Organic Chemistry of Explosives

Nitramines, nitramides and nitrimines as explosives 193

N

N N

NO 2

O 2 N NO 2

N

NN

N

NO 2

O 2 N NO 2

O 2 N NN

N

NN

NO 2

NO 2

NO 2

O 2 N

O 2 N

O 2 N

N

O 2 N

NO 2

NO 2

N

CH 2 CH 2 ONO 2

CH 2 CH 2 ONO 2

O 2 N

NO 2

NO 2

NO 2

O 2 N

N

H 3 C

6

1,3,3-trinitroazetidine

(TNAZ)

5

2,4,6,8,10,12-hexanitro-2,4,6,8,

10,12-hexaazaisowurtzitane

(CL-20)

4

1,3,5,7-tetranitro-1,3,5,7-

tetraazacyclooctane

(HMX)

3

1,3,5-trinitro-1,3,5-

triazacyclohexane

(RDX)

7

N-nitrodiethanolamine

dinitrate (DINA)^8

N,2,4,6-tetranitro-N-

methylaniline (tetryl)

N

Figure 5.3

explosion in the magazine of ships. The use of explosives in a polymeric matrix greatly reduces

the risk of premature detonation from impact and friction, but the performance suffers when

the polymer and plasticizer are inert. The use of energetic polymers and plasticizers is one

field of research. The main field of research is the synthesis of new high performance energetic

materials with favourable physical properties. Much of the continuing research into nitramines

is focused on finding and synthesizing materials for use in insensitive munitions. This has led to

the synthesis of high performance explosives like CL-20 (VOD∼9380 m/s,d= 2 .04 g/cm^3 )

(5) and TNAZ (6). TNAZ is a potential melt-cast explosive (m.p. 101◦C). Both TNAZ and

CL-20 are now synthesized on a pilot plant scale. These and other caged and strained ring

nitramines are discussed more fully in Chapter 6.

A number of important explosives contain nitramino functionality in conjunction with

nitrate ester orC-nitro functionality.N-Nitrodiethanolamine dinitrate (DINA) (7) is a powerful

explosive which can be melt-cast into charges.N,2,4,6-Tetranitro-N-methylaniline (tetryl)

(8) exhibits high brisance (VOD∼7920 m/s,d= 1 .73 g/cm^3 ) and has found application

in both detonators and boosters, in addition to being a component of some composite high

explosives.

O

O

NCH 2 CH 2 ONO 2

NCH 2 CH 2 ONO 2

NO 2

NO 2

O

O

NCH 3

NCH 3

NO 2

NO 2

S

NCH 3

NCH 3

NO 2

NO 2

O

O

10

N,N'-dinitro-N,N'-

dimethylsulfamide

9

N,N'-dinitro-N,N'-

dimethyloxamide

11

N,N'-dinitro-N,N'-bis(2-hydroxyethyl)-

oxamide dinitrate (NENO)

Figure 5.4