Zur Chemie der 1,3,5-Triaza-2-phosphorin-4,6-dione, Teil XIII. Darstellung und Röntgenstrukturanalyse des 1,3,5-Trimethyl-2-trichlormethyl-Derivats. Reaktionen einiger 1,3,5-Trimethyl-1,3,5-triaza-2-(R)-phosphorin-4,6-dione/Chemistry of the l,3,5-Triaza-2-phosphorine-4.6-diones, Part XIII. Synthesis and X -Ray Crystal Structure Determination of the 1,3,5-Trimethyl-2- trichlorom ethyl Derivative. Reactions of Some 1,3,5-Trimethyl-1,3,5-triaza-2-(R )-phosphorine-4,6-diones

Abstract

Abstract Upon heating 1,3,5-trimethylbiuret (1) with trichloromethyldichlorophosphine in the presence of triethylamine, 2-trichloromethyl-1,3,5-trimethyl-1,3,5-triaza-2σ3λ3-phosphorine-4,6-dione (2) was obtained in good yield. Aside from NMR spectroscopic characterization, compound 2 was investigated by X-ray crystal structure analysis, representing the first case of the solid state characterization of a 2-trihalomethyl-1,3,5-trimethyl-1,3,5-triaza-2σ3λ3-phosphorine-4,6-dione derivative. The heterocycle presents an envelope conformation with phosphorus out of the plane of the other atoms. Reaction of the monochloromethyl derivative (3) corresponding to 2, with a sterically demanding azide led by oxidation of phosphorus to the stable σ4λ5-P derivative (4). 2-Hydro-1,3,5-trimethyl-1,3,5-triaza-2-oxo-2σ4λ5-phosphorine-4,6-dione (5) reacted with p-nitrobenzylidene benzylimine with formation 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 1H NMR and IR spectroscopy. Reaction of 2-(methylamino)-methyl-1,3,5-trimethyl-1,3,5-triaza-2-oxo-2σ4λ5-phosphorine-4,6-dione (7) with diethylamino-trimethylsilane led to the corresponding N-trimethylsilylated compound 8. Compound 9. bearing a peptoid group, was formed by reaction of 7 or 8 with 3-(chloroformyl)propionic acid methyl ester. The preferred method of synthesis of 9 is indicated.