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Copyright 2009, 2001, 1997, 1992, 1988 New Age International (P) Ltd., Publishers
Published by New Age International (P) Ltd., Publishers
The logarithmic tables have been dropped. The diagrams have been redrawn. It is a
very useful and handy book for all graduate and postgraduate level students.
I am indebted to all those readers and users of this book who have laboured to send
me their comments and suggestions from time to time. I will certainly welcome their feedback
in future as well.
I also wish to put on record my gratitude to the authors and publishers of books,
monographs and articles whose hard work has immensely guided me in the preparation of
this edition.
It gives me a great pleasure to acknowledge the love and support of my wife during
the preparation of this project.
Finally, I gratefully acknowledge the collaboration and dedication of all professionals
at the New Age International (P) Ltd., Publishers, New Delhi for the adept handling of
this edition.
SAFETY IN THE
CHEMICAL LABORATORY
These affect the eyes and the respiratory system. In general, many low boiling
compounds can also be listed under this category. These reagents should be handled in the
fume hood.
Burning Chemicals and Clothing from low boiling inflammable organic solvents is
the most common fire hazard in the laboratory. If the fire is limited to a small container
like a beaker then cover it with a wire gauze. Since all inflammable solvents are less dense
than water, water should never be used to extinguish fire. Sand is often useful. For larger
fires, a fire extinguisher is required which should be available in the laboratory. Learn the
location and operation of a fire extinguisher. For fires beyond control, the fire alarm should
be sounded and fire services summoned.
In the event of ones clothes catching fire, the victim should roll over on the ground to
extinguish the fire or should be covered with a fire blanket. A fire extinguisher should not
be used on a person.
*TLV (Threshold limit value) is the concentration of an airbone constituent to which a worker may be
repeatedly exposed without adverse effect for a normal 8 hr work day.
SAFETY IN THE CHEMICAL LABORATORY 5
Aniline:It is colorless oily liquid, b.p. 184 oC. It darkness on exposure to air. TLV is 5
ppm. It causes dizziness, nausea, abdominal pain and malaise.
Benzene: It is a colorless to yellow liquid, b.p. 80oC and highly flammable. TLV is 10
ppm. Breathing benzene causes euphoria, headache, narcosis, dizziness and rapid heart
rate. Long term exposure to benzene can affect the bone marrow and decrease red blood
cells leading to anemia.
Bromine:It is a dark raddish brown liquid, b.p. 58.8oC only slightly soluble in water.
Bromine rapidly vaporizes at room temperature, the fumes are very irritating and is an
extremely unpleasant chemical. TLV is 0.1 ppm. It causes skin burns, dizziness, headache,
bronchitis and nausea. Store in a cool dry place and out of direct sunlight.
n-Butanol:It is a colorless liquid, b.p. 177oC. It has a moderate fire risk. TLV is 100
ppm. On inhalation it causes respiratory inflammation, paralysis and dizziness.
n-Butyl acetate:It is a volatile liquid with fruity odor, b.p. 126.5oC. TLV is 150 ppm.
It causes conjunctivitis, cough, headache and anorexia (loss of appetite).
n-Butyllithium: Commercially a stable solution of n-butyllithium is obtained in pentane
or heptane. It is strongly irritant and toxic and ignities on contact with moist air. The
solution should be preserved below 15 oC.
Carbon disulfide:It is a colorless or faintly yellow liquid, b.p. 46 o C and very
flammable. Carbon disulfide is a potentially fire hazard and toxic. TLV is 20 ppm. It causes
headache, vomiting and abdominal pain.
Carbon tetrachloride:It is colorless non-flammable heavy liquid, b.p. 77oC. TLV is
10 ppm. It has sweet odor and is toxic. Carbon tetrachloride causes irritation of eyes,
headache, abdominal cramps and nervousness.
Chlorine:It is a greenish-yellow gas having a suffocating odor. Chlorine is toxic and
irritating. TLV is 1 ppm. Its inhalation causes irritation of eyes, difficult breathing, cough,
pain, nausea and cyanosis.
Chloroacetyl chloride: It is a colorless or slightly yellow liquid, b.p. 106 o C.
Decomposes with water, and is non-combustible. It causes irritation of eyes, nose and throat.
Chloroform: It is a colorless, heavy liquid, b.p. 61o C and possesses a sweet taste. It is
volatile. TLV is 50 ppm. Chloroform causes unconsciousness, shortness of breath and
vomiting.
Diazomethane: It is a yellow gas at room temperature and soluble in ether. It
decomposes explosively by water or alcohol. It possesses a severe explosion hazard. TLV is
0.2 ppm. Diazomethane is severely toxic and irritant.
Diethyl ether: It is a colorless, very volatile and flammable liquid, b.p. 34.5oC. It has
a very low flash point. It travels considerable distance to the source of ignition. TLV is
400 ppm. Ether has a penetrating smell. On inhalation it causes headache, vomiting, paralysis
and irritation of respiratory tract. Store in a cool area.
6 LABORATORY MANUAL OF ORGANIC CHEMISTRY
1, 2- Dichloroethane: It is colorless oily liquid with chloroform like odor, b.p. 83o C. It
is slightly soluble in water but flammable. TLV is 50 ppm. It causes irritation of respiratory
tract, headache, weakness, anxiety and convulsions.
Formaldehyde: It is a colorless gas with pungent odor, easily soluble in water. It is
highly reactive and readily polymerizes with many organic substances. TLV is 3 ppm.
Formaldehyde causes conjunctivitis, corneal burns and dermatitis.
Hydrazine: It is a colorless, fuming liquid, b.p. 113.5o C. It has penetrating ammoniacal
odor. It is highly dangerous. It has fire and explosion risk. TLV is 1 ppm. Hydrazine causes
conjunctivitis, irritation of tracheal tract and skin as well as nausea.
Hydrogen cyanide: It is a colorless gas possessing faint aromatic odor. It is miscible
with water and alcohol. It is flammable and a fire hazard. TLV is 10 ppm. Hydrogen cyanide
causes nausea, headache, palpitation, unconsciousness and death.
Hydroxylamine : It constitutes of large white flakes or needles, m.p. 33o C. It is highly
hygroscopic and unstable. It causes headache, dizziness, dispnea (difficult breathing),
vomiting and jaundice.
Iodine: It forms heavy, greyish black plates or granules, has a characteristic odor,
m.p. 113.5oC. Iodine is soluble in alcohol, carbon disulfide, ether and chloroform. It causes
headache, dizziness, cough, pulmonary endema and difficult breathing.
Mercury: It is silvery and heavy liquid and has a low vapor pressure (0.002 mm/20 oC).
TLV is 0.1 mg/m3. Swallowing causes burning in the mouth and throat, thirst, nausea and
bloody diarrhea. Inhalation of mercury vapors cause inflammation of mouth, abdominal
cramps, cough and fever.
Phenol: It is a white crystalline mass but turns pink on exposure to air, b.p. 182oC. It
absorbs moisture from the atmosphere and liquifies. TLV is 5 ppm. Phenol causes burns on
contact with skin, pharynx, vomiting, cough and pulmonary endema.
Phosgene: It is a colorless gas soluble in water forming pale yellow liquid and non-
combustible. Phosgene is extremely toxic. TLV is 0. ppm. It causes headache, rapid
respiration, cough, cyanosis, vomiting and pain in the upper abdomen.
Phosphorus pentachloride: It is a yellow powder and sublimes at 160165o C without
melting. It is flammable, TLV is 1 mg/m3. It causes irritation of eyes, bronchitis and nephritis
(inflammation of kidney).
Potassium cyanide: It is white amorphous powder. It has a faint almond-like odor.
TLV is 5 mg/m3. It is immensely toxic.
Pyridine: It is a slightly yellow or colorless liquid, flammable with nauseating odor,
b.p. 115oC. TLV is 5 ppm. Pyridine causes conjunctivitis, pruitus (itching), eczema, headache,
vomiting and abdominal pain.
Styrene: It is a colorless to yellowish oily liquid with penetrating odor and sparingly
soluble in water. Styrene readily undergoes polymerization. TLV is 100 ppm. It causes
conjunctivitis, lack of appetite, nausea, weakness and drowsiness.
SAFETY IN THE CHEMICAL LABORATORY 7
Thionyl chloride: It is a pale yellow, pungent liquid, b.p 79oC. It is decomposed readily
by water. TLV is 5 ppm. It causes conjunctivitis, dermatitis (skin inflammation) and
pneumonia.
Toluene: It is a colorless and flammable liquid with benzene like odor, b.p. 110.6oC. It
is miscible with alcohol, chloroform, ether and acetone. TLV is 200 ppm. Toluene causes
dermatitis, nausea, weakness and incoordination. Toluene is also known to cause cancer
and nervous system disorders.
References
1. Hazards in the Chemical Laboratory, 4th edn., (Ed. by L. Bretherick), Royal Society
of Chemistry, London (1986).
2. Prudent Practices for Handling Hazardous Chemicals in Laboratories, National
Research Council, National Academy Press, Washington, D.C. (1981).
3. M.J. Pitt and E. Pitt, Handbook of Laboratory Waste Disposal, Wiley, New York
(1985).
4. Sigma-Aldrich Library of Chemical Safety Data, 2nd edn., (Ed. by R.E. Lenga)
(1988).
5. D.A. Pipitone, Safe Storage of Laboratory Chemicals, Wiley, New York (1991).
6. M.J. Lefevre, First Aid Manual for Chemical Accidents, Dowden et al., Stroudsberg,
Pa (1980).
7. Safe use of Solvents, (Ed. by A.J. Collins and S.G. Luxon), Academic Press, New
York (1982).
Chapter 2
In an organic chemistry laboratory a variety of glasswares and techniques are used for the
synthesis, separation and purification of organic compounds as well as for routine work.
The apparatus, however, becomes more sophisticated in a research laboratory. It is highly
desirable that the student be familiar with the use and handling of the apparatus. The
laboratory techniques described here are basic to almost all experimentation in organic
chemistry.
2.1 GLASSWARES
A brief discussion of the common types of glasswares and apparatus used in the chemical
laboratory is given here.
(a) Flasks
These are the common types of flasks used for a variety of purposes. Flasks (a) to (e) are
employed for refluxing and distillation. Flasks with standard-taper ground glass joints and
those without are in common use in a chemical laboratory. Flasks (a) and (b) are the ones
with the ground glass joints. They require greasing and proper cleaning after use.
LABORATORY EQUIPMENTS AND TECHNIQUES 9
The Erlenmeyer flask (f) is used for mixing and titration. Figs. (g) to (i) represent
different distillation flasks with condensers attached. The first two are the regular distillation
flasks but (i) is called the Claisen flask with a fractionating column.
(c) Condensers
The condensers (a) and (b) are used for refluxing and routine distillation. The air condenser
(c) is employed if the liquid distilling has a very high boiling point.
(d) Funnels
Figure (a) shows an long stem funnel used for transferring or filtering of liquids and reagent
solutions, while (b) is the Hirsch funnel for filtering very small solid samples. Whereas (c)
and (d) are the separatory funnels used for the extraction of a product from a reaction
mixture; (e) is a dropping funnel employed for the addition of a reactant to a reaction flask.
LABORATORY EQUIPMENTS AND TECHNIQUES 11
During the extraction of a product while working with alkaline solutions it is observed
that an emulsion is usually formed which prevents the separation of two immiscible layers.
The emulsion so formed can be broken up by one of the following two methods.
(i) Gently swirling the separatory funnel while holding it in an upright position.
(ii) Saturating the aqueous layer of the reaction mixture with a salt such as sodium
chloride.
The second technique decreases the solubility of the inert organic solutes as well as
the extraction solvents such as ether in the water layer. This process is referred to as the
salting-out effect. The Buchner funnel and the Buchner flask are used extensively in
synthesis for filtration of a solid product.
The arrangement for filtration (c) using a water pump or aspirator is shown in
Figure (2.1):
A water trap is included between the system and the water aspirator. This tends to
prevent water sucking back into the apparatus when a sudden drop in pressure occurs. The
vacuum generated depends on the speed of water rushing though the aspirator.
(e) Stirrers
These figures represent various types of stirrers used for stirring purposes. These are
usually made of glass but those made of stainless steel or teflon are also in common use. A
stirrer is attached directly to a small electric motor with the aid of a small pressure tubing
and mechanical agitation is achieved.
A magnetic stirrer on the other hand, is a useful device for small quantities and non-
viscous reaction mixtures. The stirring is achieved by a magnetic spinner bar which is
added to the reaction mixture.
Large scale and viscous reaction mixtures require a mechanical stirrer and need greater
power of an external motor unit for turning a stirrer blade. A typical model is shown in
fig. 2.2.
LABORATORY EQUIPMENTS AND TECHNIQUES 13
The bottom of the desiccator may be filled either with anhydrous calcium chloride or
conc. sulfuric acid. Sometimes, it is difficult to remove the moisture completely from a wet
solid in a vacuum desiccator. In that case complete removal of moisture can be achieved
using the Abderhalden drying pistol. The apparatus is shown in figure (c). In this case,
the solid product is enclosed in a small boat (A) in a glass-stoppered drying tube (B). This
tube is heated continuously by refluxing a suitably selected liquid (such as toluene) in the
flask (C). The drying tube is connected to a chamber (D) containing an efficient desiccant.
Both the drying tube and the desiccant chamber are evacuated by applying vacuum through
the stopcock (E). On heating the solvent, the drying tube is surrounded by the hot vapors.
The water vapors from the sample are captured by a chemical drying agent such as
phosphorus pentoxide placed in (D).
(g) Adapters
Adapters (a) and (d) are normally used to facilitate the delivery of a distillate from the
condenser to a receiver. A vacuum can also be applied to adapter (d) if needed. Fig. (b)
represents a simple distillation head while (c) is the widely used Claisen distillation head.
2.3 DISTILLATION
Distillation is a classical technique in the laboratory for the purification of liquids from
volatile and non-volatile impurities. It may also be used for the separation of two miscible
liquids. The process of distillation may be described as the partial vaporization of a liquid
and carrying over and condensation of these vapors back to liquid in a different part of the
distillation apparatus. The distilled liquid is called the distillate, depending on the nature
and boiling point of the substance to be distilled, different methods of distillation are employed
in a chemical laboratory.
while glycerine does so slowly because the vapor pressure of ether is low. The vapor pressure
increases with the increase in temperature. If the temperature is raised, the liquid starts
boiling. The boiling point of a liquid is defined as the temperature at which its vapor
pressure is equal to the external pressure. If the external pressure is 760 mm (i.e., the
atmospheric pressure) a liquid starts to boil till its vapor pressure reaches this value. The
presence of impurities lowers the vapor pressure and thus increases the boiling point. As
stated above, vapor pressure increases as the temperature is raised. This is illustrated
nicely in Fig. 2.4. As it is obvious when a pure substance is heated and if the temperature
6 00
Va po r p ress ure (a tm )
4 00
2 00
0 20 40 60 80
is raised, the vapor pressure of the substance becomes equal to the atmospheric pressure
and the substance boils. For instance, water boils at 100oC when the external pressure is
760 mm (1 atm). Therefore, water has a vapor pressure 760 mm Hg at 100C. Two liquids
can be separated from one another provided their boiling points are not too close together.
Usually the difference in boiling points should not be less than 70oC or more. The apparatus
for carrying out a simple distillation is pictured in Fig 2.5.
The assembly consists of a round-bottomed distillation flask equipped with a thermometer,
a stillhead and a water condenser. Cold water is circulated into the condenser from the lower to
upper end. The other end of the condenser is attached to a receiving flask through a receiving
adapter. Normal grease is used for greasing the joints.
The liquid (or the mixture of liquids) to be distilled is transformed to the distillation flask
with the help of a funnel. The flask should not be filled with the liquid more than half. It is now
heated with a proper heat source. A water or steam-bath is recommeded for low boiling solvents.
An electrically heated oil-bath is needed for high boiling liquids. A Bunsen burner should never
be used. Also avoid using a heating mantle, as the temperature is not controllable. The heating
should be carried out slowly to prevent super heating of vapors, i.e., rise of temperature above
the boiling point, and causing bumping. Bumping is the stage at which a periodically sudden
ejection of excessive vapors takes place. At times it can become very dangerous.
LABORATORY EQUIPMENTS AND TECHNIQUES 17
Before heating the liquid 2-3 small boiling chips should be added to the distillation flask. A
boiling chip is a small piece of porcelain tile. The escaping gas bubbles from the boiling chip
will break the surface of the liquid and will promote smooth boiling and prevent bumping.
The rising vapors of the liquid will pass through the neck of the flask, get condensed by
the cold neck and drop back into the flask. This process will continue till an equilibrium is
reached between the rising vapors and the condensing liquid. The vapors will then reach the
thermometer and through the side tube into the condenser. Since cold water is being circulated
through the condenser, the vapors will condense and collect by means of a curved adapter into
the receiving flask. The temperature will remain constant till all the liquid has distilled. The
impurities remain in the flask. The thermometer should not be immersed into the liquid because
in that case, a temperature above the boiling point of liquid is recorded. To observe the correct
boiling point, the thermometer be placed ideally in the vapors. The distillation of a liquid may
be accomplished either at atmospheric pressure or under reduced pressure. In general, if the
boiling point of the sample is above 180C, then a reduced pressure distillation is recommended.
In distillation, we often distill a mixture of two miscible liquids that form ideal solution.
An ideal solution is sometimes defined as one which obeys Raoults law. However, there are
a number of liquid mixtures that fail to obey this law. Such liquids may form an azeotrope. An
azeotope or an azeotropic mixture is a mixture of definite composition that distills at a
constant temperature as if it were a pure liquid. The boiling point of an azeotrope differs
slightly in some cases from the boiling point of only one component. A familiar example is ethyl
alcohol and water containing 95.5 percent ethyl alcohol and 4.5 percent water and boils at 78.15
C whereas pure alcohol boils at 78.3C. An azeotropic mixture cannot be separated by simple
distillation.
18 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Questions
2.1 What is the function of adding boiling chips to the liquid before heating?
2.2 Describe super heating.
2.3 If a liquid boils at a constant temperature over the whole range, could you conclude
that it is pure?
2.4 Why is cold water circulated through a condenser from the lower to the upper end?
2.5 Could you record the correct boiling point if the thermometer tip is immersed into the
liquid?
A packed column provides a large surface area for efficient distillation. The efficiency
of a column is expressed in terms of theoretical plates. A theoretical plate is the column
within the column that is equal to a simple distillation. Therefore, a column with n theoretical
plates is equal to n number of distillations. A fractionating column performs the function of
several hundred distillations. The apparatus for fractional distillation is shown in Fig. 2.6.
This assembly differs from that of simple distillation in that a fractionating column
has been incorporated between the distilling flask and the stillhead. A boiling chip is added
and the liquid is heated as usual in the distilling flask. The more volatile liquid vaporizes
faster than the high boiling liquid, these vapors get condensed on the column packing. This
continues and eventually the vapors get enriched in the lower boiling component.
Equilibrations occur in all parts of the column and vapors that pass into the receiver are
20 LABORATORY MANUAL OF ORGANIC CHEMISTRY
those of the pure low boiling liquid. The residue in the flask is the high boiling liquid. The
temperature remains constant till all the more volatile liquid has been distilled. The
temperature than drops a little indicating one component of the mixture has been removed.
More heat should be applied at this stage, and the second liquid commences to distill.
Questions
2.6 Define a theoretical plate.
2.7 Explain why a packed fractionating column is more efficient at separating a mixture
of closely boiling liquids than an unpacked one.
2.8 If the rate of distillation through a packed column in too rapid, what will be its effect
on the efficiency of separation?
Fig. 2.7: (a) Apparatus for distillation under reduced pressure (b) Pressure measuring device.
Question
2.9 When 1-phenylethanol is purified by distillation, reduced pressure is always employed?
Explain.
Steam from the generator (or a steam line) is passed through a flask containing the
mixture to be separated. The steam inlet tube extends to the bottom of the flask. This flask
is also heated directly by a Bunsen burner. The flask is also fitted with a Claisen head and
a stillhead. The stillhead contains the thermometer while its other end is attached to a
condenser. Since the compounds distil along with water, it is essential to incorporate an
adapter between the generator and the distilling flask. Steam also contains water, therefore,
it should be removed before admitting the steam into the flask in order to prevent the
volume of liquid in the flask which will become exceedingly large. After the distillation is
over, the organic compound can be separated from the water-compound mixture in a
separatory funnel. If the quantity of the compound is small, then it can be extracted with
ether. The ether solution is dried with a drying agent and ether evaporated.
Questions
2.10 Describe the principle of steam distillation.
2.11 Can a mixture of salicyclic acid and p-dichlorobenzene be separated satisfactorily by
steam distillation? Give reasons.
2.12 Would you expect bromobenzene to be purified by steam distillation?
LABORATORY EQUIPMENTS AND TECHNIQUES 23
2.4 CRYSTALLIZATION
Crystallization is the most effective technique of purifying solid organic compounds. It is
though not applicable to substances that react chemically with water. Products of organic
reactions are seldom pure as they may be contaminated either with the starting material or
some side-product. This will result in lowering of the melting point. Therefore, to obtain
reasonably satisfactory physical constants, the substance needs to be purified. To accomplish
this, different methods have been employed depending on the physical state of the organic
compound. Distillation methods as described earlier are used for the purification of liquids.
For solids, on the other hand, the technique of crystallization is employed. A solid substance
is dissolved in a suitable solvent at its boiling point and then precipitated in a crystallized
form on cooling. The substance is said to be crystallized and this process is referred to as
crystallization. Crystallization depends on the differential solubility of a substance in a
hot and a cold solvent. It is desirable that the solubility of the substance be high in the hot
and low in the cold solvent. The glasswares shown below are frequently used in crystallization.
If a single solvent is not found satisfactory than a mixture of two solvents may help.
The binary mixture of solvents is so chosen that the substance is soluble is one while
insoluble in the other. In such a case, the compound is dissolved in one solvent on heating
and to the hot solution, the other solvent is added dropwise with swirling the flask till a
turbidity appears. At this stage a few drops of the first solvent are added till the solution
becomes clear. Keep the solution undisturbed for crystallization.
Samples to be crystallized often contain soluble extraneous coloring matter. Therefore,
a small amount of activated charcoal, i.e., Norit should be added to the solution and boiled
for a few minutes. The amount of charcoal should be kept to a minimum as some of the
desired product is invariably absorbed on charcoal. The solution is filtered while still hot to
minimize evaporation of the hot solution during filtration. If this is not done, the solvent is
likely to crystallize on the filter paper. The filtrate is cooled slowly at first and then in an
ice-bath if necessary. Slow cooling of the solution is necessary because it will result in large
crystals. Rapid cooling and stirring will lead to smaller crystals. The size of the crystals
depends on the rate of cooling.
It may be pointed out that rapid formation of solid material amounts to precipitation
and is not exactly the same as crystallization.
If after cooling the solution, no crystals appear, then it is wise to induce crystallization
by adding a few seed crystals of the pure substance already available to the solution. This
will provide a nucleus for the crystals to grow, this process is called seeding. If this fails,
alternatively the sides of the container may be scratched with a glass rod. This process
proves effective in inducing crystallization. But if this also fails then probably there is too
much solvent which should be removed by boiling and the remaining solution cooled again.
Finally, the solution may be cooled in dry ice-acetone bath if all these attempts fails. If the
compound is incapable of crystallization, some other technique such as chromatography
may prove helpful.
LABORATORY EQUIPMENTS AND TECHNIQUES 25
After the crystallization is complete, the crystals are filtered in a small Buchner funnel.
The filtrate or the solution remaining after the removal of crystals is called the mother
liquor. This also contains a significant quantity of crystals. Some solvent may be evaporated
from this solution and the remaining solution left for crystallizations to obtain a second
crop of the substance. Crystals from mother liquor are almost always somewhat less pure
than the crystals which separate first. The crystals are then freed of adhering solvent. For
this the crystals are pressed between the folds of filter paper and squeezed. They are then
transferred to a clean watch glass. Crystals may be dried in air at room temperature or in
a vacuum desiccator. Small samples can be dried in an Aberhalden pistol. The melting
point of the substance is finally determined. Two or more crystallizations may be necessary
in some cases if a satisfactory melting point is not obtained of the crystallized sample.
Questions
2.13 How is colored product decolorized from a preparation?
2.14 During crystallization, the solution should not be rapidly cooled in ice. Why?
2.15 What objection might be offered to the use of a particularly drying agent in the case
listed below:
(a) Calcium chloride for aniline.
(b) Phosphorus pentoxide for isopropyl alcohol.
(c) Potassium hydroxide for methyl butyrate.
2.16 Would you recommend suction filtration for a solution in which petroleum ether is the
solvent?
2.17 How does the size of crystals depend on the rate of cooling of the solution?
2.18 What is the affect of impurities on the melting point of a compound?
2.19 During recrystallization the solution should not be suddenly cooled in ice. Why?
Sodium sulfate (Na2SO4): It is a high capacity reagent but possesses low action and
efficiency. It combines with seven and ten molecules of water, and is recommended for
removal of water, especially from ether solution of organic compounds. It is less efficient
than MgSO4.
Calcium chloride (CaCl2) : It is good in terms of both intensity and capacity, though,
it cannot be used to dry amines, alcohols, phenols, acids and esters. It is good for halides
and hydrocarbons.
Potassium carbonate (K2CO3): It is a basic drying agent and is fairly good. It reacts
with two molecules of water. It is good for oxygen and nitrogen containing compounds.
Phosphorus pentoxide (P2O5): It is an acidic drying reagent. The dried solution can
be distilled from the drying agent.
DETECTION OF ELEMENTS
In qualitative organic analysis the principal concern is with the detection and identification
of unknown organic compounds. The unknown may be a solid or liquid. The process of
identification involves a series of steps that help to establish the identity of the unknown
compound. The analysis commences with certain preliminary tests which offer the worker
certain clues about the type and class of compound under examination. Any conclusion
drawn, however, depends on ones chemical intuition and experience. A systematic analysis
of detecting the elements is initially carried out which enables a rational choice of subsequent
tests to be performed. It is thus advisable to start with the determination of physical
properties and the types of elements present in the unknown compound.
3.2 COLOR
Note the color of the unknown compound. Not many organic compounds are colored. A
colored sample, therefore, may be characteristic of certain groups of substances or functional
group present in the unknown. The color of a compound is attributed to the presence of
28 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Compound Color
p-Nitrotoluene Lemon
o-Nitrophenol, iodoform Yellow
o-Nitroaniline Orange
m-Nitroaniline Golden yellow
p-Nitroaniline Pale yellow
o-Nitrobenzoic acid Colorless
Resorcinol Light pink
p-Cresol Dark pink
m-Cresol Dark pink
>-Naphthol Chacolate
Sulfanilic acid Grey
Aniline hydrochloride Colorless but becomes
black on keeping
Picric acid Yellow
Azobenzene Orange
p-Benzoquinone Yellow
3.3 ODOR
Since a large number of organic compounds possess characteristic odors, it is anticipated
that olfaction may disclose the presence of certain groups of substances. Except aromatic
carboxylic acids other compounds such as alcohols, esters, aldehydes, amines and ketones
possess odor. Care must be exercised in smelling organic compounds as the vapors of a
large number of compounds are dangerous. Depending on the experience of the worker it
may be possible to relate the unknown to a certain class of compounds, for instance, esters
have familiar fruity odor while aromatic hydrocarbons possess characteristic aroma.
dioxane and tested with litmus paper. A change in color from blue to red indicates that the
substance is acidic and red to blue indicates a basic substance. On the other hand, if there
is no change then the compound is neutral such as aldehydes, ketones, esters or
hydrocarbons. Amines are basic.
3.6 SOLUBILITY
In general, low molecular weight organic compounds containing polar functional groups
are soluble in water. Others are soluble in common organic solvents such as ethanol, acetone,
benzene, chloroform, etc. The solubility characteristics of a compound may be useful in the
classification of the unknown. The quantity of the compound and the solvent employed in
the solubility test are critical if reliable information is to be derived. Normally a compound
is considered soluble if the solubility of that compound is greater than 3 parts of compound
per 100 parts of the solvent at room temperature. In other words, the compound is soluble
if it dissolves to the extent of about 30 mg of solid or one drop of the liquid in 1 ml of the
solvent. The solvents recommended for use in this test are water, 5% sodium hydroxide,
5% hydrochloric acid and 5% sodium bicarbonate. By checking the solubility of a compound
in these reagents, it may be possible to determine whether the unknown has a low molecular
weight, neutral compound, an acid, a base or a salt. The following scheme may be useful for
classification by means of solubility (p. 30).
This chart offers only a guideline of classifying the compounds by means of solubility.
It is not essential to test the compounds in all of the solvents, but solvents should be used
in the order listed. In case the substance is soluble in water, it should be tested in ether in
order to determine if it is a salt. However, if the compound is insoluble in water there is no
need to try ether as solvent, rather treated with sodium hydroxide, hydrochloric acid, sodium
bicarbonate. If there is a doubt whether or not an appreciable quantity of the substance has
dissolved in acid or base, the clear solution should be separated from the rest of the
compound and neutralized to see if the original compound separates.
Questions
3.1 What are the inferences drawn from the solubility test?
3.2 Ethyl iodide is polar but unlike such polar compounds as alcohol and acetic acid it is
insoluble in water. Explain.
30 LABORATORY MANUAL OF ORGANIC CHEMISTRY
DETECTION OF ELEMENTS 31
Chemical reactions:
(i) Na +
C, N Na CN
(ii) H2 O
+ 2
S Na2 S
+
X Na X
X = Cl, Br, I
During this process sodium metal combines with the elements present in the sample
and converts them into water soluble salts as shown in the above equations.
shaking till a clear solution is obtained. A Prussian blue color indicates the presence of
nitrogen. This is called the Lassaigns test.
Chemical reactions:
On boiling the alkaline solution some ferric ions are produced by the oxidation of
ferrous ions by air. Both ferrous and ferric hydroxides dissolve on adding dil. sulfuric acid.
The ferrocyanide reacts with ferric ions to produce the Prussian blue color of ferri-
ferrocyanide.
The alkaline solution should not be acidified by hydrochloric acid because the yellow
color due to the ferric chloride formed causes Prussian blue to appear greenish. Ferric
chloride, as is usually recommended, should not be added for the same reason.
Questions
3.3 Why should ferrous sulfate solution be fresh and saturated in the test for the detection
of nitrogen?
3.4 Would hydrazine hydrochloride give Lassaignes test for nitrogen?
Chemical reactions:
Na 2+ S 2 + 2CH3COOH 2CH3COO Na + + H 2S
Chemical reaction:
[
Na 2 + S 2 + Na 2 Fe(CN) 5 NO ] [
Na 4 Fe(CN) 5 NOS ]
Sodium nitroprusside (Deep red or violet)
Chemical reactions:
Na
C + N + S NaCNS
Sodium thiocyanate
3 NaCNS + FeCl3 Fe (CNS)3 + 3 NaCl
Ferric sulfocyanide
(d) Tests for halogens
(i) Beilstein test:
Make a small loop (23 mm diameter) at one end of a copper wire (10 cm or
longer). Insert the other hand of the wire in a cork. Heat the loop to redness in a
flame and then cool it. Dip the loop into the unknown and heat it in the non-
luminous (blue) flame of the burner appearance of green or blue flame indicates a
halogen compound.
Try this test, first taking a simple halogen compound such as chlorobenzene.
(ii) Silver nitrate test:
Acidify 2 ml of the sodium fusion extract with dil. nitric acid and boil. Add several
drops of silver nitrate solution. If halogens are present a flocculent white or yellow
precipitate which darkens on exposure to light and is soluble in ammonium
hydroxide indicates the presence of halogens. The acidification of the sodium
fusion extract is necessary before adding silver nitrate solution to prevent the
precipitation of silver hydroxide or silver oxide.
34 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Chemical reaction:
dil. HNO3
Na + X + AgNO3 AgX + NaNO 3
The above test shows the presence of halogens in the sample. Since all the halogens
precipitate in this test as AgX, this determination is incomplete, therefore, the presence of
individual halogen has to be made. Fluorine is not detected in this test since silver fluoride
is soluble in water. In order to detect the individual halogens proceed as follows.
Acidify 2 ml of the sodium extract with dil. nitric acid and boil. Add 45 drops of carbon
tetrachloride and 1 ml of fresh chlorine water. Shake the contents vigorously. If the resultant
carbon tetrachloride layer is colorless and also a flocculent white precipitate is obtained on
the addition of silver nitrate which is soluble in ammonium hydroxide, then it indicates
chlorine. A brown color of the carbon tetrachloride layer indicates bromine while a violet
color indicates iodine. The advantage in this test is that bromine and iodine have
characteristic colors.
Chemical reactions:
Chemical reaction:
Iodine is removed from this solution by a repetition of the above process till the carbon
tetrachloride layer becomes colorless. Boil the aqueous layer to remove nitrous oxide.
DETECTION OF ELEMENTS 35
Cool and add a pinch of lead oxide and boil the mixture. If bromine is present a strip of
fluorescein paper placed across the mouth of the tube turns pink.
Chemical reaction:
Remove bromine and acidify the aqueous layer with nitric acid and add silver nitrate
solution, a heavy white precipitate soluble in ammonium hydroxide indicates chlorine.
Chemical reaction:
Alternatively the following procedure may be used if chlorine or one of the other
halogens is present.
Acidify 2 ml of the sodium extract with dil. nitric acid and add silver nitrate solution.
Filter the precipitate and wash twice with distilled water. Transfer the precipitate to a
small test tube and shake with 3 ml of ammonium carbonate solution and 2 ml of ammonium
hydroxide solution. Filter again and acidify the clear filtrate with dil. nitric acid. Appearance
of a flocculent precipitate indicates the presence of chlorine. With another test portion of
the sodium extract proceed as in Sec. 2.7(d) to test for bromine or iodine.
Chemical reactions:
NaCN + HNO3 HCN + NaNO3
A slight turbidity is not a positive test. To detect the individual halogens proceed as in
Sec. 3.7 (d).
Fluorine as stated earlier is not detected because silver fluoride is soluble in water. If
it is desired to detect fluorine, the following test could be performed.
36 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Take 2 ml of sodium fusion extract and acidify it with glacial acetic acid. Boil the
mixture and reduce the volume to one half. With a glass rod, spot this solution on a zirconium
- alizarin red S paper. The appearance of a yellow spot is a positive test for the presence of
fluorine.
Questions
3.5 Why is the sodium fusion extract acidified before testing for halogens?
3.6 Why should hydrogen cyanide and hydrogen sulfide be expelled before a test is made
for halide ion?
3.7 How will you distinguish between a halogen present in the side chain and that in the
aromatic nucleus?
3.8 How will you detect chlorine in the presence of iodine?
3.9 Write all the pertinent chemical reactions involved for the detection of chlorine in the
presence of nitrogen.
3.10 Why is fluorine not detected in the sodium fusion extract with silver nitrate? Suggest
a method for its detection.
Chapter 4
Detection of a functional group is the next step in the identification of an unknown organic
compound. A careful detection of elements is of great help in the establishment of the
nature of the functional group. A number of assorted tests for individual groups need to be
performed for their identification. In this chapter tests for some selected functional groups
will be described.
Chemical reaction:
Chemical reactions:
Chemical reactions:
A positive test depends on the fact that alcohol is soluble in the reagent while the
alkyl chloride is not.
This test fails if zinc chloride is not anhydrous or if the reagent had been sitting on the
shelf for a long time. In case of doubt whether the alcohol is tertiary or secondary, conc.
hydrochloric acid may be employed.
To 1 ml of alcohol in a test tube add 5 ml of conc. hydrochloric acid and shake. A layer
of alkyl chloride separates immediately in the case of tertiary alcohol but secondary alcohols
react slowly and the solution remains clear (or it may become turbid after sometime).
Chemical reaction:
Dissolve 1 drop (10 mg) of the unknown alcohol in 1 ml of pure acetone. Add 1 drop of
the above reagent while shaking, the orange color disappears. Primary and secondary alcohols
react to give a precipitate that cause the solution to become opaque with a greenish or
greenish blue tint. Tertiary alcohols do not react and the test solution remains orange. Any
of these changes taking place after two min may be disregarded. For the success of this test
the sample should not contain an aldehyde function.
Chemical reactions:
Questions
4.1 What is the basis of the Lucas test?
4.2 Why is it essential to use anhydrous zinc chloride in the Lucas test?
Green >-Naphthol
The color produced may not be permanent, therefore, observation should be made at
the time of addition. Always use a dilute solution of phenol. This test is negative with
m-and p-hydroxybenzoic acids.
Chemical reaction:
The reaction takes place in polar solvents, therefore, a few drops of pyridine are needed
if it is carried out in a non-polar solvent, ( ether, benzene, etc.) . Certain phenols like
o-nitrophenol and quinol do not give any color in this test.
Ferric complexes are formed in these reactions and polar solvents like methanol is
the most suitable medium. Nitrophenols can be expressed as mesomeric structures with a
positive charge on the nitrogen atom and competing with ferric ions in their influence on
electron pair thus weakening the iron-oxygen bond. Addition of acids destroys the color in
this test, p-hydroxybenzoic acid does not give color for this reason. Salicylic acid, on the
other hand gives a blue color because it forms a strong complex with ferric chloride.
Question
4.3 Why does o-nitrophenol give no color with FeCl 3 solution?
42 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Chemical reaction:
Only those phenols possessing a free para position respond to this test. Resorcinol
responds to this test.
Pink Phenol
Blue Catechol
No color p-Cresol
TESTS FOR FUNCTIONAL GROUPS 43
Chemical reaction:
Questions
4.4 In the bromination (Br 2 + H 2O) of phenol though hydrogen bromide is evolved but its
evolution is not observed why?
4.5 Is bromination of phenol faster in water or carbon tetrachloride?
Tests for the detection of aldehydes and ketones groups will be discussed under
this section. These are neutral compounds and contain reactive carbonyl group. In most
chemical reactions aldehydes are more reactive than ketones. In many cases they undergo
similar reactions, for example, addition and reduction. Thus it is necessary at first to
44 LABORATORY MANUAL OF ORGANIC CHEMISTRY
distinguish them from alcohols. One useful method to do this is to treat them with 2,4-
dinitrophenylhydrazine, whereby a bright orange crystalline solid separates out in the case
of carbonyl compounds only, but not alcohols.
The high reactivity of the compounds with this reagent is due to the character of the
carbonyl group.
In a test tube take 0.1 g (3 drops if liquid) of the unknown and dissolve in 2 ml of 95%
ethanol. Add 23 drops of the 2, 4-dinitrophenylhydrazine solution into the tube and shake.
Allow the tube to stand for 15 minutes or till a precipitate is formed. Scratch the sides of
the tube if necessary formation of a crystalline yellow or orange-red precipitate indicates
an aldehyde or ketone.
Aldehydes are generally more reactive than ketones, the former are identified by
oxidizing reagents such as Tollens, Benedict and chromic acid.
Chemical reaction:
Ketones, ethers and even alcohols do not respond to this test because like aldehydes
they cannot be oxidized to carboxylic acids. Aromatic aldehydes respond poorly.
=-Hydroxyketones are oxidized, though, to diketons.
TESTS FOR FUNCTIONAL GROUPS 45
Chemical reactions:
The appearance of color is not caused by simple oxidation to fuchsine rather represents
a specific reaction of the aldehyde group. Fuchsine leukosulfonic acid (I) reacts with aldehyde
and sulfurous acid which on elimination of a molecule of sulfurous acid yields the colored
mesomeric cation (II ). The reaction mixture should not be heated otherwise a pink color is
obtained even in the absence of an aldehyde. In a strongly acidic solution, formaldehyde
yields a blue-violet color. All aliphatic and aromatic aldehydes and p-hydroxybenzaldehyde
respond to this test, but salicylaldehyde does not.
46 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Chemical reaction:
Chemical reactions:
Ketones respond negatively to the above tests and thus can be distinguished from
aldehydes. The following test can be employed for the detection of ketones.
substance). To this add 1 ml of 10% sodium hydroxide solution and iodine-potassium iodide
reagent dropwise till a definite dark color of iodine persists. Allow it to stand for several
minutes at room temperature. If the color disappears add more reagent till the color persists.
Allow to stand for 15 min. A positive test is indicated by the formation of a yellow precipitate
of iodoform (m.p. 120 oC) of characteristic odor. If the substance was insoluble in water then
at the end of the reaction dilute with 10 ml water.
Chemical reactions:
This reaction takes place through the formation of a carbanion, therefore, the hydroxyl
ions should always be present in excess.
48 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Aliphatic ketones ( acetone, methyl ethyl ketone, 2-heptanone, methyl propyl ketone,
etc.), mixed ketones (acetophenone and its p-substituted derivatives) and alcohols (ethanol,
iso-propanol, sec-butanol, 2-octanol, etc.) also respond to this test.
Since certain alcohols which can be oxidized to methyl ketones give a positive test in
the iodoform reaction this test thus only be carried out if presence of a carbonyl group is
confirmed.
Questions
4.6 Why are aldehydes more reactive than ketones?
4.8 Aldehydes react with neutral potassium permanganate to discharge the purple color
and give brown precipitate. Why is this not used as a test for aldehydes?
4.9 A compound gives a positive test with 2, 4-dinitrophenylhydrazine but it does not
reduce Tollens reagent. What is the nature of the compound?
4.10 Given are three samples of 3-pentanone, pentanal and 2-pentanone. How would you
determine by simple tests which is which? Write chemical reactions.
4.12 How would you distinguish between aliphatic and aromatic aldehydes?
TESTS FOR FUNCTIONAL GROUPS 49
Carboxylic acids do not give characteristic color reactions therefore, for this class of
compounds the detection depends on their acidity. This is determined by means of litmus
paper for water soluble acids (lower molecular weight acids) and with sodium bicarbonate
for water insoluble acids.
Chemical reaction:
This test also differentiates between acids and phenols as the latter are insoluble in
sodium bicarbonate solution. However, those phenols which contain electron-withdrawing
groups such as 2, 4-dinitrophenol are soluble in sodium bicarbonate. A satisfactory
identification of an acid requires the preparation of its appropriate derivative.
Questions
4.13 How would you distinguish between benzoic acid and phenol?
4.14 Would you expect a carboxyl group to form an oxime?
Esters are neutral and many of them possess characteristic fruity smell.
indicator and two drops of 0.1 sodium hydroxide solution. If on heating the pink color
disappears then an ester is indicated.
Chemical reactions:
4.6 CARBOHYDRATES
Mono- and - disaccharides are colorless solids soluble in water but insoluble in most organic
solvents. They do not possess sharp melting points rather decompose on heating. They
contain reactive groups which give certain color reactions. A classification into reducing
and non-reducing sugars can be affected by the Benedicts reagent.
All monosaccharides and many disaccharides are reducing sugars. This is ascribed to
the presence of an aldehyde or =-hydroxy keto group in the sugar that can partake in an
oxidation-reduction reaction. Disaccharides in which one of the rings is a hemiacetal are
reducing sugars, but those in which both rings are in acetal or ketal form are non-reducing
sugars. This is based on the fact that they cannot be in equilibrium with the aldehydic or
the ketonic form.
TESTS FOR FUNCTIONAL GROUPS 51
Chemical reaction:
Identification of individual sugars is established by preparing the osazone (see chapter 6).
Certain individual tests may also be employed for each sugar.
Glucose
Take 2 ml of the aqueous solution of sugar in a test tube add 50 mg of lead acetate and
heat to boiling. Add 5 ml of dil. ammonium hydroxide and boil the mixture again for 1
minrose pink color appears.
Fructose
To 2 ml of the aqueous solution of sugar in a test tube add an equal volume of conc.
hydrochloric acid and 10 mg of resorcinol warm the tube in a beaker of boiling water for 2
mina deep red color appears followed by a precipitate.
52 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Galactose
Place 0.5 g of the substance in a dry test tube and add 1.5 ml of 50% nitric acid. Allow
the tube to stand in a beaker of boiling water until red fumes evolve. Then keep the tube
for 15 min in another beaker containing water at 70oCa white precipitate results.
Sucrose
Sucrose does not reduce Fehlings solution. On treatment with conc. sulfuric acid, it
gets charred even in cold. Sucrose also responds to color tests.
Dissolve 0.5 g of the substance in 2 ml of distilled water. To this add 0.1 g of resorcinol
and 1.5 ml conc. hydrochloric acid. Boil the mixture for 2 mina deep wine red color
appears.
Questions
4.15 What is the color due to in the Molisch test for carbohydrates?
4.16 How will you distinguish between reducing and non-reducing sugars?
Chemical reactions:
This test is applicable if the original unknown gives a negative Tollens test.
TESTS FOR FUNCTIONAL GROUPS 53
Chemical reaction:
Question
4.18 Is the evaluative test for the nitro group applicable to p-nitrobenzaldehyde? Explain.
Chemical reaction:
Chemical reaction:
This reaction should be performed in the fume chamber. Both aliphatic and aromatic
primary amines respond to this test. This test is negative both for secondary and tertiary
amines. Before pouring into the sink, the mixture should be acidified with dil. hydrochloric
acid. This would convert the isonitrile into the corresponding hydrochloride of the amine.
A distinction between a primary aliphatic and aromatic primary amines can be made by the
coupling test (part a).
An additional test for primary aliphatic amines may be performed.
Add 12 drops of the substance (0.1 g for solid) in a test tube. Add 3 ml water followed
by 1 ml acetone. Shake to mix. Add 2 drops of 1% aqueous solution of sodium nitropruside.
A red-violet color appears.
As in the case of alcohols it is also essential to distinguish between primary, secondary
and tertiary amines. This can be achieved by the Hinsberg test.
Chemical reaction:
Primary amine
Secondary amine
The presence of a secondary amine as indicated by the Hinsberg test can be confirmed
as follows:
Dissolve 0.1 g of NiCl2 . 6H2O in 20 ml of water and add sufficient carbon disulfide
until a small globule remains undissolved after the mixture has been shaken vigorously.
To 1 ml of this reagent add 1 ml of conc. ammonium hydroxide followed by a solution of
0.1 g of the unknown in 5 ml of water, to which 2 drops of conc. hydrochloric acid have been
added, if necessary to complete dissolution of the amine. Shake a precipitate is formed.
Chemical reaction:
Questions
4.19 How will you distinguish between a primary and secondary amine?
4.20 2, 4-Dinitroaniline does not form a salt with 20% hydrochloric acid. Suggest a reason.
4.21 Why are benzamides of primary amines insoluble in aqueous alkali while the
corresponding sulfonamides are soluble?
4.26 During diazotisation why the mineral acid should be used in excess?
56 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Chemical reactions:
This test fails if hydrogen at the nitrogen atom is replaced by an alkyl or aryl group,
then an amine is produced.
Chemical reactions:
A nitrile can also be hydrolyzed to a carboxylic acid salt similar to a primary amide.
TESTS FOR FUNCTIONAL GROUPS 57
Nitriles are slowly hydrolyzed than amides. They can be rather easily hydrolyzed in conc.
sulfuric acid.
A nitrile group also undergoes the hydroxamic acid test to form the following red
colored species of ferric hydroxymate.
Note it should be performed only in the absence of an aromatic primary amino group.
58 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Place 0.2 g of the compound in a boiling tube. Add 56 ml of 75% sulfuric acid to it and
boil the contents for 5 minutes. Dilute it with 3 ml distilled water and filter. Cool the
filtrate in ice to 0 5oC. In the cold solution add 2 ml of 10% sodium nitrite solution. To this
mixture add a precooled 50 mg solution of >-naphthol in 2 ml of 10% sodium hydroxide.
solution. Formation of an orange to red dye indicates an anilide group.
4.11 HYDROCARBONS
Hydrocarbons are neutral compounds and do not contain any functional group. Aromatic
hydrocarbons possess characteristic odor and burn with a smoky flame. These are insoluble
in water but dissolve in many organic solvents. The following two color tests may be applied
for their identification. The colors abtained are usually intense. A light yellow color is
inconclusive or negative.
Benzene (b.p. 110oC) and Dark red color (with some black
monoalkylated derivatives precipitate)
A Friedel-Crafts reaction probably takes place to form colored derivatives. This test
should be performed on aromatic hydrocarbons that have been shown insoluble in conc.
sulfuric acid.
4.12 UNSATURATION
Chemical reaction:
Chemical reaction:
This test may sometimes lead to wrong conclusions because certain other compounds
such as aldehydes, phenols, arylamines, primary and secondary alcohols also decolorize
potassium permanganate solution. Therefore, it should be carried out judiciously. This test
is thus more general and less specific than the addition of bromine.
Questions
4.27 How will you differentiate between cyclohexene and benzene?
4.28 Name an aromatic compound which reacts readily with bromine both by addition and
substitution.
Chemical reactions:
Thiourea also evolves ammonia gas on heating alone or in the presence of base similar
to urea.
Questions
4.31 What happens when urea is
(a) reacted with hydrazine.
(b) heated alone.
(c) refluxed with a base.
4.32 What happens when urea is heated with alkaline KMnO 4 solution?
Chapter 5
A large number of organic compounds contain more than one functional groups, and the
properties of one group may be masked by the other. Therefore, to classify the compound
correctly, additional tests need to be performed. The final decision, however, would rest on
the preparation and identification of its derivative (Chapter 6). In some cases such tests to
be described in this chapter may even assist in identifying the compound itself.
It is soluble in water.
(a) Add 1 drop of the aqueous solution of alcohol to 2 ml of iodine solution followed by
the addition of dil. sodium hydroxide solution dropwise, till the deep brown color
of iodine changes to pale yellow. Shakeyellow precipitate of iodoform appears.
(b) On boiling with conc. hydrochloric acid it yields sec butyl chloride, b.p. 67C.
On boiling with hot potassium dichromate and dil. sulfuric acid, isobutyraldehyde distils
over. This can be tested by the Schiffs reagent.
160 Cyclohexanol
It is soluble in water.
(a) On boiling with potassium dichromate and dil. sulfuric acid, it forms cyclohexanone,
b.p. 115C, but on oxidation with hot conc. nitric acid, adipic acid m.p. 149C is
obtained.
(b) Distillation of cyclohexanol in the presence of catalytic amount of phosphoric acid
or conc. sulfuric acid yields cyclohexene, b.p. 83C.
176 o-Chlorophenol
It is slightly soluble in water but completely so in alcohol and ether. It gives violet color
with ferric chloride solution.
196 o-Bromophenol
197 Linalool
(a) Add 2 drops of the aqueous solution of the alcohol to 3 ml of bromine water in a
test tube. The bromine color immediately disappears. This shows the presence of
unsaturation in linalool.
(b) Acetate, b.p. 103C/30 mm.
(c) =-Naphthyl carbamate, m.p. 53C.
202 m-Cresol
214 m-Chlorophenol
On reaction with 50% nitric acid in the cold it yields a 4-nitro derivative, m.p. 133C.
It is soluble in water and the aqueous solution has the odor of rose oil.
(a) On oxidation (described above under benzyl alcohol ) it yields benzoic acid, m.p.
121C.
(b) Acid phthalate, m.p. 188C.
TESTS FOR COMMON ORGANIC COMPOUNDS 67
222 Citronellol
(a) It possesses a pleasant odor and unsaturation which can be detected by bromine
water.
(b) Acetate, b.p. 120C/15 mm.
230 Geraniol
m.p. (C)
30 o-Cresol
It has a carbolic acid odor and gives violet color with ferric chloride solution.
(a) In a dry test tube place a few milligrams of phthalic anhydride and twice the
amount of the compound. Add 2 drops of conc. sulfuric acid and heat the mixture
on a flame gently till the mixture attains a red-brown color. Cool and add a few
drops of water to the mixture followed by dil. sodium hydroxide solution dropwise
till the solution is alkaline.
Appearance of red color indicates o-cresol or phenol.
(b) To 2 ml of conc. ammonium hydroxide solution add a pinch of the compound. If
the compound is undissolved then it shows o-cresol, but if a clear solution is
obtained then it is phenol.
33 Cinnamyl alcohol
compound and shake. The brown color of bromine disappears forming a dibromide
(m.p. 74C).
(b) On oxidation with potassium permaganate it yields benzoic acid, m.p. 121C.
35 Terpineol
36 p-Cresol
42 Phenol
43 p-Chlorophenol
45 o-Nitrophenol
It is yellow in color and has a tarry odor. It is readily soluble in hot water and most organic
solvents. It gives no color with ferric chloride solution.
(a) Dissolve 25 mg of the compound in water and add 2 ml of dil. sodium hydroxide
solution. Shakedeep red color.
(b) With conc. nitric acid and sulfuric acid it is nitrated to give yields picric acid, m.p.
114C.
64 p-Bromophenol
94 =-Naphthol
It gives no color with neutral ferric chloride solution but a white precipitate.
(a) Place 0.5 ml of the compound in a test tube. Add 2 ml of dil. sodium hydroxide
solution, and 1 drop of chloroform. Warm the mixturea blue color is obtained
with both =- and >-napththols.
Take a mixture of 10 ml of iodine solution and dil. sodium hydroxide solution in a
test tube and add 50 mg of the compound. A violet precipitate appears which
darkens rapidly=-naphthol. If there is no change in the solution>-naphthol.
(b) Warm a pinch of the substance with dil. sodium hydroxide solution, carbon
tetrachloride and some copper powder in a test tubea blue color appears.
70 LABORATORY MANUAL OF ORGANIC CHEMISTRY
97 m-Nitrophenol
It is pale yellow in color but odorless and is soluble in hot water and most organic solvents.
(a) Dissolve 25 mg of the compound in hot water, add 2 ml dil. sodium hydroxide
solutionorange-red color.
(b) Dissolve 25 mg of the compound in 5 ml of water and heat to boiling. Cool and
add a few drops of ferric chloride solution violet-red color.
105 Catechol
It is readily soluble in water and yields green color with ferric chloride solution.
(a) To the aqueous solution of the alcohol in a test tube, add an equal volume of lead
acetate solution a white precipitate appears immediately.
(b) With bromine it yields a tetrabromo derivative, m.p. 192C.
110 Resorcinol
It is readily soluble in water and gives blue-violet color with ferric chloride solution.
(a) In a dry test tube place 25 mg of phthalic anhydride, 50 mg of the compound and
2 drops of conc. sulfuric acid. Heat gently on a flame until the mixture is red-
brown in color. Cool and add a few drops of water followed by dil. sodium hydroxide
solution till the solution is alkaline. Place one drop of this solution in a second
tube and fill it up with water a yellow green fluorescence.
(b) Warm 50 mg of the alcohol with dil. sodium hydroxide solution and chloroform
red color with green fluorescence.
114 p-Nitrophenol
It is pale yellow in color but odorless. It is soluble in hot water, alcohol and ether.
(a) To 25 mg of the compound in a test tube add 1 ml of water followed by 2 ml of dil.
sodium hydroxide solution an intense yellow color.
(b) Dissolve 25 mg of the compound in 5 ml of water and add 2 drops of ferric chloride
solution violet red color.
TESTS FOR COMMON ORGANIC COMPOUNDS 71
It is light yellow in color and soluble in hot water, alcohol and benzene.
(a) To 5 ml of dil. sodium hydroxide solution, add 25 ml of the compound and heat
just to boiling. To the intense yellow colored solution obtained, add a drop of
ammonium sulfide solution a deep red color.
123 >-Naphthol
133 Pyrogallol
It is a white crystalline substance which turns black on exposure to air. It is readily soluble
in water.
(a) To 2 ml of the aqueous solution add a pinch of ferrous sulfate and shake a blue-
violet color.
(b) Triacetate, m.p. 161C.
(a) To 1 ml of copper sulfate solution in a test tube, add ammonium hydroxide solution
till the blue color initially obtained becomes colorless. To this ammoniacal copper
sulfate solution add 0.1 g of the substance and shake blue precipitate is formed.
(b) Hexaacetate, m.p. 119C.
(c) Hexabenzoate, m.p. 124C.
170 Quinol
It is soluble in water and gives a transient blue color with ferric chloride solution.
(a) Dissolve 50 mg of the compound in 2 ml dil. sulfuric acid in a test tube by warming.
Cool the solution and add 25 mg of potassium dichromate immediate precipitate
of quinhydrone consisting of green needles.
(b) Diacetate, m.p. 123C.
174 o- Aminophenol
186 p-Aminophenol
218 Phloroglucinol
It is soluble in water and gives a transient blue color with ferric chloride solution.
(a) Triacetate, m.p. 105C.
TESTS FOR COMMON ORGANIC COMPOUNDS 73
m.p. (C)
76 Phenylacetic acid
It is soluble in water and loses water of crystallization at 130C, forming anhydrous acid
(m.p. 153C).
(a) To 3 ml of the neutral solution add 1 ml of calcium chloride solution and heat the
mixture to boiling for 1-2 min a heavy white precipitate of calcium citrate.
(b) To 1 ml of the neutral solution add 2 drops of sodium introprusside solution a
red color which changes to violet on adding acetic acid.
(c) Amide, m.p. 215C
It is soluble in water.
(a) Place 50 mg of the acid in a test tube and add 5 drops of conc. sulfuric acid. Gently
warm the tube on the flame and turn the mouth of the tube periodically to the
flame carbon monoxide burns with a blue flame.
(b) In a test tube place one crystal of oxalic acid and a small amount of diphenylamine
and heat the mixture with twice the amount of zinc chloride. The mixture first
melts and then turns blue due to the formation of a triphenylmethane dye.
(c) Dimethyl oxalate, m.p. 54C.
It is soluble in water.
To 50 mg of the compound in a test tube add equal volumes of aqueous potassium
permanganate and sulfuric acid and heat odor of benzaldehyde.
It is sparingly soluble in water and gives no color with ferric chloride solution.
To 50 mg of the substance in a dry test tube add 10 drops each of methyl alcohol and
conc. sulfuric acid and heat gently. Cool and pour into 5 ml of water taken in a beaker
smell of methyl salicylate ( oil of wintergreen).
(a) Amide, m.p. 138C.
76 LABORATORY MANUAL OF ORGANIC CHEMISTRY
It is pale yellow in color and only slightly soluble in water. Gives the test (a) as in
o-nitrobenzoic acid.
It is soluble in water
(a) Place 20 mg of the compound in a test tube and add twice the amount of resorcinol
and 2 drops of conc. sulfuric acid. Heat the mixture gently till it turns reddish-
brown. Cool and add several drops of water and then dil. sodium hydroxide solution
till alkaline. Take 1 ml of this solution into another test tube and fill it up with
water violet-red color.
(b) Amide, m.p. 220C.
It is soluble in hot water and yields toluene on heating with soda lime.
Amide, m.p. 158 C.
It is slightly soluble in water. On heating with soda lime it yields anisole, m.p. 154C.
It is soluble in water.
Place 20 mg of the substance in dry test tube and add twice the amount of resorcinol
and 2 drops of conc. sulfuric acid. Gently heat the mixture till it is reddish-brown. Cool and
add several drops of water followed by dil. sodium hydroxide solution till alkaline. Take
1 ml of this solution into another test tube and fill it with water a yellow green
fluorescence.
It is a white solid, soluble in hot water and sparingly soluble in ether and alcohol.
(a) On heating above 150C, it forms phthalic anhydride, m.p. 132C.
TESTS FOR COMMON ORGANIC COMPOUNDS 79
(b) Mix 0.2 g of the acid with 0.4 g of resorcinol and add 1 ml of conc. sulfuric acid in
a test tube. Heat the mixture on a flame till a red-brown in color. Cool and pour
in cold water. Add a few drops of 10% sodium hydroxide solution orange-green
fluorescence.
(c) Amide, m.p. 220C.
It is a colorless solid and has needle-like crystals. It is insoluble in water but soluble in
alcohol and acetone. It gives a violet or red color with ferric chloride solution.
(a) Amide, m.p. 162C
(b) Acetate, m.p. 185C
(c) p-Toluidide, m.p. 208C
Heat 20 mg of the acid with twice the amount of soda-lime in a dry test tube odor of
nitrobenzene.
b.p. (C)
21 Acetaldehyde CH3CHO
It is miscible with water and has a pungent smell. In dilute aqueous solution the odor
resembles that of apples.
(a) To 20 ml of the aqueous solution add 2 ml of the 20% potassium hydroxide solution.
Heat to boiling for 30 sec the solution turns yellow and then yellow precipitates
appear changing to orange.
(b) To 2 ml of the aqueous solution and 2 ml of sodium nitroprusside solution then
add 5 drops of sodium hydroxide solution a deep wine red color.
49 Propionaldehyde CH3CH2CHO
It is soluble in water and has an odor resembling that of acetaldehyde.
(a) To 2 ml of the aqueous solution add 1 ml of dil. sodium hydroxide solution. Boil
for 1 min a white precipitate appears which dissolves to give a clear pale yellow
solution.
(b) 2,4-Dinitrophenylhydrazone, m.p. 155C.
56 Acetone
It is miscible with water and has a pleasant odor.
(a) With iodine solution and dil. sodium hydroxide solution, it yields iodoform (m.p.
119C) in cold.
(b) To 1 ml of aqueous solution of the substance add a few drops of sodium nitropruside
solution a red color.
(c) 2, 4-Dinitrophenylhydrazone, m.p. 128C.
TESTS FOR COMMON ORGANIC COMPOUNDS 81
63 Isobutyraldehyde
75 n-Butyraldehyde CH3CH2CH2CHO
It is soluble in cold water.
2,4-Dinitrophenylhydrazone (m.p. 122C)
115 p-Hydroxybenzaldehyde
130 Cyclopentanone
155 Cyclohexanone
179 Benzaldehyde
196 Salicyldehyde
It is sparingly soluble in water and gives a violet color with ferric chloride solution.
It is oxidized by alkaline potassium permanganate solution to salicylic acid, m.p. 155C.
202 Acetophenone
It is sparingly soluble in water.
On oxidation with alkaline potassium permanganate solution it yields benzoic acid,
m.p. 121C.
Add 2 drops of the ketone to 2 ml of sodium nitroprusside solution followed by 2 drops
of sodium hydroxide solution a wine red color.
TESTS FOR COMMON ORGANIC COMPOUNDS 83
207 Menthone
210 Propiophenone
220 Cinnamaldehyde
225 p-Methylacetophenone
232 p-Chloroacetophenone
248 Citral
It possesses an odor of lemon and forms an addition compound on shaking with an aqueous
solution of sodium bisulfite.
Semicarbazone, m.p. 164C.
248 p-Anisaldehyde
It is insoluble in water.
In a 250 ml round-bottomed flask place 250 mg of potassium permanganate and 50 ml
of water. Heat to dissolve and cool the solution. Add 1 ml of the aldehyde. Gently shake
until the color of potassium permanganate disappears. Cool, filter and acidify the filtrate
with conc. hydrochloric acid. Filter the anisic acid, wash with cold water and dry, m.p.
184C.
252 Cinnamaldehyde
It is a colorless oily liquid. It possesses cinnamon odor. It is insoluble in water but soluble
in ether.
(a) Take 2 ml of the Tollens reagent in a test tube and to it add 0.1 g of the aldehyde.
Shake and place in boiling water for 5 min appearance of silver mirror along
the sides of the tube.
(b) To 2 ml of bromine water in a test tube, add 0.1 g of the substance and shake
disappearance of bromine color.
(c) Oxime, m.p. 138C.
(d) Phenyl hydrazone, m.p. 168C.
m.p. (C)
44 o-Nitrobenzaldehyde
It is yellow in color, slightly soluble in water but soluble in most organic solvents.
With potassium permanganate it is oxidized to o-nitrobenzoic acid, m.p. 147C.
Oxime, m.p. 58C.
TESTS FOR COMMON ORGANIC COMPOUNDS 85
47 p-Chlorobenzaldehyde
Oxidation with potassium permanganate solution yields p-chlorobenzoic acid, m.p. 236C,
2, 4-dinitrophenylhydrazone m.p. 265C.
48 Benzophenone
It is insoluble in water and forms a yellow solution in conc. sulfuric acid.
(a) Fuse a pinch of the compound with a small piece of sodium metal blue color.
(b) 2, 4-Dinitrophenylhydrazone, m.p. 265C.
58 m-Nitrobenzaldehyde
134 Benzoin
It is insoluble in water.
To 100 mg of the substance in a test tube add 1 ml of Fehlings solution and 1 ml of
water. Heat to boiling for 30 sec a red precipitate of cupric oxide.
179 Camphor
5.4 ESTERS
b.p. (C)
57 Methyl acetate
It is colorless liquid. It has fruity smell, soluble in cold water and alcohol.
d 0.939
77 Ethyl acetate
It is colorless and soluble in cold water and alcohol.
In a 50 ml round-bottomed flask place 1 g of the compound and 20 ml of potassium
hydroxide solution. Reflux for 20 min. Distil off the ethyl alcohol and perform the iodoform
test with the distillate.
79 Methyl propionate
(a) 3, 5-Dinitrobenzoate, m.p. 108C.
98 Ethyl propionate
(a) 3, 5-Dinitrobenzoate, m.p. 88C.
It is slightly soluble in water. With excess ammonium hydroxide it yields an oxamide which
sublimes without melting.
It is a colorless compound. It smells like winter green oil (an aromatic liquid distilled from
the leaves of wintergreen plant) . It is insoluble in water but soluble in alcohol and ether.
m.p. (C)
36 Methyl cinnamate
It is colorless, insoluble in water, soluble in hot alcohol. It decolorizes aqueous bromine
solution.
37 Ethyl mandelate
45 Methyl anisate
51 Methyl oxalate
58 Methyl mandelate
68 Phenyl benzoate
It is colorless, insoluble in water but soluble in hot alcohol.
70 Methyl p-hydroxybenzoate
78 Phenyl cinnamate
5.5 AMINES
b.p. (C)
17 Ethylamine C2H5NH2
It is soluble in water, alcohol and ether. It has an ammoniacal odor.
(a) Benzoyl derivative, m.p. 71C.
49 n-Propylamine CH3CH2CH2NH2
It is miscible with water, alcohol and ether.
(a) Hydrochloride, m.p. 159C.
55 Diethylamine
77 n-Butylamine CH3CH2CH2CH2NH2
It is miscible with water.
d 0.741
Hydrochloride, m.p. 195C.
89 Triethylamine
105 Piperidine
184 Aniline
It is insoluble in water.
(a) It responds to carbylamine test with potassium hydroxide and chloroform.
(b) Acetyl derivative, m.p. 113C.
199 m-Toluidine
(a) Dissolve 2 drops of the substance in 2 ml of 50% sulfuric acid and add a few drops
of potassium dichromate solution a yellow-brown color.
(b) Acetyl derivative, m.p. 65C.
92 LABORATORY MANUAL OF ORGANIC CHEMISTRY
200 o-Toluidine
209 o-Chloroaniline
230 m-Chloroaniline
It is colorless, insoluble in water but soluble in alcohol and gives the dye test with
>-naphthol.
Acetyl derivative, m.p. 72C.
251 m-Bromoaniline
It is colorless, insoluble in water but soluble in alcohol. It gives the dye test with >-naphthol.
Acetyl derivative, m.p. 87C.
m.p. (C)
32 o-Bromoaniline
It is colorless, insoluble in water but soluble in alcohol and ether. It responds to the dye
test with >-naphthol.
Acetyl derivative, m.p. 99C.
TESTS FOR COMMON ORGANIC COMPOUNDS 93
45 p-Toluidine
51 p-Anisidine
It is sparingly soluble in water but soluble in alcohol. It gives the dye test with >-naphthol.
(a) Solution of its hydrochloride in water yields violet color with ferric chloride
solution.
(b) Acetyl derivative, m.p. 127C.
54 Diphenylamine C6H5NHC6H5
It is insoluble in water but soluble in alcohol.
(a) Dissolve 20 mg of the compound in conc. sulfuric acid then add a drop of sodium
nitrite solution a blue color.
(b) Dissolve another 20 mg of the substance in 1 ml hydrochloric acid and add a few
drops of HNO3 a deep blue coloration.
60 =-Naphthylamine
66 p-Bromoaniline
It is a colorless substance insoluble in water, soluble in alcohol. It responds to the dye test
with >-naphthol.
Acetyl derivative, m.p. 167C.
94 LABORATORY MANUAL OF ORGANIC CHEMISTRY
70 p-Chloroaniline
It is soluble in hot water and alcohol. It gives the dye test with >-naphthol.
Acetyl derivative, m.p. 179C.
71 o-Nitroaniline
78 s-Trichloroaniline
113 >-Naphthylamine
It is an odorless but pink colored compound and sparingly soluble in hot water with >-
naphthol.
(a) It does not give a blue precipitate with ferric chloride solution.
(b) Acetyl derivative, m.p. 132C.
114 m-Nitroaniline
It possesses a yellow color and soluble in hot water. It responds to the dye test.
Acetyl derivative, m.p. 155C.
140 p-Phenylenediamine
It is colorless and darkens on exposure. Sparingly soluble in water but soluble in alcohol.
TESTS FOR COMMON ORGANIC COMPOUNDS 95
147 p-Nitroaniline
It is yellow in color and soluble in hot water. It gives the dye test with >-naphthol.
Acetyl derivative, m.p. 215C.
b.p. (C)
105 Formamide
It is soluble in water. On heating it decomposes evolving ammonia gas.
(a) To 2 ml of mercuric chloride solution add 1 drop of the compound and heat to
boiling for 30 sec a white precipitate of mercurous chloride is obtained.
(b) Dissolve 25 mg of the substance in 2 ml of water and then add 2 drops of ferric
chloride solution a wine-red color which on heating forms a brown precipitate.
m.p. (C)
79 Propionamide
It is soluble in water and ether.
(a) With 75% sulfuric acid at 120C it yields propionic acid, b.p. 140C.
(b) One heating with aniline it yields propionanilide, m.p. 103C.
82 Acetamide
It is readily soluble in water and alcohol.
(a) To 2 ml of the aqueous solution, add an equal volume of ferric chloride solution
a wine red color yielding a reddish brown precipitate on warming.
(b) Picrate, m.p. 107C.
96 LABORATORY MANUAL OF ORGANIC CHEMISTRY
114 Acetanilide
It is soluble in hot water.
With 1 mole of bromine in acetic acid it yields p-bromo derivative, m.p. 167C.
115 n-Butyramide
It is readily soluble in water, alcohol and ether.
On heating with aniline it yields n-butyranilide, m.p. 90C.
129 Benzamide
133 Salicylamide
157 Phenylacetamide
162 Benzanilide
(b) Add bromine solution to 0.5 g of the anilide in a test tube p-bromoanilide, m.p.
204C.
176 o-Nitrobenzamide
201 p-Nitrobenzamide
219 d-Phthalamide
233 Phthalimide
242 Succinamide
418 Oxamide
b.p. (C)
132 Chlorobenzene
On warming to 80C with conc. nitric acid (1 mole) and conc. sulfuric acid it yields
p-nitro derivative (m.p. 83C).
157 Bromobenzene
It is slightly colored and pleasant smelling liquid. Insoluble in water but soluble in alcohol
and ether.
With conc. nitric acid and sulfuric acid at room temperature, it yields a p-nitro derivative,
m.p. 120C.
Bromobenzene responds to the Beilstein test.
159 o-Chlorotoluene
162 m-Chlorotoluene
162 p-Chlorotoluene
181 o-Bromotoluene
hydroxide solution. and reflux for 3 hr. Cool and pass sulfur dioxide gas until any
purple color and brown precipitate have disappeared. Filter off the white solid,
wash with cold water) o-bromobenzoic acid is obtained, m.p. 147C.
183 m-Bromotoluene
m.p. (C)
53 p-Dichlorobenzene
89 p-Dibromobenzene
It is a white crystalline solid, possesses characteristic aromatic odor and insoluble in water
but soluble in benzene and ether.
Immerse a 50 ml round-bottomed flask in ice-cold water and charge it with 1 ml of the
substance, add 2 ml each of ice-cold conc. nitric acid and conc. sulfuric acid through a
dropping funnel dropwise. After the addition is complete keep the flask in a hot water-bath
for 15 min. Cool and pour the mixture on ice cold water. Crystallize the solid 1,4-dibromo-
2-nitrobenzene from ethanol, m.p. 126 C.
b.p. (C)
83 Cyclohexene
210 Nitrobenzene
It is yellow liquid with odor of bitter almonds and insoluble in water. It is soluble in organic
solvents.
(a) On warming with fumming nitric acid and conc. sulfuric acid it yields
m-dinitrobenzene, m.p. 90C.
(b) Boil 1 ml of the compound with 4 ml of stannous chloride solution in conc.
hydrochloric acid. To 2 ml of the resulting aniline solution add sodium nitrite
solution. Cool and add alkaline solution of >-naphthola scarlet red dye.
220 o-Nitrotoluene
265 o-Nitroanisole
268 o-Nitrophenetol
It is insoluble in water but miscible with organic solvents. With conc. nitric acid and sulfuric
acid, it yields, 2, 4-dinitro derivative, m.p. 86C.
m.p. (C)
36 Azoxybenzene
It has bright yellow needles, insoluble in water but soluble in alcohol and ether.
In aqueous alcoholic solution, with zinc dust forms orange-red colored azobenzene,
m.p. 68C and then hydrazobenzene, m.p. 131C.
54 p-Nitroanisole
54 p-Nitrotoluene
59 p-Nitrophenetol
It is insoluble in water, sparingly soluble in cold alcohol but readily soluble in ether.
With conc. nitric acid and sulfuric acid in cold, it yields a 2, 4-dinitro derivative, m.p.
76C.
65 Benzenesulfonic acid
68 Azobenzene C6H5N=NC6N5
It is orange-red in color and sparingly soluble in water.
TESTS FOR COMMON ORGANIC COMPOUNDS 103
(a) When treated with bromine in acetic acid it gives a dibromo derivative, m.p.
187C.
(b) With zinc dust and sodium hydroxide it yields hydrazobenzene, m.p. 131C.
69 p-Toluenesulfonyl chloride
115 p-Benzoquinone
137 p-Toluenesulfonamide
It is sparingly soluble in cold water but soluble in dil. sodium hydroxide solution, ether or
alcohol.
(a) On treatment with a mixture of benzyl chloride and sodium hydroxide in alcohol,
it yields a benzyl derivative, m.p. 116C.
(b) On oxidation with potassium permanganate solution it produces
p-sulfonamidobenzoic acid, m.p. 280C.
153 Benzenesulfonamide
153 o-Toluenesulfonamide
It is a colorless substance but turns black on storage. It is soluble in water but insoluble in
benzene or ether.
Dissolve 25 mg of the substance in distilled water in a test tube and a few drops of
silver nitrate solution and shake heavy white precipitate of silver chloride.
(b) To a solution of 50 mg of the compound in hot water add bromine solution (10 ml
bromine) and 1.5 g potassium bromide in 100 ml water. Stir till the liquid is pale
yellow. Filter the solid, wash with cold water and dry, 2,4,6-tribromoaniline, m.p.
199C.
Chapter 6
PREPARATION OF DERIVATIVES
The tests in the preceding chapters help to recognize the unknown into its specific class
such as an aldehyde, amine or a carboxylic acid. Then the physical properties of the unknown
are compared with those of the representative compounds. Such a comparison often presents
several possibilities. The choice, however, can be narrowed down by preparing a derivative.
A derivative is usually a solid material which can readily be prepared from the unknown
and can be easily isolated and purified. Moreover, it should be crystalline and differ in
physical properties from the unknown. Formation of a derivative involves a reaction between
the functional group and another reagent. It is thus desirable that the reaction be
accomplished in a short period and conditions are controllable. Prepare the derivatives
carefully because you are working with small amounts of compounds. Always recrystallize
till a constant melting point is obtained. The melting point of a derivative can be used as a
proof for the identity of the unknown. A description of various derivatives is intended in
this chapter.
(a) Acetates
Acetate esters are particularly useful in the characterization of polyhydric alcohols and are
usually easy to prepare.
106 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: In a boiling tube place 0.5 g (10 drops of the liquid) of alcohol sample, 4 ml
pyridine and add 2 ml of freshly distilled acetic anhydride with shaking. Heat the mixture
on a water-bath for 5 min. Pour the contents onto ice taken in a beaker and filter off the
solid, wash it with dil. hydrochloric acid to remove pyridine. Finally wash with cold water.
Recrystallize from hot aqueous ethanol. Take the melting point and compare from the
tables.
(b) p-Nitrobenzoates
This is generally the most useful ester derivative for the characterization of alcohols.
Procedure: In a small test tube place 0.5 g (10 drops of the liquid ) of alcohol sample, 4 ml
pyridine and 1 g p-nitrobenzoyl chloride. Heat the contents for 10 min and pour the mixture
on ice water. Filter off the solid on a Buchner funnel, wash with dil. hydrochloric acid to
remove pyridine. Recrystallize from aqueous ethanol.
Both the above reactions proceed well with primary and secondary alcohols but not
with tertiary alcohols.
Question
6.1 Why do tertiary alcohols not react with p-nitrobenzoyl chloride?
Procedure: Take the unknown alcohol 1 g (1 ml if liquid) in a dry test tube and to it add
0.5ml of =-naphthyl isocyanate. Shake the contents and allow the tube stand at room
temperature for 5 min with occasional shaking. A solid should appear after this period. In
case no solid is formed warm on a water-bath and cool again. Scratch the sides of the tube
if necessary. Filter the solid and recrystallize from light petroleum.
PREPARATION OF DERIVATIVES 107
(a) Benzoates
The hydroxyl group of phenols can be esterified by the Schtten-Baumann reaction using
benzoyl chloride and a base.
Procedure: Place 0.5 ml of the phenol in 2.5 ml of water in a test tube. To this add 2.5 ml
of 10% of sodium hydroxide solution followed by 0.3 ml of benzoyl chloride. Stopper the
tube and shake for several minutes. The odor of benzoyl chloride should disappear. Collect
the solid on a Buchner funnel and wash with cold water. Recrystallize from hot alcohol.
Question
6.2 Write a mechanism for the Schtten-Baumann reaction.
(b) 3, 5-Dinitrobenzoates
3, 5-Dinitrobenzoate esters are useful for both phenols and alcohols.
Procedure: In a 100 ml round bottomed flask equipped with a reflux condenser, place 0.5 g
of phenol, 5 ml of pyridine and 1.3 g of 3, 5-dinitrobenzoyl chloride and reflux the mixture
gently for 30 min. Cool the contents and pour onto 50 ml of 5% sulfuric acid. Shake the
mixture, filter the solid and wash with water. Suspend the solid in 50 ml of 5% sodium
hydroxide solution to remove any 3, 5-dinitrobenzoic acid and filter again. Recrystallize the
derivative from hot aqueous ethanol.
108 LABORATORY MANUAL OF ORGANIC CHEMISTRY
(a) 2, 4-Dinitrophenylhydrazones
2, 4-Dinitrophenylhydrazones, semicarbazones, oximes, etc. are colored solids and have
sharp melting points.
Question
6.3 Why is adjustment of pH essential in the above reaction?
(b) Semicarbazones
Semicarbazones are easily formed and have sharp melting points.
Shake the mixture for a few minutes then warm in a beaker containing water at 7075C
for 10 min. and then allow to cool. The semicarbazone precipitates out from the cold solution
on standing. Recrystallize the derivative from hot aqueous ethanol.
(c) Phenylhydrazones
Procedure: Dissolve 0.4 g of phenylhydrazine in 1.5 ml of water and add solution of 0.2 g of
aldehyde or ketone dissolved in 5 ml ethanol. Boil the mixture for 1 min, add 2 drops of
glacial acetic acid and boil again for 5 min. Cool and add water till a solid separates out.
Filter the solid and recrystallize from hot ethanol.
(d) Oximes
Aldehydes and ketones form crystalline oxime derivatives on reaction with hydroxylamine
hydrochloride.
Procedure: Dissolve or suspend 0.25 g of the acid in 1 ml of water in a test tube. Add 1 drop
of phenolphthalein indicator and then neutralize with 1 N sodium hydroxide solution till a
110 LABORATORY MANUAL OF ORGANIC CHEMISTRY
pink color is obtained. Add 3 drops of 0.1 N hydrochloric acid till the solution is neutral.
Now add 1 g of s-benzylisothiouronium chloride dissolved in 3 ml of water. Cool the mixture
in an ice-bath. Filter the solid and recrystallize from hot aqueous ethanol. The solution at
this stage should become faintly pink. Make sure the solution is neutral.
(b) Amides
Amides are useful drivatives of carboxylic acids and can be easily prepared.
Procedure: In a mortar, grind together 0.5 g of the unknown acid and 2 g of phosphorus
pentachloride until the mixture becomes liquid. To the crude acid chloride so obtained add
slowly 10 ml of liquor ammonia. After the vigorous reaction has stopped, stir and cool.
Filter the solid and wash with cold water and recrystallize from hot ethanol.
Question
6.4 Why are amides preferably prepared by the above method and not by treatment of
acids with NH3 followed by heating?
Procedure: Take 1 g of the unknown acid and prepare the acid chloride either by using
PCl5 as in the above experiment or the acid for 30 minutes with 2.5 ml of thionyl chloride
in a small round bottom flask.
Cool the acid chloride solution and to this add 2 g of amine solution in 20 ml benzene
and warm the mixture in a hot water-bath. Cool and transfer the solution in a separatory
funnel. Wash the benzene layer successively with 2 ml water, 5 ml of 5 % hydrochloric acid,
PREPARATION OF DERIVATIVES 111
5 ml of 5% sodium hydroxide solution and finally with 5 ml water. Distil benzene and
recrystallize the residue from alcohol.
Procedure: Neutralize with 10% sodium hydroxide solution, a 0.5 g of the acid suspended
in 3 ml of water. To this add 5 ml of ethyl alcohol and 0.5 g of p-bromophenacyl bromide and
reflux for 1 hr. Cool and collect the solid, wash with water and recrystallize from hot ethanol.
Procedure: Mix 2 ml of the ester with 1.5 g of 3,5-dinitrobenzoic acid and 2 drops of conc.
sulfuric acid in a 50 ml round bottom flask fited with a reflux condenser. Heat the mixture
in an oil-bath at 150C for 45 min. Cool and add 25 ml ether and transfer the solution to a
separatary funnel. Wash the ethereal solution with 5% sodium carbonate solution to remove
the acid. Wash the ether solution with water twice. Dry ether solution on sodium sulfate.
Filter and evaporate ether. Recrystallize the solid from hot aqueous ethanol.
(a) Osazones
Carbohydrates bearing an aldehyde or keto group react with excess phenylhydrazine to
produce osazones. In the formation of osazones one carbonyl group is oxidized, therefore, a
number of isomeric sugars (of the type OCHCHOHR and CH2OHCOR, i.e., D-glucose,
D-mannose and D-fructose) form osazones.
112 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: In a test tube place 0.2 g sugar, 0.4 g phenylhydrazine, 0.6 g sodium acetate
and 4 ml distilled water. Place the tube in a beaker of boiling water. Note the time of
immersion and the time of precipitation of the osazone. Shake the tube occasionally. The
time required for the precipitation of the osazone may be taken as evidence for the
identification of the unknown sugar. The melting points of the osazones being too close are
generally of no value.
Question
6.5 Why is it easy to isolate an osazone than a sugar itself?
PREPARATION OF DERIVATIVES 113
(b) Acetates
A carbohydrate need to be completely acetylated in order to avoid any contamination. For
this purpose an excess of the acetylating agent, i.e., acetic anhydride is used. The = - or the
> - form of the acetate may be obtained depending on the catalyst employed.
>-Acetate
Procedure: Dissolve 1 g of powdered unknown carbohydrate and 1 g of powdered fused
sodium acetate in 10 ml of acetic anhydride by warming under reflux in a round-bottomed
flask. The dissolution may take 30-35 min. After a clear solution is obtained heat for a
further period of 2 hr. Pour the hot reaction mixture carefully into 50 ml of ice-cold water
with stirring. Stir vigorously with a glass rod to decompose the excess acetic anhydride.
Filter the solid and wash with cold water. Recrystallize from hot ethanol.
=-Acetate
>-Acetate may be converted into =-acetate as follows:
Procedure: Dissolve 0.5 g of the >-acetate in 2.5 ml 2% anhyd. zinc chloride in acetic
anhydride in a 100 ml round-bottomed flask. Reflux the mixture on a water-bath for 30 min.
Cool and pour the contents into 25 ml ice-cold water and stir vigorously. Filter the solid and
wash with cold water. Recrystallize from hot ethanol.
(c) Benzoates
Crystalline benzoate derivatives of glucose and fructose are prepared using benzoyl chloride.
Procedure: The properties of carbohydrates are listed in table 6.1. In a 100 ml Erlenmeyer
flask, dissolve 0.5 g glucose in 5 ml water. To this solution add 15 ml of 10% sodium hydroxide
solution and 1 ml of benzoyl chloride. Stopper the flask and shake until the odor of benzoyl
chloride has disappeared and a crystalline solid has separated. Filter the solid and wash it
with a small quantity of water. Recrystallize from hot ethanol.
114 LABORATORY MANUAL OF ORGANIC CHEMISTRY
(a) Benzamides
The benzoylation of a primary or secondary amine is frequently achieved by the Schtten
Baumann reaction.
Procedure: In a boiling tube heat about 0.3 g (0.2 ml for liquid) of amine, 3 ml of 10%
sodium hydroxide solution. To the mixture add 0.8 ml of benzoyl chloride slowly with vigorous
shaking. Heat on a steam-bath for 15 min. Cool and add an excess of 10% sodium hydroxide
solution to make the solution alkaline. Collect the solid and recrystallize from hot aqueous
ethanol.
Question
6.6 Why do tertiary amines fail to react in this reaction?
(b) p-Toluenesulfonamides
p-Toluenesulfonyl chloride reacts with amines to form a p-toluene sulfonamide.
B. Tertiary amines
Picrates are frequently employed as derivatives of the tertiary amines using picric acid.
Picrates are colored solids.
Procedure: In a test tube dissolve 1 g of the amine in a minimum amount of ethanol and
add a solution of 0.5 g of picric acid also dissolved in a minimum amount of ethanol. Heat on
a water-bath at 80C for 510 min and shake occasionally. Cool and pour the contents onto
ice water. Collect the solid, wash thoroughly with water and recrystallize from hot ethanol.
(a) Picrates
A large number of hydrocarbons also react with picric acid to form addition products, called
picrates and are useful in the identification of aromatic hydrocarbons.
with the melting and boiling points. Both these constants particularly the melting point
represent important criteria for purity of the substance.
Procedure: A small amount (0.1-0.2 g) of the compound (benzoic acid or urea) is first
powdered with a spatula on a porous plate using a glass rod. The substance is then introduced
into a capillary tube ( 5 cm long) to pack it to a height of 3 mm. The capillary is now
attached to a thermometer by means of a small rubber band. Note that the top of the
thermometer and the capillary tube are at the same level. The thermometer along with the
tube is now immersed in a heating bath. A Thiele tube or a Kjeldahls flask with an
appropriate liquid may be used. A Thiele tube clamped on iron-stand containing liquid paraffin
or conc. sulphuric acid is shown in Fig. 6.1. Heat the bath slowly. The temperature at
which the compound commences to liquefy and at which it is completely liquid is recorded
as the melting point range.
A number of commercially available apparatus are available nowadays. The one shown
in Fig. 6.2 requires no liquid and heating is done electrically. Such systems give more
reliable melting points.
Questions
6.7 The sample for the determination of melting point should not be powdered on the
filter paper. Why?
6.8 Would a pure compound always give a sharp melting point?
6.9 What does a mixed melting point determination indicate?
pure liquid. A liquid as a rule, will boil at a constant temperature provided the pressure
remains constant. Because of its dependence on pressure and its erratic response to
impurities the boiling point is generally less reliable than is the m.p. of solids. However,
most mixture of liquid boil over a fairly wide temperature range even at constant
temperature.
A mixture of two different substances of the same melting point will show a melting
point below that of each pure substance of the mixture. In contrast, a mixture of two liquids
of the same boiling point will have the same boiling point as each individual one. Thus the
boiling point is less useful for identification than the melting point. Boiling point can be
determined in an apparatus shown in Fig. 6.3.
Procedure : Place 3-4 drops of the liquid whose boiling point is to be determined in an
ignition tube. Immerse a capillary tube sealed at the other end in the liquid (if the liquid
rises in the tube in means that it is not properly sealed). Attach the ignition tube to a
thermometer by means of a rubber band. Suspend the thermometer in a long-necked flask
containing paraffin oil or in a Theile tube. Heat the flask uniformly with a burner, until a
rapid stream of bubbles starts coming out of the capillary tube (because the air inside the
tube warms and expands) . At this point remove the burner and permit the flask to cool.
The steam of bubbles become slower and the temperature drops until a point is reached
PREPARATION OF DERIVATIVES 121
when the bubbling ceases, and the liquid commences to rise in the capillary tube. This is
the boiling point of the liquid.
Question
6.10 If two miscible liquids are found to boil at exactly the same temperature, could the
conclusion be drawn that they are identical?
Derivatives
p-Ethylphenol 47 130 81 60
p-Methoxyphenol 55
Benzhydrol 68 141
123
(Contd...)
124
(1) (2) (3) (4) (5) (6) (7) (8)
2,4-Dinitrophenol 114
o-Bromophenol 195
m-Bromophenol 236
PREPARATION OF DERIVATIVES
Table 6.4: Carboxylic Acids
Derivatives
Acetoacetic acid 37 54 95
2-Phenylbutanoic acid 42 85
Bromoacetic acid 50 91 91
Iodoacetic acid 83 95
125
(Contd...)
126
(1) (2) (3) (4) (5) (6) (7) (8)
127
128
Table 6.5: Aldehydes
Derivatives
1-Naphthaldehyde 34 221
o-Aminobenzaldehyde 40 247
3, 5-Dichlorobenzaldehyde 65
2, 4-Dichlorobenzaldehyde 74
p-Bromobenzaldehyde 67 113
n-Butyraldehyde 74 131
Chloral 96
Pentanal 103
(Contd...)
PREPARATION OF DERIVATIVES
(1) (2) (3) (4) (5) (6) (7)
o-Bromobenzaldehyde 230
129
130
Table 6.6: Ketones
Derivatives
(Contd...)
(1) (2) (3) (4) (5) (6) (7)
PREPARATION OF DERIVATIVES
Cyclohexanone 155 Sol 160 166
131
132
Table 6.7: Esters
Dimethyl succinate 18
Diethyl tartarate 18
Benzyl benzoate 18
Elhyl mandelate 37
Phenyl salicylate 42
Dimethyl tartarate 49
Methyl mandelate 53
Phenyl benzoate 69 93
Ethyl formate 54 93
(Contd...)
PREPARATION OF DERIVATIVES
(1) (2) (3) (4)
133
(Contd...)
134
(1) (2) (3) (4)
C-Butyrolactone 204
Derivatives
Ethylmethylamine 36
N-Benzylamine 37
2, 6-Dichloroaniline 39
Indole 52
8-Hydroxyquinoline 75
Pyrrolidine 75
2, 4-Diaminotoluene 99
135
(Contd...)
136
(1) (2) (3) (4) (5) (6) (7) (8)
a-Nitroaniline 71 94 98 73 142
o-Phenylenediamine 102
Ethylenediamine 116
Triphenylamine 127
2-Picoline 129
Cyclohexylamine 134
2-Aminoethanol 171
(Contd...)
PREPARATION OF DERIVATIVES
(1) (2) (3) (4) (5) (6) (7) (8)
o-Hydroxyaniline 174
m-Aminoaniline 180
Benzyldimethylamine 181
p-Aminophenol 184
Dimethylamine 193 65
2, 4, 6-Trinitroaniline 190
m-Bromoaniline 251
Dibenzylamine 300
137
138
Table 6.9: Amides
Derivatives
(Contd...)
PREPARATION OF DERIVATIVES
(1) (2) (3) (4)
139
140
Table 6.10: Hydrocarbons
Naphthalene 80 81 (1)
Benzene 80 89 (1, 3) 84
m-Nitroanisole 38
Benzoic anhydride 42
o-Bromonitrobenzene 43
p-Dichlorobenzene 53 173
p-Nitrotoluene 54 238
m-Chlorotoluene 72
p-Bromobenzene 89
Acetanilide 114
Iodoform 119
p-Nitrobromobenzene 127
o-Chloronitrobenzene 246
141
(Contd...)
142
(1) (2) (3)
Bromoform 151
Anisole 155
o-Chlorotoluene 159
m-Chlorotoluene 162
p-Chlorotoluene 162
Phenetole 172
o-Dichlorobenzene 180
o-Bromotoluene 182
p-Bromotoluene 184
2, 4-Dichlorotoluene 201
Nitrobenzene 211
o-Nitrotoluene 220
m-Nitrotoluene 233
Chapter 7
Qualitative organic analysis has been the subject of the preceding chapters, for the
identification of organic compounds. It is intended to discuss and perform some experiments
of quantitative estimation of functional groups. In these exercise utmost care is needed for
accurate working and measurement of correct data. For the preparation of standard
solutions, the amounts stated within parenthesis represent the number in g/l of the solution.
Chemicals
Acetic anhydride distilled.
Procedure: First prepare the acetylating mixture by mixing one volume (11.5 g) of acetic
anhydride and three volumes (34.5 ml) of dry pyridine in a clean Erlenmeyer flask. Fill a
clean dry burette with this mixture and cork it.
For the preparation of alcoholic sodium hydroxide solution. Prepare a saturated solution
of sodium hydroxide in distilled water in a corked Erlenmeyer flask. Take 14 ml of this
solution in a 500 ml volumetric flask and fill it if with ethyl alcohol. Standardize this solution
with 0.5 N hydrochloric acid or sulfuric acid or preferably oxalic acid using phenolphthalein
indicator.
In a 250 ml Erlenmeyer flask equipped with a water condenser, weigh accurately (by
transference method) 11.3 g sample (phenol, n-hexanol, cyclohexanol, or benzyl alcohol)
and to this add 9 ml acetylating mixture from the burette (use double the amount if the
alcohol is dihydric). Shake and reflux the contents on a water-bath for 45 min after replacing
the condenser. Remove the flask and add 20 ml distilled water through the condenser and
shake to ensure complete hydrolysis of the remaining acetic anhydride. Cool the flask and
titrate the contents ( Note I ) against standard sodium hydroxide solution using
phenolphthalein as indicator. Carry out a blank control experiment simultaneously using
the above procedure with 9 ml of the acetylating mixture without adding alcohol or phenol.
The difference in the volumes of sodium hydroxide solution required in the two experiments
is equivalent to the difference in the amount of acetic acid formed, i.e., to the acetic acid
derived from the acetic anhydride consumed in the actual acetylation of the sample. If the
molecular weight of the alcohol is known, the number of OH groups in the alcohol can be
determined. The advantage of control experiment is that the absolute concentration of the
reagent (hence the exact concentration of acetic anhydride in pyridine) need not be
determined. If the same volume of reagent is used in the actual and in the blank or control
experiment, the difference gives the actual amount used.
Calculations
Weight of the sample = W g
Suppose the sample requires V ml and the blank requires V1 ml of 0.5 N sodium
hydroxide solution.
Difference = (V1 V ) ml of 0.5 N NaOH
(V1 V )
or ml of 1 N NaOH
2
1000 ml of 1 N NaOH = 1 g mol. wt. of NaOH
= 1 OH group/molecule of alcohol
(V1 V ) (V1 V )
\ ml of 1 N NaOH = OH groups
2 1000 2
ESTIMATION OF FUNCTIONAL GROUPS 145
(V1 V )
W g of the alcohol sample contains OH groups
1000 2
94 g (assuming the sample to be phenol) contains
(V1 V ) 94
OH groups/molecule
1000 2 W
Note I: For better results the sample after refluxing may be diluted to 100 ml in a measuring
flask and 10 ml aliquot titrated against a dilute solution (0.1 N) of NaOH.
Question
7.1 What is the purpose of running a blank?
2 KI + Br 2 2 KBr + I2
Chemicals
Calculations
Weight of phenol taken = W g
(V1 V )
(V1 V) ml 0.I N Na2S2O3 = 0 .1 g equiv. weight of Na2S2O3 solution
1000
(V V ) 1
= Equivalent weight of bromine = 1 0.1 mole of phenol (since according to
1000 6
the reaction above, 6 g equivalent of bromine = 1 mole of phenol)
(V1 V ) 0 .1 94
g of phenol (Mol. wt. of phenol = 94)
1000 6
(V1 V ) 0.1 94
W g of the sample contains g of phenol
1000 6
Question
7.2 How can monobromination of phenol be achieved?
ESTIMATION OF FUNCTIONAL GROUPS 147
Chemicals
Calculations
Weight of silver salt taken = W g
Equivalent wt. of the acid = Equivalent wt. of silver salt Atomic wt. of Ag
107.9 W
+ The wt. of H replaced by Ag = 107.9 + 1.
w
The molecular weight can be obtained by multiplying the basicity with the equivalent
weight.
Chemicals
Calculations
Weight of the acid taken = W g in 100 ml solution
Assume 25 ml of the acid consumes V ml of 0.2 N NaOH
100 V
100 ml of the acid will consume = of 0.2 N NaOH
25
= 100/25 V 1 / 5 N NaOH
= 4 V/5 1 N NaOH
4/5 V ml of 1 N NaOH is equivalent to W g of the acid
100 W 5
1000 ml of 1 N NaOH is equivalent to = g of acid.
4V
ESTIMATION OF FUNCTIONAL GROUPS 149
This is also the equivalent weight of the acid. To obtain the molecular weight multiply
by basicity.
Chemicals
Procedure: First prepare a standard potassium hydroxide solution in ethanol. For this
dissolve 2 g of potassium hydroxide pellets in 100 ml of 95% ethanol in an Erlenmeyer
flask. Allow the solution to settle and then decant it in a volumetric flask. Standardize it
with 0.5 N hydrochloric acid solution.
Transfer 10 ml of potassium hydroxide solution by means of a pipette into a 50 ml
glass-stoppered Erlenmeyer flask. Accurately weigh about 0.5 g of the ester (ethyl benzoate
or benzyl acetate) into the flask and replace the stopper. Swirl the flask to mix the ester
with potassium hydroxide solution. Reflux the contents of the flask for 3040 min. Wash
down the condenser with 25 ml water and cool. Add 2 drops of phenolphthalein and titrate
against 0.5 N or 0.25 N hydrochloric acid. Note the volume of the acid consumed. Also run
a blank under similar conditions.
Calculations
Weight of the ester taken = W g
W 1000
Saponification equivalent =
( ml Normality )alkali (ml Normality )acid
For an ester of a mono-basic acid the value is equal to the molecular weight whereas
for a dibasic acid it will be one half the molecular weight.
150 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Questions
7.3 Can one esterify a carboxylic acid in the presence of a base?
7.4 List some other methods of esterification of a carboxylic acid.
Methyl ketones can be estimated by treating with excess standard iodine in an alkaline
medium and then titrating the unreacted iodine with standard sodium thiosulfate solution.
Chemicals
Procedure: In a 250 ml Erlenmeyer flask fitted with a ground glass stopper weigh accurately
0.20.25 g of a ketone (acetone, acetophenone, ethyl methyl ketone, etc.). To this add 30
ml of 1 N sodium hydroxide solution and shake for 10 min. From a burette run 50 ml of 0.1
N iodine solution with constant stirring. Shake thoroughly for 1015 min till yellow crystals
of iodoform appear. Acidify the solution with sulfuric acid and titrate against standard sodium
thiosulfate solution using starch indicator.
ESTIMATION OF FUNCTIONAL GROUPS 151
Calculations
Weight of the ketone taken = W g
6000 ml of 1 N I2 solution
120 (50 V )
W g sample contains = g of the ketone
6000 10
An aldehyde is treated with an excess of sodium bisulfite solution and the unused sodium
bisulfite solution is determined idometrically.
152 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Chemicals
Calculations
Wt. of the aldehyde taken = W g
Assume 50 ml of NaHSO3 solution requires V ml of 0.1 N I2 solution and excess NaHSO3
solution requires V1 ml of 0.1 N I2 solution.
(V V1 )
(V V1) ml of 0.1 N I 2 solution =
1000
M / 20 equivalent of the aldehyde
(V V1 )
Percentage purity of the aldehyde = M / 20 100 / W
1000
Note I: Considerable variations of and fading in end-point are experienced during titration. It is
probably due to the reversibility of the reaction and instability of the sodium bisulfite
adduct. The result may not be very accurate.
Question
7.5 Why is a sharp end-point not observed in the estimation of aldehydes?
ESTIMATION OF FUNCTIONAL GROUPS 153
Chemicals
Calculations
Weight of thiourea taken = W g
Weight of barium sulfate precipitate = w g
According to the above reaction = 233.4 g of BaSO4 contains 32 g of S
32
Therefore, w g of BaSO 4 = M g of 5
233 .4
154 LABORATORY MANUAL OF ORGANIC CHEMISTRY
32
W g sample of thiourea contains = M g of S
233.4
32 w
Percentage of sulfur in thiourea = 100
233.4 W
Notes I: If the color of potassium permanganate disappears during heating, add more of it.
II: Wash till chloride ions are removed. Check the filtrate with silver nitrate solution.
Question
7.6 Why does the purple color disappear on adding hydrochloric acid?
Catalyst [a mixture of K 2SO4 (20 g), selenium powder (1 g ) and CuSO4. 5H2O (1 g)]
flask. In the meantime set up the distillation apparatus as depicted in Fig. 7.2 ( Note II)
Transfer the mixture from the Kjeldahl flask into the chamber C. Pass steam into the
outer chamber B by turning the stopcock A. Introduce carefully 40 ml of 50% sodium
hydroxide solution through the funnel E. Take 50 ml of standard sufuric acid in an Erlenmeyer
flask G. Continue to pass steam for 5060 min. to ensure that all the ammonia evolved has
been absorbed by the acid. Turn off the stopcock A to cut off the flow of steam. Excess water
can be removed from the outlet H.
The excess of the acid in the Erlenmeyer flask ( G) may be titrated against standard
sodium hydroxide solution, using phenolphthalein indicator.
156 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Calculations
Weight of the nitrogenous compound taken = W g
Volume of 0.1 N H2 SO 4 taken = 50 ml
Volume of 0.1 N NaOH solution required to back-titrate the excess acid = V ml
Volume of 0.1 N H2SO4 used up for reaction with the ammonia evolved = (50 V) ml
(50 V) ml 0.1 N H2SO4 = (50 V) ml of 0.1 N NH3
1000 ml of 1 N NH3 = 17 g of ammonia = 14 g of nitrogen
1000 ml of 0.1 N NH 3 corresponds to 1.4 g of nitrogen.
(50 V) 1.4
(50 V) ml of 0.1 N NH3 corresponds to g of nitrogen.
1000
Chemicals
Acetic anhydride distilled.
Procedure: Prepare the acetylating mixture described as before (Section 7.1.1). In a 250 ml
Erlenmeyer flask fitted with a water condenser, weigh accurately about 11.5 g of the
amine (aniline, benzylamine, a-naphthylamine, etc.) sample and add 9 ml of the acetylating
mixture. Reflux the contents for 45 minutes with frequent stirring. After this period, cool
the flask under tap water. Add 15 ml of water to the flask slowly and swirl the flask, cool in
ice water. Titrate against 0.5 N sodium hydroxide solution immediately. Also carry out a
blank simultaneously using 9 ml of the reagent only.
Calculations
Calculate the number of amino groups as was done in the case of alcoholic OH group
estimation.
Chemicals
Calculations
Weight of the amid sample taken = W g
Vol. of 1 N HCI used = V ml
1000 ml of 1 N NaOH = 1 g mol. wt. of NaOH
= 1 g mol. wt. of HCI
= 1 amide group
158 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Question
7.7 Write a chemical reaction for the hydrolysis of an amide in the presence of aqueous
acid.
Chemicals
(Note I ). Pipette 25 ml of glycine solution prepared above in a second Erlenmeyer flask and
add 2 drops of phenolphthalein and make it faintly alkaline by the addition of sodium
hydroxide solution ( Note I). To this add 10 ml of the above neutralized formalin solution.
The pink color disappears and the solution becomes sufficiently acidic. Titrate the mixture
against 0.1 N sodium hydroxide solution till the pink color is restored and note the volume
of alkali consumed.
Calculations
Weight of glycine taken = W g
Assume 25 ml of the standard glycine solution ( after adding formaldehyde) require V
ml of 0.1 N NaOH
250 ml will require 250/25 V ml of 0.1 N NaOH or V ml of 1 N NaOH
1000 ml of 1 N NaOH = 75 g of glycine
V 75
1 ml of N NaOH = g of glycine
1000
V 75 100
% purity of glycine =
1000 W
The calculation in based on the fact that 1000 ml of 1 N NaOH corresponds to 1 mole of
glycine or 75 g of glycine. Thus knowing the molecular weight of the acid its purity can be
determined, also if the basicity is given then the molecular weight of the amino acid can
also be obtained.
Note I: These operations are carried out before mixing the two solutions because formalin contains
invariably some formic acid while the amino acids are seldom completely neutral.
Question
7.8 What is the function of adding formalin?
Chemicals
Fehlings solution A.
Fehlings solution B.
Glucose ( AR grade).
Calculations
Assume 20 ml of the Fehlings solution requires V ml of the unknown glucose solution.
Since 1 ml of the Fehlings solution = 0.0051g of glucose
20 0.0051 100
100 = g of glucose
V
20 0.0051 100
Therefore g of glucose has been dissolved in 100 ml unknown solution.
V
If the weight ( W) of the impure glucose sample is known, then the percentage purity can be
calculated.
ESTIMATION OF FUNCTIONAL GROUPS 161
20 0.0051 100
Percentage purity = 100 / W
V
Note I: To check for the completion of the reaction, place a drop of the solution with the help of
[ ]
glass rod on a glazed tile. Add a drop of K 4 Fe(CN )6 solution (5% solution in 10% glacial
acetic acid). Absence of any red precipitate of cupric oxide indicates that the end-point
has reached.
Chemicals
Pipette out 25 ml of this solution and titrate against 0.1 N hydrochloric acid using
phenolphthalein as indicator.
Calculations
Weight of the oil or fat taken = W g
Assume 25 ml solution requires V ml of 0.1 N HCl
and 250 ml solution would require = 250/25 V ml of 0.1 N HCl
= 10 of V ml 0.1 N HCl
10 V 0.1
= ml of 0.1 N HCl
0 .5
= 2V ml of 0.1 N HCl
(50 2 V) 28
(50 2 V) ml of 0.5 N KOH = g of KOH
1000
(50 2 V)
W g of the fat requires = 28 g of KOH
1000
(50 2 V) 28
1 g of the fat requires = g of KOH
1000 W
(50 2 V) 28
or 1000 mg of KOH
1000 W
Therefore, by definition this is the saponification value of the oil or the fat.
estimated. Most of the classical methods for the determination of unsaturation were
concerned primarily for the analysis of animal and vegetable fats and oils. The unsaturation
value so determined were expressed as iodine number or bromine number. This value
represents the amount of free halogen in grams required for 100 g of the sample molecule.
These value display considerable variation by the use of different halogens and thus are of
little quantitative organic analysis. Nevertheless, the determination of iodine number will
be described here.
Chemicals
Wijs solution.
Procedure: Weigh accurately 0.150.3 g oil or fat ( cotton seed oil, corn oil, peanut oil,
etc. ) in a 250 ml glass-stopped flask (Iodine flask) . To this add 2530 ml of chloroform or
carbon tetrachloride to dissolve the sample, warm if necessary. To the solution add 25 ml of
the Wijs solution, stopper the flask and shake vigorously for a few minutes. Allow the flask
to stand for 30 min with occasional shaking. After this period, add 25 ml of potassium iodide
solution and dilute the mixture with 50100 ml of water. Titrate it immediately against
0.1 N sodium thiosulfate solution taken in a burette. Shake vigorously after each addition
and again titrate until the yellow color almost disappears. Add starch solution and titrate
again to the disappearance of the blue color.
Simultaneously perform a blank titration using 25 ml of the iodine monochloride
solution.
Calculations
The iodine number can be calculated from the following formula:
Iodine number =
(V1 V2 ) N 127 100
W 1000
Where
log K/Ka = r s
where K and K a are the ionization constants of substituted and unsubstituted benzoic acids
s is the substituent constant.
r is the reaction constant.
A plot of log K/Ka against s is linear with slope equal to r. The reaction constant
measures the susceptibility of a reaction to the polar effects of the substituents. The
magnitude of the value of r indicates that the reaction in sensitive to the polar effects. It
provides information about the nature of the transition state involved in the reaction. A
negative value of r shows that the reaction in aided by electron-donating groups and vice
versa. To estimate r several substituted benzoic acids are taken and pKas are determined.
Since Ka =
K a = H+
+
or pKa = log H = pH
Therefore, a plot of the Hammet equation is drawn between pK (substituted), pKa
(unsubstituted) versus s. The s values for several substitutents have been determined and
are given in Table 7.1.
ESTIMATION OF FUNCTIONAL GROUPS 165
Group m p
NH 2 0.161 0.660
CH2 0.069 0.170
OH 0.002 0.357
H 0 0
NO 2 0.710 0.778
Cl 0.373 0.227
CN 0.678 0.628
Br 0.390 0.232
Chemicals
Benzoic and substituted benzoic acids.
Procedure: Weigh accurately about 0.2 g benzoic (Note I) in a 100 ml Erlenmeyer flask.
Dissolve it in one-half equiv. of standard 0.01 N sodium hydroxide solution in 50 ml of
ethanol (Note II). Let the solution equilibrate (it may take 3045 min), then note the
temperature. Measure the pH of this solution on a pH meter and calculate the corresponding
pKa. Draw a plot between pKa and of the corresponding acids and obtain .
Notes I: Each student is assigned an acid.
II: For 0.2 g (0.001 mole) of benzoic acid, 0.0005 equiv. of sodium hydroxide (half equiv.) is
needed. If sodium hydroxide is 0.01 N, then use 5 ml of this solution.
Chemicals
Sulfuric acid and silver sulfate (dissolve 0.45 g of silver sulfate in 5 kg conc. sulfuric
acid and leave for two days).
Ferroin indicator.
Procedure: In a 250 ml round-bottomed flask equipped with a reflux condenser place 0.4 g
of mercuric sulfate (Note I), 20 ml of waste water sample (Note II) and mix. Add to this
mixture 10 ml standard potassium dichromate solution followed by 30 ml sulfuric acid
containing silver sulfate ( Note III) , with constant shaking. Add boiling chips, replace, the
condenser and reflux for 2 hrs to oxidize the carbonaceous matter. Cool and wash the
condenser with 20 ml of distilled water. Transfer the mixture to a 250 ml Erlenmeyer flask.
Rinse the round-bottomed flask twice with distilled water. Titrate against 0.1 N ferrous
ammonium sulfate solution using 23 drops of ferroin indicator. The end-point is indicated
by a change of color from blue-green to reddish brown. A blank using 20 ml of distilled
water should also be run simultaneously.
Calculations
(V V1 ) N 8000
mg/l COD =
ml sample
Chemicals
Procedure: Weigh accurately 6.5 g of ethyl acetoacetate in a 100 ml volumetric flask and
fill it to the mark with methanol to give 0.5 M solution. (Note I) Pipette 10 ml of this
solution in a 250 ml Erlenmeyer flask. Add 10 ml of 0.1 M bromine solution and shake.
Immediately add 10 ml of 10% solution of b-naphthol (Note II ). Shake the flask vigorously
for 2 min. Add 25 ml of app. 0.1 M aqueous potassium iodide solution and allow to stand for
15 min at room temperature with occasional shaking. Then titrate against standard sodium
thiosulfate solution (no indicator ). The solution passes from a wine-red to a colorless form
to a light yellow color (Note III). Note the volume of sodium thiosulfate solution consumed.
168 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Calculations
Assume volume of 0.1 M Na 2S2O3 solution used = V ml
V ml of 0.1 M Na2S2O3 = V/2 ml of 0.1 M I2
= 10 0.5 130 mg
= 650 mg
Therefore, keto from = 650 6.5 V
6.5V
Keq =
650 6.5V
This value is around 0.07.
Notes I: The concentration of the ester should be known exactly.
II: Use a graduated cylinder to measure bromine and b-naphthol solutions.
III: The end-point should persist for at least 3 min.
Questions
7.9 Why does the enolic from react with bromine?
7.10 Why is it not necessary to know the exact concentration of Br 2 and b-napthol?
R OCH 3 + HI R OH + CH3I
ESTIMATION OF FUNCTIONAL GROUPS 169
A rather more convenient procedure is to absorb the liberated methyl iodide in acetic acid
and sodium acetate solution containing bromine and then estimated volumetrically. First
iodine monobromide is formed which is further oxidized to iodic acid. Then potassium iodide
solution is added to liberate iodine which is titrated against standard sodium thiosulfate
solution. The following reactions take place:
HIO3 + 5 HI 3 I 2 + 3 H 2O
Apparatus
The apparatus employed is shown in Fig. 7.3. It consists of a pyrex glass two necked round-
bottomed flask A. A Liebigs condenser C and a trap D is fitted in one joint and an inlet
carbon dioxide tube B is attached to the second joint. The trap D is connected to two receivers
E and F. The reaction flask A is immersed in an oil-bath. The left hand side assembly H is
a device by means of which the vapor of chloroform boiling in the flask can be passed
through the condenser C.
Chemicals
Acetic acid-sodium acetate-bromine solution. Dissolve 10 g anhydrous sodium acetate
in 100 ml glacial acetic acid. Add 0.3 ml of bromine per 10 ml of solution before use.
The oil-bath should attain temperature of 140C in about 75 min. During this period the
reaction is usually complete. In a 250 ml flask fitted with a glass stopper and containing 10
ml of 25% sodium acetate solution, transfer the contents of receivers E and F. The sodium
acetate is required to buffer the HBr formed. To destroy excess of bromine, formic acid
(90%) is added dropwise unit the smell of bromine is no longer detected (Note III). Replace
the stopper and shake the flask. Dilute the contents of the flask to 100 ml with water , 1 g
of potassium iodide and 10 ml of sulfuric acid, stopper the flask immediately, swirl gently,
allow to stand undisturbed for 3-4 min. The solution is then titrated against standard
thiosulfate solution, using starch indicator. A blank may be run using phenol and propionic
anhydride.
Calculations
According to the equations above a convenient conversion factor is obtained as follows:
31 V1
V1 ml of 0.05 N of Na2S2O3 solution = g OCH3 groups
120,000
ESTIMATION OF FUNCTIONAL GROUPS 171
31 V1
Therefore, W g of the unknown contains g OCH 3 groups
120,000
31 V1 100
Percentage OCH3 group = =X
120,000 W
If the molecular weight (M) of the unknown is given then the number of methoxy
groups is given by:
M X
OCH 3 groups (One OCH 3 group = 31).
100 31
Notes I: These reagents help dissolve as alkoxy compound. Chips of carborundum prevent bumping.
II: The constant boiling acid ( b.p. 120C/760 mm ) containing 57% of hydroiodic acid is
satisfactory.
III: To test destruction of bromine add a drop of methyl red indictor. Decolorization indicates
the presence of bromine. Add more formic acid.
Chemicals
Dye Solution: Dissolve sodium salt of the dye (0.125 g) in 240 ml of distilled water in
a 250 ml volumetric flask. Make up to the mark with phosphate buffer (equivalent to 0.0165
of K2HPO 4 and 0.0202 g of KH2PO 4 per 250 ml of the solution ).
Standard Ascorbic Acid Solution: Dissolve (just before use) pure 10 mg ascorbic
acid in distilled water in a 100 ml volumetric flask.
Source of Vitamin C
A vitamin C tablet or fruit juice can be used to estimate the amount of Vit. C.
Vitamin C Tablet
Take a Vit. C tablet containing minimum 100 mg of the vitamin. Weigh the tablet accurately.
Crush it on a filter paper and transfer the powder to a 100 ml Erlenmeyer flask. Add 500 ml
of a cold 1% oxalic acid solution in distilled water. Leave it for some time. Filter the mixture
directly into a 1000 ml volumetric flask. Wash the Erlenmeyer flask and the filter paper
with 200 ml, 1% oxalic acid solution into the volumetric flask. Fill the flask to the mark
with additional 1% oxalic acid solution and mix thoroughly. For calculating the normality
of the dye against a standard ascobic acid sample. The normality and the amount of Vit. C
can be determined using 5 ml of Vit. C solution.
Fruit Juice
Filter 10 ml of orange juice either from the fruit (orange) or from canned juice to remove
the pulp. With the help of a burette, transfer 5 ml of the juice in a 50 ml volumetric flask.
Dilute the orange juice with 1% oxalic acid solution up to the mark.
Procedure: In a clean 100 ml Erlenmeyer flask, pipette 5 ml of juice (Vit. C tablet or fruit
juice). Titrate it with 2, 6-dichlorophenolindophenol dye taken in a burette with constant
shaking. The end-point is reached when a pink color is obtained. Also carry out a blank
without the sample using 5 ml of distilled water only. This is an alternative method to the
one described under Vit. C.
Calculations
Weight of ascorbic acid dissolved in 100 ml = W g
distilled water
Volume of dye needed for fruit juice = V ml
Volume of dye needed for ascorbic acid = V1 ml
Volume of dye needed for blank = V2 ml
ESTIMATION OF FUNCTIONAL GROUPS 173
V V2
Total amount of Vit. C in fruit juice = W Dilution factor
V V1
Dilution factor: In the above case 5 ml fruit juice is diluted to 50 ml therefore, the
dilution factor is equal to 10.
Tf = K f m
Chemicals
Naphthalene, camphor, acetanilide.
Determination of molecular weight of acetanilide involves the following two steps:
Determination of Kf for camphor: Weigh a clean, dry weighing bottle and place
about 0.2 g of naphthalene in it and determine its accurate weight. Add approximately 2 g
powdered camphor and also determine the accurate weight of the mixture. Put a glass
stopper on the weighing bottle and gently heat on a flame to obtain a clear solution. Shake
the bottle to get a homogeneous solution. Cool and withdraw a small portion of the solidified
mixture and determine the melting point of the mixture in a capillary tube. Repeat to
obtain a satisfactory melting point.
Determination of molecular weight of acetanilide: Repeat the procedure described
in the above step using approximately the same amounts of chemicals but replace acetanilide
for naphthalene. Determine a satisfactory melting point of the mixture.
Calculations
Weight of naphthalene = W g
Weight of camphor = W1 g
(176 J ) 1289
Kf =
91 1000
w K f 1000
Molecular weight = .
W (176 t1 )
Chapter 8
ORGANIC PREPARATIONS
The student of organic chemistry is also concerned with an important class of laboratory
experiments, i.e., organic preparations. It is necessary, therefore, to give an adequate
training in this area, such exercises will give the necessary experience and confidence to
work later as a skilled research work. The synthetic experience gained at the laboratory
stage can be adopted on a large scale. It is intended to describe a number of diverse
experiments which meet a number of criteria, i.e., be readily performable within the
stipulated laboratory period, cover adequately some concept of organic chemistry and finally
the experiment poses some interesting questions in the mind of the student. Furthermore,
the selection of experiments is also governed by the ease of the availability of chemicals
and essential apparatus. Laboratory procedure and synthetic experiments of various
compounds of proven value will be discussed. As far as possible, experiments that involve a
certain analytical technique; concept or reaction type have been grouped together. All the
experiments will utilise the techniques discussed in Chapter 2.
It is important to note that all organic compounds are potentially dangerous and fire
hazards are large, and many compounds are poisonous. One should, therefore, be aware of
the potential dangers and for safe working, the fume hood should be used as much as possible.
where
176 LABORATORY MANUAL OF ORGANIC CHEMISTRY
( )
Mechanistically a nitronium ion NO2+ is first produced form nitric acid and sulfuric
acid which attacks the aromatic ring as outlined in the following steps:
Procedure: Take a 200 ml round-bottomed flask fitted with a cork holding a thermometer
(the bulb extends to the bottom of the flask) and a glass tube (air-condenser) about 30
inches long. Place 16 ml of conc. nitric acid (d 1.42) and 17 ml of conc. sulfuric acid (d 1.84)
and cool the nitrating mixture in cold water. To this mixture add dropwise with constant
shaking 15 ml (13 g) of benzene. During the addition the temperature should not rise above
60oC (Note I ). Cool the flask in a bath of ice-cold water if necessary. After the addition is
complete replace the condenser and warm the flask on a water-bath for 50 min maintaining
a temperature between 5060oC. Shake the flask occasionally. Cool and pour the contents
in a beaker containing 100 ml of water. Transfer the mixture to a small separatory funnel,
ORGANIC PREPARATIONS 177
and shake. Save the lower organic layer and discard the upper aqueous phase. Wash the
organic layer twice with 60 ml portions of water followed by 15 ml of 1 M sodium hydroxide
solution and again with water to remove excess nitric acid. Take the organic layer in an
Erlenmeyer flask and shake with anhydrous calcium chloride to dry nitrobenzene and filter
in a 50 ml distillation flask. Distil using an air-condenser and collect the fraction boiling
between 206210oC (Note II). Nitrobenzene is obtained as a clear pale yellow liquid yield,
15-16 g.
Notes I: If the temperature is allowed to rise above this limit then dinitration of benzene takes
place.
II: Do not distil to dryness as the brown mass consisting of m-dinitrobenzene and higher
nitro compounds may decompose and cause explosion.
Questions
8.1 Why should the temperature not rise above 60 oC?
8.2 What will happen if the temperature is lowered to 10 oC?
8.3 How will the absence of sulfuric acid influence the rate of nitration?
Usually, all but one of the reactants are present in excess of the stoichiometric amounts
in a preparation. The percentage yield is calculated here by considering the above nitration
experiment. In this case nitric acid and sulfuric acid are present in excess, therefore,
calculation is made on the basis of benzene alone. From the equation it is evident that
theoretically 78 g benzene would yield 123 g of nitrobenzene. Using 13 g of benzene, the
13 125
theoretical yield would be = 20.5 g. .
78
The actual yield obtained is 16 g.
16
Thus the percentage yield is equal to 100 = 77.3
20.5
178 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Yields are obtained frequently in the range of 5580% and are considered satisfactory.
In a preparation a yield of 100% in impossible to obtain because loses occur during work-up.
However, yields of > 99% are reported as quantitative.
The nitration is facilitated under mild conditions because phenol contains a strong
activating hydroxyl group and dilute nitric acid is sufficient to introduce the nitro group.
The temperature should be controlled otherwise tarry oxidation products are formed.
Procedure: In a 250 ml bolt-head flask, mix 18 ml of conc. sulfuric acid with 55 ml of water
(Note I). Dissolve 20 g sodium nitrate in this solution and cool in a cold water-bath. In a
dropping funnel mix 12.5 g of melted phenol with 2.5 ml water to form an emulsion. Add
this emulsion to the above solution with constant stirring at such a rate that the temperature
does not rise above 20 oC. After the addition is complete, leave the mixture at room
temperature for 1 hr shaking occasionally. Then add 50 ml of water, shake well and allow
to stand. Decant the aqueous layer and discard it. Repeat this process of washing 23 times
with water to ensure the removal of the acid. At this stage a crude mixture of o- and p-
nitrophenols is obtained.
the hot solution and allow the filtrate to crystallize. Colorless crystals of p-nitrophenol are
obtained. The yield is 2.6 g, m.p. 112oC.
Note I: Acid should be added to water very slowly. Instead 21 ml of conc. nitric acid and 51 ml of
water may be used.
Questions
8.4 Why does o-nitrophenol distil over but not the p-isomer?
8.5 Which of the two isomers is more soluble in water and why?
Question
8.6 Why does polybromination take place in aniline? How can it be controlled?
Procedure: Place 7.5 g of phenol and 20 ml of conc. sulfuric acid in a dry round-bottomed
flask. Shake the mixture and heat on a water-bath for 30 min. During this period a clear
solution of o- and p-phenolsulfonic acids are obtained. Cool the flask in an ice-bath. Now
add 22 ml of conc. nitric acid dropwise with constant shaking. An exothermic reaction takes
place and copious red fumes (oxides of nitrogen) are evolved and the liquid becomes deep
red in color. Heat the flask in a water-bath (80100oC) for 2 hrs with occasional shaking.
Cool the mixture and pour it carefully into about 100 ml of cold water. Filter the solid on a
Buchner funnel and wash thoroughly with cold water. Recrystallize the crude picric acid
from hot aqueous alcohol, yield 11.5 g., m.p. 122C.
Procedure: The procedure is designed for a class of 10 students. The idea is to study the
rate of bromination for a group of aromatic compounds. These compounds may be divided
into two groups. First prepare the following solutions:
Dissolve 2 g bromine in 250 ml of 90% acetic acid to obtain a 0.05 M bromine solution
and use this as stock solution. Dissolve separately 1.56 g benzene in 100 ml ethyl acetate
and in separate containers dissolve phenol (2 g), benzoic acid (1.2 g), methyl benzoate
(2.72 g),chlorobenzene (1.0 g), toluene (1.0 g), p-xylene ( 1.0 g), nitrobenzene ( 1.2 g),
each in about 50 ml of ethyl acetate to give a 0.2 M solution. Now place five clean 2 15
mm test tubes on a test tube stand. Add 2 ml of each solution (group A ) in each test tube
(Note I) and 2 ml of bromine solution in each tube from a burette. Note the time of addition
in each case. Shake the tubes for a few seconds and then put them on the stand (Note II).
Record the time for the loss of bromine color in each test tube (Note III) . Discard the
solution in the sink ( fume hood), wash with a small quantity of acetone and dry. Repeat the
experiment with the second group of compounds ( group B) using the same volumes of
reagents followed by bromine solution. Again note the time for the decolorization of bromine
color. Record the results in a tabular form.
ORGANIC PREPARATIONS 181
GroupA
C6H6 2 ml 2 ml
C6H5OH 2 ml 2 ml
C6H6OCH3 2 ml 2 ml
C6H5COOCH3 2 ml 2 ml
C6H5COOH 2 ml 2 ml
Group B
C6H6 2 ml 2 ml
C6H5Cl 2 ml 2 ml
C6H5CH3 2 ml 2 ml
2 ml 2 ml
C6H5NO2 2 ml 2 ml
By a comparison of time it will be noticed that the color disppears faster in case of
compounds bearing electron-donating groups.
Questions
8.7 Why is chlorobenzene less reactive than benzene in electrophilic substitution?
8.8 List five common electrophilic substitution reactions as applied to aromatic
compounds.
such as nitrobenzene, carbon disulfide, etc. may be employed if needed. However, if the
aromatic compound is an inexpensive liquid hydrocarbon, for example, benzene it is used
both as a reactant and a solvent.
Procedure: In a 250 ml round-bottomed flask fitted with a water condenser and drying
tube to the top of the condenser place 5 g phthalic anhydride and 25 ml thiophene-free
benzene ( Note I) . Then add 10 g anhydrous aluminum chloride ( Note II) and shake
vigorously. An exothermic reaction usually commences at this stage with the evolution of
hydrochloric acid gas. A gas trap is attached to the top of the drying tube. After the initial
reaction has subsided, heat the flask under reflux in a boiling water-bath carefully for
20 min with frequent shaking. Cool the flask in an ice-bath at the end of heating and add 40
g of crushed ice in small lots with constant shaking. Now add 50 ml of water and 7 ml conc.
hydrochloric acid to hydrolyse the addition complex (Note III) . Remove excess benzene by
steam distillation. Transfer the remaining solid to a beaker and allow it to cool in ice-bath.
Filter the acid on a Buchner funnel at the pump and wash with cold water. Dissolve the
solid in 40 ml of 10% aqueous sodium carbonate solution and filter again to remove insoluble
aluminum hydroxide. Acidify the filtrate with conc. hydrochloric acid stirring with a glass
rod. The acid separates out as a solid. Filter and dry in air.
The acid obtained above usually has a low melting point (approx. 94oC). The pure
anhydrous acid can be prepared by dissolving it in 40 ml of benzene in a round-bottomed
flask and heating for 15 min. Transfer to a separatory funnel and remove the water layer.
Concentrate the benzene solution to half its volume and precipitate the acid by adding
petroleum ether, simultaneously cooling it in an ice-bath. Filter the solid and dry in a
vacuum desiccator. The yield of the pure acid is 6.51 g, m.p. 128oC.
Notes I: Thiophene-free benzene can be prepared by shaking commercial benzene with conc. sulfuric
acid several times in a separatory funnel, subsequently washing with water and distilling
after drying over anhyd. calcium chloride.
ORGANIC PREPARATIONS 183
Question
8.9 What is the principle involved in the preparation of thiophene-free benzene by washing
with conc. sulfuric acid?
Procedure: In a 250 ml round-bottomed flask, place 19.3 g distilled benzyl chloride and
75 ml sodium-dry benzene. Fit the flask with a water condenser, and a gas trap for collecting
hydrochloric acid gas evolved in the reaction is connected to the top of the condenser with
the help of a rubber tubing. In a stoppered bottle weigh 6 g of anhyd. aluminum chloride
(Note I). Immerse the flask in an ice-bath. Add about 1 g of aluminum chloride through the
condenser and shake. An exothermic reaction commences with the evolution of hydrochloric
acid gas. When the reaction has subsided add another 1 g portion of aluminum chloride.
Repeat the addition and shake. Keep the flask well cooled. After the addition is complete,
184 LABORATORY MANUAL OF ORGANIC CHEMISTRY
reflux the contents of the flask for 20 min on a boiling water-bath. Allow to cool, add 50 g of
crushed ice and 50 ml water to the flask and shake. Transfer the mixture to a separatory
funnel. Discard the lower aqueous layer. Wash the benzene layer with 10% hydrochloric
acid followed by water. Dry the benzene solution over anhydrous calcium chloride. The
dried liquid is filtered into a distilling flask and distilled to remove benzene. Distil the
residue using an air condenser and collect diphenylmethane between 250275 oC (b.p. of
pure diphenylmethane is 262oC). The yield is 14.0 g.
Note I: Usually an excess of anhydrous aluminum chloride in used.
Question
8.10 What are the limitations of the Friedel-Crafts alkylation?
Procedure: Fit a 250 ml dry round-bottomed flask with a reflux condenser and a drying
tube at the top of it. Charge the flask with 4.2 g of succinic anhydride and 25 ml dry benzene.
Support the flask over a water-bath in the fume cupboard (Note I) and add accurately
weighed (Note II) 12.5 g powdered anhyd. aluminum chloride in one portion. First cool the
mixture. After the exothermic reaction ceases replace the condenser immediately and heat
the flask for 30 min. Shake frequently during this period. If an uncontrollable reaction
occurs during heating, cool the flask in a bath of cold water again. Pour the cold mixture in
a 250 ml beaker and immerse it in ice. To this add slowly with constant stirring 20 ml of
50% hydrochloric acid. Filter the solid on a Buchner funnel at the pump wash the solid with
10 ml cold dil. hydrochloric acid followed by cold water. Dissolve the crude product so
obtained in sodium carbonate solution (5 g of sodium carbonate dissolved in 30 ml of water )
by boiling. Break the lumps with a glass rod. Filter the solution and cool. Acidify the cold
filtrate with 13 ml of conc. hydrochloric acid. Filter the solid, wash with cold water and dry.
The yield is 7.0 g, m.p. 115o C.
Procedure: Place 3 g of pure anthracene, 30 ml of dry xylene (Note I) and 1.5 g of maleic
anhydride in a 100 ml dry round-bottomed flask. Attach a water condenser and reflux the
186 LABORATORY MANUAL OF ORGANIC CHEMISTRY
contents on a water-bath for 25 min with frequent shaking. Cool the mixture and collect
the solid on a Buchner funnel. Recrystallize the adduct from ethyl acetate. The yield is 3.3
g, m.p. 262263 oC.
Note I : Dry benzene may be used but the refluxing time should be increased. The yield in this
solvent may also be low.
Question
8.11 Write the structure of the Diels-Alder product between cyclopentadiene and
benzoquinone.
in an oil-bath at 170180oC for 90 min. Foaming occurs initially because of the evolution of
carbon dioxide. Cool the flask and add 75 ml of water followed by the addition of 10% sodium
hydroxide solution till alkaline. Extract the clear solution with two 35 ml portions of ether
to remove any unchanged benzaldehyde. Acidify the aqueous layer with conc. hydrochloric
acid until no more carbon dioxide evolves. Filter off the precipitated solid on a Buchner
funnel at the pump, wash with water and recrystallize from hot water. The yield is 8.5 g,
m.p. 133oC.
Note I: Do not use sodium hydroxide a strong base, otherwise the Cannizzaro reaction will take
place.
Questions
8.12 By what mechanism would sodium bisulfite remove unchanged benzaldehyde from the
reaction mixture?
8.13 Write an equation for the reaction of a mixture of benzaldehyde and formaldehyde
with conc. sodium hydroxide solution.
Pour the mixture onto 40 g of ice, taken in a beaker. Collect the solid on a Buchner funnel.
Recrystallize from hot aqueous ethanol. The yield is 9 g, m.p. 122o C.
Step B: Preparation of 2, 5-dihydroxyacetophenone
Procedure: In a 100 ml round-bottomed flask, place 4 g powdered hydroquinone diacetate
weigh 8.5 g anhyd. aluminum chloride. Grind in a pestle and mortar and immediately add
to the flask. Attach an air condenser filled with a drying tube and heat the flask between
115120o C in an oil-bath in the fume hood for 30 min. After this duration, raise the
temperature to 150oC. When the evolution of hydrochloric acid gas commences heat at this
temperature for 1 hr. Cool the flask, add 50 g of crushed ice and 4 ml conc. hydrochloric
acid and swirl. Collect the solid on a Buchner funnel and wash it with cold water. Recrystallize
from aqueous boiling ethanol. The yield is 1.8 g, m.p. 202203o C.
Question
8.14 Discuss the mechanism of the Fries rearrangement.
Procedure: In a 100 ml Erlenmeyer flask place 2.6 g (2.5 ml ) of aniline and 25 ml of 10%
aqueous sodium hydroxide solution. To this add 4.3 g (3.5 ml) of benzoyl chloride in small
portions with vigorous shaking for 1 min after every addition. Cork the flask and shake
vigorously for 10 min. The reaction is exothermic and the flask becomes hot. Benzoyl
derivative may separate out as a white powder when the reaction is complete ( Notes I and
ORGANIC PREPARATIONS 191
II). Filter the solid on a Buchner funnel at the pump. Wash several times with water and
drain. Recrystallize from boiling alcohol. The yield is 4.4 g, m.p. 162oC.
Notes I: This can be established when the reaction mixture no longer smells of benzoyl chloride.
II: At this point make sure that the reaction mixture is alkaline.
Question
8.15 Why is an aromatic acid chloride less reactive than the aliphatic acid chloride in the
Schtten-Baumann reaction?
The CN ion is a specific catalyst for condensation. The specificity is attributed to
many factors. Through for many years it was believed that only cyanide ion can catalyze
the benzoin condensation, however, recently thiamine hydrochloride (Vitamin B 1) has been
found to be an effective catalyst as well.
192 LABORATORY MANUAL OF ORGANIC CHEMISTRY
This preparation involves the following three steps. However, the reaction is frequently
accomplished by taking benzin.
Procedure: Place 3 g of benzil in a 100 ml round-bottomed flask and to this add a solution
of 3 g of potassium hydroxide in 10 ml of water. Also add 7 ml of ethanol and shake to obtain
a bluish-black solution. Replace the water condenser and reflux the mixture on a water-
bath for 15 min. Transfer the contents to a China dish and cool it in an ice-bath for 30 min.
The potassium salt of benzilic acid separates out. Filter the solid and wash thoroughly with
cold water. Dissolve the salt in 30 ml water and acidify the solution with conc. hydrochloric
acid with constant stirring. A red-brown precipitate of the acid is formed. Filter and wash
with cold water. Recrystallize from boiling water using some activated charcoal. The yield
is 3 g, m.p. 150oC.
Note I: KCN is a fatal poison, it should be handled carefully and wisely. This reaction should be
performed under the strict supervision of the teacher. This preparation should, prefectly
be carried out by taking benzil.
Question
8.16 Would alphatic aldehydes undergo step A?
ORGANIC PREPARATIONS 193
orange-red liquid remains in the flask. Acidify it with dil. sulfuric acid carefully and steam
distil the mixture again until no more oily drops of salicylaldehyde pass over. The residue
in the flask contains p-hydroxybenzaldehyde. Extract the distillate with ether twice to obtain
salicylaldehyde as well as some unreacted phenol. Remove ether on a hot water-bath in a
hood and transfer the remaining liquid to a separatory funnel and add twice the amount of
a saturated solution of sodium bisulfite and shake vigorously for 30 min. Then clamp the
separatory funnel on an iron-stand and allow it to stand for 1 hr. Filter the bisulfite adduct
on a Buchner funnel. Wash it with a little alcohol and then with ether to remove any
phenol. Take the bisulfite compound in a beaker, add dil. sulfuric acid and warm on a
water-bath. Cool and extract salicylaldehyde with ether and distil. The product distils between
19597oC. The yield is 2.4 g.
To obtain p-hydroxybenzaldehyde (by-product) filter the residue while hot through a
filter paper and cool. Extract with ether and remove the solvent on a hot water-bath.
Recrystallize the crude solid so obtained from boiling water. The yield is 0.55 g, m.p. 116o C.
Note I: The temperature of the bath may be adjusted by cooling or heating as is deemed essential.
Nascent oxygen is the active oxidizing opecies and is available according to the following
reactions:
Procedure: In a 250 ml Erlenmeyer flask, place 20.5 g Na2Cr2O7.2H2O, 100 ml water and
add carefully 9.5 ml conc. sulfuric acid. Shake and cool the resulting orange-red solution of
chromic acid to 15o C. In a second Erlenmeyer flask, take 10 g of cyclohexanol and cool this
ORGANIC PREPARATIONS 195
also to 15o C. Use a thermometer. Pour the dichromate solution in one lot to the flask
containing cyclohexanol. Shake the flask vigorously. Since the reaction is exothermic and
if the temperature rises above 60oC, cool it in an ice-bath (Note I ). When the temperature
stops rising allow the flask to stand for 30 min at room temperature. Transfer the reaction
mixture to a 250 ml round-bottomed flask, add 100 ml of water, a few pieces of boiling
stones and distil without using a thermometer. Distil the mixture until 70 ml of the distillate
has collected. Place the distillate in a separatory funnel and shake with a saturated solution
of sodium chloride. Collect the upper organic layer. Wash the aqueous layer with 20 ml of
ether. Combine the extract with the organic layer and dry (Na 2SO4). Filter and remove
ether on a water-bath in a hood. Distill the residue and collect the fraction between
154156 o C. The yield is 6.6 g.
Note I: The temperature should not fall below 55 oC or rise above 60 oC.
Question
8.17 Would it be possible to attempt preparation of benzaldehyde by permanganate
oxidation of toluene?
Procedure: Fit a 500 ml three-necked flask equipped with a small dropping funnel, a
thermometer and an exit tube needed to exit the evolved oxides of nitrogen over the surface
ORGANIC PREPARATIONS 197
of a 50 ml 10% sodium hydroxide contained in a large bottle. Place 20 ml of conc. nitric acid
(d 1.42 ) in the flask and dilute it with 10 ml of water. Take 4 ml of cyclohexanol in the
dropping funnel. Heat the diluted acid to about 85o C and add one drop of cyclohexanol at a
time from the dropping funnel. A highly exothermic reaction commences immediately,
when the temperature has fallen to 80o C, add another drop of cyclohexanol (Note I). The
addition of cyclohexanol is usually complete in 1520 min. Finally warm the contents of the
flask to 99100oC for 5 min and then cool in an ice-bath, adipic acid crystallizes out. Filter
the adipic acid under suction and wash with cold water. Recrystallize the acid from a minimum
amount of hot water. Filter again and wash with cold water. The yield is 3.1 g, m.p. 152oC.
Note I: Do not attempt to add fresh drop of cychlohexanol until the previous one has reacted.
Moreover, do not allow any cyclohexanol to accumulate in the flask otherwise an almost
violent explosion may take place.
Question
8.18 What type of ketones are oxidized by sodium hypobromite?
This acid alternatively can also be obtained from Grignard reaction by carbonation of
t-butyl chloride followed by protonation of the intermediate complex.
Place 35 ml cold conc. sulfuric acid in 50 ml of water into the larger dropping funnel.
In the second funnel place 10% sodium thiosulfate solution. Cool the contents of the flask
to around 70oC then add sulfuric acid slowly. Because of the presence of excess hypobromite
solution, evolution of bromine takes place as the mixture in the flask is acidified. When the
red color of bromine appears, stop adding acid and run in some sodium thiosulfate solution.
Continue the process of alternate addition of acid and thiosulfate solutions. After the addition
is over the solution should be acidic to litmus. At this stage the solution is colorless and
trimethylacetic acid separates out as an oil. Distil the mixture and collect the acid which
distils over with water. Collect about 75 ml of the distillate, separate the acid in a separatory
funnel. The yield is 56 ml, b.p. 164o C/760 mm.
*Alternatively, triethylene glycol (b.p. 278C) (HOCH2 CH2 O CH2 CH2 O CH2 CH2 OH) may be used.
200 LABORATORY MANUAL OF ORGANIC CHEMISTRY
hydrazine hydrate. Add 23 boiling chips. Heat the mixture on a water-bath till most of the
potassium hydroxide has dissolved. Attach a water condenser to the flask and reflux on the
flame for 1 hr. After this period remove the condenser and distil off most of the water and
hydrazine until the temperature of the liquid rises to 200oC (Note I) and collect the distillate.
Separate the organic layer in a separatory funnel. Extract the aqueous layer twice with
ether. Combine the organic layer and the extracts, dry over anhydrous sodium sulfate.
Remove ether and distil the residue and collect the fraction between 134137 oC. The yield
is 5.8 g.
Procedure: Place 6.3 g benzophenone, 65 ml ethanol, 6.3 g sodium hydroxide and 6.3 g of
zinc powder in a 200 ml bolt-head flask. Equip the flask with a reflux condenser. Mix the
contents and then warm gently on a water-bath for 1.5 hr. Allow the flask to cool to 60o C
and then filter the reaction mixture by suction. Wash the residue on the filter paper twice
with 5 ml portions of ethanol. Pour the clear filtrate in 250 ml cold water and acidify with
25 ml of conc. hydrochloric acid. A viscous oil separates out which solidifies on cooling or
keeping overnight. Filter the solid under suction and recrystallize from 10 ml of hot ethyl
alcohol. The yield is 3.9 g, m.pt. 58oC.
Separation of Isomers
Azobenzene displays geometric isomerism and exists in the following syn-and anti-
forms.
These two forms can be separated by column chromatography and their identity is
established by ultraviolet spectroscopy.
Notes I: Put a glass wool plug at the bottom of a 25 ml burette. Now pour 20 ml of pet ether in the
burette and add 10 g of alumina from the top in a continuous stream. The burette should
be maintained in a vertical position and clamped on an iron-stand. Then add a layer of
sand and drain off the solvent till its lavel is about 2 cm above the level of packing.
II: Do not use an old sample of azobenzene.
III: Alternatively carbon paper can be wrapped.
202 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Proceduce: In a 100 ml round-bottomed flask, place 11.3 g (7.5 ml) of fuming nitric acid, to
this slowly add 18.4 g ( 10.5 ml) of conc. sulfuric acid. Fit the flask with a reflux condenser
and through it, add 7.5 g (6.3 ml) of nitrobenzene in four small portions with thorough
shaking. After the addition is complete reflux the mixture on a water-bath in a fume hood
for 15 min. With frequent shaking, cool and pour the contents into 200 ml of cold water
taken in a 600 ml beaker. The product separates out as a pale yellow solid. Filter on a
Buchner funnel and wash thoroughly with cold water to remove the acid. To purify m-
dinitrobenzene, take the crude product in a 100 ml round-bottomed flask with 40 ml of
ethanol and reflux on a water-bath till all the solid has dissolved. Filter the hot solution
and allow the filtrate to cool. Separate the solid by suction and dry. The yield is 7.2 g, m.p.
8990oC.
Step B: Preparation of m-nitroaniline
Procedure: In a 250 ml Erlenmeyer flask dissolve 15.0 g of sodium bisulfite (Na 2S. 9H 2O)
in 30 ml of water and to the solution add 5.0 g of powdered sodium bicarbonate in small
portions with constant stirring. Then add 40 ml of methanol and cool the mixture to 20o C.
Filter to remove the precipitated sodium carbonate and wash the solid with a little methanol.
The filtrate contains sodium bisulfite (NaHS) solution needed for reduction.
Transfer 5 g of m-dinitrobenzene in a 250 ml round-bottomed flask, add 45 ml of
methanol and warm. To this add sodium bisulfite solution prepared above. Fix a reflux
condenser to the flask and reflux for 20 min (Note I) . Allow the flask to cool and distil most
of methanol from a water-bath. Pour the residue from the distilling flask into a beaker and
keep stirring. Collect the yellow m-nitroaniline on a Buchner funnel and wash with water.
Recrystallize from 75% methanol. The yield is 3.1 g, m.p. 114oC.
Note I: Some sodium carbonate may also precipitate at this stage, ignore it.
mild reducing agent and exhibits considerable selectivity. It reduces aldehydes and ketones
Questions
8.19 Write the products obtained by the reduction of m-nitroacetophenone with Sn/HCl
and NaBH4 respectively.
8.20 What other reagents besides NaBH4 will reduce acetophenone to 1-phenyl-1-ethanol?
Benzoic acid can be prepared by treating phenyl magnesium bromide (the Grignard
reagent) with carbon dioxide and subsequent hydrolysis of the complex.
Procedure: In a 250 ml round-bottomed flask fitted with a reflux condenser, place 2.4 g of
dry magnesium turnings in 30 ml of sodium dry ether. To this add slowly 15.7 g (10 ml) of
dry bromobenzene (Note I) and a crystal of iodine. There is an immediate commencement
of reaction with ether appearing milky white. If, however, the reaction does not start,
warm the flask on a water-bath and remove it after the mixture starts refluxing. This will
usually promote the reaction. The reaction subsequently will start itself, boil for 3540
min. After this heat the flask in a beaker of warm water for an additional period of 10 min.
Place approximately 15 g of crushed dry ice in a 250 ml beaker and pour into it slowly the
Grignard reagent prepared above, with constant stirring. A vigorous reaction ensues and
the contents in the flask turn into a pasty mass. Stir it till all the carbon dioxide has
evaporated. Add 50 ml of warm water and then acidify the contents with dil. hydrochloric
acid in order to generate benzoic acid as well as dissolve the magnesium salt. Cool the
beaker in ice and filter. Recrystallize from hot water, yield 6.0 g, m.p. 122oC.
Question
8.21 Suggest three additional methods for the preparation of benzoic acid.
Question
8.22 Why are absolutely dry conditions necessary for this reaction?
Procedure: In a 250 ml three-necked fitted with a reflux condenser, mercury seal, stirrer
and a small dropping funnel combined with a glass inlet, place 20 ml of anhydrous ether and
flush the flask with dry nitrogen gas. Add 0.95 g of lithium metal (Note I) in the form of
shavings and stir. Take a solution of 10.8 g of p-bromotoluene in 20 ml of dry ether in the
dropping funnel. Add about 1 ml of this solution into the flask. An exothermic reaction
commences immediately because lithium reacts more rapidly with organic halide than
magnesium does. Add the remaining solution slowly within a period of 15 min with constant
206 LABORATORY MANUAL OF ORGANIC CHEMISTRY
stirring and simultaneous passage of nitrogen gas. Reflux the resultant solution on a water-
bath for 2530 min to complete the reaction. Cool the flask in an ice-bath, dilute with 25 ml
of ether and cool again to 50C with the acid of acetone dry ice mixture. In a 500 ml beaker
take 200 g of crushed dry ice and 50 ml ether and stir. To this add slowly the solution of
lithium derivative of p-bromotoluene. Rinse the flask with a small quantity of ether and
pour into the beaker. Allow the mixture to stand at room temperature for 23 hrs for
complete evaporation of dry ice. After this period add 100 ml of water. At this point a solid
may appear which dissolves on standing. To this add 20 ml of ether and transfer the contents
to a separatory funnel, shake and withdraw the aqueous layer. Wash the aqueous layer
twice with ether. Save the extract in a beaker. Shake the remaining aqueous layer with 25
ml of 10% sodium hydroxide solution to obtain the acid as its sodium salt. Heat on a water-
bath to drive off the dissolved ether and then cold the solution to 5oC, and strongly acidify
with conc. hydrochloric acid to separate p-toluic acid. Collect the solid on a Buchner funnel,
wash with cold water and dry. Recrystallize the acid from hot ethanol. The yield is 5.1 g,
m.pt. 176177oC.
A by-product, namely, di-p-tolylketone is also obtained which can be easily separated
from the main product. Dry the combined ether extract over anhydrous megnesium sulfate
and remove ether over a water-bath. Recrystallize the residue from hot alcohol, yield 1.8 g,
m.pt. 95o C.
8.12 DEHYDRATION
Alcohols, acids, oximes, etc. can be made to lose a molecule of water under the action of
different types of catalysts. The result is the formation of an unsaturated product.
Procedure: Introduce 10 ml of 9 M sulfuric acid into a Claisen flask. Add a few boiling
chips. In one opening fit a 50 ml dropping funnel (a separatory funnel may be used) and
place 20 g cyclohexanol. Fit the other opening with a fractionating column and a thermometer
and attach a Liebigs condenser. Make sure that all the glass stoppers fit tightly to prevent
losses due to evaporation. Heat the flask in an oil-bath at 160170oC. From the dropping
funnel add cyclohexanol dropwise over a period of 45 min. After the addition is complete,
raise the temperature to 190200oC (Note I) and distil. The temperature at the top of the
column should remain below 90C. Transfer the distillate to a separatory funnel and shake
with saturated sodium chloride solution. Discard the lower layer. Take the upper layer and
dry (MgSO4) . Distil the crude cyclohexene from a 10 ml distilling flask and collect the
fraction passing over at 8183oC. The yield is 13 g. The residue remaining in the distillation
flask is largely unreacted cyclohexanol.
Notes I: 85% phosphoric acid is less efficient and gives less yield.
II: Use a thermometer.
Questions
8.23 What other side-products may be formed in the above reaction?
8.24 Write the dehydrohalogenation product.
208 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: Place 7.5 g of succinic acid in a dry 100 ml round-bottomed flask fitted with a
reflux condenser and a drying tube. To this carefully add 12.5 ml of acetic anhydride and
heat the mixture on a steam-bath with occasional shaking until a clear solution is obtained.
Heat for an additional period of 30 min. Then cool the flask in an ice-bath. Collect the
crystals on a Buchner funnel at the pump and wash with ether (Note I ). The yield is
5.2 g, m.p. 119120oC.
Note I: Test the product with cold sodium bicarbonate solution for the presence of unchanged
succinic acid.
t
[ ] D = l c
where []tD is the specific rotation at toC, is the number of degrees through which the
incident beam has been rotated, l ( decimeter) is the length of the sample tube and C is the
concentration of solution in g/ml of the solution. The specific rotation is expressed as a
dimensionless figure. If the specific rotation of an enantiomer of say menthol is quoted as
[]20
D
= + 49.2, the ( +) sign before the value indicates that the plane of incident hight has
In order to allow the polarized light to pass freely, the analyzer must thus be rotated
so that it is tilted at the same angle as the emerged polarized light from the sample. For
this purpose the analyzer is mounted on a circular dial marked in degrees. The angle of
rotation for maximum light to pass through the sample is recorded.
The extent of rotation in terms of specific rotation is calculated with the help of the
above expression.
Notes I: Add the amine solution slowly and cautiously to avoid foaming.
II: May be kept till the next laboratory period.
III: The filtrate contains one isomer.
Acrolein
Glycerol is first converted into acrolein by conc. sulfuric acid which subsequently reacts
with aniline, followed by oxidation by nitrobenzene to form quinoline.
Procedure: Fit a three-necked 250 ml flask with a mechanical stirrer, a reflux condenser
and a thermometer. In the flask place 10 g (9.8 ml) of aniline, 15 g glycerol and 400 mg
iodine. Stir the mixture and pour 30 g (16.4 ml) of conc. sulfuric acid slowly down the
condenser. An exothermic reaction begins and the temperature rises to 100105o C. Heat
the flask gently on an oil-bath at 140 oC. After 15 min raise the temperature to 170 oC and
heat for 1 hr. Cool the flask and add 90 ml of 6 N sodium hydroxide solution slowly with
212 LABORATORY MANUAL OF ORGANIC CHEMISTRY
constant shaking. Steam distil the mixture. Distil till no oily drops pass over. Extract the
distillate with two 25 ml portions of ether, dry and remove ether on a water-bath. Dissolve
the crude product, containing some aniline, in 100 ml of 2.5 N hydrochloric acid in a 250 ml
beaker, warm and add 13 g of zinc chloride solution in 22 ml of 2.5 N hydrochloric acid with
constant stirring. Cool the beaker in ice and filter the solid quinoline chlorozincate (Note I)
on a Buchner funnel and wash with dil. hydrochloric acid. Transfer the salt to a 250 ml
beaker, add 6 ml of water followed by 10% sodium hydroxide solution until the initial
precipitate of zinc chloride dissolves completely. Pour the mixture in a separatory funnel
and extract quinoline with two 25 ml portions of ether. Dry the combined extracts over
anhyd. magnesium sulfate and evaporate ether on a hot water-bath. Distil the residue and
collect the fraction distilling between 236238oC. The yield is 6.8 g.
Note I: Since quinoline is contaminated with a small amount of aniline, the latter is removed
by making its chlorozincate salt which is soluble in water but that of quinoline
[(C 9 H7 N)2 ZnCl 4]H2 is insoluble.
Notes I: Phenylhydrazine is very poisonous, if it comes in contact with the skin wash well with
water.
II: Commercial polyphosphoric acid is difficult to handle because of its high viscosity. It may
be prepared fresh by mixing 26 g of phosphorus pentoxide and 14 g of commercial
orthophosphoric acid (density = 1.7).
III: Use a thermometer.
Procedure: Place 6.4 g of freshly distilled ethyl acetoacetate and 5.4 g of phenylhydrazine
in a large test tube or a 100 ml round-bottomed flask. Heat the mixture on a water-bath in
a hood with occasional stirring. The clear solution soon becomes turbid due to the formation
214 LABORATORY MANUAL OF ORGANIC CHEMISTRY
of droplets of water. Fit an air condenser and continue heating (135145 oC) for 1 hr. and
during this period a heavy reddish syrup separates out. Pour this into a beaker and cool.
Stir it with 40 ml of ether. As soon as the crystals separate, cool the beaker in ice and
collect the solid on a Buchner funnel. Wash with ether and recrystallize from hot water or
alcohol. The yield is 6.5 g., m.p. 127oC.
8.15 DIAZOTISATION
The process of forming a diazonium compound from an appropriate primary aromatic amine
in the presence of nitrous acid is callled diazotisation. The diazonium compounds are
extremely useful in organic syntheses. This is due to the fact that the diazonium group can
be replaced by groups such as hydroxy, cyano, halo and hydrogen with great ease. Many
compounds that could not be obtained by other means, are easily available through
replacement of the diazonium group. The reaction starts by the diazotisation of an amino
group of an aniline using sodium nitrite and a mineral acid.
216 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Question
8.25 Why should the temperature be maintained below 5oC in this preparation?
Step B: Diazotisation
Procedure: Place 11 g of p-toluidine, 15 ml of water and 25 ml of conc. hydrochloric acid in
a 250 ml Erlenmeyer flask and shake. Keep the flask in an ice-bath. The salt p-toluidine
hydrochloride separates out. Dissolve 7 g sodium nitrite in 20 ml of water and add this
solution dropwise to the amine salt keeping the temperature between 05oC. Occasionally
add ice into the flask. After the addition is over, a clear solution of the soluble diazonium
salt is obtained ( Note II).Keep the flask in ice.
Notes I: On adding sodium chloride a small precipitate of basic copper chloride may be formed.
II: At this stage a small excess of nitrous acid should be present. A blue color should be
obtained with a starch iodide paper when touched with a drop of the solution.
+
III: Due to the presence of a double salt of p-CH3C6 H4 N2 Cl . CuCl.
IV: To remove any p-cresol present.
continuous stirring. Some coupling takes place in the acid medium and the dye imparts red
color to the solution. Now add 35 ml of 10% sodium hydroxide solution to produce an orange
colored sodium salt. Stir well with a glass rod and add 25 g sodium chloride. Heat the
mixture to boiling, then cool in an ice-bath for some time. The dye separates out as orange
crystals. Filter, wash with a little ethanol and dry. The yield is 56 g.
Question
8.26 In the preparation of methyl orange, why is sulfanilic acid converted into its sodium
salt?
Procedure: Take 19 of phenol in a large tube to this add 0.79 of phthalic anhydride and
mix well with a glass rod. Add about 1012 drops of conc. sulfuric acid and stir well with a
thermometer. Heat the viscous mass for 45 min at approximately 160 oC. Pour the hot
melt into 100 ml of water in a beaker. Filter the solid and wash with cold water. Weigh the
dry sample.
220 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: Grind 5 g phthalic anhydride and 7.4 g resorcinol in a mortar. Transfer the
mixture to a 250 ml Erlenmeyer flask, immerse a thermometer and heat the flask slowly to
180oC on a sand-bath. In the meantime weigh 2.3 g of anhyd. zinc chloride (Note I) in a
small stoppered bottle and add it to the reaction mixture in small lots by stirring with the
thermometer after each addition. Continue heating the mixture till it becomes dark red
and highly viscous (Note II). Cool the flask to about 90o C and to this add 70 ml water and
3.5 ml conc. hydrochloric acid. Heat again till zinc salts have dissolved. Filter the colored
salt on a Buchner funnel, wash with water, drain well and dry in an oven at 100 oC. The
yield is 8.6 g.
Notes I: If ZnCl2 appears moist, dry by fusing it in a procelain dish in an oven.
II: This may take about 4050 min.
Question
8.27 Why is anhydrous zinc chloride needed in the preparation of fluorescein dye?
ORGANIC PREPARATIONS 221
Procedure: Take 5 g of the dried fluorescein in a 250 ml Erlenmeyer flask and add 25 ml of
ethanol and shake. Weigh 10.8 g of bromine (Note I) and transfer to a dropping funnel. Add
bromine slowly to fluorescein solution with constant stirring. When about half of the bromine
has been added a solid appears (Note II). More tetrabromofluorescein precipitates out as
the addition is continued. Allow the mixture to stand for 1 hr at room temperature. Filter
the solid on a Buchner funnel, wash twice with ethanol and dry in an oven at 100 o C. The
yield of the orange dye is 7.2 g.
Notes I: Work with bromine is the fume hood.
II: This is so because dibromofluorescein is soluble in ethanol.
Questions
8.28 Why do you not observe the evolution of HBr gas during bromination?
8.29 Why do these four places in fluorescein get brominated?
The ketone has been used for the preparation of pivalic acid by oxidation with sodium
hypobromite.
The preparation is carried out in two steps:
Step A: Preparation of pinacol
Procedure: Reduction of acetone with most reducing agents yields isopropyl alcohol and a
small quantity of pinacol as by-product. However, reduction in the presence of amalgamated
magnesium yields a considerable amount of the bimolecular reduction product, pinacol.
Procedure: Fit a 500 ml dry two-necked flask ( Note I) with a reflux condenser, a dropping
funnel and place 8 g of magnesium turnings and 100 ml dry benzene. Take a solution of 9 g
of mercuric chloride in 75 ml dry acetone in the dropping funnel. Add about 20 ml solution
to the flask. If the reaction does not start immediately warm the flask on a steam-bath.
Cool the flask in an ice-bath in case the reaction becomes too vigorous. Add the remaining
solution from the dropping funnel slowly. After the addition is complete, heat the flask on
a steam-bath for 1 hr with occasional shaking. If the formation of solid magnesium pinacolate
makes stirring difficult, break the lumps with a glass rod. At the end of 1 hr pour 20 ml of
water through the condenser and boil the mixture for 30 min with frequent stirring. This
brings about hydrolysis of magnesium pinacolate to magnessium hydroxide and pinacol
dissolves in benzene-acetone mixture. Filter the hot solution and return the precipitate of
magnessium hydroxide to the flask and reflux again for 1520 min after adding 50 ml of
ordinary benzene. Filter the solution again. The combined benzene solution is evaporated
in a beaker on a steam-bath to 1/3 of its volume. Then add 15 ml water and cool well in an
ice-bath. Pinacol hydrate separates as an oil which immediately solidifies. Filter on a Buchner
funnel, wash with cold benzene and drain. Recrystallize the solid from hot water (Note II) .
The yield is 1820 g, m.p. 4647 oC.
Notes I: A three-necked flask may instead be used.
II: Pinacol hydrate is highly soluble in hot water. If the solution is too dilute to permit
crystallization, evaporate some water.
Questions
8.30 Explain the mechanism for the fromation of 2-3-dimethyl-1, 3-butadiene in the
preparation of pinacolone.
8.31 From which glycol can the following compound be synthesized by a pinacol-pinacolone
rearrangement? Write the mechanism.
Notes I: Do not allow the column to get dry, it will develop cracks.
II: The completion of elution can be periodically checked by exposing the column to u.v. light.
Anthracene shows a strong fluorescene.
Dry the plate again, and it will be possible to observe as many as eight colored spots.
Determine the RF values. In the order of decreasing RF values, the spots may be identified
as carotenes (2 spot, orange ), chlorophyll a (1 spot, blue and green), chlorophyll b (1 spot,
green) and xanthophylls (4 spots, yellow).
Most of the amino acids give blue color (except proline which gives a yellow color) it
indicates that the colored product formed is the same in this reaction.
Questions
8.32 What factors govern the choice of a solvent in column chromatography?
8.33 Why do iodine vapors yield colored spots on TLC?
8.34 Why should the initial spots of amino acids must not be too large?
8.19 POLYMERIZATION
A polymer may be described as a large molecule formed by linking together a number of
smaller molecules. These smaller molecules have low molecular weights and are joined by
covalent bonds. The smaller unit is called a monomer.
Monomer (Monomer)n
(A polymer)
Those polymers in which the two monomers are bonded end-to-end in a linear manner
usually dissolve, become soft when heated and can be moulded are referred to as
thermoplastic. On the other hand, if the polymer chains are linked together at several
points, the polymer is one large three-dimensional net-work, insoluble and infusible, and
ORGANIC PREPARATIONS 231
cannot be moulded, such polymers are called thermosetting. These polymers are crosed-
linked polymers. The process of making high molecular weight compounds is said to be
polymerization. Such a process can be initiated by an ionic or radical reaction. Two types
of polymers are recognized: (a) addition (b) condensation polymers.
Polymers, nowadays, are not difficult to prepare because of the easy availability of the
raw material. The synthetic polymers are made from smaller molecules by chemical means.
They are also referred to as man-made polymers.
lump at the bottom. Pour out the liquid from the beaker in the sink and collect the thiokol
rubber. Wash it thoroughly with water under the tap. Dry in the folds of filter papers. The
yield is about 1.5 g. Determine the solubility of the polymer in benzene, acetone, 5% sulfuric
acid and nitric acid.
Question
8.35 How does sodium hydroxide remove the antioxidant from styrene?
ORGANIC PREPARATIONS 233
Question
8.36 Describe interfacial polymerization.
Note I: Naphthalene may be obtained from the organic layer by making its picrate with picric
acid.
Method B: The second method consists of the reduction of cinnamic acid by diimide generated
in situ by the copper catalyzed oxidation of hydrazine in the presence of an oxidizing
agent (H2O2).
ORGANIC PREPARATIONS 235
Question
8.37 Name other reducing agents which add in a syn manner to alkenes.
add one drop of glacial acetic acid ( Note I). Stopper the flask tightly which is wired in place.
Invert the flask in a 100 ml beaker and expose it to direct bright sunlight. The formation of
benzopinacol can be followed by the appearance of colorless crystals around the walls of the
flask, as it is only sparingly soluble in alcohol. After 45 hrs some crystals separate out,
and 95% of the reaction is complete in about four days (Note II). Chill the flask and filter
the crystals on a Buchner funnel. Wash the solid with a small amount of cold ethanol.The
product is generally pure, m.p. 188189o C.
Notes I: A drop of glacial acetic acid must be added, otherwise enough alkali may be derived from
the flask to cleave the diol to benzhydrol and benzophenone.
II: If any benzophenone crystallizes out it must be dissolved in alcohol by warming.
Procedure: Dissolve 0.5 g commercial azobenzene in 500 ml benzene and store the solution
in a stoppered brown bottle. Take two thin-layer chromatography (TLC ) plates and spot
each of these plates, using an ordinary capillary tube about 1 cm from the bottom of the
plate. Place one plate in the locker where it can be protected from light but expose the
other to sunlight for 1 hr. Then develop both the plates in a chamber containing 3 : 1
cyclohaxane-benzene (v/v) to a depth of about 0.5 cm.
Remove the plates after the solvent front has travelled to within 1 cm of the top of the
silica layer on the plates. Two spots of yellow compound would be visible on each plate. The
spot near the starting point is that of the more polar cis-azobenzene while the spot with a
larger RF value is due to the non-polar trans-isomer. Measure the relative areas of the two
spots on each plate. It may be noticed that depending on the previous history of azobenzene,
the cis-compound may be obtained on the irradiated plate.
ORGANIC PREPARATIONS 237
When methyl ketones react with halogens (X2) in aqueous sodium hydroxide
solution they are cleaved to yield a carboxylic acid and haloform (CHX3 ). Accordingly,
iodoform is obtained using iodine halogen and a methyl ketone.
Procedure: Boil on a Bunsen burner 20 g of tea leaves in a 500 ml beaker with 250 ml of
distilled water for 25 min. Filter through a Buchner funnel without using the filter paper at
the pump to remove the spent tea leaves. To the clear filtrate add, while stirring 60 ml of
10% lead acetate solution to precipitate tannins (naturally occurring polyphenols ). Leave
the mixture undisturbed for 23 days. After this period filter it through a glass wool plug
and concentrate the filtrate on a sand-bath to about 30 ml. Cool the residual solution and
extract it thrice with 25 ml protions of chloroform ( Note I). Combine the chlorform extracts
and remove most of the chloroform by simple distillation. Cool the residue and add 40 ml of
petroleum ether and stir the mixture for 5 min.
The yellow color of the organic extract can be decolorized by shaking with 2 ml of 10%
sodium hydroxide solution followed by washing with the same volume of water. Dry the
washed extract and remove the solvent under vacuum. Recrystallize the crude caffeine
from minimum ( < 1 ml) quantity of boiling water. Determine the yield ad the melting point
of the product, m.p. 235237o C.
Question
8.38 State two sources of caffeine and its color test.
In this exercise you will learn to isolate a product from natural source and purify it
using column chromatography.
Procedure: Weigh about 10 g of red tomato paste (ripe tomatoes can be mashed to prepare
a paste ) into a 250 ml round-bottomed flask. Add 25 ml of methanol and 30 ml of
ORGANIC PREPARATIONS 239
dichloromethane. Heat the mixture under reflux for 5 min on a steam-bath with frequent
shaking. Filter the mixture under suction and transfer the filtrate to a separatory funnel.
Wash this mixture containing lycopene with three portions of 150 ml each with sodium
chloride solution. Dry the organic larger over anhydrous magnesium sulfate. Filter and
evaporate most of the solvent in vacuum without heating.
To separate lycopene from the crude pigment extract, pack the chromatographic column
with about 40 g of TLC grade silica gel using hexane. Dissolve the crude red pigment is 5 ml
of light petroleum and transfer on the top of the column with a pipette. Elute it with
hexane till a yellow band appears. At this stage, change the eluent to 10% acetone in hexane.
An orange-red color band will start to appear. Collect a sample of the eluate from the
center of this band. Evaporate to dryness under vacuum. Determine the approximate yield
of lycopene.
The other constituents of pepper being volatile oils (1.3%), starches (2040%) and
water (813%). Piperine can be isolated by extraction of ground pepper with 95% ethanol.
In an ideal case the extraction should be carried out in a Soxhlet apparatus as shown in
Fig. 8.4. This method requires only a small amount of the organic solvent.
240 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: In a 500 ml round-bottomed flask fitted with a reflux condenser add about
350 ml of 95% ethanol. Pack the thimble with 30 g of powdered pepper and place it in the
apparatus as shown. The flask is heated for 3 hrs. Material is extracted out of the solid into
the hot solvent. Filter the ethanol solution and concentrate the filtrate to 25 ml by distillation.
To this residue add 30 ml of warm 2 N ethanolic potassium hydroxide solution. Stir the
warm mixture and filter to remove any insoluble material. Warm the solution on a steam-
bath and add 1520 ml of water. At this stage turbidity appears and yellow needles may
separate. Keep this solution till the next laboratory period and filter the crude piperine.
Recrystallize from acetone to obtain fine yellow needles, m.p. 129131oC.
Question
8.39 Is the piperine isolated expected to be optically active?
of certain prostaglandins can promote the formation of blood clots that lead to heart attack
and strokes while others cause pain, fever and inflammation. Thus, there is a posibility
that aspirin reduces these problems by blocking the overproduction of prostaglandins in
the body. Aspirin also brings about a reduction of swelling in the joints and leads to relief of
pain in people suffering from arthritis.
Isolation
Procedure: An aspirin tablet contains aspirin and a starch binder. Powder an aspirin tablet
on a filter paper and transfer it to a 25 ml. Erlenmeyer flask. To this add 10 ml of absolute
alcohol and boil the mixture on a steam-bath. Aspirin will dissolve. Filter the hot solution
and again heat to dryness. Recrystallize the residue from benzene, m.p. 130135 oC.
Estimation
The amount of aspirin in a commercial table is determined by titration of its solution in
alcohol against standard sodium hydroxide solution.
Procedure: Weigh an aspirin table accurately. Powder it on a filter paper and dissolve it in
10 ml of absolute alcohol by boiling. Filter the hot solution in a 150 ml Erlenmeyer flask.
Wash the insoluble residue on the filter paper with 3 additional 5 ml portions of hot ethanol.
Make sure all the washings are done carefully. Add 20 ml of distilled water and 3 drops of
phenolphthalein to the combined filtrates. Titrate the solution against 0.1 M sodium
hydroxide solution to a faint pink color end-point. Note the volume of alkali consumed, the
total volume of solution is 25 ml. Calculate the amount of aspirin by using the equation:
N V = N 1 V1
Question
8.40 Would you expect the triptycyl anion to be stable?
chloroform is complete, continue shaking for 30 min. Pour the reaction mixture into a
separatory funnel containing 25 ml water. Shake and collect the aqueous layer in a beaker.
Extract the aqueous layer thrice with 25 ml portions of petroleum ether (b.p. 4050oC) .
Combine the extracts and dry this solution over anhydrous sodium sulfate. Filter and
evaporate the solvent on a hot plate. Distil the residue at reduced pressure to obtain the
pure product. The product is obtained as a colorless liquid. Determine its yield.
Note I: Remove the oily layer on the potassium metal by pressing it between the folds of filter
papers before use.
Question
8.41 Suggest a method for the formation of an ester in which an equilibrium of the above
type is not involved?
Aspirin reacts with sod. hydroxide solution to form a salt, sod. acetylsalicylate which
is soluble in water. Aspirin is the most popular drug in the world. It lowers fever, releives
pain and reduces inflammation. There is evidence available that aspirin inhibits the
production of prostaglandins ( hormone-like compounds that regulate body functions ) in
the body.
Question
8.42 How will you differentiate qualitatively between aspirin and salicylic acid? Suggest a
color test.
Questions
8.43 Why excess of acetic anhydride is used in the preparation of acetanilide ?
8.44 Between o-nitroaniline and p-nitroaniline, which is more high boiling ?
ORGANIC PREPARATIONS 247
Note I: Discard the aqueous layer into the drain in the sink.
248 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Question
8.45 How do you eliminate the production of hydrocyanic acid in the above preparation?
Question
8.46 Write a mechanism for the formation of phthalimide from phthalic anhydride and
urea.
addition maintaining a temperature below 100C. After the addition is complete heat the
mixture on a water-bath for 1.5 hr. Cool and pour the contents of the flask on 500 g of
crushed ice taken in a one litre beaker. Filter the solid and recrystallize from hot alcohol.
The yield is 7.0 g, m.p. 53C.
Procedure: In a 250 ml Erlenmeyer flask dissolve 2.8 g of resorcinol, 3.3 g ethyl acetoacetate
in 50 ml of water. To the solution add 40 g of polyphosphoric acid and heat on a water-bath
at 7080C stirring with a thermometer. After 20 min, pour the mixture into 200 ml of
water contained in a beaker. Collect the yellow solid at the suction. Wash with cold water
and dry in the oven at 60C. Recrystallize from hot ethanol. The yield is 4.1 g, m.p. 105C.
presence of a base (saponification) leads to glycerol and soap, i.e., sodium salt of the long
chain fatty acid. Soaps constitute just one type of detergent. A detergent is any substance
employed for cleaning an object.
Questions
8.47 Describe a soap. Explain the technique salting out.
8.48 What is the reaction of soap with hard water?
Question
8.49 Write a mechanism for the acid hydrolysis of p-bromoacetanilide to p-bromoaniline.
Chapter 9
SPECTROSCOPIC METHODS
The analytical methods discussed in the earlier chapters have been available to organic
chemists since long, and undoubtedly have proven of immense value in the identification
and structure determination of organic compounds. These are, however, exceedingly time
consuming and the information obtained is often inconclusive. Nowadays various
spectroscopic methods have greatly facilitated the analysis and they supplement the classical
methods. Spectroscopy is a technique for the measurement of the amount of radiation
absorbed by the substance at various wavelengths. The spectrum evolves useful information
about the functional group and the molecular structure. Only two techniques, namely,
infrared ( i.r.) and nuclear magnetic resonance (n.m.r) will be discussed because these are
probably readily available and in conjunction with the wet analysis often provide sufficient
information to complete the structural identification of molecules. The spectroscopic methods
possess the added advantage in that the measurements can be made in a short time with a
very small amount of the material.
The infrared region of the electromagnetic spectrum of interest to the organic chemist
occurs rather in a narrow range, i.e., 2 (4000 cm1) to 15 (666 cm1), 1 = 10 4 cm
(10, 000 ) and is capable of providing useful information. Both wavelength and frequency
are commonly used to describe an infrared absorption. The conversion of wavelength to
frequency can be affected by the following equation:
( )
v cm 1 =
104
( in )
9.1.1 Instrumentation
An infrared instrument may be designed either on a single beam or a double beam principle.
A single beam spectrometer consists of a radiation source, an electrically heated carborundum
rod, a Nernst filament which is passed through the sample and the emergent beam that is
dispersed by a monochromator into its individual wavelengths. The spectrum is then scanned
on a special chart paper.
A double beam instrument works on a similar principle, except that the original radiation
is divided into two beams, one of which passes through the sample while the other through a
reference cell. Such an instrument records the difference in the intensities of the two beams.
amount of absorption in the i.r. region, solvents often employed are carbon tetrachloride,
chloroform and carbon disulfide etc. The solvent used should be completely dry. In addition
to the sample cell, a reference cell filled with the same solvent is placed in the reference
beam of the instrument. If the solvent absorbs weakly in a given region of the spectrum, its
absorption may be cancelled out.
The strong absorption at 3350 cm1 (2.98 ) is typical of the polymeric association of hydroxyl
groups. The non-bonded absorption peak is barely perceptible. If the infrared spectrum is
run in a very dilute solution of alcohol in carbon tetrachloride in order to decrease the
chances of hydrogen bond, the band would appear at a shorter wavelength ( higher energy)
due to the stretching mode of a free hydroxyl group. The stretching mode of hydrogen
bonded OH bonds occurs at a lower energy.
stretching appears at 1715 cm1 (5.83 ). The position of absorption is sensitive to ring size and
to the degree of conjugation. Thus in cyclopentanone, the group absorbs at 1751 cm1
(5.7 ) i.e., at a higher wave number. In case of conjugation, absorption occurs at a lower wave
number thus methyl tolyl ketone, absorbs at 1675 cm1 (5.95 ).
Another example which demonstrates the utility of i.r. is that of benzamide (Fig. 9.4) .
The NH stretching absorptions appear as two bands at 3356 cm 1 ( 2.98 ) and
3110 cm1 ( 3.182 ) . The C O stretching appears at 1670 cm1 (5.98 ).
When the spinning nucleus is placed in an external magnetic field H 0, the magnetic
dipole may either orient with or against the field. The former orientation is a state of high
energy while the latter that of low energy. The axis of the spinning proton under the
influence of the external field precesses about the axis of the applied field. The frequency,
w of precession is given by:
0 = H 0 = 2 0
angles to the applied field, the applied frequency is said to be in resonance with the
processional frequency when w = n. At this stage the radiation is absorbed by the nucleus
and it undergoes a flip to the next higher energy level. An absorption peak is obtained
which can be detected electronically and recorded as a peak on a chart. This is achieved
experimentally by applying frequencies which in the case of proton are in the radio frequency
range, generally 60 MHz ( mega Hertz) and corresponds to a wavelength of 5 102 cm at a
magnetic field of 14,092 gauss. The condition of resonance for a proton can be achieved
either by holding H 0 constant and varying n or by maintaining n at a constant value and
changing H0. The latter approach, however, is more convenient. Nuclei that have spin and
are important to an organic chemist are 1H, 13C, 19F, etc. Most n.m.r. studies have been
carried out on hydrogen (proton ) nuclei and the technique is thus referred to as proton
magnetic resonance (p.m.r. or H n.m.r.).
In an n.m.r. spectrum an absorption peak is obtained for each type of proton in the
molecule and at a different frequency of resonance. This depends on the environment in
which the nuclei are present, i.e., the neighbouring nuclei and electrons. A proton in a
molecule is surrounded by a cloud of electronic charge. In a magnetic field the electrons
orient in such a way that their motion induces a magnetic moment that ordinarily opposes
the applied field. As a result the nucleus is exposed to an effective field that is somewhat
smaller (but in some cases larger also) than the external field. In other words, the net
magnetic field is slightly less than the applied field. Since the nucleus experiences a smaller
field it is said to be shielded. A higher magnetic field must thus be applied to achieve
resonance. This gives rise to chemical shift which is described as the difference in the
absorption position of a particular proton of a sample from that of the reference proton.
There are several types of reference compounds but for protons the positions of the absorption
peaks are noted with reference to tetramethylsilane (TMS) a volatile liquid, b.p. 26.4C
used as an internal standard. For this compound a single sharp resonance line occurs at the
highest field end of the range of observed proton shifts where it is unlikely to obscure any
other proton resonance arising from the sample. This standard is assigned a chemical shift
of 0 Hz.
The chemical shift of a proton is determined in units of cps, depending on the oscillator
frequency. It has been found convenient to convert such shift into frequency independent
units, expressed as delta (d ):
The d values are expressed as parts per million (ppm). An alternative scale is tau (t)
scale. TMS is assigned an arbitrary value of 10.00. To convert a chemical shift given on the
delta scale to tau scale, simply subtract the shift as measured on the delta scale from 10, i.e.,
t = 10.00 d
The chemical shifts (t) for a wide variety of hydrogens are given in Table 9.2.
Chemicals shift
t (ppm d)
RCH3 9.1 0.9
R2CH2 8.7 1.3
R3CH 8.5 1.5
C=CH 4.5 5.4 4.6 5.9
ArH 1.5 4 6 8.5
C=CCH3 8.3 1.7
C=CCH3 8.2 1.8
CICH 6.7 3.4
Cl2CH 4.2 5.8
BrCH 6 7.5 2.5 4
O2NCH 5.4 5.8 4.2 4.6
RCH 01 9, 10
ROH 4.5 9 1 5.5
ArOH 26 4 12
O
The integral tracing is recorded from left to right. The height to which the tracing
rises for each group of protons is proportional to the area enclosed by each peak, and
therefore, to the number of protons.
The spectrum of ethanol ( neat) is shown below (Fig. 9.8 ). As is evident from the
structure of ethanol it contains three types of protons and they absorb at different values
and correspond to OH (4.63 t), CH2 (6.58 t) and CH3 (8.83 t) . The area beneath each
peak corresponds to a numerical ratio of 1 : 2 : 3. Thus n.m.r. is a convenient measure of
not only the type but also the number of different protons in the molecule.
SPECTROSCOPIC METHODS 263
If the spectrum of ethanol is recorded under high resolution (Fig. 9.9) it is found that
the spectrum is split, i.e., each peak is split into several peaks. Thus methyl group is split
into a triplet and the methylene group into a quartet. This splitting is attributed to the fact
that the magnetic field of one set of nuclei is influenced by the spin arrangements of the
nuclei in the neighbouring group. In other words, there is a small interaction or coupling
between the two groups of nuclei. This phenomenon is known as spin-spin splitting. The
spacing (in cps) of the three components of the methyl group triplet is found to be equal to
the spacing of the four components of the methylene group quartet. This spacing is referred
to as coupling constant, J, and is a measure of the effectiveness of coupling between two
protons with different chemical shifts.
Questions
9.1 What is the importance of fingerprint region in i.r.?
9.2 What is the purpose of TMS in n.m.r.?
9.3 A compound with the molecular formula C7H6O2 has the following i.r. and n.m.r. spectra.
Propose a structure.
SPECTROSCOPIC METHODS 265
266 LABORATORY MANUAL OF ORGANIC CHEMISTRY
9.4 The n.m.r. spectrum of compound with molecular formula C 2 H3 Cl 3 is shown below,
suggest a suitable structure.
9.5 An aromatic compound with molecular formula C 10H12O2 gives the hydroxamic acid
test and on acid hydrolysis yields C 8H10O and C 2H4 O2 . The n.m.r. spectrum is given
below. Suggest a structure for this compound.
SPECTROSCOPIC METHODS 267
1. R.L. Shriner, R.C. Fuson and D.Y. Curtin, The Systematic Identification of Organic
Compounds, 5th edn., John Wiley, New York (1964).
2. N.D. Cheronis and J.B. Entriken, Identification of Organic Compounds, 2nd edn., John
Wiley, New York (1963).
3. D.J. Pasto and C.R. Johnson, Organic Structure Determination, Prentice-Hall, Englewood
Cliffs, N.J. (1969).
4. K.T. Finley and J.Wilson, Laboratory Manual in Fundamental Organic Chemistry, Prentice-
hall, Englewood Cliffs, N.J. (1970).
5. (a) P.E. Fanta and C.S Wang, Limitations of Hinsberg Method for Primry Amines, J.
Chem. Educ. 41, 280 (1964).
(b) C.R. Gambill, T.D. Roberts and H. Shechter, ibid, 49, 287 (1972).
6. M. Veera and Gaspario, Detection and Identification of Organic Compounds, Plenum Press,
New York (1971).
7. H.T. Clark A Handbook of Organic Analysis, Longman, Rochester, N.Y. (1966).
8. A.I. Vogel, Qualitative Organic Analysis, Longman (ELBS). London (1972).
9. J.R. Dyer, Applications of Absorption Spectroscopy of Organic Compounds, Prentice-Hall,
Englewood, N.J. (1969).
10. R.M. Silverstein and G.C. Bassler, Spectroscopic Identification of Organic Compounds,
2nd edn., John Wiley, New York (1967).
11. L.J. Bellamy, The Infrared Spectra of Complex Organic Molecules, 2nd edn., John Wiley,
New York (1958).
12. K. Nakanishi, Infrared Absorption Spectroscopy, Holden-day, San Franciso (1962).
13. L.M. Jackman and S. Sternhall, Nuclear Magnetic Resonance Spectroscopy, 2nd edn.,
Pergamon Press, New York (1969).
14. A.I. Vogel, Elementary Practical Organic Chemistry, Part I, 2nd edn., Longman, London
(1966).
270 LABORATORY MANUAL OF ORGANIC CHEMISTRY
15. G.Brieger, A Laboratory Manual for Modern Organic Chemistry, Harper and Row, New
York (1969).
16. P.T.S. Law and M.Kestner, Preparation of Heterocyclics, J. Org. Chem. 33, 4426 (1968).
17. D.L. Pavia, Caffeine Isolation J. Chem. Educ. 50, 791 (1973), also see R. O. Connor, J.
Chem. Educ. 42, 492 (1965).
18. K.L. Lockwood, Solvent Effect on Keto-Enol Equilibrium of Acetoacetic Ester, J. Chem.
Educ. 42, 481 (1965).
19. R.K. Bansal, A Textbook of Organic Chemistry, 5th edn., New Age International, New
Delhi (2007).
20. G.K. Helmkamp and H.W. Johnson, Jr., Selected Experiments in Organic Chemistry, W. H.
Freeman and Co., San Francisco (1964).
21. R.Q. Brewster, C.A. Vanderwerf and W.E. McEwen, Unitized Experiments in Organic
Chemistry, 2nd edn., Van Nostrand, New York (1964).
22. W.P. Sorenson and T.W. Campbell, Preparative Methods of Polymer Chemistry, John Wiley,
New York (1963).
23. P. Yates and P. Eaton, Lewis-Acid Catalyzed D. A. Reaction, J. Am. Chem. Soc., 82, 4436
(1960); Also see R.K. Bansal, A.W. McCulloch, P.W. Rasmussen and A.G. Mclnnes, Canad,
J. Chem. 53, 138 (1975).
24. K.B. Wiberg, Laboratory Techniques in Organic Chemistry, McGraw-Hill, New York (1960).
25. J. Casanova, Relative Rates of Electrophilic Substitution J. Chem. Educ., 41, 341 (1964).
26. R.M. Roberts, L.B. Rodewald and A.S. Wingrove, An Introduction to Modern Experimental
Organic Chemistry, Holt, Rinehart and Winston, New York (1985).
27. J.A. Moore and D.L. Dalrymple, Experimental Methods in Organic Chemistry, P.A., (1976).
28. J.W. Hass, J. Chem, Educ., 61, 346, (1974).
29. R.K. Bansal, Organic Reaction Mechanisms, 3rd edn., Tata McGraw-Hill, New Delhi (1998).
30. E.L. Skan and J.C. Arthur, Jr., in Techniques of Chemistry, A. Weissberger and B. W.
Rossiter. Ed., Wiley Interscience, New York (1971), Vol. 1, Part 5. Chapter 3.
31. L.M. Harwood, C.J. Moody and J.M. Percy Experimental Organic Chemistry, 2nd edn.
Blackwell Scientific Publications, Oxford, Lodon, (1999).
32. J.W. Lehman, Multistep Operational Organic Chemistry, Prectice Hall, Inc. Upper Saddle
River, New Jersey.
Appendix 1
PREPARATION OF REAGENTS
PURIFICATION OF SOLVENTS
distilled with the exclusion of moisture. The alcohol so obtained should be properly stoppered.
Extremely dry ethyl alcohol is prepared by treating the alcohol obtained with magnesium
turnings and iodine. The following reactions take place:
2C2H5OH + Mg Mg(OC2H5)2 + H2
One litre of alcohol is taken in a found-bottomed flask, and 3.5 of pure dry magnesium turnings
and a pinch of iodine crystals are introduced into the flask and the mixture refluxed. Heating is
continued till all the metallic magnesium has been converted into its ethylate. Additional amount of
iodine is introduced, if necessary. The absolute alcohol is distilled off directly into a container and
stoppered properly. Ethyl alcohol is a highly inflammable solvent.
acetaldehyde and glycol acetal Glycol is hydrolyzed on keeping with the resultant
formation of peroxide.
A mixture of 1 litre commercial dioxane, 13.5 ml conc. hydrochloric acid and 100 ml water is
refluxed for 12 hrs. A stream of dry nitrogen gas is simultaneously bubbled to entrain acetaldehyde.
The solution is allowed to cool to room temperature and solid potassium hydroxide is added till no
more of it dissolves and a second layer separates out. Dioxane layer is decanted and refluxed with
sodium metal for 1012 hrs and distilled. Peroxide present as impurity, if desired, can be removed
by passing the distilled solvent through a column of alumina (80 g for 100200 ml of dioxane).
Dioxane vapors are very poisonous.
Preliminary drying is carried out by keeping ether over anhyd. calcium chloride for 24 hrs.
Alcohol and water can thus be removed to a great extent. It is filtered into another clean bottle and
sodium wire is introduced into it directly from the sodium press and allowed to stand for another
24 hrs. The bottle is stopped when evolution of hydrogen has ceased. Ether may be distilled on a hot
plate in the hood. If it is exposed to air, slight oxidation of ether occurs with the formation of peroxide
C2H5 OOC2H5. This may cause explosion if ether is distilled to dryness. The presence of peroxide
in ether may be detected by the liberation of iodine (brown coloration or blue color with starch) when
a small sample is shaken with an equal volume of potassium iodide (2%) solution and a few drops of
dil. hydrochloric acid. Peroxides can be destroyed by shaking ether with 5% solution of ferrous sulfate
which is weakly acidified with sulfuric acid. Alternatively, either can be passed over a column of
alumina (80 g of alumina for 750 ml of ether) whereby the peroxide is retained by alumina.
It is very important to note that while working with ether there should be no flame in the
vicinity.
CH3OCH2CH2
Diglyme O , b.p. 160C
CH3OCH2CH2
Diglyme (diethylene glycol dimethyl ether) is an excellent medium for reduction by diborane. It
is purified by distilling from lithium aluminum hydride.
conc. sulfuric acid to remove the oxidizable components. Finally, it is washed with water dried over
anhyd. calcium and distilled. Peroxides are removed as in the case of ether by running over a column
of alumina.
Molecular 36.5 63 60 98 98 35
weight
A Anthraquinone, 196
Aspirator, 11
Abderhalden drying pistol, 13 Azeotrope, 17
Acetamide, 95 Azeotropic mixture, 17
Acetanilide, 96, 244 Azobenzene, 102, 200, 236
Acetic acid, 73
Acetophenone, 82
Acetophenonephenylhydrazone, 213
B
Acetylsalicylic acid, 135 Bayers test, 60
Activated charcoal, 24 Beckmann rearrangement, 186
Adapters, 14 Beilstein test, 33
Adipic acid, 77, 196 Benedicts solution, 272
Adipoyl chloride, 233 Benedicts test, 46, 51
Adsorbent, 225 Benzamide, 96, 272
Alkene derivative, 116 Benzanilide, 186, 190
Alkyne derivative, 116 Benzaldehyde, 82
Allyl alcohol, 64 Benzenesulfonamide, 103
Aluminum chloride test, 59 Benzenesulfonic acid, 102
Amalgamated magnesium, 223 Benzhydrol, 200
p-Aminobenzoic acid, 78 Benzil, 192
o-Aminophenol, 72 Benzilic acid, 191
p-Aminophenol, 72 Benzilic acid rearrangement, 191
2-Amino-4-nitrodiphenylamine, 215 Benzoic acid, 75, 197
Ammonia evolution test, 55 Benzoin, 85, 192
Aspirin, 75, 244 Benzophenone, 85, 235
p-Anisaldehyde, 84 Benzopinacol, 235
Aniline, 91 p-Benzoquinone, 103, 214
Aniline hydrochloride, 104 o-Benzoylbenzoic acid, 182
Anisic acid, 78 >-Benzoylpropionic acid, 184
p-Anisidine, 93 s-Benzylisothiouronium chloride, 109
Anthranilic acid, 76, 144, 217, 221, 241, 248 Benzyl alcohol, 66
286 LABORATORY MANUAL OF ORGANIC CHEMISTRY
E H
Ethyl benzoate, 88 Haloform reaction, 237
Ethyl p-hydroxybenzoate, 90 Hinsberg test, 54
Elution, 225 Hoffmann bromamide reaction, 248
Eosin, 221 Hydrazine, 234
Erlenmeyer flask, 9 Hydrocinnamic acid, 233
Esterification, 243 Hydroquinone, 214
Estimations, 143 Hydroquinone diacetate, 189
Estimation of a keto group, 150 Hydroxamic acid test, 56
Estimation of amino group, 156 p-Hydroxybenzaldehyde, 81
Estimation of an aldehyde, 151 5-Hydroxy-1,3-benzoxazol-2-one, 214
Estimation of aspirin, 240 m-Hydroxybenzoic acid, 79
Estimation of glycine (amino acid), 158 p-Hydroxybenzoic acid, 79
Estimation of hydroxyl group in alcohols, 143 7-Hydroxy-4-methylcoumarin, 250
Estimation of keto-enol equilibrium, 166 8-Hydroxyquinoline, 270
Estimation of methoxy group, 168
Estimation of nitrogen (Kjeldahl method), 154
Estimation of H, 164 I
Estimation of sulfur (Messengers method), 153 Ideal solution, 17
Estimation of unsaturation, 162 Indophenol, 42
Infrared spectroscopy, 253
F Interfacial polymerization, 233
Iodine solution, 270
Fehlings solution, 160 Iodoform, 100, 237
Ferric chloride test, 61 Iodoform test, 46
Ferrous hydroxide test, 52 p-Iodonitrobenzene, 216
Finger print region, 255 s-Benylisothiouronium chloride, 110
Fischer-indole synthesis, 212
Eluorescein test paper, 271
Fluorescein, 220 K
Flasks, 8 Keto-enol tautomerism, 166
Formalin test, 58 Kjeldahl's flask, 155
Fractional distillation, 18
Friedel-Crafts reaction, 181
Fries rearrangement, 189 L
Fuchsine (p-rosaniline hydrochloride), 45
Lassaign's test, 32
288 LABORATORY MANUAL OF ORGANIC CHEMISTRY
W
U
Water pump, 11
Urea, 61 Widmer column, 18
Urea nitrate, 61 Wiz's solution, 163
Urethane, 106 Wolff-Kishner reduction, 199
V X
Vacuum desiccator, 13 Xanthate test, 37