urbaf2

202 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES

The reaction is of great practical importance and is described in detail in the

appropriate places (pp. 231, 308, 332 and 379).

It is well known that the presence of nitro groups in aromatic amines makes

diazotization of the amino group more difficult.

The presence of nitro groups in diazonium compounds considerably facilitates

coupling to yield azo-compounds. For example the diazonium salt of picramide

couples readily with mesitylene [157].

A nitro group attached to an aromatic ring may activate the ring. Owing to

this the nitro-substituted aromatic ring can take part in reactions in which it usu-

ally remains more or less inactive. Nucleophilic reactions of nitro compounds

should be mentioned here first.

Nitro compounds, particularly the higher nitrated derivatives, readily enter into

nucleophilic reactions. The reactions of aromatic halogenonitro compounds with

bases (p. 453), as well as the addition of potassium methoxylate on to sym-trini-

trobenzene resulting in the formation of an anisole derivative will be discussed

below. Similar addition reactions of potassium methoxylate to trinitrotoluene

(p. 301) and trinitroanisole (p. 546) are also known. These reactions were described

in detail by Meisenheimer [36-38]. Confirmation of such an interpretation

of the reaction is provided by the fact that in the reaction of potassium ethoxylate

with trinitroanisole the same dark coloured product (I) is obtained, as when

potassium methoxylate is reacted with trinitrophenetole:

(19)

When treating the addition product (I) with dilute sulphuric acid, Meisen-

heimer obtained a mixture containing trinitrophenetole. Jackson and Earle [39]

confirmed Meisenheimer’s results as regards the preparation of the product.

Hammick and Foster [40] investigated the infra-red absorption spectra of the

products obtained by both routes. The visible spectra were examined by Foster

[41]. Both spectra were found to be identical in each case.

Gitis and Glaz [42] also confirmed Meisenheimer’s view. They found that the

ultra-violet spectrum of the addition product resulting from the reaction of potas-

sium ethoxylate with trinitroanisole was identical with that of the addition product
of potassium methoxylate and trinitrophenetole. Both products showed an absorp-

tion maximum at 485 mμ.
Moreover, the same authors found that heating the product with potassium