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186 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES

(7a)

(7b)

The reaction was discovered by Nef [50] and was investigated later by Namet-

kin [66], and by Johnson and Degering [671.

A very characteristic feature of primary and secondary nitro compounds is

their ability to add on aldehydes in a weak basic medium to form nitroalcohols

(X, XI). Formaldehyde is particularly readily added:

(8a)

(8b)

Nitroalcohols X and XI may be utilized as starting materials for the manu-

facture of nitric acid esters having explosive properties (see Vol. II). In the

presence of primary or secondary amines or ammonia the reaction leads to

formation of aminonitroalcohols (XII)

XII

When R’ = H (i.e. in the case of primary amines), the product may react fur-

ther with formaldehyde to form a tetrahydro-1,3-oxazine ring, or with an amine

and formaldehyde to form a hexahydropyrimidine ring. When using ammonia,

(R’ = R” = H), the same rings may be formed (Hirst, J. K. N. Jones, T. Urban-

ski et al. [68]).

All nitro compounds, even the tertiary ones, which contain no “active hydrogen”

atoms, react with the Grignard reagent (Oddo [84]). Thus, according to Gilman and

Fothergill [69], nitrobenzene reacts in the Zerevitinov reaction as if it contained two

active hydrogen atoms. Further studies of Gilman and Fothergill have proved