Organic Chemistry of Explosives

Oxidation and nitration of C N bonds 21

NH 2

NH 2

NH 2

NH 2

NH 2

H

H H

H

H 2 N

NO 2

NO 2

NO 2

NO 2

NO 2

NO 2

NO 2

O 2 N

O 2 N

O 2 N

O 3 (excess),

silica gel, -78 °C

20 - 28 %

1. NaOH (aq)


2. MgSO 4 , KMnO 4
   45 % (2 steps)

159

162

150

165

DMDO, (CH 3 ) 2 CO,

91 %

170

Table 1.7

Synthesis of energetic polynitropolycycloalkanes via amine oxidation

Amine

(64) (65)

(66) (67)

(68) (69)

(70) (71)

ClCH 2 CH 2 Cl,

m-CPBA, reflux

38 %

ClCH 2 CH 2 Cl,

m-CPBA, reflux

40 %

Conditions/reagents Product Ref.

NH 3 Cl

+–

NH 3 Cl

Cl H +–

3 N

• 
  
  
  
  • 
    
  
  
  
  

Cl H 3 N

• 
  
  
  
  • 
    
  
  
  
  

and prevents oxidation, whereas use of a buffer in these reactions results in acylation of the

amine.^163 However, peroxytrifluoroacetic acid is an extremely useful reagent for the synthesis

of polynitroarylenes from the oxidation of nitroanilines (see Section 4.7.1.5).^167

Primary, secondary and tertiary aliphatic amines are efficiently converted to nitro com-

pounds in 80–90 % yield with dimethyldioxirane,^168 a reagent prepared^169 from the reac-

tion of oxone (2KHSO 5 -KHSO 4 -K 2 SO 4 ) with buffered acetone. Dimethyldioxirane (DMDO)

has been used for the synthesis of 1,3,5,7-tetranitroadamantane (71) from the corresponding

tetraamine as the tetrahydrochloride salt (70) and is an improvement over the initial synthesis^159

using permanganate anion (Table 1.7).^170 Oxone is able to directly convert some aromatic

amines into nitro compounds.^171

A recent method reported for the oxidation of primary aliphatic amines to nitro compounds

usestert-butylhydroperoxide (TBHP) and catalytic zirconium tetra-tert-butoxide in presence

of molecular sieves.^172

1.6.3 Nitration of nitronate salts

Nitronate salts and the tautomericaci-form of nitroalkanes, known as nitronic acids, are

converted togem-dinitro compounds on treatment with dinitrogen tetroxide.^173 –^175 Novikov

and co-workers^173 synthesized phenyldinitromethane by treating phenylnitromethane with

dinitrogen tetroxide in ether and later^174 reported the synthesis of some substituted

phenyltrinitromethanes from the direct nitration of the nitronate salts of phenylnitromethanes.

Phenyltrinitromethanes are similarly obtained from the nitration ofgem-nitronitronate salts

with a solution of dinitrogen tetroxide in ether. 1,1,1-Trinitroethane (73) can be formed in this

way from the potassium salt of 1,1-dinitroethane (24).^176 Nitrolic acids, the products formed