Organic Chemistry of Explosives

40 Synthetic Routes to AliphaticC-Nitro

Frankel^258 synthesized 2-nitro-3-acetoxy-1-propene (139) by heating 1,3-diacetoxy-2-

nitropropane (138) with sodium acetate under reduced pressure. The reaction of 2-nitro-3-

acetoxy-1-propene with 1,1-dinitroethane yields 2,2,4,6,6-pentanitroheptane. The same re-

action with nitroform provides 1,1,1,3,5,5,5-heptanitropentane (142), a powerful explosive

(VOD∼9230 m/s) with an excellent oxygen balance.^258 ,^274 ,^275 The synthesis of 1,1,1,3,5,5,5-

heptanitropentane from 2-nitro-1,3-propanediol^276 and 2-nitro-1-propen-3-ol^277 has also been

reported and involves a similar mechanism.

143

R^1

NO 2

H

H

• HNR 2 R^2 CH 2 NO 2

(^144145)
C
NO 2
H
R^1 CH 2 NR 2 CH 2
NO 2
H
CC
NO 2
H
R^1 R^2
Figure 1.66
Some 1,3-dinitroalkanes (145) have been synthesized from the reaction of nitroalkanes with
α-nitroalkenes (144) generatedin situfrom the decomposition of Mannich bases (143) derived
from primary nitroalkanes.^274 Reported yields for these reactions are low and the formation of
by-products limits the feasibility of the method.
R^2
NO 2
R^1
R
NO 2
R^1 NO 2
R R^2
R^1
R^3
NO 2
NO 2
R R^2
R^3 O 146
148 147

1. R^3 OH, NaOH


2. C(NO 2 ) 4 2. C(NO 2 ) 4
   
   
   1. R^3 Li, THF
   
   
   
   

R^3 = alkyl R^3 = alkyl or Ar

Figure 1.67

Nielsen and Bedford^279 synthesizedgem-dinitroalkanes (147) from the Michael addition

of organolithium reagents toα-nitroalkenes (146) followed by quenching of the resulting

nitronate anion with tetranitromethane. The same reaction using alkoxides as bases provides

β-alkoxy-gem-dinitroalkanes (148).^279

1.10.2.3 Dinitroethylation

B:

Pathway 1

+B:NO 2

33

149

C NO 2

O 2 N

H 3 C

CCH 3

NO 2

NO 2

O 2 N

Figure 1.68

Shechter and Zeldin^280 discovered that 1,1,1-trinitroethane (33) can undergo two reactions

on treatment with base. First, and typical of the chemistry of 1,1,1-trinitromethyl compounds,

the base can attack one of the electron deficient nitro groups of 1,1,1-trinitroethane (33) and