Organic Chemistry of Explosives

Synthetic routes to polyols and derivatives 111

C

CH 2 OH

CH 2 OH

AcOCH 2 CH 2 OH C

CH 2 ONO 2

CH 2 ONO 2

AcOCH 2 CH 2 ONO 2

C

CH 2 ONO 2

CH 2 ONO 2

C HOCH 2 CH 2 ONO 2

CH 2 OH

CH 2 OH

HOCH 2 CH 2 OH

C

CH 2 ONO 2

CH 2 ONO 2

ROCH 2 CH 2 ONO 2

81

82 83

62

80 % HNO 3 ,

80 % H 2 SO 4

46–51 %

1. Me 2 CO,
   H 2 O, NaOH


2. HCl
   94 %

100 % HNO 3

99 %

84, R = propionate, 83 %

85, R = benzoate, 61 %

86, R = 3,5-dinitrobenzoate, 70 %

87, R = p-nitrobenzoate, 60 %

Figure 3.41

on the synthesis of nitrate ester analogues of pentaerythritol. Pentaerythritol trinitrate (81) is a

key starting material for the synthesis of many of these analogues. Pentaerythritol trinitrate (81)

has been synthesized via the controlled nitration of pentaerythritol (62) with mixed acid. The

yields for this nitration average 48 % after the removal of PETN.^144 Pentaerythritol trinitrate

(81) is also obtained from the nitration of pentaerythritol mono-acetate ester (82) followed by

selective hydrolysis of the acetate group.^145

Marans and co-workers^145 used pentaerythritol trinitrate (81) to synthesize a number of

aryl and alkyl esters, including the formate, propionate (84), oxalate, succinate, benzoate (85),

3,5-dinitrobenzoate (86), andortho-,meta-,andpara-(87) nitrobenzoate esters. Thepara-

nitrobenzoate ester (87) has also been prepared from the nitration of pentaerythritol mono-

benzoate with mixed acid.^146

O 2 NOCH 2

CH 2 ONO 2

CH 2 ONO 2

CCCH 2 NH 3 NO 3 NO 3 H 3 NCH 2 CH 2 NH 3 NO 3

CH 2 ONO 2

CH 2 ONO 2

88 89

Figure 3.42

Hiskey and co-workers^147 prepared a series ofO-nitro amino nitrates by reacting the parent

aminoalcohols with absolute nitric acid followed by precipitation of the salt with an organic

solvent. Two of these compounds, (88) and (89), show similar thermal stability to PETN but are

less sensitive to impact. Such compounds show a useful solubility in water and have potential

for use as sensitizers in explosive slurries.