Ryan and O'Riordan — On a-, $-, and y-Trinitrotoluenes. 183 



Anschiitz and Ziminermann (Ber. d. Dtsch. Oliora. Ges. xlviii (1915), 

 pp. 152-155). 



Ten grams of a-trinitrotoluene were dissolved in 50 c.c. of absolute alcohol 

 on the water-bath, and the solution was cooled with shaking. In this way a 

 tine suspension of trinitrotoluene was obtained. One c.c. of concentrated 

 ammonia was then added, and the mixture was cooled in ice. A current of 

 gaseous sulphuretted hydrogen was passed through, the colour of the mixture 

 changing from deep violet to reddish-orange in about half an hour. The 

 mixture was boiled and filtered, the residue (sulphur) being washed with 

 alcohol. The filtrate was poured into water, and the precipitated solid was 

 filtered and dried. 



The dry solid was extracted with benzene in a Soxhlet apparatus. The 

 first three or four extracts were neglected ; the later ones which, according 

 to Anschiitz and Zimmermann, contain mainly 2-6-dinitro-4-hydroxylamino- 

 toluene, deposited a yellow substance melting at 127-130° C. (the melting- 

 point of the, hydroxylamino compound is 135-136° 0.). 



One and a half grains of this substance were heated on the water- bath 

 for three quarters of an hour with 15 c.c. of concentrated hydrochloric acid. 

 The mixture was cooled and filtered, and the residue was washed with warm 

 hydrochloric acid. When dried and re-crystallised from benzene, it formed 

 colourless, prismatic needles, melting at 210° C. On treatment with sodium 

 amalgam and alcohol, a violet-blue coloration was developed. Its alcoholic 

 solution gives a violet-blue colour, with caustic soda. Since a mixture of this 

 substance with that obtained by the action of sodium carbonate on a-trinitro- 

 toluene melted at 183-186° U., the two substances cannot be identical. 



(d) Attempt to prepare Hexanitrodibenzyl. 



Dibenzyl was prepared in the usual manner by the action of metallic 

 sodium on benzyl chloride, and was then treated as follows: — 



Six grams of dibenzyl were added in small quantities to a mixture of 

 50 c.c. of nitric acid (sp. gr. 1*44) and 150 c.c. of concentrated sulphuric acid, 

 with constant shaking. The dibenzyl all dissolved and, on standing, a solid 

 began to separate. It was allowed to remain overnight, and was then heated 

 on the water-bath for about 2| hours, and the mixture was then poured into 

 water. The solid was separated and, when dried, melted at 130° C. 



This solid was further nitrated by heating with 60 c.c. of concentrated 

 sulphuric acid and 32 grams of potassium nitrate on the water-bath for eight 

 hours. This yielded a product which, when washed with alcohol and re-crys- 

 tallised from benzene, formed colourless prisms melting at 165 C. This 

 substance was probably the 2.4.2'.4'-tetranitro-dibenzyl, obtained by Braun 

 and Rawicz (Ber. d. Di.sch. Ghem. Oes., xlix (1916), p, 799). 



[2 B 2] 



