Organic Chemistry of Explosives

References 85

Olah and co-workers^36 reported the synthesis of 3,3,7,7-tetranitro-cis-bicyclo[3.3.0]octane

(139) from the diketone (137). In this synthesis treatment of the dioxime of (137) with a buffered

solution of peroxytrifluoroacetic acid gives 3,7-dinitro-cis-bicyclo[3.3.0]octane (138), which

on oxidative nitration yields (139) in 76 % yield.

2.8.3 Bicyclo[3.3.1]nonane

HON

140 142

1. Cl 2 , CH 2 Cl 2


2. NaOCl, Bu 4 NHSO 4
   59 % (2 steps)


3. H 2 , Pd/C, NaOH,
   NOH MeOH, 61 % 141

NaNO 2 , NaOH,

AgNO 3 , MeOH (aq)

NO 2

NO 2

NO 2

NO 2

O 2 N

O 2 N

17 %

Figure 2.31

Baum and Archibald^32 reported the synthesis of 2,2,6,6-tetranitrobicyclo[3.3.1]nonane (142).

This synthesis starts from the dioxime (140), which on halogenation with chlorine, followed

by oxidation with hypochlorite and reductive dehalogenation with hydrogen in the presence

of palladium on carbon, yields 2,6-dinitrobicyclo[3.3.1]nonane (141). Oxidative nitration of

(141) with sodium nitrite and silver nitrate under alkaline conditions yields 2,2,6,6-tetranitrobi-

cyclo[3.3.1]nonane (142). The greater molecular freedom in 2,2,6,6-tetranitrobicyclo[3.3.1]

nonane (crystal density-1.45 g/cm^3 ) compared to the isomeric 2,2,6,6-tetranitroadamantane

(crystal density-1.75 g/cm^3 ) is reflected is their considerably different crystal densities.

References

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