Organic Chemistry II- lab
PHR 122
Experiment 1: Preparation of 2-iodobenzoic acid from anthranilic acid (2-amino
benzoic acid)
Principle/ Theory:
2-iodobenzoic acid is rapidly prepared by Sandmeyer reaction from anthranillic acid (2-amino
benzoic acid). Sandmeyer reaction is a versatile means of replacing the amine group of a
primary aromatic amine with a number of nucleophilic substituent. The reaction proceeds
through the diazotization reaction, where the diazonium salt is formed by the reaction with
nitrous acid with the amine in acid solution. Nitrous acid is not stable and must be prepared in
situ, in strong acid it dissociates to form nitroso ions ( ), which attack the nitrogen of the amine.
The intermediate so formed loses a proton, rearranges, and finally loses water to from the
resonance stabilized diazonium ion. The diazonium ion is reasonably stable in aqueous solution
at O°C. If the diazonium ion is allowed to react with KI solution, the diazonium group is replaced
by iodide ion and produces the desired compound.
Diazonium ion
Apparatus:
Round bottom flask (100 ml)
Addition funnel
Ice-water bath
Erlenmeyer flask (50 ml)
Heater
Materials Used:
1. Antranilic acid 3.0 g (21.8 mmol) MW = 137
2. Sodium nitrite (NaNO2) 1.6 g MW = 69
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Organic Chemistry II- lab
PHR 122
3. Conc. HCl 5.5 ml
4. Potassium Iodide (KI) 3.7 g MW = 166
5. Water (H2O) 22 ml
6. Water to dissolve NaNO2 2-3 ml
7. Water to dissolve KI 4-5 ml
8. 95% ethanol q.s for recrystalization
9. Sodium bisulphite Very small amount
10. Charcoal for decolorization q.s.
Procedure:
1. In a 100 ml round-bottom flask, take 3.0 g of anthranilic acid, 22 ml of water and 5.5 ml
of concentrated HCl. Heat the mixture until the solid is dissolved.
2. Take the flask on ice-water bath and record the temperature.
3. When the temperature reaches 0-5°C, a solution of 1.6 g of sodium nitrite in H2O (2- 3
ml) is added slowly by the addition funnel into the flask.
4. After 5 minutes a solution of 3.7 g of Potassium Iodide in 4-5 ml of water is
added. A brown complex partially separates.
5. The mixture is left stand without cooling for 5 minutes and then warmed to 40°C,
at which point a vigorous reaction ensures (gas evolution, separation of the
solid).
6. After 10 minutes the mixture is heated on the steam bath for 10 minutes and then
cooled in ice,. A pinch of sodium bisulfate is added to destroy any iodine present
and the granular formed will be controlled and washed with water.
Purification:
The still moist product is dissolved in 15 ml of 95% ETHANOL, 8 ml of hot water is added, and
the brown solution is treated with decolorizing charcoal, filtered diluted at the boiling point
with 8-10 ml of water, and let stand 2-Iodobenzoic acid separates in large, slightly yellow
needles of satisfactory purity (mp 164°C) for the experiment.
Calculation of the yield percentage:
% Yield = mmol of the product/ mmol of the SM x 100
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Organic Chemistry II- lab
PHR 122
Experiment 2: Synthesis of an Azo Dye- the Coupling Reaction of Benzenediazonium
Ion with Naphthalen-2-ol.
Principle:
To prepare the azo dye 1-(4-hydroxyphenylazo)-2-naphthol by the diazonium coupling
reaction of naphthalen-2-ol with the benzenediazonium ion obtained from 4- aminophenol:
Materials:
NaOH
Naphthalen-2-ol
4-Aminophenol
Sodium nitrate(III)
Concentrated hydrochloric acid
Ice-water bath
Apparatus:
150-cm3 Conical flask Büchner funnel
100-cm3 Conical flasks (2 pcs.) Glass rods
50-cm3 Beakers (2 pcs.) Melting-point apparatus (optional)
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Organic Chemistry II- lab
PHR 122
Filter paper Droppers
Filtering flask/suction flask Weighing balance
Spatula Watch-glass
Experimental Procedure:
1.Prepare 30 cm3 of ~10% aqueous sodium hydroxide solution by dissolving 3 g of sodium
hydroxide in 27 cm3 of water in an 150-cm3 conical flask.
2.Weigh 1.44 g of naphthalen-2-ol (0.01 mol) and dissolve it into the sodium hydroxide
solution. Stir the mixture until complete dissolution. Cool the solution with an ice-water bath.
3. The benzenediazonium salt solution can be prepared as below:
(a)Dissolve 0.70 g of NaNO2 (0.01 mol) in 5 cm3 of water.
(b) Put 1.20 g of 4-aminophenol (0.011 mol) into 45 cm3 of water in a 100-cm3 conical flask.
Add slowly 12 cm3 of concentrated hydrochloric acid and stir the mixture until the 4-
aminophenol is dissolved completely.
(c)Cool the 4-aminophenol solution in an ice-bath. Some 4-aminophenol may precipitate out
upon cooling. While keeping the solution at 0 °C add the sodium nitrate(III) solution slowly with
a dropper. The mixture should be well-stirred during addition. When the addition is completed,
stir the mixture for another 2 - 3 minutes. The slightly turbid pale grey solution is the
benzenediazonium salt solution.
4.To the alkaline naphthalen-2-ol solution add the benzenediazonium salt solution slowly. A
large amount of brick red precipitate forms during addition. The addition takes about 5
minutes. The reaction mixture should be stirred efficiently and cooled in an ice-water bath
during the addition.
5.When the addition is completed, stir the mixture at 0 °C for 5 - 10 minutes. This is to ensure
the reaction goes to completion.
6. Filter the mixture by suction filtration. Wash the solid product on the Büchner funnel with a
small amount of cold water. Dry the product on the Büchner funnel with the suction turning on
for a few minutes.
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Organic Chemistry II- lab
PHR 122
7. Transfer the product to a watch-glass. Allow the product to dry for 1 - 2 days. Weigh the
product and determine the percentage yield for the reaction.
Calculation:
Mmol of product x 100
% Yield =
Mmol of SM1 + mmol of SM2
Result:
% yield of the product
Precaution:
1. The experiment should be performed in a well-ventilated laboratory or fume hood.
2. Handle all chemicals with great care. Avoid direct contact of chemicals with skin.
3. The dissolution of sodium hydroxide in water is exothermic and should be performed
with care. When diluting concentrated acids, it is important to add the acids to water
and never do it in the reverse manner. Heat is evolved in mixing concentrated acids and
water. The heat generated during the mixing process may not be able to dissipate
efficiently and may cause the solution to boil and spill out.
4. Both naphthalene-2-ol and 4-aminophenol are harmful organic solids. Handle them in a
good ventilated area to minimize exposure. Naphthalene-2-ol is a mild irritant and
usually in a fine powdery form. Be careful not to breathe in the fine powder.
5. The product 1-(4-hydroxyphenylazo)-2-napthol is an azo dye. All azo dyes are mildly
toxic. Handle the product with care.
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Organic Chemistry II- lab
PHR 122
Experiment 3: Preparation and purification of Acetanilide
Principle:
This experiment involves four functional groups common in organic chemistry. The substrate
(reactants) are both liquids and one of the products is solid. The reaction of aniline with acetic
anhydride is a transformation in which products, acetanilide and acetic acid are obtained. A
solid product is often desirable since it may be recrystallized to purify the compound and
melting point determined. Solids prepared in this manner serve a derivative, whose melting
point may be correlated with known values and thus is a means of identification and serves as a
test for homogeneity or purity. Acetanilide is prepared according to the reaction below.
Apparatus:
1. Erlenmeyer flask/ Conical flask
2. Beaker
3. Hot plate
4. Stirring rod
5. Balance
6. Graduated cylinder
7. Ice-bath
8. Filter paper
Materials:
1. Aniline 2.12 g (about 2 ml)
2. Acetic anhydride 2.5 ml
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Organic Chemistry II- lab
PHR 122
3. Water 15 ml
Procedure:
The aniline (2.12 g about 2 ml), 15 ml distilled water and 2.5 ml acetic anhydride were stirred
together in an Erlenmeyer flask. Heat was given off as the reaction proceeded. The product will
be obtained as solid and was purified by recrystallization.
Recrystallization:
75 ml hot water was added to crude acetanilide, the chosen recrystallization. Next activated
charcoal was added and the solution was run through a hot filtration. After that the solution
flask was placed in a ice-bath and cool it for about 40-50 min. Finally the crystals were collected
by filtration.
Calculation:
Mmol of product x 100
% Yield =
Mmol of SM1 + mmol of SM2
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Organic Chemistry II- lab
PHR 122
Experiment 4: Separation of Benzoic acid, Phenol and Aniline from their mixture by
acid-base extraction.
Principle:
Acid base extraction involves carrying out simple acid-base reaction in order to separate strong
organic acids, weak organic acids or basic organic substances. The principle behind this
separation is due to the salt formation properties of acidic and basic compounds when they are
treated with base and acid respectively. By using aqueous/organic phase system, the
compounds can be separated based on the differences of solubility of the individual
compounds or their salts in organic solvent and water.
Apparatus: Benzoic acid is most commonly found in industrial settings
to manufacture a wide variety of products such as
1. Erlenmeyer flask (50ml, 100ml) perfumes, dyes, topical medications and insect
repellents. Benzoic acid's salt (sodium benzoate) is
2. Separatory funnel (200ml) commonly used as a pH adjustor and preservative in food,
3. Beakers (50ml, 100ml) preventing the growth of microbes to keep food safe.
Materials: Phenols are widely used in household products and as
intermediates for industrial synthesis. For
example, phenol itself is used (in low concentrations) as a
4. Benzoic acid: 2.0 g disinfectant in household cleaners and in
5. Phenol: 2 g mouthwash. Phenol may have been the first surgical
6. Aniline: 2.0 g antiseptic.
7. Ether Aniline, an organic base used to make dyes, drugs,
explosives, plastics, and photographic and rubber
8. Aqueous saturated NaHCO3 solution chemicals.
9. 10% NaOH aqueous solution
10. Dilute HCl (5%)
Procedure:
11. Three organic compounds Benzoic acid, Phenol and Aniline are dissolved in ether.
12.The ether solution is shaken with a saturated aqueous solution of NaHCO3. Sodium
benzoate is formed, dissolved in aqueous layer and is removed.
13. The ether portion is separated using a separatory funnel. A 10% NaOH aqueous solution
is added and the mixture is shaken.
14. The strong base NaOH reacts with weak acid phenol to form sodium phenoxide, an ionic
compound that is dissolved in water and is removed.
15. The ether now contains aniline. Evaporation of ether leaves aniline.
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Organic Chemistry II- lab
PHR 122
6. The other two compounds are separated by adding acid (dil. HCl) to sodium benzoate
and sodium phenoxide to regenerate the covalent compounds benzoic acid and phenol.
7. Now they are extracted with ether (20 ml). The ether portion is collected and
evaporated to get the compounds.
Fig: Flow diagram for the separation of a strong acid, a weak acid, a neutral compound, and a
base-benzoic acid, phenol, naphthalene, and aniline
For phenol with a Ka of 10-10 the minimum hydroxide ion concentration that will produce the
phenoxide anion in 99% conversion is 10-2 M. le concentration of hydroxide in 10% sodium
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Organic Chemistry II- lab
PHR 122
hydroxide solution is 10-1 M and so phenol in strong base is entirely converted to the water
soluble salt.
Liquid/liquid extraction and acid/base extraction are employed in the majority of organic
reactions because it is unusual to have the product crystallize from the reaction mixture or to
be able to distill the reaction product directly from the reaction mixture.
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