232 PROCEEDINGS OF THE AMERICAN ACADEMY 



diethylether C 6 OH(OC 2 H 5 ) 2 (K0 2 ) 3 , melting at 89°, or trinitro- 

 phloroglucine itself, C 6 (OH) 3 (N0 2 ) 3 , (which melts at 167° instead 

 of 158°, the point given by Benedikt,*) and these substances pass 

 into the aqueous wash-waters as sodium salts. It follows there- 

 fore that the action of sodic ethylate on tribromtrinitrobenzol con- 

 sists of the two following reactions, which take place parallel to 

 each other : — 



C 6 Br 8 (NO a ) 8 + 3 NaOC 2 H 5 = C 6 (OC 2 H 5 ) 3 (N0 2 ) 3 + 3 NaBr. 

 C 6 Br 3 (N0 2 ) 3 + 2 NaOC 2 H 5 = C 6 Br,NO a (OC 2 H 6 ) 2 + 2 NaNO r 



We observed further, that, if benzol and alcohol were used as the 

 solvents instead of alcohol alone, more of the phloroglucine ether was 

 obtained than when the solvent was only alcohol, and this led us to 

 study the action quantitatively by determining the amounts of sodic 

 nitrite and bromide formed, when we found that the amount of 

 nitrite averaged with the benzol and alcohol 33.49 per cent; with 

 alcohol alone, 45.92 per cent. There was also a difference in the 

 reverse direction with the sodic bromide, but the percentages of 

 this obtained under parallel conditions varied so materially that no 

 careful comparison was possible. The percentages of sodic nitrite 

 removed were, on the other hand, remarkably constant. We have 

 not succeeded in finding any satisfactory explanation for this effect 

 of the presence of benzol in promoting the formation of the trinitro- 

 phloroglucine triethylether (produced by the first reaction), and di- 

 minishing the amount of tribromnitroresorcine diethylether formed 

 by the second reaction given above. 



We have also tried the action of several other alcoholates 

 on tribromtrinitrobenzol, obtaining the following compounds : — 

 C 6 Br 3 N0 2 (OCH 3 ) 2 , melting at 126°; C c (OCH 3 ) 2 OH(N0 2 ) 3 , melt- 

 ing at 77-78° ; C 6 (OC 3 H 7 ) 3 (N0 2 ) 8 , from normal propyl alcohol, 

 melting point 109-110°; the corresponding isocompound melting 

 at 130° ; and C 6 (OCH 2 C 6 H 5 ) 3 (N0 2 ) 3 , melting at 171°. A quantita- 

 tive comparison of the amounts of sodic nitrite formed b} T different 

 alcoholates indicated that the percentage removed diminishes as the 

 molecular weight of the alcohol increases, but there were several 

 exceptions to this general rule. 



We have also found that sodic ethylate decomposes the triphenyl- 

 ether of trinitrophloroglucine, converting it into the trieth t ylether, 

 while phenol is set free; and that sodic ethylate when heated with 



* Ber. d. ch. Ges., XI. 1376. 



