Rvan and O'Riokdan — On a-. /S-, and y- Trinitrotoluenes. 181 



More dilute caustic soda reacts similarly with fcrinitrobenzene. Thus 

 5 grams of fcrinitrobenzene when heated for a quarter of an hour with one 

 per cent, caustic soda gave a dark-brown solution and a solid residue con- 

 sisting of somewhat impure tetranitro-azoxy benzene. 



Five per cent, sodium carbonate reacted similarly, but more slowly, with 

 the trinitrobenzene. 



In all eases more tarry products tended to be formed when the time of 

 heating was prolonged. 



II. Action of Sodium n-Butylatc on a- Trinitrotoluene. 



One gram of a-trinitrotoluene was dissolved in a mixture of approxi- 

 mately equal parts of benzene and w-butyl alcohol. The solution was 

 cooled in a freezing mixture, and to it was added a solution of - l gram of 

 sodium in butyl alcohol. On addition of the sodium butylate a red solid 

 separated. The mixture was allowed to stand for half an hour, the solid was 

 then filtered, washed with benzene and butyl alcohol, and allowed to remain 

 in a desiccator over calcium chloride until dry. Excess of trinitrotoluene 

 was removed from it by washing with benzene, and the substance was freed 

 from benzene. 



On analysis the body was found to contain 8"3 per cent, of sodium, the 

 percentage of sodium required by the formula 



CH 3 C c H 2 (N0 2 ) 3 NaOOA 



being 7"1 . Two other analyses from different preparations gave S'2 and 8 - 3 

 per cent, of sodium. 



Probably the body contained a small amount of a r/j'-alcoholate, since 

 Busch (loc. cit.) has shown that the higher alcoholates have a tendency to 

 form such compounds. 



This compound explodes when heated over a Bunsen flame. It does not 

 explode on heating slowly to 220° O, nor on being dropped into a tube 

 heated to 160° 0. ; but, on the other hand, explodes when dropped into a 

 tube heated to 170° C. 



III. Action of Caustic Potash on a- Trinitrotoluene in the presence of Iodine. 



One gram of trinitrotoluene was dissolved in benzene and a solution of 

 1'6 grams of iodine in methyl alcohol was added to it. The mixture was 

 cooled in a freezing mixture, and to it a solution of l"b' grams of caustic 

 potash in methyl alcohol was added in small quantities, and with constant 

 shaking. During the addition of the potash the temperature did not rise 

 above -5° C. 



R.I.A. PROC, VOL. XXXIV, SECT. B. [2 B] 



