The Chemistry of Powder and Explosives - Sciencemadness Dot Org

TETRANITROANILINE 173
Both trinitroanisol and trinitrophenetol were found to be as satisfactory
as compressed TNT for use as a booster charge in 75-mm.
shells loaded with schneiderite.
Trinitroaniline (picramide)
2,4,6-Trinitroaniline, orange-red crystals from alcohol, m.p.
186°, has but little interest as an explosive for the reason that
other more powerful and more valuable explosives may be prepared
from the same raw materials. It may be prepared by nitrating
aniline in glacial acetic acid solution or by the use of mixed
nitric-sulfuric acid in which no large excess of sulfuric acid is
present. The presence of nitrous acid must be avoided, as this
attacks the amino group, replaces it by hydroxyl, and results in
the formation of picric acid. The nitration of aniline in the presence
of a large amount of concentrated sulfuric acid yields
m-nitroaniline 73 and later the nitro compounds which are derived
from it.
Tetranitroaniline (TNA)
2,3,4,6-Tetranitroaniline, discovered by Flurscheim, 74 has interesting
explosive properties but is such a reactive chemical
substance that, when all things are considered, it is unsuitable for
use. It was used to some extent during the first World War and
was studied very thoroughly at that time.
Flurscheim prepared TNA by a one-stage nitration 75 of
m-nitroaniline sulfate, that substance being procured by the reduction
of m-dinitrobenzene with sodium polysulfide. The nitration
proceeds smoothly, and the entering- groups take the positions
indicated by the strongly ortho-para orienting amino group.
The yield is about 120 per cent of the weight of the m-nitroaniline.
73 van Duin, Rec. trav. chim., 37, 111 (1917).
u Chem. News, 1910, 218; Brit. Pats. 3224, 3907 (1910); Ger. Pats.
241,697, 243,079 (1912); U. S. Pat. 1,045,012 (1912); Z. ges. Schiess- u.
Sprengstoffw., 1913, 185; Mon. Sci.T 1914, 490.
75 Other studies on the nitration: Stettbacher, Z. ges. Schiess- u. Sprengstoffw.,
11, 114 (1916); van Duin, loc. cit. A laboratory method for the
preparation of TNA direct from aniline is described in Stettbacher's book,
op. cit., p. 201.