124 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVEScarbons are nitrated to mononitro derivatives in a yield close to theoretical. Toluene
was nitrated to a mixture of 88% of o- and 12% of p- nitrotoluene and phenol
to a mixture of 51% o- and 48% p- nitrophenol. Mononitro compounds are not
nitrated further to dinitro derivatives by acetyl nitrate.
Benzoyl nitrate C 6 H 5 COONO 2 (prepared by reacting silver nitrate with benzoyl
chloride) can in certain cases be a useful nitrating agent (Francis [181]). For example,
thiophene is nitrated with this compound in theoretical yield, while if conventional
methods are used, only a low yield is obtained and this only with great difficulty.NITRATES OF SOME ORGANIC BASESBattegay and Brandt [181a] succeeded in nitrating anthracene to 9-nitro-
anthracene with 70% yield by heating anthracene with pyridine nitrate and excess
of pyridine to 125°C. Naphthalene was nitrated to a-nitronaphthalene (40% yield)
at 130°C in presence of zinc chloride.
Okoli [181b] has prepared picrylpyridinium nitrate I by acting on picrylpyridi-
nium chloride with nitric acid or metal nitrates:I (m.p. 103-105°C)Okon and Hermanowicz [181c] have found that the nitrate I can serve as a nitrat-
ing agent.
Thus the authors prepared α− nitronaphthalene from naphthalene with the yield
of 80% by warming I with naphthalene. In a similar way toluene was nitrated
at 80°C to 2,4-dinitrotoluene (yield 65%). By warming chloroform with I at40-50°C chloropicrine resulted with the yield of ca. 30%.
ALIPHATIC NITRO COMPOUNDS
Some nitro compounds (C-nitro compounds and nitramines-N-nitro compounds)
can serve as nitrating agents.
Tetranitromethane and hexanitroethane
In the presence of alkalis, tetranitromethane shows nitrating properties. This is
explained by the fact that alkalis decompose it by splitting off the nitro group and
giving rise to nitroform (more exactly to its salt), according to the reaction
(Hantzsch and Rinckenberger [182]) :
C(NO 2 ) 4 + 2KOH -> KNO 3 + KC(NO 2 ) 3 + H 2 O (80a)