148 



from dilute alcohol the crystals became white and melted at 65°-G6°. It is 

 insoluble in water, acids and alkalis, but soluble in alcohol, ether, chloro- 

 form, and benzol. 



ACTION OF C'HLORC.\RBONICISOAMYLETHEn ON OXYPHENYLETHYLURETHANE. 



The ethylurethane was prepared according to Ransom's method and two 

 grams of it were dissolved in a slight excess of potassium hydroxide. To this 

 was added the calculated amount (1 mol.) of chlorcarbonicisoamylether. 

 After shaking, a light yellow oil separated which became darker on standing. 

 This was extracted with ether and the ether allowed to evaporate. An oil 

 remained which refused to solidify even in a freezing mixture. It was dis- 

 tilled under a pressure of 15 mm. at 184°-190°, the distillate solidifying to a 

 crystalline mass. After several recrystallizations it became white and melted 

 at 65°-66°. It has all the properties of its supposed isomer above described. 

 On saponifying some of the impure material two substances were obtained. 

 A part melted at 133°-134° and is i)robabl\- carbonylaminoi)henol produced 

 from the urethane by loss of alcohol. The other part after purification melted 

 at 84°-85'' and on mixing with oxyphenjdethylurethane (m. p. 86-87) the melt- 

 ing point was raised slightly. Evidently the carbethoxy group remains at- 

 tached to nitrogen and no rearrangement occurs in preparing the diacyl deriv- 

 ative by this method. Since the supposed isomer is identical with this, there 

 must have been a rearrangement during its preparation in the sense that the 

 two carboxyl radicals exchanged places, the lighter changing from oxygen to 

 nitrogen. The following equations express the reactions involved and the 

 rearrangement that must have occurred in one case. KOC6H4NHCOOC6H11 

 4- ClCOOCoHr, > CcHr,OOCOC6H4XHCOOC5H„ -f KClC2Hf,OOCOC6Tl4NH- 

 COOC5H,, > CsHMOOCOCeHiXHCOOC.II.. The final product is o-oxy- 

 phenylethyhu'ethaneisoamylcarbonate. 



SU.MMAKY. 



The work here outlined, together with that previously rejiorted, shows 

 that when two carboxyl radicals ^CC)()H and COORi) are introduced into the 

 molecule of ortho aminophenol the lighter one becomes attached to the amide 

 nitrogen, the position not being influenced by tlic order in wliidi the grou])s 

 are introduced. .\nd that to accomijli.sh tliis a molecular rearrangement 

 occurs in one case. This is also true when botli ladicals are carbonyls (COR 

 and CORi). In case one radical is carbonvl and the other carboxvl the latter 



