CHEMISTRY OF THE 1,3,5-TRIAZA-2-PHOSPHORI NE-4,6-DIONES, PART XIII - SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE DETERMINATION OF THE 1,3,5-TRIMETHYL-2-TRICHLOROMETHYL DERIVATIVE - REACTIONS OF SOME RIMETHYL-1,3,5-TRIAZA-2-(R)-PHOSPHORINE-4,6-DIONES

Upon heating 1,3,5-trimethylbiuret (1) with trichloromethyldichloropho sphine in the presence of triethylamine, methyl-1,3,5-trimethyl-1,3,5- phosphorine-4,6-dione (2) was obtained in good yield. Aside from NMR s pectroscopic characterization, compound 2 was investigated by X-ray cr ystal structure analysis, representing the first case of the solid sta te characterization of a 2-trihalomethyl-1,3,5-trimethyl-1,3,5-triaza- 2 sigma(3) lambda(3)-phosphorine-4,6-dione derivative. The heterocycl e presents an envelope conformation with phosphorus out of the plane o f the other atoms. Reaction of the monochloromethyl derivative (3) cor responding to 2, with a sterically demanding azide led by oxidation of phosphorus to the stable sigma(4) lambda(5)-P derivative (4). 2-Hydro -1,3,5-trimethyl-1,3,5-triaza-2-oxo-2 sigma(4) lambda(5)- phosphorine- 4,6-dione (5) reacted with p-nitrobenzylidene benzylimine with formati on of 6 by insertion of the C=N double bond of the imine into the P-H bond. Intramolecular hydrogen bonding in 6 was observed by H-1 NMR and IR spectroscopy. Reaction of ylamino)methyl-1,3,5-trimethyl-1,3,5-tri aza-2-oxo- 2 sigma(4) lambda(5)-phosphorine-4,6-dione (7) with diethyl amino-trimethylsilane led to the corresponding N-trimethylsilylated co mpound 8. Compound 9, bearing a peptoid group, was formed by reaction of 7 or 8 with 3-(chloroformyl)propionic acid methyl ester. The prefer red method of synthesis of 9 is indicated.