Organic Chemistry of Explosives

Miscellaneous 49

including 2-fluoro-2,2-dinitroethanol, has been given by Adolph and Koppes.^37 Many more

examples of the use of polynitroaliphatic alcohols as nucleophiles and in other reactions can

be found in numerous reviews.^37 ,^114 ,^241 ,^242

1.12 Miscellaneous

1.12.1 1,1-Diamino-2,2-dinitroethylenes

90 % HNO 3

65 %

I

I

I

I

182

NO 2

NO 2

I

I

183

HN

HN

NH

NH NO 2

NO 2

O 2 N

O 2 N

N

N

N

N

(O 2 N) 3 C C(NO 2 ) 3

184 O^2 N 185 NO^2

Figure 1.89

The nitration of 1,1,2,2-tetraiodoethylene (182) with 90 % nitric acid provides 1,1-

diiododinitroethylene (183) in good yield.^331 Baum and co-workers^331 studied the chemistry

of 1,1-diiododinitroethylene and found that displacement of the two vinylic iodide groups

is effected by treatment with simple aliphatic amines, diamines and anilines to give 1,1-

diamino-2,2-dinitroethylenes in excellent yield. Cyclic products are obtained from the reaction

of 1,1-diiododinitroethylene with 1,2-diaminoethane (ethylenediamine), 1,3-diaminopropane

and 1,4-diaminobutane. The spirocycle (184) is synthesized from the reaction of 1,1-

diiododinitroethylene (183) with 2,2-bis(methylamino)-1,3-diaminopropane.

NO 2

NO 2

I

NO 2 I

KO 2 N NO 2 K

O 2 N 183 186

NH 3 (g), CH 2 Cl 2

90 %

KNO 2 ,

MeOH (aq)

[ (NO 2 ) 2 CCN]

−

NH 4

+

74

CC

-20 °C, 74 %

Figure 1.90

The reaction of 1,1-diiododinitroethylene (183) with potassium nitrite in aqueous methanol,

and with anhydrous ammonia in methylene chloride, provides a route to the dipotassium salt of

1,1,2,2-tetranitroethane (74) (90 %) and the ammonium salt of dinitroacetonitrile (186) (74 %)

respectively.^331

Further work by Baum and co-workers^332 showed that the nitration of 1,1-diamino-2,2-

dinitroethylenes with trifluoroacetic anhydride and nitric acid in methylene chloride yields

1,1,1-trinitromethyl derivatives via addition of nitronium ion to the double bond of the

enamine; such treatment also resulting in theN-nitration of the products. In this way, trini-

tromethyl derivatives like (185) and (188) are obtained. Further treatment of these trinitromethyl

derivatives with aqueous potassium iodide results in reductive denitration and the formation