Organic Chemistry of Explosives

Addition and condensation reactions 39

Table 1.10 Michael 1,4-addition of nitroalkanes and nitramines with 2-nitroacetates (nitroalkene

precursors)

Pseudo acid Product Yield (%)

Michael additions with 2-nitrobutyl acetate

1-nitropropane 3,5-dinitroheptane 15, 19a,13b

2-nitropropane 2-methyl-2,4-

dinitrohexane

55

1,1-dinitroethane 2,2,4-trinitrohexane 65

ethylene dinitramine 5,8-diaza-3,5,8,10-

tetranitrododecane

81

Michael additions with 3-nitro-2-butyl acetate

2-nitropropane 2,3-dimethyl-2,4-

dinitropentane

33 a,b,57b,c

ethylene dinitramine 4,7-diaza-3,8-dimethyl-

2,4,7,9-tetranitrodecane

21

Michael additions with 1,6-diacetoxy-2,5-dinitrohexane

2-nitropropane 2,9-dimethyl-2,4,7,9-

tetranitrodecane

98

1,1-dinitroethane 3,3,5,8,10,10-
hexanitrododecane

94

1-nitraminobutane 5,12-diaza-5,7,10,12-

tetranitrohexadecane

88

aSolvent was anhydrous THF.b100% excess of the salt of the psuedo acid used (no sodium acetate).c

Solvent wastert-butanol.dEquivalent amounts of reactants and sodium acetate used unless otherwise

stated.eReactions conducted in aqueous methanol unless otherwise stated.

Source:Reprinted with permission from H. Feuer and R. Miller,J. Org. Chem., 1961, 26 , 1348; Copyright

1961 American Chemical Society.

a nitroalkane or another nucleophile is present during thisin situα-nitroalkene formation.

2-Nitrobutyl acetate, 3-nitro-2-butyl acetate and 1,6-diacetoxy-2,5-dinitrohexane are precur-

sors to 2-nitro-1-butene, 2-nitro-2-butene and 2,5-dinitro-1,5-hexadiene respectively. In the

presence of sodium acetate these nitroalkene precursors have been used to synthesize a variety

of polynitroaliphatic compounds in good to high yield (Table 1.10).^268

• AcOH HC(NO 2 ) 3
  
  
  • AcOH
  
  
  
  

C

CH 2 OAc

CH 2 OAc

HNO 2

NO 2

CH 2 OAc

H

H

C

NO 2

NO 2

O 2 NCH 2 C

NO 2

H

CH 2 C

NO 2

NO 2

NO 2

NO 2

CC

NO 2

O 2 N CH 2

NO 2

CH 2

NO 2

CC

NO 2

O 2 N CH 2

H

NO 2

CH 2 OAc

HC(NO 2 ) 3

138

142

139 140

141

Figure 1.65