202 Proceedings of Indiana Academy of Science 
weight of the two acyl groups concerned, or whether the latter possess 
carbonyl or carboxyl groups. Neither does the substitution of negative 
groups about the benzene nucleus affect the tendency to rearrange. 
The purpose of this investigation has been principally (1), to 
determine whether closely related alkyl radicals in the aliphatic acyl 
groups affected the rearrangement, and (2) to determine whether the 
same alkyl radical in the different acyl groups affected the rearrange- 
ment. 
EXPERIMENTAL PART. 
Acetyloxyphenylurethane, (CH;CO.OC;H:NHCO.C:H;), was prepared 
from oxyphenylurethane and acetic anhydride in alkaline solution. 
White needle-like crystals melting at 72.9° to 73.4° were obtained from 
ligroin. On saponification oxyphenylurethane was obtained, showing the 
carbethoxy group to be attached to the nitrogen in acetyloxyphenyl- 
urethane. 
Action of Ethylchloformate on o-Acetylaminophenol. 
When o-acetylaminophenol, (HOC;,H:NHCOCH;), is treated with 
ethylchlorformate in alkaline solution acetyloxyphenylurethane, and not 
its isomer, is obtained. The product of saponification is oxyphenylure- 
thane, showing the carbethoxy group attached to the nitrogen where the 
acetyl group had been. 
In connection with the behavior of the acetyl group, Raiford’s 
work with unsubstituted o-aminophenol was repeated and the exchange 
of position between the acetyl and benzoyl groups observed. 
Propionyloxyphenylurethane, (C:H;CO.OC,H:NHCO.C.H;), was pre- 
pared from oxyphenylurethane and propionic anhydride in alkaline so- 
lution. Crystals of long, white, silken needles melting at 41.7° to 42.4° 
were obtained from dilute alcohol. Saponification showed the car- 
bethoxy group to be attached to the nitrogen. 
Propionl-o-aminophenol, (HOC,H:NHCOC.H;), was prepared from 
o-aminophenol and propionyl chloride in ether solution. Small white, 
cubical crystals melting at 76.2° to 77.2° were obtained from ligroin 
slightly diluted with ether. 
Action of Ethylchlorformate on Propionyl-o-aminophenol. 
On treating propionyl-o-aminophenol, in alkaline solution, with 
ethylchlorformate a diacyl compound is formed identical with, and in 
fact is, propionyloxyphenylurethane. Saponification yields oxyphenyl- 
urethane, showing that the carbethoxy and the propionyl groups had 
exchanged places. 
When two closely related alkyl radicals, one being attached to the 
carbonyl group and the other to a carboxy group, are used in the prep- 
aration of a diacyl derivative of o-aminophenol, the acyl group con- 
taining the carboxy group is always found attached to the nitrogen. 
When necessary a molecular rearrangement takes place to effect this. 
When the same alkyl radical is used, in one case attached to a 
carbonyl group and in the other to a carboxy group, the acyl group 
containing the carboxy group, again, is found attached to the nitrogen. 
Purdue University. 
