Organic Chemistry of Explosives

36 Synthetic Routes to AliphaticC-Nitro

H 2 C CHCO 2 Me NO 2

NO 2

127

O 2 N

NO 2

NO 2

128

O 2 N

HC(NO 2 ) 3

+

Steps

C CH 2 CH 2 CO 2 Me CCH 2 CH 2 OH

Figure 1.55

for the synthesis of 3,3,3-trinitro-1-propanol (128) through a several step synthesis.^263 4,4,4-

Trinitrobutyric acid has been used for the same purpose.^264 Ross and co-workers^265 reported

a number of reactions of nitroform with unsaturated aldehydes.

CHCO 2 Me

NO 2

C

NO 2

+ 2 CCH 2 CH 2 CH 2 CH 2 CO 2 MeMeO

60 %

K 2 H 2 C

+ −

CH(NO 2 ) 2

Figure 1.56

(^129130)
(CH 2 ) 2 CC
NO 2
H
(CH 2 ) 2 CO 2 Me
NO 2
H
MeO 2 C(CH 2 ) 2 (CH 2 ) 2 CC
NO 2
(CH 2 ) 2 CO 2 Me
NO 2
MeO 2 C(CH 2 ) 2
MeO 2 C(CH 2 ) 2 (CH 2 ) 2 CO 2 Me
Figure 1.57
Dinitromethane has two acidic protons and reacts with Michael acceptors to form bis-
adducts.^251 ,^254 ,^255 Secondary nitroalkanes can only react with one equivalent of Michael ac-
ceptor. In the absence of steric effects primary nitroalkanes usually react with two equiv-
alents of Michael acceptor to form bis-adducts. Depending on the reaction stoichiometry,
1,4-dinitrobutane can be reacted with methyl acrylate to form either the bis-adduct (129) or
the tetra-adduct (130) in good yield.^249
CH 3 C(NO 2 ) 2 H 2 C CHCHO C
NO 2
NO 2
CH 3 CH 2 CH 2 CHO
74 %

• Figure 1.58
  Aliphatic compounds containing terminalgem-dinitro functionality form adducts with
  Michael acceptors.^117 ,^253 −^255 ,^259 ,^260 Of particular interest is the reaction of α,α,ω,ω-
  tetranitroalkanes with Michael acceptors.^250 Most α,α,ω,ω-tetranitroalkanes will react
  with two equivalents of Michael acceptor to form bis-adducts, like in the case of 1,1,4,4-
  tetranitrobutane, which reacts with two equivalents of methyl vinyl ketone, methyl acrylate,
  acrylonitrile etc.^250 The influence of steric effects becomes apparent with α,α,γ,γ-
  tetranitroalkanes, like 1,1,3,3-tetranitropropane, which can form either mono-adducts or
  bis-adducts depending on the Michael acceptor used; 1,1,3,3-tetranitropropane will only
  react with one equivalent of methyl acrylate and the sole product of this reaction is methyl
  4,4,6,6-tetranitrohexanoate.^250