Organic Chemistry of Explosives

Polynitrobicycloalkanes 83

NO 2

O 2 N O 2 N

HCO

OCH

O

O

H

H

O

O

NOH

HON

HCOOH CrO 3

127

126

122 123 124

125

85 % Me 2 CO, 50 %

NH 2 OH.HCl,

KOH, 71 %

TFAA, 90 % H 2 O 2 ,

CH 3 CN, Na 2 HPO 4

75 °C, 65 %

83 %

NaOH (aq), NaNO 2 ,

K 3 Fe(CN) 6 , CH 2 Cl 2

NO 2

NO 2

NO 2

Figure 2.27 ‘Olah and co-workers’ synthesis of 2,2,5,5-tetranitronorbornane^36

Olah and co-workers^36 reported the synthesis of 2,2,5,5-tetranitronorbornane (127) from

2,5-norbornadiene (122). In this synthesis formylation of (122) with formic acid yields the

diformate ester (123), which on treatment with chromium trioxide in acetone yields 2,5-

norbornadione (124). Formation of the dioxime (125) from 2,5-norbornadione (124) is followed

by direct oxidation to 2,5-dinitronorbornane (126) with peroxytrifluoroacetic acid generated

in situfrom the reaction of 90 % hydrogen peroxide with TFAA. Oxidative nitration of 2,5-

dinitronorbornane (126) with sodium nitrite and potassium ferricyanide in alkaline solution

generates 2,2,5,5-tetranitronorbornane (127) in excellent yield.

O

O

NOH

HON

Br

NO 2

NO 2

Br

O 2 N

NO 2

O 2 N

NO 2

NO 2

NO 2

124

(^127126)
125
128
NH 2 OH.HCl,
MeOH, NaOAc
94 %
NBS, NaHCO 3 ,
dioxane (aq)
36 %

1. NaBH 4 ,
   EtOH


2. AcOH,
   H 2 O
   98 %

K 3 Fe(CN) 6 , KOH,

NaNO 2 , MeOH (aq)

91 %

Figure 2.28 ‘Marchand and co-workers’ synthesis of 2,2,5,5-tetranitronorbornane^37

Marchand and co-workers^37 reported the synthesis of 2,2,5,5-tetranitronorbornane (127) at

the same time as Olah^36 and used the same dioxime (125) as a key intermediate. Marchand and

co-workers synthesized 2,5-dinitronorbornane (126) via bromination-oxidation of the dioxime

(125) followed by reductive debromination of thegem-bromonitro derivative (128). Oxida-

tive nitration was used to convert 2,5-dinitronorbornane (126) to 2,2,5,5-tetranitronorbornane

(127).