[tingle-lawrance] POLYNITRO COMPOUNDS 9 



fuming Nitric Acid (sp. g. 1-9). The Petroleum Ether all distilled 

 below 95°C. 



I. The 2,4,6,4' — tetranitrodiphenylamine was prepared by grind- 

 ing up four molecular proportions of Oxalic Acid with one of Picranilid 

 and gradually adding eighteen molecular proportions of nitric acid, 

 at room temperature; oxides of nitrogen were evolved. After a few 

 minutes standing the solution becomes thick and red; water is then 

 added and a bright yellow precipitate forms. This was recrystallized 

 from Alcohol twice. Its melting point was 2 15° -5. It is very soluble 

 in Acetone ; soluble in Acetic Anhydride and Chloroform ; slightly soluble 

 in Ether; insoluble in Carbon Tetrachloride and Petroleum Ether. 

 Analysis showed it to be a tetranitro compound; found C. 41-05, 

 calculated C. 41-29. 



All attempts to hydrolize this substance failed. 



Ten parts dilute sulphuric acid (1 :1) to one part of the compound 

 were boiled in a reflux apparatus. Twelve grams con. Sulphuric 

 Acid failed to act on 1 gram of substance after standing at room 

 temperature eight days; when kept at 35° for a few hours, complete 

 solution was efi^ected, but no hydrolysis occurred. Above this" tem- 

 perature excessive charring takes place. From the charred material. 

 Ether extracted a small quantity of a yellowish substance which 

 decomposes at 110°. Con. Sulphuric Acid containing 5 per cent 

 glacial Acetic Acid also failed to accomplish the desired result. Acetic 

 Acid (15 parts to 1 of the compound), in a sealed tube kept at 210° 

 for 24 hours, charred considerably and produced no hydrolysis. 

 Fourteen grams of Acetic Acid (to which three drops of water had 

 been added) were placed in a sealed tube with one gram of tetrani- 

 trodiphenylamine and kept at 120° for 27 hours; neither charring nor 

 hydrolysis occurred. 



Warm Barium Hydroxide dissolves this substance giving an 

 intense red colour. When the solution is acidified with Hydrochloric 

 Acid the original compound is precipitated unchanged. 



II. One molecular proportion of Picranilid and four molecular 

 proportions of Trichloracetic Acid were intimately ground together, 

 and fifteen molecular proportions of Nitric Acid were gradually added. 

 It was found advisable to keep the beaker surrounded with cold water 

 owing to the quantity of heat developed during the reaction. The 

 mixture was allowed to stand overnight. When poured into water, a 

 reddish-yellow precipitate formed. This precipitate, after washing 

 well with warm water, was treated with boiling alcohol and the residue 

 dissolved in Benzene. 



(a) The portion soluble in Benzene, after recrystallizing twice, 

 melted 190-1°. Mixed melting points show it to be identical with 



