Cupboards

About 0.5 g of iodine is placed in a small flask fitted with a long reflux air condenser and 15 cm of fuming nitric acid (b.p. 380 K) are added. The mixture is then heated on a water bath at 385-390 K in a fume cupboard until the reaction seems to be complete. This takes about an hour. The solution is then transferred to an evaporating basin and evaporated to dryness on a steam bath. The iodic acid... 

Concentrate each of the two solutions (or eluates) to about 20 ml, by distilling off the greater part of the benzene, the distilling-flask being immersed in the boiling water-bath. Then pour the concentrated solution into an evaporating-basin, and evaporate the remaining benzene (preferably in a fume-cupboard) in the absence of free flames, i.e., on an electrically heated water-bath, or on a steam-bath directly connected to a steam-pipe. Wash the dry residue from the first eluate with petrol and then dry it in a desiccator pure o-nitroaniline, m.p. 72°, is obtained. Wash the second residue similarly with a small quantity of benzene and dry pure />--nitroaniline, m.p. 148" , is obtained. Record the yield and m.p. of each component. 

Now place 35 ml. of the mixed solvent (C) in the clean cylinder E, and suspend the strip, as described above, to the horizontal arm of G (Fig. 25(A)) adjust the position of the strip so that, when the bung is firmly in position, the bottom of the paper-strip is about 5 mm. above the solvent. Place the cylinder for 5-8 hours in a draught-free place, such as a cupboard, where the temperature is reasonably constant. 

Then remove the strip and dry it in a stream of cold air, either from a blower, or by pinning it to the lower edge of a fume-cupboard window having a vigorous draught already in operation. Then spray the strip lightly but uniformly with the ninhydrin solution (D) in a fume-cupboard, and dry as before. 

Next day, hang the paper from the edge of the fume-cupboard window in the full draught of the fan to dry, and immediately mark the position of the solvent front. 

Add 15 g, of chloroacetic acid to 300 ml. of aqueous ammonia solution d, o-88o) contained in a 750 ml. conical flask. (The manipulation of the concentrated ammonia should preferably be carried out in a fume-cupboard, and great care taken to avoid ammonia fumes.) Cork the flask loosely and set aside overnight at room temperature. Now concentrate the solution to about 30 ml. by distillation under reduced pressure. For this purpose, place the solution in a suitable distilling-flask with some fragments of unglazed porcelain, fit a capillary tube to the neck of the flask, and connect the flask through a water-condenser and receiver to a water-pump then heat the flask carefully on a water-bath. Make the concentrated solution up to 40 ml. by the addition of water, filter, and then add 250 ml. of methanol. Cool the solution in ice-water, stir well, and set aside for ca. I hour, when the precipitation of the glycine will be complete. 

CAUTION. The vapour of selenium dioxide is poisonous, and all operations involving the hot material, alone or in solution, should be performed in a fume-cupboard. If lumps of selenium dioxide have to be powdered in a mortar, the latter should also be in a fume-cupboard, with the window lowered as far as possible, to avoid inhaling the fine dust. (cf. p. 191)... 

In this preparation, the ( + ) or dextro-rotatory (natural) camphor or the ( ) or racemic (synthetic) camphor can be used. Perform the oxidation in a fume-cupboard. 

Lithium aluminium hydride if carelessly manipulated may be dangerous for two distinct reasons. The material is caustic, and should not be allowed to touch the skin it is particularly important that the finely divided material should be kept away from the lips, nostrils and eyes, and consequently pulverisation in a mortar must be carried out with the mortar in a fume-cupboard, and with the window drawn down as far as possible in front of the operator. This danger from handling has however been greatly reduced, for the hydride is now sold in stated amounts as a coarse powder enclosed in a polythene bag in a metal container this powder dissolves readily in ether, and preliminary pulverisation is unnecessary. 

Assemble in a fume-cupboard a 3-necked flask fitted with a stirrer, a reflux condenser, and a dropping-funnel, the apparatus... 

This preparation must be performed in a fume-cupboard, because nitrous fumes are evolved during the nitration. A ground-glass flask and air condenser (Fig. 22(a) and (c), p. 43) should preferably be used. 

Place 0 5 ml. of the pyridine in a 200 ml. round- or flat-bottomed flask and add 34 ml. (30 g.) of benzene. Fit the flask with a reflux water-condenser, and then place it in a cold water-bath. If the experiment is conducted in a fume-cupboard, the top of the condenser can be closed with a calcium chloride tube bent downwards (as in Fig. 61, p. 105 or in Fig. 23(A), p. 45, where the outlet-tube A will carry the calcium chloride tube) and the hydrogen bromide subsequently allowed to escape if, however, the experiment is performed in the open laboratory, fit to the top of the condenser (or to the outlet-tube A) a glass delivery-tube which leads through a piece of rubber tubing to an inverted glass funnel, the rim of which dips just below the surface of some water... 

Apart from the diazotisation, the whole of the following preparation up to the completion of the steam-distillation must be carried out in a fume-cupboard having a vigorous draught. 

For this preparation, which must be performed in the fume-cupboard, assemble the apparatus shown in Fig. 67(A). C is a 150 ml. distilling-flask, to the neck of which is fitted a reflux single-surface water-condenser D, closed at the top E by a calcium chloride tube. The side-arm of C carries a cork F which fits the end E of the condenser for subsequent distillation. The side-arm of C is meanwhile plugged by a small rubber cork, or by a short length of glass rod. (Alternatively, use the ground-glass flask and condenser (Fig. 22 (a) and (c), p. 43), and... 

Assemble in a fume-cupboard the apparatus shown in Fig. 67(A). Place 15 g. of 3,5-dinitrobenzoic acid and 17 g. of phosphorus pentachloride in the flask C, and heat the mixture in an oil-bath for hours. Then reverse the condenser as shown in Fig. 67(B), but replace the calcium chloride tube by a tube leading to a water-pump, the neck of the reaction-flask C being closed with a rubber stopper. Now distil off the phosphorus oxychloride under reduced pressure by heating the flask C in an oil-bath initially at 25-30, increasing this temperature ultimately to 110°. Then cool the flask, when the crude 3,5-dinitro-benzoyl chloride will solidify to a brown crystalline mass. Yield, 16 g., i.e,y almost theoretical. Recrystallise from caibon tetrachloride. The chloride is obtained as colourless crystals, m.p. 66-68°, Yield, 13 g Further recrystallisation of small quantities can be performed using petrol (b.p. 40-60°). The chloride is stable almost indefinitely if kept in a calcium chloride desiccator. 

Mix 6 2 ml. (6 4 g.) of pure ethyl acetoacetate and 5 ml. of pure phenylhydrazine in an evaporating-basin of about 75 ml. capacity, add 0 5 ml. of acetic acid and then heat the mixture on a briskly boiling water-bath (preferably in a fume-cupboard) for I hour, occasionally stirring the mixture with a short glass rod. Then allow the heavy yellow syrup to cool somewhat, add 30-40 ml. of ether, and stir the mixture vigorously the syrup may now dissolve and the solution shortly afterwards deposit the crystalline pyrazolone, or at lower temperatures the syrup may solidify directly. Note. If the laboratory has been inoculated by previous preparations, the syrup may solidify whilst still on the water-bath in this case the solid product when cold must be chipped out of the basin, and ground in a mortar with the ether.) Now filter the product at the pump, and wash the solid material thoroughly with ether. Recrystallise the product from a small quantity of a mixture of equal volumes of water and ethanol. The methyl-phenyl-pyrazolone is obtained... 

The first part of this preparation (as far as the solidification of the sodium cyanoacetate) must be carried out in the fume-cupboard. Add 30 g. of monochloroacetic acid to 60 ml. of water contained in a wide evaporating-basin (about 12-15 diameter)... 

This preparation should be carried out in a fume-cupboard. 

Add 60 ml. of concentrated hydrochloric acid with shaking to 30 ml. of aniline in the flask, cool the mixture to about 50, and then add 45 ml. of paraldehyde and some fragments of unglazed porcelain assemble the apparatus without delay in a fume-cupboard with the condenser inclined at an angle of about 60°. 

Note. The chloroacetone, which should be freshly distilled (b.p. 119°), is lachrymatory, and therefore the distillation and the preparation should be performed in a fume-cupboard. 

Some alcohols react readily with phenylisocyanate at room temperature, and others require heating, preferably in petroleum. Phenylisocyanate is poisonous and should not be heated outside a fume-cupboard except under a condenser. 

Formation of nitrosaminey RgN NO. (a) From monomethylaniline. Dissolve I ml. of monomethylaniline in about 3 ml. of dil. HCl and add sodium nitrite solution gradually with shaking until the yellow oil separates out at the bottom of the solution. Transfer completely to a smdl separating-funnel, add about 20 ml. of ether and sh e. Run off the lower layer and wash the ethereal extract first with water, then with dil. NaOH solution, and finally with w ter to free it completely from nitrous acid. Evaporate the ether in a basin over a previously warmed water-bath, in a fume cupboard with no flames near. Apply Liebermann s reaction to the residual oil (p. 340). 

Place about 1 g. of the nitro-hydrocarbon in a boiling-tube and add 5 ml. of cone. HCl and several pieces of granulated tin. Warm the mixture and shake continuously to break up the oily drops of the nitro-compound. When all the oil has disappeared (about 3 minutes heating) pour off the liquid from any undissolved tin into a 100 ml. conical flask. Cool and add cautiously 30% aqueous NaOH solution until the precipitate formed redissolves to give a dark-coloured solution. Cool the latter thoroughly and shake well with about 15 ml. of ether. Separate the ethereal layer in a separating-funnel, wash with water and evaporate the ether in a basin on a previously heated water-bath in a fume-cupboard atoay from all flames. The residue is either... 

Nitration. Mix together in a boiling-tube 2 ml. of cone. HNO, and 2 ml. of oonc. H1SO4. Add 1 ml. of nitrobenzene with shaking and then heat the mixture over a small flame with constant shaking in a fume-cupboard for a... 

Although these nitrations proceed smoothly, attempted nitration of an unidentified substance should always be carried out with extreme care, e.g., by working in a fume-cupboard and pointing the boiling-tube away from the operator. Many organic substances e.g., alcohols and phenols) react with great violence with a mixture of nitric and sulphuric acids. 

Bromoform. Commercial bromoform should be shaken thoroughly with water, separated, dried over powdered anhydrous sodium sulphate and then fractionally distilled under reduced pressure using a water-condenser. It should be stored in a dark cupboard. It is an excellent solvent, has the advantage of a high Constant, and very seldom causes association of the solute. 

Care must be taken not to inhale dust from the seeds as they contain a poisonous protein the grinding should therefore be carried out in a fume-cupboard. 

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