Oxime Formation

This reaction is one example of the many derivatives which can be formed from
carbonyl containing molecules. Reaction of aldehydes and ketones with hydroxylamine
gives oximes.

The mechanism begins with a nucleophilic attack on the carbon of the carbonyl by
the nitrogen of the hydroxylamine. The nucleophilicity of the nitrogen on the
hydroxylamine is increased by the presence of the oxygen . This forms a tetrahedral
intermediate which then undergoes a series of proton transfers. The sp2 carbon is
reformed and water is eliminated. Oximes generally form a mixture of geometric
isomers.

Synthesis of oximes is an important reaction in organic chemistry, because these versatile oximes
are used for protection, purification, and characterization of carbonyl compounds. Nitriles,
amides via Beckmann rearrangement, nitro compounds, nitrones, amines, and azaheterocycles
can be synthesised from oximes. They also find applications for selective -activation. In
inorganic chemistry, oximes act as a versatile ligand.
The hydrolysis of oximes proceeds easily by heating in the presence of various inorganic acids,
and the oximes decompose into the corresponding ketones or aldehydes, and hydroxylamines.
The reduction of oximes by sodium metal, sodium amalgam, hydrogenation, or reaction
with hydride reagents produces amines. In general, oximes can be changed to the
corresponding amide derivatives by treatment with various acids. This reaction is
called Beckmann rearrangement.
Beckmann rearrangement is used for the industrial synthesis of caprolactam.
Preparation of benzophenone oxime

Place a mixture of 2.5 g benzophenone, 1.5 g hydroxylamine hydrochloride, 5 mL rectified spirit

and 1 mL of water in a 50 mL round-bottomed flask. Add 2.8 g of sodium hydroxide pellets in
portions with shaking; if the reaction becomes too vigorous, cool the flask with running tap
water. When all the sodium hydroxide pellets has been added, attach a reflux condenser to the
flask, heat to boiling and reflux for 5 minutes. Cool and pour the contents of the flask into a

solution of 7.5 mL of concentrated hydrochloric acid in 50 mL of water contained in a 250 mL

beaker. Filter the precipitate at the pump, wash thoroughly with cold water and dried.
Recrystallise the precipitate from methanol and record the weight of the product, and its melting
point.
(Note: The oxime is gradually decomposed by oxygen and traces of moisture into benzophenone
and nitric acid; it should be kept in a vacuum desiccator filled with pure dry carbon dioxide or
nitrogen).
Preparation of cyclohexanone oxime

Measure the 2.5 mL of 2.5 M aqueous hydroxylamine hydrochloride and the 2.5 mL of 2.5 M
aqueous sodium hydroxide solution. Add these materials and one boiling stone to a 10mL
Erlenmeyer flask. In the hood, add 0.48 g of cyclohexanone to the E. flask. Swirl the flask and
gently place the flask on a water bath. Heat for 15 minutes and remove from water bath. Let cool
slowly and undisturbed to room temperature. After flask has reached room temperature, immerse
in a 100mL beaker approximately half full of ice water. Allow to cool for a minimum of 5
minutes. Collect crystals using vacuum filtration and a Hirsch funnel. Record mass collected.
Obtain melting point.
Reaction and Useful Data

Vanillin is obtained from vanilla and is widely used as deodorant, food flavour and
one of the ingredients in pharmaceutical products