( 352 ) 



quite analogous to my own deteruiinatiou. Tlic fact however, that 

 the ester is formed principally at the surface of the Jiquid, also if 

 a 4 N. -solution of the Ba-?,£i\i is electrolysed, seems to indicate, that 

 the COCI3 plays some role in its formation. Perhaps: 



CCI3 . CO . 0' -1- HCl + COCU ^ H,0 + CCI3 . COOCCI3 ? 

 As this substance has always been previously described as a li(piid, 

 we must assume that it remains readily in the condition of an under- 

 cooled melt; this also in connection with the low melting-point and 

 the depression tliereof caused by the HJJ and the decomposition 

 products ^). Indeed afterwards I found, that the pure ester, prepared 

 by chlorination of trichloroacetic-methylester in the sunlight, remains 

 liquid in a closed, evacuated vessel for several months ! 



In dry ether it dissolves readily ; in alcohol or moist ether with 

 violent evolution of gas. With NH^ it forms a white crystalline 

 substance of a comparatively high melting-point, which appears to 

 be trichloroacet amide. 



I also wish to observe that catalysts such as A/.JJ/,.,, for instance, 

 readily split the ester into CXV^ + CO^. It would not be a matter 

 of surprise, if also the catalytic action of the light could do this. 

 In that case the photochemical decom|)osition of the ferric salt, the 

 formation therein of CO^, C^Clf^, HCl, and free CCl^ . COOH, might 

 be explained l\y assuming an intermediary formation of this substance; 

 we should then have a complete analogy of the photochemical reac- 

 tion with an electrolytic process. If, however, this should not be the 

 case, — and up to the present, everything points to this, — the form 

 of the said photochemical reaction does not seem to tally either with 

 the one or the other of the two theoretical views. 



§ 10. The fact that this singular compound is given in Bkii.stkin's '-) 

 manual as being identical with the jxnitucJiloivctliiil-estei' of chluro- 

 fonnic acid induced me to more carefully study both substances. 

 During this investigation I came across a shoi't treatise of Anschütz 

 and EMÉin^'), which authors had altcady prepared l)Otli compounds 

 in 1893 for e.vactly the same purpose. Although my results agree 



1) It should be ol>served thai the formation of a coinijoand : CY'Aj . CO . OC'CV^ ii) 

 the electfolysls of trichloroacetic acid is in complete accord willi the experiences 

 of G. Herzog (Diss. Zurich 1909), who observed with monochloro-, monobromo- 

 and dichloroacelic acid the formation of the analogously constituted esters during 

 the electrolysis of the sodium salts. 



~) Beilstein's Manual, Vol. 1. -171. (1893); corrected in Suppl. Vol. I. p. 167. 

 (1901). 



'■'■) Anschütz and Emery, Ann. der Cliem. 273. 56. (1892). 



