174 Synthetic Routes to AromaticC-Nitro Compounds
NO 2NO 2
53O 2 NNH 2
VNS aminating agent
(NH 2 OH, ATA, TMHI)
DMSO, NaOMeNH 2H 2 N NH 2NO 2NO 2
14O 2 NFigure 4.60Recently, TATB (14) has been synthesized by treating TNB and picramide (53) with VNS
aminating agents like 4-amino-1,2,4-triazole (ATA) and 1,1,1-trimethylhydrazinium iodide
(TMHI) in the presence of sodium methoxide in DMSO.^37 ,^283 Hydroxylamine has been used
but requires elevated temperatures for the same reaction. The main advantage of these methods
is the reduction in the production cost of TATB as a result of relatively inexpensive starting ma-
terials i.e. picramide (from Explosive D) and TMHI (from UDMH). Explosive D (ammonium
picrate) and UDMH are readily available in large quantities in several advanced countries as
a result of implementation of demilitarization programmes in these countries.^283
4.9 The chemistry of 2,4,6-trinitrotoluene (TNT)
2,4,6-Trinitrotoluene (TNT) is a readily available and useful precursor to many other polyni-
troarylenes. Many of the reactions utilizing TNT in this way make use of the acidity of the
methyl group protons. This is itself a consequence of the strengthened hyperconjugation in
TNT as a result of the large negative inductive effect generated by having three nitro groups
on the aromatic nucleus.
CHNO 2
137O 2 N NO 2CH 3NO 2
1O 2 N NO 2CH 2 CH 2 NEt 2NO 2
136O 2 N NO 2CH 2 CH 2 OHNO 2
138O 2 N NO 2CH 2 CH 2 ClNO 2
139O 2 N NO 2CH 2Et 2 NH, CH 2 O 1. CH 3 I- Ag 2 O
POCl 3 ,
pyridineEt 2 NHCH 2 OFigure 4.61The acidity of the methyl group in TNT is illustrated by its ability to participate in Mannich-
type reactions; in the same role as a ketone, the methyl group of TNT behaves as a nucleophile