m-DINITROBENZENE.

Place 37 • 5 g. (21 ml.) of concentrated sulphuric acid and 22 • 5 g. (15 ml.)

of fuming nitric acid, sp. gr. 1-5, in a 250 or 500 ml. round-bottomed
flask ; add a few fragments of unglazed porcelain or of broken glass.

Attach a reflux condenser and place the apparatus in a fume chamber.

Add slowly, in portions of about 3 ml., 15 g. (12-5 ml.) of nitrobenzene;

after each addition, shake the flask to ensure thorough mixing.
Heat the mixture, with frequent shaking, on a boiling water bath ; securely clamp
both the flask and condenser since the acid fumes usually attack the cork.
Allow the mixture to cool somewhat and pour it cautiously with vigorous
stirring into about 500 ml. of cold water ; the dinitrobenzene soon solidifies.
Filter with suction, wash thoroughly with cold water, and allow
to drain as completely as possible.
Transfer the crude dinitrobenzene to a 250 ml. flask fitted with a reflux
condenser, add 80-100 ml. of methylated (or rectified) spirit and heat on
a water bath until all the crystalline solid dissolves. If the resulting
solution is not quite clear, filter it through a fluted filter paper on a large
funnel which has previously been warmed or through a warm Buchner
funnel. Colourless crystals of m-dinitrobenzene (15 g.) are deposited
on cooling. If the m.p. is below 89-90°, recrystallisation is necessary
m-NITROANILINE.
Prepare a solution of sodium polysulphide by dissolving 40 g. of crystallised

sodium sulphide, Na2S.9H20 (1), in 150 ml. of water, adding 10 g.

of finely powdered sulphur, and warming until a clear solution is produced.

Heat a mixture of 25 g. of m-dinitrobenzene (Section IV,12) and 200 ml.

of water contained hi a 1-litre beaker until the water boils gently : stir

the solution mechanically. Place the sodium polysulphide solution in a

dropping funnel and clamp the funnel so that the end of the stem is

immediately above the beaker. Add the sodium polysulphide solution

during 30-45 minutes to the vigorously stirred, boiling mixture, and boil

gently for a further 20 minutes. Allow to cool; this can be accomplished

more rapidly by adding ice. Filter at the pump and wash with cold

water. Transfer to a 600 ml. beaker containing 150 ml. of water and 35 ml.

of concentrated hydrochloric acid, and boil for 15 minutes ; the m-nitroaniline

dissolves leaving the sulphur and any unchanged ra-dinitrobenzene.

Filter and precipitate the w-nitroaniline from the filtrate by

the addition of excess of concentrated aqueous ammonia solution.

Filter off the product and recrystallise it from boiling water. The yield of

m-nitroaniline (bright yellow needles) is 12 g. ; m.p. 114°.

Note.

(1) Crystallised sodium sulphide is very deliquescent and only a sample which

has been kept in a tightly-stoppered bottle should be used