Organic Chemistry of Explosives

6-Membered rings – 4N 323

3,3’-azo-bis(6-amino-1,2,4,5-tetrazine) (207) (DAAT). DAAT has a very large positive heat of

formation, initially measured^129 as 862 kJ/mol, although recent work^130 reports this could be

as high as 1035 kJ/mol.

NN

NN

NHNH 2

NHNH 2

208

N

NN

N

N N

N

H 3 C

H 3 C CH 3

CH 3

N

N

N

Cl

Cl

209

N

NN N

N

N

N

N

N

N

N

NH 2 H 2 N

N

N

N

N

NH 2

197

211

Cl 2 , CH 3 CN

2.0 eq N 2 H 4 .H 2 O,

MeCN, air (O 2 )

(210)

N

N

Na

N

Figure 7.76

Treatment of the bis(pyrazoyl)tetrazine (197) with an excess of hydrazine hydrate generates

3,6-bis(hydrazino)-1,2,4,5-tetrazine (208), a compound which might find use as an energetic

additive in high performance propellants.^131 Several salts of (208) have been reported, including

the dinitrate and diperchlorate. 3,6-Dichloro-1,2,4,5-tetrazine (209), the product from treating

(208) with chlorine in acetonitrile, reacts with the sodium salt of 5-aminotetrazole (210) to

yield (211) (C 4 H 4 N 14 – 79 % N).^131

NN

NN

NH

HN

N

N

N

NH

NN

N

N

H

NN

NN

NN

NH 2

NN

NN

NH

HN

O

O

H 2 N

NH 2

NH

NH

(^212213214)
Figure 7.77
Hiskey and co-workers at Los Alamos National Laboratory conducted extensive studies
into the synthesis of tetrazine-based energetic materials. Compounds (212), (213) and (214)
are some of the energetic tetrazines synthesized so far.^129 ,^131 ,^132
Tartakovsky and co-workers^133 reported the synthesis of the highly energetic 1,2,3,4-
tetrazino[5,6-f]benzo-1,2,3,4-tetrazine 1,3,7,9-tetra-N-oxide (TBTDO) (219). The synthesis