Organic Chemistry of Explosives

84 Polynitropolycycloalkanes

OMeMeO

O

OMeMeO

NOH

OMeMeO

NO 2

NO 2

NO 2

NO 2

H

OMeMeO

NO 2

Br

OMeMeO

NO 2

NO 2 NO 2

NO 2

O

NO 2

NO 2

HON

O 2 N

132

NH 2 OH.HCl,

MeOH, NaOAc

NBS, NaHCO 3 ,

dioxane (aq)

1. NaBH 4 ,
   EtOH


2. AcOH,
   H 2 O
   81 %

K 3 Fe(CN) 6 , KOH,

NaNO 2 , MeOH (aq)

MeOH, NaOAc,

NH 2 OH.HCl

129 130 131

81 %

133

67 %

134

H 2 SO 4 , CH 2 Cl 2

72 %

100 %

135 136

1. 98 % red HNO 3 ,
   CH 2 Cl 2 , urea,
   NH 4 NO 3 , reflux


2. 30 % H 2 O 2 (aq)
   52 % (2 steps)

92 %

Figure 2.29

Marchand and co-workers^37 also reported the synthesis of 2,2,7,7-tetranitronorbornane

(136). This synthesis is much longer and more indirect than the synthesis of the 2,2,5,5-isomer

because strained 1,3-diones like 2,7-norbornadione are susceptible to ring cleavage under both

acidic and basic conditions, a process known as Haller–Bauer cleavage. Marchand and co-

workers strategy to the 2,2,7,7-isomer (136) uses a derivative of 2,7-norbornadione where one

of the ketone groups is protected. The methyl acetal (129) was used for this purpose, which on

derivatization to the corresponding oxime (130), followed by bromination-oxidation, reductive

debromination and oxidative nitration, yields thegem-dinitro derivative (133). Ring cleavage

is no longer a problem at this point in the synthesis and so (133) is hydrolyzed to the ketone

(134) under acid catalysis. Subsequent oxime formation, followed by an oxidation-nitration

step, yields 2,2,7,7-tetranitronorbornane (136).

2.8.2 Bicyclo[3.3.0]octane

HH

O

O

H

NO 2

NO 2

HH

O 2 N

O 2 N

NO 2

NO 2

137 138 139

1. NH 2 OH.HCl, KOH

CH 2 Cl 2 , H 2 O

76 %

K 3 Fe(CN) 6 ,

NaOH, NaNO 2

2. TFAA, 90 % H 2 O 2 ,
   CH 3 CN, Na 2 HPO 4 ,
   75 °C, 60 %

H

Figure 2.30