370 



with strong sulphuric acid in ordei' lo i-emove tlie trinitrophenyl- 

 methyhiitrainine formed as a bye-product. The mother liquor was 

 poured into ice-water and yielded 2.4. 6-trinitrophenylmethylnitramine. 



The drained crystals of tetranitrophen^lmethylnitramine are washed 

 with gradually more diluted sulphuric acid and then with water 

 until the filtrate gives no reaction with barium chloride. This product, 

 having a melting point of 140° — 145°, is pure enough for most 

 purposes, but it may be further purified by dissolving in nitric acid 

 (D 1.5) adding a little strong sulphuric acid, so as to protect the 

 nitro-group in position 3, heating on a water-bath to 70° and, when 

 cold, precipitating with strong sulphuric acid. After a day or two 

 the mass is collected on glass wool, washed with sulphuric acid and 

 treated further as described. The compound is now j)erfectly pure 

 and melts at 146 — 147°. The yield mounted to 18 grams. 



From the mother liquor were obtained 6 grams of the trinitro- 

 compound. After being dissolved in nitric acid and heated to 70°, 

 the solution was allowed to cool and then poured into ice water. 

 The product then melted at 127°. 



An experiment made with absolute nitric acid gave no higher 

 yield of the ^(^//'a-nitro-compound. Considering the conditions under 

 which we operated, sulphuric acid, which according to Rkverdin ') 

 can convert nitramines into nitrosamines will not be able to exert 

 an unfavourable influence. 



Interaction of alcohoh on teAranitrophenylmethylnitramine. 



The fact mentioned previously that tetranitrophenylmethylnitramine 

 is attacked by boiling methyl and ethyl alcohol and gives an odour 

 of nitrous ethers, invited a further research. In the fii'st place it 

 might be possible that in addition to nitrous esters nitrohydrocarbons 

 were formed and further it was thought desirable to extend the 

 reaction, besides to a few more primary, also to secondary and 

 tertiary a'cohols. As will appear soon, pro])yl alcohol, wobutyl alcohol 

 and fermentation arayl alcohol form esters, whereas allyl alcohol 

 benzyl alcohol, /.^opropyl alcohol and secondary butyl alcohol, also 

 tertiary amyl alcohol, even when dried with the utmost precautions, 

 do not give the esters, but only the trinitromethylnitraminophenol 

 itself, besides the nitrite corresponding with the alcohol, except in 

 the case of benzyl alcohol. 



Methyl alcohol acts already at the ordinary temperature on the 

 nitramine. A gas is evolved that can he collected over a strong 



ij Joiun. f. pracl. Ch. 81, 177 (1910); 83, IGi (1911); Diss. Liebl, Geneve 1913. 



