Organic Synthesis

A stable liquid product

If the product doesnt decompose at the boiling temperature of the

reaction mixture, its possible to obtain it by distillation.

If the product is insoluble in water, it is treated as follows:

The distillate is washed with sodium carbonate solution in a

separating funnel. This removes any acidic impurities that maybe
present. From time to time invert the funnel and open the tap to
release the pressure of the carbon dioxide produced. Washing is
repeated until no more gas is produced. The organic and aqeous
layer form 2 distinct layers. The organic product is in the organic
layer.
The aqeous layer is discarded and the organic layer is washed again
with water. This removes any unreacted sodium salts and soluble
organic substances (e.g. ethanol).
The new aqeous layer is discarded and the organic layer is dried
usually with anhydrous calcium chloride (Anhydrous calcium chloride
cannot be used to dry amines or alcohols as they react with it. KOH
or potassium carbonate are suitable alternatives.)
The dried organic liquid is decanted off from the solid calcium
chloride and distilled, collecting the liquid that boils off at +/- 2
degrees of the boiling temperature of the organic product youre
trying to collect.

Simple distillation can be used to:

Remove a volatile liquid from non-volatile substances

Separate two volatile l

liquids that form a homogenous solution
Unfortunately this is the best diagram I could find. (this is not from
the textbook just show the connections of the flask to the tube
with 2 straight linesthey dont expect diagrams to be this
sophisticated)
For organic compounds, always use a heating mantle as they
can be flammable. Never heat them directly using a Bunsen
flame.
The directions of the flow of water through the condenser
should be shown clearly as being opposite, in from bottom and
out from top. This ensures efficient cooling of the distilled
compound so that it turns into a liquid.
Sometimes the distillate is collected in a flask in an ice bath
(beaker with iced water) especially if the distillate is volatile,
this is e.g. for the distillation of ethanal. Ethanal is highly
volatile so it might vapourise at room temperature.
Distillation purifies the final organic product as the product
has a distinct boiling temperature at which it vapourises.

Steam distillation

Steam distillation is used to extract a volatile liquid that is

immiscible with water from a complex mixture.
This can be used to extract phenylamine from the reaction mixture
after the reduction of nitrobenzene with tin and HCl.
Laboratory preparation of phenylamine
Phenylamine can be prepared by the reduction of
nitrobenzene.
 The reduction of nitrobenzene can be carried out by heating
under reflux nitrobenzene with tin and conc. HCl.
Tin reacts with HCl giving out hydrogen. Rapid effervescence is
observed due to the evolution of hydrogen gas. The hydrogen
reduces the No2 group to a NH2 group.
The reaction mixture is cooled to room temperature, the
condenser removed and excess conc. NaOH solution is added.
On addition of NaOH, tin(IV) hydroxide is initially precipitated,
but it redissolves in excess NaOH because Sn(OH)4 is
amphoteric. It is converted to the[ Sn(OH)6] 2- ion.
At this stage, phenylamine separates as an oil. Steam
distillation is now carried out to separate the mixture of
phenylamine and water from the sludge of tin hydroxide. This
is carried out by blowing steam into the mixture and
condensing the phenylamine and steam mixture that comes
off.
The distillate is initially cloudy as its an emulsion of
phenylamine and water. When the distilling liquid becomes
clear, only water is distilling over and distillation is stopped at
this point (as all the phenylamine has distilled over now).
The distillate is placed in a separating funnel and powdered
NaCl is added and shaken well to reduce the solubility of
phenylamine in water. (the saturated aqeous solution of NaCl
is ionic therefore phenylamine is much less soluble in this than
just pure water)
Ethoxyethane is added to the separating funnel and shaken,
relieving the pressure in the separation funnel occasionally by
opening the tap. The layers are allowed to separate and the
aqeous layer is run off into a beaker.
Pellets of KOH is added to dry the ethoxyethane extract.
Ethoxyethane is distilled off and finally phenylamine is distilled
off.

Preparation of benzendiazonium chloride

Phenylamine and HCl are mixed and the mixture cooled to about 0
degrees Celsius, in ice.
A solution of NaNO2 (sodium nitrite) is also cooled in the same ice
bath and slowly added to the phenylamine mixture, making sure that
the temperature does NOT rise above 10 degrees as the reaction is
exothermic.
 The HNO2 (nitrous acid) which reacts with phenylamine has to be
made in situ by reacting NaNO2 with HCl, as HNO2 is unstable at
room temperature.
If the temperature of the above ice bath is below 0, the reaction is
too slow. If it rises above 10, benzene diazonium chloride
decomposes. (its actually hydrolysed to phenol).

Solvent extraction

Separates an organic product from inorganic substances by adding a

solvent that only the organic product dissolves in. The organic
solution is separated, washed with sodium carbonate solution and
then with water. It is then dried with anhydrous calcium chloride (as
long its not an amine or alcohol). The organic solvent initially used
is then distilled off.

Recrystallisation:

A method used to purify solids. A solvent has to be found in which the

substance is soluble when the solvent is hot but insoluble when the
solvent is cold.

1. Dissolve the impure solid in the minimum amount of hot solvent.

This produces a saturated solution ( we dont want the final crystals
to have too much liquid).
2. Remove any undissolved impurities by filtering the hot solution
through a fluted filter paper using a PRE-HEATED funnel. Its
preheated so that the solution doesnt crystallize on its suface. Its
filtered into a conical flask.
This step removes insoluble impurities.
3. Allow the solution to cool. This allows maximum crystallization.
4. Filter the mixture of the pure solid and the solvent under reduced
pressure (using a Buchner funnel). The reduced pressure is produced
by the suction pump. Reduced pressure is used so that filtration
happens faster. Collect the solid on the filter paper and discard the
solvent which has soluble impurities.
 This step removes soluble impurities.
5. Wash the solid on the filter paper with little ice cold solvent (to wash
off any soluble impurities on the surface of the crystals).