop, with constant shaking,
until almost all of the precipitate of silver oxide
dissolves. Don't use more than 3 mL of
ammonia. Then dilute the entire solution to a
final volume of 10 mL with water.
Positive Test
Formation of silver mirror or a black precipitate
is a positive test.
Complications
• The test tube must be clean and oil-free if a
silver mirror is to be observed.
• Easily oxidized compounds give a positive test.
For example: aromatic amine and some phenols.
Cleaning up
Place all solutions used in this experiment in an
appropriate waste container.
Jones (Chromic Acid) Oxidation Test for
Aldehydes
Aldehydes
Standard : Acetone
Procedure
If the substance to be tested is water soluble,
dissolve 4 drops of a liquid or an estimated 50
mg of a solid in 2 mL of water in a large test
tube. Add 2 mL of 3 M sodium hydroxide and
then slowly add 3 mL of the iodine solution.
Stopper the test tube and shake vigorously. A
positive test will result in the brown color of the
reagent disappearing and the yellow iodoform
solid precipitating out of solution. If the
substance to be tested is insoluble in water,
dissolve it in 2 mL of 1,2-dimethoxyethane,
proceed as above, and at the end dilute with 10
mL of water.
Positive Test
Formation of solid iodoform (yellow) is a
positive test. (Iodoform can be recognized by its
odor and yellow color and, more securely, from
the melting point 119o-123oC).
Complications
Test will not be positive if the R group is a di-
ortho substituted aryl group
Tes untuk Aldehida dan Keton
Standar
Cyclohexanone, Benzophenone, dan
Benzaldehyde
Prosedur
Tambahkan larutan 1 atau 2 tetes atau 30 mg
yang tidak diketahui dalam 2 mL etanol 95% ke 3
mL reagen 2,4-dinitrofenilhidrazin. Kocok kuat-
kuat, dan, jika tidak segera terbentuk endapan,
biarkan larutan bertahan selama 15 menit.
Pereaksi 2,4-dinitrophenylhydrazine sudah
disiapkan untuk Anda.
Tes positif
Pembentukan endapan adalah tes positif.
Komplikasi
• Beberapa keton menghasilkan minyak yang
tidak akan mengeras.
• Beberapa alkohol alilik dioksidasi oleh pereaksi
menjadi aldehida dan memberikan tes positif.
• Beberapa alkohol, jika tidak dimurnikan, dapat
mengandung pengotor aldehida atau keton.
Tes Tollen untuk Aldehydes
Aldehida
Standar
Cyclohexanone dan Benzaldehyde
Prosedur
Tambahkan satu tetes atau beberapa kristal
yang tidak diketahui ke 1 mL reagen Tollens
yang baru disiapkan. Pemanasan lembut dapat
dilakukan jika tidak ada reaksi yang segera
diamati.
Pereaksi Tollens: Ke dalam tabung reaksi yang
telah dibersihkan dengan 3M natrium
hidroksida, tempatkan 2 mL larutan nitrat 0,2 M
perak, dan tambahkan setetes 3M hidroksida
3M. Tambahkan 2,8% larutan amonia, tetes
demi tetes, dengan pengocokan konstan, hingga
hampir semua endapan perak oksida larut.
Jangan gunakan lebih dari 3 mL amonia.
Kemudian encerkan seluruh larutan ke volume
akhir 10 mL dengan air.
Tes Positif
Pembentukan cermin perak atau endapan hitam
adalah tes positif.
Komplikasi
• Tabung reaksi harus bersih dan bebas minyak
jika cermin perak harus diamati.
• Senyawa yang mudah teroksidasi memberikan
tes positif. Misalnya: amina aromatik dan
beberapa fenol.
Membersihkan
Tempatkan semua solusi yang digunakan dalam
percobaan ini dalam wadah limbah yang sesuai.
Tes Oksidasi Jones (Chromic Acid) untuk
Aldehydes
Aldehida
Procedure:
Test the solubility in water of each amine you
will use by adding ten drops of it to 10 mL water
in a small test tube, shaking the mixture and
checking for any material floating on top. Add 8-
10 drops of a primary amine to a large test tube.
Add 10 mL 10% KOH. Add 10 drops benzene
sulfonyl chloride. Shake vigoroulsy to mix (use a
cork). Check for the odor of benzenesulfonyl
chloride by waving your hand toward you over
the mouth of the tube. (DO NOT TAKE A DEEP
BREATH WITH THE TUBE DIRECTLY UNDER YOUR
NOSE.). If there is a small layer of material on
the bottom or the main layer (and another small
layer on the top of the main layer), this is
unreacted sulfonyl chloride. Add 1-2 drops more
aniline and shake vigorously until the small
bottom layer disappears. The amine on the top
of the water layer must come into contact with
the sulfonyl chloride on the bottom of the
water. Be careful to not add too much additional
aniline as this may form a layer on the top of the
aqueous layer if the amine is water insoluble.
The trick is to get exactly stoichiometric
amounts of the sulfonyl chloride and the amine.
At this point you should see only one layer. If
there still seems to be benzene sulfonyl
chloride, you may need to warm the test tube in
a water bath for 10 min at 80-90 °C. Usually,
however, this is not necessary. If you see only
one layer with the benzenesulfonyl chloride,
then it means you have a primary amine.
Confirm this by adding concentrated HCl until
the pH is less than 4 (blue to Congo Red). At this
point you should see a precipitate.
Repeat the benzene sulfonyl chloride treatment
using a secondary amine and a tertiary amine.
With the secondary amine you should see two
layers. Draw off the lower aqueous layer with a
separatory funnel and see if the organic layer is
soluble in 5% HCl. If it is not, you have a
secondary amine. With tertiary amines,
solubility will depend on the amine. Those that
are water-soluble will remain water-soluble
during all of the above procedures. Those that
are not water-soluble will remain so and float on
top during the Hinsberg test. This top layer,
however, will be soluble in 5% HCl and this
distinguishes tertiary from secondary amines.
Repeat the Hinsberg test with your unknown.
Nitrous Acid Test:
Confirm the results of your Hinsberg Test using
the nitrous acid test. Practice the test first using
a known primary, a secondary and a tertiary
amine before trying it with your unknown.
Treatment of the primary aliphatic amine (Figure
16.4) with sodium nitrite in the presence of
hydrochloric acid generates the very reactive
and electron deficient nitroso ion which reacts
rapidly with the nucleophilic amine to give a
nitrosammonium adduct which then loses water
to give the diazonium salt. This is unstable and
immediately loses N2 gas which bubbles out of
the solution.