348 Mr Crocker, On the interaction of Thiocyanates, 



Another picryl chloride now adds on across the triple " bond " 

 in the - C = N group, the chlorine going to the carbon and the 

 picryl radicle to the nitrogen, 



C 6 H 2 (N0 2 ) 3 - S - C = N + C 6 H 2 (N0 2 ) 3 C1 



-C 6 H 2 (N0 2 ) 3 -S-C = N 



I I 

 CI C 6 H 2 (N0 2 ) 3 



This would be a strongly acidic chloride, and would act on the 

 alcohol, giving hydrochloric acid and an ethoxy-body, 



C 6 H 2 (N0 2 ) 3 - S - C = N + EtOH 



CI C 6 H 2 (N0 2 ) 3 



-*. C 6 H 2 (N0 2 ) 3 -S-C=N 



EtOC B H 2 (N0 2 ) 3 + HCl 



This body is a picrimido-picryl-thio-carbonic ester. Putting 

 Pi for C 6 H 2 (N0 2 ) 3 , the relation to carbonic ester is easily seen : 



Pi-S-C-O-Et 

 II 

 N-Pi 



If this view of the constitution is correct, the body should 

 hydrolyse somewhat in this way : 



Pi_S-C-0-Et O PiNH 2 +Pi -S-C-0 -Et 

 II + - II 



N - Pi H 2 



And indeed one of the products of hydrolysis is picramide. 

 The above explanation suggested that different alcohols should 

 give new bodies of similar structure. Both methyl and normal 

 propyl alcohols gave corresponding derivatives. It was somewhat 

 unexpected, however, to discover that there were two isomeric 

 methoxy-derivatives, easily transformable one to the other. Mere 

 crystallisation from different solvents effected the transition, the 

 form produced in some cases being dependent on the concentra- 

 tion of the solutions. The more stable form melted at 169° and 

 the less stable at 157 — 8°. The former occurred in woolly masses 

 of a pale yellow colour, while the latter appeared as compact, heavy, 

 brilliant crystals of a golden yellow colour, so alike the ethoxy- 

 body as to be indistinguishable from it, by mere inspection. The 

 analysis in both cases gives the empirical formula C 14 H 7 N 7 S0 13 . 



The number of methoxy-groups was determined in both cases 

 and was found to correspond to that required by theory. 



