Nucleophilic aromatic substitution 165
NH CH 3
NO 2
NO 2
NO 2
NO 2
O 2 N
O 2 NO 2 2 NNO NO 2
NO 2
Cl CH 3
NH 2
107
(PADNT)
+
85 %
MeOH, 65 °C
87 46
Figure 4.43
2,4,6-trinitrotoluene (α-TNT) with hydrogen sulfide in concentrated ammonium hydroxide.^240
PADNT shows considerable insensitivity to impact and friction and may find use as a new
energetic ingredient for the development of safe and insensitive explosive and propellant for-
mulations.
NHCH 2 CH 2 NH
NO 2
NO 2
O 2 N
H 2 N NH 2 H 2 N
NO 2
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
108
N
H
NO 2
NO 2
NO 2
109
NH 2
Figure 4.44
N,N′-Bis(3-aminopicryl)-1,2-ethanediamine (108) (m.p. 275◦C) is prepared from the re-
action of ethylenediamine with two equivalents of 3-chloro-2,4,6-trinitroaniline.^241 The same
chemists^241 reported 3,3′-diamino-2,2′,4,4′,6,6′-hexanitrodiphenylamine (109), a heat resistant
explosive (m.p. 232–237◦C) prepared from the reaction of 1,3-dichloro-4,6-dinitrobenzene
with 3-chloroaniline followed by mixed acid nitration and subsequent chloro group displace-
ment with ammonia. The potassium salt of 3,3′-diamino-2,2′,4,4′,6,6′-hexanitrodiphenylamine
shows very high thermal stability.^242
Cl
Cl
NO 2
O 2 N NO 2
O 2 N
NH 2
Cl
H
N
NO 2
NH 2
H
N
O 2 N NO 2
O 2 N
NO 2 O 2 N
NO 2
NO 2
H 2 N
H
N
NO 2
H
N
O 2 N NO 2
Cl Cl
+ 2
106
110
111
112
- H 2 SO 4 , HNO 3
- NH 3
Figure 4.45
The thermally insensitive explosive (112) is synthesized by a similar route from the reaction
of 1,3-dichloro-2,4,6-trinitrobenzene (106) (styphnyl chloride) with two equivalents of 3-
chloroaniline, followed by nitration and subsequent displacement of the chloro groups with
ammonia.^241