178 REPORTS O^ INVESTIGATIONS AND PROJECTS. 



CHEMISTRY. 



Acree, Solomon F., Johns Hopkins University, Baltimore, Maryland. Grant 

 No. 372. Accurate physical investigations on the urasoles. (For pre- 

 vious reports see Year Book No. 4, pp. 134, 135, and Year Book No. 5, 

 p. 140.) $300- 



Professor Acree submits the following abstracts of several investigations 



carried out with the aid of the above grant : 



On the Salts of Tautomeric Compounds. (By S. F. Acree: American 

 Chemical Journal, vol. 37, p. 71.) — It is well known that when the silver 

 salts of some tautomeric compounds, such as amides, are treated with 

 alkyl halides, at ordinary temperatures, oxygen esters are formed in large 

 amounts, whereas the potassium and sodium salts yield, at higher temper- 

 atures, largely nitrogen esters. If acetoacetic ester is heated with a mixture 

 of silver oxide and an alkyl halide, both oxygen and carbon derivatives are 

 formed, but the sodium salt, under the same conditions, gives practically 

 only a carbon derivative. In general, however, when a salt of a tautomeric 

 amide is treated with an alkyl halide, both oxygen esters and nitrogen esters 

 are formed. 



To account for such reactions of amides, several theories have been 

 proposed : 



(I) The potassium and silver salts have different but definite structures. 

 The potassium salt is a nitrogen compound and the silver salt is an oxygen 

 derivative (Comstock's older theory). 



(II) When one salt yields with a certain reagent two products, one is 

 formed directly and the second by rearrangement of the first (Wheeler's 

 theory). Wheeler assumed that all salts of the amides are oxygen deriva- 

 tives, and that these first yield oxygen esters which then form addition 

 products with the alkyl halide and rearrange into nitrogen derivatives. 



(III) When one salt yields with a certain reagent two products, one is 

 formed by direct substitution of the metal and the other by the formation 

 of an unstable intermediate addition product between the salt and the other 

 reagent (theories of Nef and of Michael). 



(IV) The writer presents tentatively the following theory: a salt of 

 any tautomeric compound reacts with an alkyl halide, or other reagent, and 

 forms two derivatives, because the tautomeric salt is really a mixture of two 

 tautomeric salts in equilibrium, each of which reacts with the alkyl halide 

 in independent side reactions. This reaction may, in certain cases, be com- 

 plicated by the simultaneous rearrangement of one of the reaction products 

 into the other or some other product. 



In order to test experimentally each of the above theories, the writer and 

 his co-workers have studied quantitatively the alkylation of some salts of 



