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310 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES

According to Heinke [104], trinitrotoluene reacts with diazomethane, three

molecules of the latter losing their nitrogen atoms and combining with a molecule

of trinitrotoluene as methylene groups, the fourth molecule of diazomethane being

directly attached to the same molecule of trinitrotoluene:

C 6 H 3 N 3 O 6 + 4CH 2 N 2 -> C 10 H 11 N 5 O 6 + 3N 2 (15)

The constitution of the product has been determined by de Boer [161].

The reactivity of the methyl group in trinitrotoluene is also evident in the reaction

with formaldehyde, a molecule of the latter being attached to form a trinitro de-

rivative of phenylethyl alcohol (XVII) [162]:

The methyl group is readily oxidizable, giving rise to trinitrobenzoic acid which,

because of the accumulation of nitro groups, is unstable and in turn loses its CO 2

to form trinitrobenzene:

Addition products

Trinitrotoluene, like other highly nitrated aromatic hydrocarbons, easily forms

addition products with polycyclic hydrocarbons and amines. The addition products

formed by α− trinitrotoluene have been extensively studied by Hepp [35] and

Kremann [104a,104b]. Some of the products are listed below (Table 69).

α− Trinitrotoluene also forms addition compounds (1 : 1) with α− nitronaphthalene

m. p. 64.7 (melts with simultaneous dissociation) (Wogrinz and Vári [105]; Taylor

and Rinkenbach [40]; Frolova [106]).

The β− and γ− isomers of trinitrotoluene also form molecular compounds (1 : 1)

with naphthalene, acenaphthene, fluorene, phenanthrene and anthracene (Jefremov

and Bogush [107]; Jefremov and Frolova [107a]).

According to T. Urbaliski [log], α− trinitrotoluene forms with erythritol tetra-

nitrate an unstable addition compound, (4 : l), melting at about 65°C.

The composition of various eutectics of α− trinitrotoluene were given on p. 295.