Organic Chemistry of Explosives

88 Synthetic Routes to Nitrate Esters

of nitroglycerine has been reported for composite modified double-base (CMDB) propellants

intended for use in some missiles.

C

CH 2 ONO 2

CH 2 ONO 2

O 2 NOCH 2 CH 2 ONO 2

321

pentaerythritol tetranitrate

(PETN)

ethylene glycol dinitrate

(EGDN)

glyceryl trinitrate, GTN

(nitroglycerine, NG)

O 2 NO O ONO 2

2 NO

ONO 2

ONO 2

Figure 3.1

Ethylene glycol dinitrate (EGDN) (2) is very similar to nitroglycerine in physical appear-

ance, being a viscous pale yellow to colourless oil. It is a powerful explosive (VOD∼7800–

8000 m/s atd= 1 .49 g/cm^3 ) with a perfect oxygen balance for the full combustion of its

aliphatic skeleton. It is considered more stable than nitroglycerine and less sensitive to impact

but more volatile. Ethylene glycol dinitrate is mainly used in mixtures with nitroglycerine for

the manufacture of nonfreezing dynamites and as an energetic plasticizer.

Pentaerythritol tetranitrate (PETN) (3) is a powerful explosive which exhibits considerable

brisance on detonation (VOD∼8310 m/s atd= 1 .77 g/cm^3 ). It is the most stable and least

reactive of the common nitrate ester explosives. The relatively high sensitivity of PETN to

friction and impact means that it is usually desensitized with phlegmatizers like wax and the

product is used in detonation cord, boosters and as a base charge in detonators. Pentaerythritol

tetranitrate can be mixed with synthetic polymers to form plastic bonded explosives (PBXs)

like detasheet and Semtex-1A. A cast mixture of PETN and TNT in equal proportions is known

as pentolite and has seen wide use as a military explosive and in booster charges. The physical,

chemical and explosive properties of PETN commend its use as a high explosive.

6

triethylene glycol dinitrate

(TEGDN)

O

O

4

C

CH 2 ONO 2

CH 2 ONO 2

CH 3 CH 2 ONO 2

metriol trinitrate

(MTN)

O 2 NO

O 2 NO

O 2 NO

O 2 NO

O

ONO 2

ONO 2

ONO 2

ONO 2

O 2 NO ONO

2

ONO 2

ONO 2

ONO 2

CH 3

5

diethylene glycol dinitrate

(DEGDN)

1,2,4-butanetriol

trinitrate (BTTN)

7

1,2-propanediol

dinitrate (PDDN)

8

erythritol tetranitrate

9

Figure 3.2

The nitrate esters of metriol (1,1,1-trimethylolethane), diethylene glycol (DEG), triethylene

glycol (TEG) and 1,2,4-butanetriol (BT) i.e. metriol trinitrate (MTN, VOD∼7050 m/s) (4),

diethylene glycol dinitrate (DEGDN/DGDN, VOD∼6750 m/s) (5), triethylene glycol dinitrate

(TEGDN) (6) and 1,2,4-butanetriol trinitrate (BTTN) (7) respectively, were also synthesized by

the reaction of the parent alcohol with mixed acid around the time of discovery of nitroglycerine.