Organic Chemistry of Explosives

Adamantanes 81

NOH

HON

O

Br

O 2 N O 2 N

O 2 N O 2 N

NO 2 NO 2

NO 2

NO 2

NO 2

109, 68 %

NO 2

108, 20 %

Br

H

H

+

105

NBS, NaHCO 3 ,

dioxane (aq)

24 %

NaBH 4 ,

THF (aq)

66 %

KOH, EtOH,

C(NO 2 ) 4

(^106107)
Figure 2.22
NOH
NOH
NO 2
NO 2
HNO 3 , CH 2 Cl 2
110 111
reflux, 10 %
O
−
O
−
N

• N


• 
  

  Figure 2.23
  2,4-adamantanedione (110). However, this synthesis was unsuccessful, possibly due to se-
  vere steric crowding at the 2- and 4-positions. Archibald and Baum^32 explored the feasibility
  of using pure nitric acid in methylene chloride for the direct oxidation-nitration of oximes. This
  strategy failed when applied to the dioxime of 2,6-adamantanedione (105) and led to oxime
  hydrolysis. The same strategy applied to the dioxime of 2,4-adamantanedione (110) gave a
  10 % yield of 2,4-dinitro-2,4-dinitrosoadamantane as its internal dimer (111). Attempted ox-
  idation of (111) to 2,2,4,4-tetranitroadamantane (117) was unsuccessful. These results have
  implications for the synthesis of highly nitrated adamantanes.
  O
  O
  O
  O NOH
  O
  O
  NO 2 NO 2 NO 2
  NO 2
  NO 2
  NO 2
  NO 2 NO 2
  NOH O
  (^112113114)
  117 115116
  98 % HNO 3 ,
  CH 2 Cl 2 , urea
  NH 4 NO 3 , 35 %
  NH 2 OH.HCl
  EtOH, NaOAc
  NH 2 OH.HCl
  EtOH, NaOAc
  84 %
  reflux, 29 % 79 %
  98 % HNO 3 , urea
  CH 2 Cl 2 , NH 4 NO 3
  steps
  Figure 2.24