Organic Chemistry of Explosives

268 Nitramines and Their Derivatives

O 2 NCH 2 OH

CH 2 OH

CH 2 OH

35

N

O 2 N

t-Bu

NaOH (aq)

O 2 NCH 2 NHtBu.HCl

CH 2 OH

CH 2 OH

37

N .HCl

t-Bu

38

O 2 N

N

t-Bu

39

O 2 N

Na

NaOH

• CH 2 O

N

t-Bu

17

O 2 N

NO 2

18

NaNO 2 (aq)

• CH 2 O

CH 3 NO 2 + 3 CH 2 O

36

CH 2 O, t-BuNH 2

HCl (aq),

heat, 94 %

DIAD,

Ph 3 P, MEK

74 %

NH 4 NO 3 , Ac 2 O

K 3 Fe(CN) 6 , 90 %

Na 2 S 2 O 8

91 %

C

CH 2 OH

O

C

CH 2 OH

NO 2

N

O 2 NNO 2

Figure 6.8 Archibald, Coburn and Hiskey’s route to TNAZ^9

solution, the latter is treated with formaldehyde andtert-butylamine to form the 1,3-oxazine

(36). Reaction of the oxazine (36) with one equivalent of hydrochloric acid, followed by

heating under reflux leads to ring cleavage, elimination of formaldehyde, and the formation of

the aminodiol (37), which on reaction with DIAD and triphenylphosphine under Mitsonubu

conditions forms the hydrochloride salt of azetidine (38) in good yield. Reaction of the azetidine

(38) with an alkaline solution of sodium persulfate and sodium nitrite in the presence of

catalytic potassium ferricyanide leads to tandem deformylation–oxidative nitration to yield

1-tert-butyl-3,3-dinitroazetidine (17). The nitrolysis of (17) with a solution of ammonium

nitrate in acetic anhydride completes the synthesis of TNAZ (18).

6.4 Cubane–based nitramines

The incorporation of the nitramino group into the core of cubane has not yet been achieved.

However, a number of cubane-based energetic nitramines and nitramides have been

synthesized.

40 41 NH

H

N

C

NCO

NCO

42 N

N

C

NO 2

NO 2

THF, H 2 O

acetone

100 % HNO 3 ,

Ac 2 O, CH 2 Cl 2

O O

Figure 6.9