Organic Chemistry of Explosives

Miscellaneous methods 107

R NH 2 R ONO 2

-15 °C to -10 °C

CH 3 CN, NO 2 F

R = alkyl, FC(NO 2 ) 2 CH 2 , FC(NO 2 ) 2 CH 2 CH 2

Figure 3.32

Eremenko and co-workers^117 used nitryl fluoride for the deamination of amines at sub-

ambient temperatures in acetonitrile. The same reaction occurs with primary nitramines and

their alkali metal salts; bis-nitramines react to give the corresponding bis-nitrate esters.^117 ,^118

The reaction of primary aliphatic amines and nitramines with nitronium salts also leads to

deamination and the formation of alkyl nitrates.^117 ,^119

Katritsky and co-workers^120 reacted primary amines with the triflate salt of 5,6,8,9-

tetrahydro-7-phenyl-dibenzo[c,h]acridine to generate the correspondingN-substituted acri-

dinium triflate salts, which on refluxing in dioxane in the presence of benzyltrimethylammo-

nium nitrate, yield the corresponding nitrate esters.

3.8 Miscellaneous methods

Cyclopropanes are reported to react with a suspension of thallium (III) nitrate in pentane

at room temperature to give 1,3-dinitrate esters.^85 This reaction is interesting but its scope

cannot be accessed because only one example appears in the literature.

Cyclopropane is reported to react with dinitrogen pentoxide in methylene chloride at sub-

ambient temperature to yield 3-nitro-1-propanol nitrate.^121

Treatment of primary nitramines with absolute nitric acid yields the corresponding nitrate

ester and nitrous oxide.^122

Alkyl hydroperoxides react with nitrous acid to give the corresponding nitrate ester. 123

Acyl nitrates react with low molecular weight aliphatic alcohols to give the alkyl nitrate

ester and the corresponding carboxylic acid.^124

2-Nitratoalkyl perchlorates have been synthesized from the cleavage of epoxides with ni-

tronium perchlorate. These materials are extremely dangerous with little value as practical

explosives.^125

Nitrite esters can be oxidised to nitrate esters, usually in excellent yields, on treatment with

ozone or dinitrogen pentoxide.^26 ,^75

Dinitrogen pentoxide reacts with alkanes in carbon tetrachloride at 0◦C via a radical mech-

anism to give nitration products which can include nitrate esters.^126 −^129 Reactions of alka-

nes with dinitrogen pentoxide in nitric acid are complex and of little synthetic value.^130

1-Adamantyl nitrate is one of the products obtained from the photochemical irradiation of

a solution of adamantane and dinitrogen pentoxide in methylene chloride.^131

Propyleneimine is reported to react with a solution of absolute nitric acid in methy-

lene chloride to yield 1,2-propanediol dinitrate, presumably via the intermediate primary

nitramine.^132