The Chemistry of Powder and Explosives - Sciencemadness Dot Org

TRINITROBENZENE 137
+ CHsONo
H. ,OCH,
probably the product of the 1,6-addition of sodium methylate
to the conjugate system which runs through the ring and terminates
in the oxygen of the nitro group. Busch and Kogel 16 have
prepared di- and tri-alcoholates of TNB, and Giua 17 hrj isolated
a compound of the empirical composition TNB NaOH, to which
he ascribed a structure similar to that indicated above. All these
compounds when dry are dangerous primary explosives. They
are soluble in water, and the solutions after acidification contain
red, water-soluble acids which yield sparingly soluble salts with
copper and other heavy metals, and the salts are primary explosives.
The acids, evidently having the compositions TNB CH3OH,
TNB H2O, etc., have not been isolated in a state of purity, and
are reported to decompose spontaneously in small part into TNB,
alcohol, water, etc., and in large part into oxalic acid, nitrous
fumes, and colored amorphous materials which have not been
identified. All the polynitro aromatic hydrocarbons react similarly
with alkali, and the use of alkali in any industrial process
for their purification is bad practice and extremely hazardous.
Trinitrobenzene reacts with hydroxylamine in cold alcohol
solution, picramide being formed by the direct introduction of an
amino group. 18
NH2-OH > I I +H2O
NO2
Two or three nitro groups on the aromatic nucleus, particularly
those in the 2,4-, 2,6-, and 2,4,6-positions, have a strong effect in
increasing the chemical activity of the group or atom in the
ls Ber., 43, 1549 (1910V
17 Gazz. ckim. ital, 45, II, 351 (1915).
18 Meisenheimer and Patzig, Ber., 39, 2534 (1906).