VOL.
XXII.
[JULY,
No. 7 .
rgoo.]
THE JOURNAL OF T H E
AMERICAN CHEMICAL SOClETY. [CONTRIBUTIONSFROM
THE
SHEFFIELD LABORATORY OF YALE UNIVERSITY. ]
ON UREAIMIDO ESTERS, THIOUREAInIDO ESTERS, ACYLTHIOUREAIMIDO ESTERS, AND UREAAMIDINES. [PRELIMINARY PAPER.] B Y HENRYL. W H E E L E R AND
R
W.M U R R A Y
SANDERS.
EPRESENTATIVES of new classes of compounds, isomeric
or metameric with the acylpseudourea ethers, acylpseudothiourea ethers and diacylpseudothiourea ethers, can be prepared by combining isocyanates, mustard oils, and acyl rhodanides with imido esters. T h e imido esters immediately combine with phenyl isocyanate, at ordinary temperatures, giving a quantitative yield of an addition product as follows: NOONHC,H, C6HSC HNH+CONC,Hs = C,H,C // \OR \OR This class of compounds, perhaps, may be called ureainlido esters or carbamidimido esters, since they have the structure of imido esters and ureas combined. They are extremely sensitive towards hydrogen chloride by which reagent, just as the acylpseudourea ethers’ (11)they are readily and quantitatively converted in the cold, with loss of alkyl chloride, into acylureas. 1
StieglitzanriDains: This Jourual, ai, 136.
366
H E N R Y L. W H E E L E R A N D W. X C R R A T S.4NDERS.
This reaction with these two classes of compounds proceeds as follo.cvs : Ce,H,C=NCONHCaH, C,H,CON=C-NHC,H,
\
OR +HCl - RCl
-
(11)
-C,H,CON HCON H C,H, I t will be noticed that the imido ester grouping in the different positions in these isomers are affected alike, inasmuch as under similar conditions both compounds give with hydrogen chloride the same derivative, benzoylphenylurea. The ureaimido esters ( I ) readily react with aniline, at the temperature of the steambath, and ureaamidines are formed as follows: NCONHC,H, NCONHC,H, C,H,CN H,NC,H, = C,H,CN ROH \OR \NHC,H,
+
+
(111)
Whether the structure shown in formula (111) or the tautomeric form is to be assigned to these amidines must be decided later. These amidines have little or no basic properties. T h e mustard oils, phenylmustard oil and allyl mustard oil, react less energetically than phenyl isocyanate with the imido esters. On long standing or on warming, the mixtures deposit crystals. These compounds, for which the name thioureaimido esters (TV)is proposed, are closely similar to the above oxygen analogues, since with hydrogen chloride, under similar conditions, they readily separate alkyl chloride and give the corresponding acylthio ureas. T h e mechanism of the reaction is as follows: NCSNHC,H, NHCSNHCBH, C6HsC,0R -C,H,C
