Mr Ruhemann, The Action of Acidchlorides, etc. 313 



The Action of Acidchlorides of Acetylenic Acids on Ketonic 

 Compounds. By S. Ruhemann, M.A., Caius College. 



[Read 26 February 1906.] 



Some months ago Ruhemann and Merriman {Trans. Chem. Soc, 

 1905, lxxxvii. 1383) published the results of an investigation on 

 the action of phenylpropiolyl chloride on sodioacetylacetone, and 

 showed that a yellow compound C 14 H 12 3 was formed which, 

 under the influence of piperidine, changed into a red isomeride. 

 This was found to dissolve in alkalis, their carbonates or organic 

 bases to yield blue solutions and, on boiling with sodium carbonate, 

 to suffer a transformation into a colourless acid which had the 

 same molecular composition as the former two compounds. These 

 changes were symbolised thus : 



C fi H,.CH -C— Q— C.CH, 



CO- 



-C . CO . CH 3 



C(OH):C.C 6 H 5 



\ 

 C.CH, 



aH\.C:C.C0 9 H 



CO C . CO . CH, CH, . C : C . CO . CH,. 



I have now undertaken the further study of these substances 

 with the view of supporting the above constitutional formulae. 

 My attention has been directed especially to the red isomeride 

 C 14 H 12 3 the properties of which closely resemble the colourless 

 triethyl oxalylaconitate (see Ruhemann and Hemmy, Trails. 

 Chem. Soc, 1897, LXXI, 34), and Claisen and Ewan's oxalyldibenzyl- 

 ketone (Annalen, 1895, cclxxxiv, 245). The analogy of these 

 three compounds is indicated, also, by the similarity of their 

 structural formulae : 



C(OH) = C.CO,.C 2 H 5 C(OH) = C.C 6 H B 



C(OH)— C.C 6 H 5 



\ 



C.OH 



CO CC 6 H 5 



Oxalyldibenzylketone Triethyl oxalylaconitate 



CO- 



CCO^CoHs 

 -C.COoCH, 



CO- 



C.CH 3 

 -C.CO.CH, 



Oxalylphenylmethyl 

 acetylpropene. 



21—5 



