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98 CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES

C 6 H 5 -CH=CH-CH=CH-C 6 H 5 + N 2 O 4 ->

IX

A further analogy with halogen derivatives discovered by Wieland lies in the

fact that compound IX, when treated with an alcoholic solution of potassium

hydroxide, gives off an HNO 2 molecule to form 1,4-diphenyl-1-nitrobutadiene (X):

X

Subsequently Wieland found that on treating unsaturated compounds contain-

ing a carbonyl group, of the general formula

XI

with N 2 O 3 or N 2 O 4 , three types of compounds were obtained:

(1) On treating with N 2 O 3 first the compound XII was formed which then iso-

merized to give the oxime (XIII), which in turn gave off water to form isoxazole

(XIV):

XII XIII XIV

(2) N 2 O 4 was added on, giving the dinitro compound (XV):

XV

(3) The R radical attached to the carbonyl group, when treated with N 2 O 4 ,

underwent nitration:

XVI

where R’H is the radical R.

In such a way, by treating cyclohexene with N 2 O 4 , Wieland and Blümich [79]

obtained a dinitro compound which, under the influence of an alkali hydroxide,

was converted to nitrocyclohexene :