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308 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES

XIII XlVa

The authors isolated the intermediate product XI but the products XII and

XIII are hypothetical.

Naoum [100] found that trinitrotoluene, when exposed to light, yields a product

of the formula C 14 H 8 O 10 N 5 , insoluble in benzene or water, and exceptionally

sensitive to impact. In addition, a water-soluble red dye is formed.

Krauz and Turek’s suggestion [101] that on exposure to sunlight mainly picric

and trinitrobenzoic acids are formed has not been confirmed by other authors

(Wichert and Donat [102]).

The fact that trinitrotoluene undergoes marked changes when exposed to sunlight

indicates the necessity of shielding it against radiation. All the windows in TNT

factory buildings should be protected against the sunlight (e.g. painted blue).

Reaction with sodium sulphite

α− Trinitrotoluene reacts only very slowly with aqueous solutions of sodium

sulphite, thus differring from its unsymmetrical isomers which can react very rapidly

(p. 332). The trend of the reaction of α− trinitrotoluene may also be different. α− Trini-

trotoluene reacts with dilute (5%) solutions of sodium sulphite at room temper-

ature to yield red coloured addition products. According to Muraour [103]. at

room temperature

a 3% solution of sodium sulphite dissolves 0.3% α− trinitrotoluene

a 6% ., ,, ,,, ,. 0.6%

a 12% ,, ,,, ,, ,, 2.3% .,

α− Trinitrotoluene can be recovered from the solutions by acidifying it or simply

by dilution with water.

At higher temperatures, however, the α− trinitrotoluene undergoes a more drastic

transformation. This is the result of both the action of Na 2 SO 3 and of the high

pH of the solutions: one NO 2 group is substituted by an SO 3 Na group. Thus the

reaction proceeds in essentially the same way as in the case of the unsymmetrical

isomers.

CH 3 C 6 H 2 (NO 2 ) 3 + Na 2 SO 3 -> CH 3 C 6 H 2 (NO 2 ) 2 SO 3 Na + NaNO 2

For more details see also pp. 332-335.

Other reactions

The methyl group in trinitrotoluene becomes strongly activated by the nitro

groups present. This could be ascribed to the hyperconjugation of toluene (p. 200)