Investigation of reaction intermediates of the urea-diacetylmonoxime reaction.
1. An investigation of the intermediates of the urea-diacetylmonoxime reaction and the isolation of the protochromogen has been described. A comparative spectral study of the protochromogen with that of the literature values suggested the structure of the protochromogen to be a diureide. 2. The diureides of 1-phenyl-1,2-propanedione-monoxime and 2,3-pentanedione were synthesized and their visible, U.V., I.R., NMR, and mass desorption spectrometry data were analyzed. The study suggests that the structure of each of these compound is that of a diureide. When these diureides were redissolved in acid media, they gave the color expected of the corresponding chromogens found from the respective diketones and urea. 3. The 3a-methyl-6a-phenyl-glycoluril was synthesized by a base-catalyzed reaction. When this glycoluril was dissolved in concentrated HCl, a pink color was obtained, similar to that of the corresponding diureide. These studies indicate that both the diureide and the glycoluril (if formed at all in acid-catalyzed reaction) are converted to the same chromogen, possibly via a rearrangement. 4. When 2,3-butanedionemonoximethiosemicarbazone was reacted with urea in acid medium, characteristic spectral data were obtained which were very similar to those of the urea-diacetylmonoximethiosemicarbazide reaction. This tends to indicate that the possible structures of the protochromogens are similar and of the open chain diureide type.