EXPERIMENT ONE

PREPARATION OF BENZOPHENONE OXIME

1. Procedure

A mixture of 100 g. (0.55 mole) of benzophenone (Org. Syn. Coll. Vol.

I, 1941, 95), 60 g. (0.86 mole) of hydroxylamine hydrochloride (Org.

Syn. Coll. Vol. I, 1941, 318), 200 cc. of 95 per cent ethyl alcohol, and

40 cc. of water is placed in a 2-l. round-bottomed flask. To this is

added in portions, with shaking, 110 g. (2.75 moles) of powdered

sodium hydroxide. If the reaction becomes too vigorous, cooling with

tap water may be necessary. After all the sodium hydroxide has been

added, the flask is connected to a reflux condenser, heated to boiling,

and refluxed for five minutes. After cooling, the contents are poured

into a solution of 300 cc. of concentrated hydrochloric acid in 2 l. of

water. The precipitate is filtered with suction, thoroughly washed with

water, and dried, (Note) the yield obtained. Find the melting point of

the product and calculate the percentage yield?

 2. Notes

1. This crude material dried overnight at about 40° is practically pure

and if used at once is satisfactory for the preparation of

diphenylmethane imine hydrochloride.

2. In the presence of oxygen and traces of moisture, benzophenone

oxime is gradually converted into a mixture of benzophenone and

nitric acid. A good method of preserving this oxime is to dry it in a

vacuum desiccator, fill the desiccator with pure carbon dioxide, re-

evacuate, and fill again with carbon dioxide. The preparation may

then be transferred to a bottle, also filled with carbon dioxide, and

sealed against access of air.

1. Discussion
Benzophenone oxime has been prepared in quantity by treating an

aqueous alcoholic mixture of benzophenone and hydroxylamine

hydrochloride with hydrochloric acid, with sodium carbonate, with

alcoholic potassium hydroxide, or with aqueous sodium hydroxide. It

has also been obtained by treating bisnitrosylbenzohydryl with

alcoholic potassium hydroxide,6 and by the oxidation of α-

aminodiphenylmethane with magnesium persulfate solution.

 EXPERIMENT TWO
PREPARATION OF BENZPHENONE OXIME TO BENZANILIDE (BECKMANN
REARRANGEMENT)

Applications

Benzanilide is used to make dyes, active pharmaceutical ingredients

and perfumes. It is also used to study the influence of beta-

cyclodextrin on photorearrangement of acetanilide, benzanilide and

ethyl phenyl carbonate. Further, it is used as an amide model

compound to study the reaction between the amide and epoxy. In

addition to this, it reacts with aryltriflates in the presence of palladium-

based catalyst system to get N-(2,6-diarylbenzoyl)anilines.

 Procedure

Dissolve 2 g of benzophenone oxime in 20 mL of anhydrous ether in

a 100 ml round-bottomed flask and add 3 ml of pure thionyl chloride

or 3 gm of powdered phosphorus penta chloride (this step should be

carried out in a fume cupboard). Distill of the solvent or other volatile

products on a water bath. Add 25 ml of water boil for several minutes

and break up any lumps which may be formed. Decant the

supernatant liquid (filter at the pump if necessary), and recrystallise

the product from methanol (toxic!). Record weight of the product,

calculate the yield and its physical constant.

Discussion

Benzanilide can be prepared by the treatment of aniline with benzoyl

chloride,1 benzoic anhydride, or benzoic acid. Benzanilide has also

been prepared from benzamide, aniline, and boron fluoride. The

method described in the procedure is essentially that of Nägeli