148 



from dilute alcohol the crystals became white and melted at 6o°-66°. It is 

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

 form, and benzol. 



.VCTION OK CHLORCARBONK'ISO.\MYLETHER ON OXYPHENYLETHYLtlRETHANE. 



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 

 crj'stalline 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 imp\u-e material two substances were obtained. 

 A part melted at 133°-134° and is probably carbonylaminophenol produced 

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

 at 84°-8o° and on mixing with oxyphenylethylurethane (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 jn-eparing 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 anil the 

 rearrangement that must have occurred in one case. KOC6H4NHCOOC5H11 

 + CICOOC2H, > C:H,,0()COC6H4NHCOOC.Hu + KClCaH.OOCOCeH.NH- 

 COOCsHi, > CrJInOOCOCeH^NHCOOCdl;,. The final product is o-oxy- 

 phenylethylurethaneisoamylcarbonate. 



SUMM.VRY. 



Tlie work here outlined, togethei- witli that |)reviously icported. shows 

 that when two carboxyl radicals K'OOK and C'OOR,) arc introduced into the 

 molecule of ortho aminopheno! tlic lighter one beconu's attaclicd to the ;nni(h' 

 nitrogen, tlie position not being inllnenccd by the older in wliidi tlie gi-oui)s 

 are inti'oduced. .\nd th.'it to accoiiiplisli tliis a nioh'culai' I'earrangenient 

 occurs in one case. Tliis is also true when liotli radicals .-iif carljonyls (('()1{ 

 .and COKi). In case one radical is carboUNl and the other carbowl liie latter 



