Chemistry of the 1,3,5-Triaza-2-phosphorin-4,6-diones, Part XII*. Synthesis and Characterization of 2-PhenyI-2-(p-tolylthio)-1,3,5- trimethyI-1,3,5-triaza-4,6-dione-2-phosphorinonium Salts

Abstract

The reaction of 1,5-bis(trimethylsilyl)-1,3.5-trimethylbiuret (1) with p-tolylsulfenyl chloride (2) furnished l-(p-tolylthio)-5-trimethylsilyl-1,3,5-trimethylbiuret (3). In the reaction of 3 with phenyldichlorophosphine, 2-phenyl-2-(p-tolylthio)-1,3,5-trimethyl-1,3,5-triaza-4,6-dione- 2-phosphorinonium chloride (4) was formed. The same product was obtained from the reaction of 2-phenyl-1,3,5-trimethyl-1,3,5-triaza-2λ3- phosphorin-4,6-dione (6) with p-tolylsulfenyl chloride (2). Compound 4 was isolated and characterized in the form of the hexachloroantimonate (4a). The spirophosphorane 2-phenyl-1,3,5-trimethyl-1,3,5-triaza-7,10-dioxa-8,9- perchlorobenzo-2λ5-phosphaspiro-[4.5]decan-4,6-dione (7) was prepared by the reaction of 4 with tetrachloroorthobenzoquinone. The new products were characterized by 1H - and 13C NMR spectroscopy, elemental analysis, 31P NMR spectroscopy in the case of 4a. 6 and 7, and mass spectrometry (4a). Single-crystal X-ray structural analyses of compounds 4a and 7 were conducted. The phosphorus atom of 4a has the expected tetrahedral geometry, with a rather short P-S bond of 204.9(2) pm. In 7 the geometry at phosphorus is almost ideal trigonal bipyramidal. Weak hydrogen bonds are formed from a C (:O) group to deuterochloroform of solvation.

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

“…In den letzten fünf Jahren w urde die V erbin dungsklasse d er l,3,5-T riorgano-l,3,5-triaza-2phosphorin-4,6-dione eingehend untersucht [1] und eine Vielzahl von V erbindungen m it P hosphor in unterschiedlichen O xidations-und K oordina tionszahlen beschrieben.…”

“…Von besonderem Interesse w ar die D a r stellung und röntgenographische U ntersuchung des 2-trichlorm ethylsubstituierten D erivates, da * Teil I-X II siehe Lit. [1], ** Sonderdruckanforderungen an R. Schmutzler. die S tru k tu r entsp rech en d er V erbindungen mit stark elektronegativen, an Phosphor gebundenen G ru p p e n (wie z.…”

“…52b, 1510-1516 (1997); eingegangen am 6. August 1997 l,3,5-Trimethyl-l,3,5-triaza-2-(R)-phosphorine-4,6-diones, Staudinger Reaction, Diastereotopy, Peptoid Group, X-Ray Upon heating 1,3,5-trimethylbiuret (1) with trichloromethyldichlorophosphine in the pres ence of triethylamine, 2-trichloromethyl-l,3,5-trimethyl-l,3,5-triaza-2a3A3-phosphorine-4,6dione (2) was obtained in good yield. Aside from NMR spectroscopic characterization, com pound 2 was investigated by X-ray crystal structure analysis, representing the first case of the solid state characterization of a 2-trihalomethyl-l,3,5-trimethyl-l,3,5-triaza-2cr,/l3-phosphorine-4,6-dione derivative.…”