Professional Documents
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Curtin
and Fuson
The Systematic Identification
of Organic Compounds
J. Wiley and sons, INC.
8th Edn. 2004
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Identification of Unknown
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Identification of Unknown
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Determination of Physical
Properties
Melting Points
Boiling Points:
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2. If comparisons are made of alcohols of the same type, the greater the
branching of the chain, the lower the boiling point.
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Sulfur
Procedure (a) for Sulfur : Acidify 1 mL of the sodium fusion nitrate with
acetic acid. Add two drops of 1% lead acetate solution. A black
precipitate of lead sulfide indicates the presence of sulfur in the unknown.
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Prussian blue
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11
Cl
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Br
12
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AgI
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AgBr
AgCl
14
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Solubility in Water,
Aqueous Acids and Bases,
and Ether
16
A1: Strong organic acids: carboxylic acids with more than six carbons;
phenols with electron-withdrawing groups in the ortho and/or para
position(s); -diketones (l,3-diketones).
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Determination of Solubilities
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Theory of Solubility
Polarity and Solubility
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A1: Strong organic acids: carboxylic acids with more than six carbons;
phenols with electron-withdrawing groups in the ortho and/or para
position(s); -diketones (l,3-diketones).
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32
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Solubility in Water
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36
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39
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Functional
Groups
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Classification Tests
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Experiment 2: Hydroxamic
Acid Test
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(a) Add a few drops or a few crystals of the unknown sample to 0.5 mL of
aniline. Pour the mixture into 5 mL of water. A positive test is the
precipitation of the solid anilide.
(b) In a small flask, place 0.2 mL of aniline, 1 mL of water, and 0.2 mL or
0.2 g of the unknown. Add in portions, with vigorous shaking, 10 mL of
20% sodium hydroxide solution. Shake the mixture in a stoppered flask
for several minutes, and then test the solution with litmus paper to make
sure that it is still alkaline. A positive test is the formation of a precipitate.
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Acyl Halides
The same experiments that are used to the detect the presence
of acid anhydrides can be used for acyl halides. Theory
predicts that the acyl halides are more reactive. Acid halides can
be hydrolyzed to carboxylic acids (Experiment 1, p. 252). Addition
of sodium bicarbonate to the solution produces the observable
evolution of carbon dioxide gas, the sodium salt of the acid, and
water.
To distinguish between the acid anhydride and the acyl halide,
the silver nitrate test for halides (Experiment 35, p. 320) is used.
The acyl halide is hydrolyzed to form the carboxylic acid and
hydrogen halide. The hydrogen halide undergoes reaction with
silver nitrate to give an immediate precipitation of silver halide.
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Alcohols
Several methods are available for the analysis of the hydroxyl group, the functional group present in
alcohols. Sodium metal undergoes reaction with hydroxyl groups of many alcohols to liberate
hydrogen gas and form the salt of the alcohol (Experiment 5, p. 262). The rate is highly variable and
depends upon the alcohol structure.
Another method of detecting such an active hydrogen is by adding acetyl chloride to the alcohol to
form the ester (Experiment 6, p. 264), which is less dense than the aqueous layer.
Another method of testing for the presence of the alcoholic hydrogen involves ceric ammonium
nitrate (Experiment 7, p. 265). The yellow ceric ammonium nitrate forms a red organometallic
compound with alcohols. Positive results are obtained from alcohols of 10 or fewer carbons.
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The Jones oxidation, in conjunction with the sodium metal test and
the Lucas test, may be used to differentiate among primary (10),
secondary (2), and tertiary (3) alcohols. The Jones oxidation
(Experiment 8, p. 268) only detects the presence of a hydroxyl
substituent that is on a carbon bearing at least one hydrogen. Thus,
only primary and secondary alcohols are oxidized to the corresponding
carboxylic acids and ketones. Tertiary alcohols are not oxidized under
these conditions. As the alcohol is oxidized, the
solution changes from an orange-red color from the Cr+6 ion, to a
blue to green color from the Cr3+ ion.
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Lucas Test
Substrates that easily give rise to cationic character at the carbon
bearing the hydroxyl group undergo the Lucas test (Experiment 9, p.
269) readily. Therefore, only secondary (2) and tertiary (3)
alcohols form the alkyl halide, which appears as a second liquid
layer, tertiary alcohols being the most reactive. Primary (1)
alcohols undergo reaction with the zinc chloride and hydrochloric
acid either negligibly slowly or not at all.
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The iodoform test (Experiment 11, p. 273) gives positive results for
secondary alcohols in which a methyl group is attached to the
carbon bearing the hydroxyl group. This type of alcohol is oxidized to
a methyl ketone and under these basic conditions it forms a triiodo
intermediate, which is then oxidized to the sodium salt of the acid
and iodoform. Iodoform is a foul-smelling yellow precipitate.
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To 0.25 mL or 0.25 g of the sample, add small thin slices of freshly cut
sodium until no more will dissolve. Evolution of hydrogen gas indicates
the presence of an acidic hydrogen, such as a hydroxyl group in an
alcohol, a hydrogen attached to the nitrogen in a primary or secondary
amine, or a hydrogen in a terminal alkyne. Cool the solution, and
observe. Add an equal volume of ether. Another positive test is the
formation of the solid salt.
A methylene group, adjacent to an activating group or between two
activating groups, possesses hydrogen atoms that may be displaced by
sodium. This hydrogen may also be difficult to observe due to its
subsequent reaction with unsaturation in the original organic compound.
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Perform this test in the hood. Add drop by drop 0.2 mL of acetyl
chloride to 0.2 mL or 0.2 g of the unknown. Evolution of heat and
hydrogen chloride gas is a positive test. To destroy any unreacted
acetyl chloride, allow the mixture to stand for a minute or two and
the pour it cautiously into 1 mL of water. Alcohols and phenols
react with acetyl chloride to form esters, which is indicated by the
formation of a top layer in the flask. Primary and secondary
amines react with acetyl chloride to form amides, which
precipitate from the solution.
Only primary and secondary amines will react with acetyl
chloride to form amides.
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The iodoform is a test for methyl ketones and secondary alcohols that
have a methyl group adjacent to the carbon bearing the hydroxyl group.
Place four drops of the liquid or 0.1 g of the solid to be tested in a test
tube. Add 5 mL of dioxane and shake until all the sample has gone into
solution. Add 1 mL of 10% sodium hydroxide solution, and then
slowly add the iodine-potassium iodide solution, with shaking, until a
slight excess yields a definite dark color of iodine. If less than 2 mL of
the iodine solution is decolorized, place the test tube in a water bath at a
temperature of 60C. If the slight excess of iodine already present is
decolorized, continue the addition of the iodine solution (keep the
iodine solution at 60C),with shaking, until a slight excess of iodine
solution again yields a definite dark color. Continue the addition of iodine
until the dark color is not discharged by 2 min of heating at 60C.
Remove the excess of iodine by the addition of a few drops of 10%
sodium hydroxide solution, with shaking. Now fill the test tube with
water and allow to stand for 15 min. A positive test is indicated by the
formation of a foul-smelling yellow precipitate (iodoform). Collect the
precipitate by filtration and dry. Obtain the melting point.
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ALDEHYDES
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Add one drop or a few crystals of the sample to the freshly prepared
Tollens reagent. A positive test is the formation of silver metal or
colloidal silver. If no reaction takes place in the cold, the solution
should be warmed slightly on a steam bath or in a hot water bath.
However, excessive heating will cause the appearance of a false
positive test by decomposition of the reagent.
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AMIDES
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(a) Diazotization
Dissolve 0.5 mL or 0.5 g of the sample in 1.5 mL of concentrated
hydrochloric acid diluted with 2.5 mL of water, and cool the
solution to 0C in a beaker of ice. Dissolve 0.5 g of sodium nitrite
in 2.5 mL of water, and add the solution dropwise, with shaking,
to the cold solution of the amine hydrochloride. Continue the
addition until the mixture gives a positive test for nitrous acid.
Perform the test by placing a drop of the solution on starch-iodide
paper; a blue color indicates the presence of nitrous acid. If the
test is positive, move 2 mL of the solution to another test tube,
warm gently, and examine for evolution of gas.
The observation of rapid bubbling or foaming as the aqueous
sodium nitrite solution is added at OC indicates the presence of a
primary aliphatic amine. The evolution of gas upon warming
indicates that the amine is a primary aromatic amine, and the
solution should be subjected to the coupling reaction (b).
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Diazotization
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CARBOXYLIC ACIDS
With NaHCO3
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ESTERS
Complex
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ETHERS
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HALIDES
In both the silver nitrate test (Experiment 35, p. 320) and the
sodium iodide test (Experiment 36, p. 323), the halide is
displaced from the alkyl halide to form an insoluble salt. The
reaction of the alkyl halide with silver nitrate yields a silver halide
precipitate.
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The sodium iodide test can be used to test for the presence of
bromine or chlorine. Sodium halide precipitates from the
solution.
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2. Oxonium salts.
3. Carbonium halides.
4. Low-molecular-weight acid chlorides. Many of these are easily
hydrolyzed by water and produce the halide ion.
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HYDROCARBONS-ALKANES
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HYDROCARBONS-ALKENES
HYDROCARBONS-ALKENES
The carbon-carbon double bond of alkenes (olefins) can be detected
very easily by chemical tests. Alkenes can be detected by the use of
iodine (Experiment 33, p. 317). If an alkene is present, a tan solid
is formed while retaining the purple solution of the iodine solution.
Addition across the double bond occurs in both the bromine test
(Experiment 37, p. 326) and the potassium permanganate test
(Experiment 38, p. 328). Since the ionic characters of the bromine
and potassium permanganate reactions are very different, there is
some complementary character between the two tests. For example,
some alkenes bearing electron-withdrawing groups undergo rapid
reaction with potassium permanganate but often slow or negligible
reaction with bromine. Bromine adds across the carbon-carbon double
bond,
with dissipation of the brown-red bromine color.
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(right)
110
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HYDROCARBONS-ALKYNES
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HYDROCARBONS-AROMATIC
The most vigorous test will be described first, and the tests that follow
will be described in decreasing order of the severity of conditions. A
few of the most inert aromatic compounds may remain unchanged
after even the most vigorous test; characterization of those compounds
may rely more on the spectral and physical tests than is usually the
case.
Fuming sulfuric acid converts aromatic compounds to arylsulfonic
acids (Experiment 39, p. 334). The aromatic compound dissolves
completely with the evolution of heat.
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Place 0.5 mL or 0.4 g of the dry compound in a clean, dry test tube;
add one crystal of azoxybenzene and about 25 mg of anhydrous
aluminum chloride. Note the color. If no color is produced
immediately, warm the mixture for a few minutes. Wait for up to 30
min to observe any color change. If the hydrocarbon is a solid, a
solution of 0.5 g of it in 2 mL of dry carbon disulfide may be used.
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Naphthalenes
Biphenyl
Purple
Phenanthrene Purple
Anthracene
Green
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KETONES
Many of the same reactions that are described above (Section 9.4,
pp. 276--286) in the classification of aldehydes can also be used to
classify ketones. The addition of 2,4dinitrophenylhydrazine to
ketones to precipitate the 2,4-dinitrophenylhydrazones (Experiment
12, p. 278) is probably the most useful of these reactions.
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NITRILES
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NITRO COMPOUNDS
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PHENOLS
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This test must be done in the hood. Add 30 to 50 mg of the solid unknown
or four to five drops of the liquid unknown to 2 mL or pure chloroform in
a clean, dry test tube. Stir the solution. If the unknown does not seem to
dissolve, even partially, add an additional 2-3 mL of chloroform and warm
gently. Cool to 25C and add two drops of 1% solution of anhydrous ferric
chloride in chloroform followed by three drops of pyridine. Shake the tube
and note the color produced immediately. A positive test is shown by
production of a blue, violet, purple, green, or red-brown solution.
Frequently the colors change in a few minutes.
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The Preparation of
Derivatives
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