September 30, 1898.] 



SGIENOE. 



419 



2. The defines predominate in this de- 

 composition. 



3. An alcohol with w-carbon atoms is in- 

 variably formed if the acid contains n + 

 1-carbon, and its structure is not always 

 what we might expect. 



So much for the acids. Plainly this par- 

 ticular line of inquiry needs and deserves 

 further attention from the investigator. 



The changes induced in organic sub- 

 stances by the electric current are, as a 

 rule, so complex that their study is sur- 

 rounded by vastly more and greater diffi- 

 culties than obtain in the electrolysis of 

 inorganic bodies, v. Miller, recognizing 

 this feature, has adopted means of con- 

 tinuously exposing and withdrawing elec- 

 trolyzed products from the field of action. 

 In this manner he has striven to obtain a 

 more complete picture of what actually 

 occurs under the influence of the current. 

 In the electrolysis of a mixture of potas- 

 sium acetate and potassium glycoUate the 

 product was ethyl alcohol : 



CH^'bH.CoSi = K^ + 2C0. + CH3.CH,0H. 



True, the quantity of alcohol was not 

 great, but its formation was certainly very 

 significant. Through the instrumentality 

 of the current even iodine and the nitro- 

 group have been introduced into organic 

 derivatives. Thus, the electrolysis of po- 

 tassium propionate, in the presence of 

 potassium iodide, yielded ethyl iodide, and 

 that of sodium propionate and sodium 

 nitrite, nitroethane. 



Brown and Walker, keeping in view the 

 fact that Kolbe had synthesized hydrocar- 

 bons by electrolyzing fatty acids and the 

 additional knowledge that ester groups are 

 electrolytically inactive (first observed by 

 Guthrie), effected some most interesting 

 electrosyntheses, an outline of which is all 

 that I can now give you. They reasoned 

 in this way : If the mono-esters of dicar- 

 boxylic acids are electrolyzed, carbon di- 



oxide will be eliminated and a diester of 

 some higher dicarboxylic acid will be 

 formed. 



2CjH5.00C.CH,.COOK = 

 C2H5.OOC.CH2.CH2.COOC2H5 + 2CO2. 



The experiment was performed with po- 

 tassium ethyl malonate. The concentrated 

 solution of this salt was introduced into a 

 platinum crucible, which served as the 

 kathode. A heavy platinum wire, in spiral 

 form, constituted the anode. The current 

 density approached 300 amperes per square 

 decimeter. A yield of 60% of the theoret- 

 ically required succinic ester was obtained. 

 They further synthesized adipic acid and 

 sebasic acid. In all of these syntheses sec- 

 ondary changes were noticed, so that it is 

 in no wise surprising that the reaction of 

 Brown and Walker was not entirely suc- 

 cessful with the ester salts of unsaturated 

 dicai-boxylic acids, in which an ethylene 

 union is present. The ester potassium salts 

 of phthalic acid, of benzyl malonic acid and 

 the salts of oxyacids, such as malic, proved 

 unavailable for synthetic purposes. 



I must not omit mention of a rather in- 

 teresting result, recently communicated by 

 V. Miller and Hofer. As observed, these 

 chemists have entered quite largely into the 

 study of the electrolysis of what may be 

 termed mixtures. They have applied the 

 new method to tricarballylic acid with the 

 view of determining constitution. This 

 acid, as you are all aware, is tribasic : 



CH2.COOH 



I 

 CH.COOH 



CHj.COOH. 



From it we can obtain two different mono- 

 esters, two di-esters and one tri-ester. 

 Quoting von Miller and Hofer freely, I shall 

 say that there is no ordinary chemical pro- 

 cedure which will determine, for example, 

 the position of the ester groups in the di- 

 esters. So these investigators set about 



