Ryan and O'Riordan — On a-, /3-, and y- Trinitrotoluenes. 189 



X I V. Action of Aldehydes on a- Trinitrotoluene. 



Following the method of Pfeiffer and Monath (Ber. d. Dtsch. Chem. 

 Ges. xxxix (1900), pp. 1304-1306), the following compounds were prepared 

 by condensing a-trinitrotoluene with benzaldehyde, anisaldehyde, and 

 piperonal. respectively, in the presence of piperidine : — 2.4.6-trinitrostilhene, 

 2.4. 6-trinitro-4'-methoxystilbene, and 2.4. 6-trinitro-3'. 4'-methylenedioxy- 

 stilbene. The first two substances have been previously obtained by Pfeifl'er 

 (Ber. d. Dtsch. Chem. Ges. xxxix (1906), pp. 1304-1306; xlviii (1915), 

 p. 1777). 



The last-named substance, which has not previously been obtained, was 

 prepared in the usual manner by adding 5 or 6 drops of piperidine to a 

 mixture of 3 grams of n-trinitrotoluene and 2 grams of piperonal, and 

 heating the mixture on the water-bath for about half an hour. 



The product was re-crystallised several times, first from benzene and 

 alcohol, afterwards from benzene. It separates from the latter solvent in 

 the form of dull yellow prisms which on standing or on being heated become 

 scarlet, owing to loss of benzene of crystallisation. The scarlet substance 

 melts at 1 56-157° C. It was heated to a temperature of 90-100° C. before 

 analysis. 



" 1 1-39 grams substance gave ll - 8 c.c. moist nitrogen at 16° O. 

 and 758'6 m.m.p. 



corresponding to N 12'05 

 C 15 H 9 N" 3 8 requires N 11-7. 



XV. Action of Aldehydes on /3- and on 7- Trinitrotoluene. 



All attempts to prepare stilbene derivatives from the /3- and 7-trinitro- 

 toluenes by methods similar to that described for the a-isomer were unsuc- 

 cessful, even when the reaction was tried at temperatures of 125-130° C, 

 and the time of heating was prolonged to several hours. The trinitro- 

 toluenes were generally recovered unchanged from the mixtures. 



When the ^-isomer was heated with piperonal, first on the water-bath for 

 an hour, and then to a temperature of 130° C. for five hours, a brown amor- 

 phous substance, almost insoluble in all solvents, except acetone, was obtained. 



XVI. Action of Phenanthrene on a- Trinitrotoluene. 



Eijuimolecular proportions of o-trinitrotoluene and phenanthrene were 

 dissolved in benzene, and the warm solutions were mixed. On cooling, the 

 mixture deposited bright yellow needles, which were recrystallised from 

 glacial acetic acid. The same substance, mixed with excess of phenanthrene. 



B.I. A. PKOC, VOL. XXXIV, SECT. B. - (.' 



