The Chemistry of Powder and Explosives - Sciencemadness Dot Org

TRINITROTOLUENE 151
CH,
NO, " ~" a CHO "\N^ Ha
NO,-/VNO,
NO, NH,
If a drop of piperidine is added to a pasty mixture of TNT and
benzaldehyde, the heat of the reaction is sufficient to cause the
material to take fire. The same substances in alcohol or benzene
solution condense smoothly in the presence of piperidine to form
trinitrostilbene. 34
NO, r~.— NO,
r\ > C { H / ' W > S-NOf/ >CH=CH-/ S
f \g H' '
Preparation of Trinitrostilbene. To 10 grams of TNT dissolved in 25
cc. of benzene in a 100-cc. round-bottom flask equipped with a reflux
condenser, 6 cc. of benzaldehyde and 0.5 cc. of piperidine are added,
and the mixture is refluxed on the water bath for half an hour. The
material, while still hot, is poured into a beaker and allowed to cool and
crystallize. The crystals, collected on a filter, are rinsed twice with alcohol
and recrystallized from a mixture of 2 volumes of alcohol and 1 of
benzene. Brilliant yellow glistening needles, m.p. 158°.
Trinitrotoluene, in addition to the usual reactions of a nitrated
hydrocarbon with alkali to form dangerous explosive materials,
has the property that its methyl group in the presence of alkali
condenses with aldehydic substances in reactions which produce
heat and which may cause fire. Aldehydic substances from the
action of nitrating acid on wood are always present where TNT
is being manufactured, and alkali of all kinds ought to be excluded
rigorously from the premises.
Giua 35 reports that TNT may be distilled in vacuum without
the slightest trace of decomposition. It boils at 210-212° at 10-20
mm. When heated for some time at 180-200°, or when exposed to
M Pfeiffer and Monath. Ber., 39, 1306 (1906); Ullmann and Geschwind,
ibid., 41, 2296 (1908).
35 Giua, "Chimica delle sostanze esplosive," Milan, 1919, p. 248.