Manfred Kubjacek

Fluordiazadiphosphetidine, 10. Mitt.: Die Reaktion von 1,3-Dialkyl-2,2,2,4,4,4-hexaflouro-1,3,2λ5,4λ5-diazadiphosphetidine mitN-Trimethylsilylmethylamin

Reaction of (RNPF3)2 compounds (R=CH3, C2H5,n-C3H7,n-C4H9,i-C4H9) withN-trimethylsilyl-methylamine leads to nucleophilic substitution of one or two fluorine atoms by the methylamino group, depending on the molar amounts of the reactants. In the case ofR=CH3, two by-products are formed: in the first step a compound with coordination numbers IV, V and VI for the three phosphorus atoms in C5H17F7N5P3 and in the second step a monospiroflourodiaza-λ5, λ5-diphosphetidine.

Fluordiazadiphosphetidine, 7. Mitt. Die reaktion von 2,2,2,4,4,4-Hexafluoro-1,3-dimethyl-1,3,2λ5,4λ5-diazadiphosphetidin mit mono-und bissilyliertemN,N′-Dimethylharnstoff

The reaction of (CH3NPF3)2 with mono-and bissilylatedN,N′-dimethylurea yields a crystalline solid which has been identified as a cuban-like P-N-compound with two dimethylurea-bridges. The conditions of formation and the NMR-spectra are discussed.

Fluordiazadiphosphetidine, 5. Mitt.

Reaction of (CH3NPF3)2 with equimolar amounts of N-methylhexamethyldisilazane yields a reaction product, which can be separated in a polymer and a crystalline fraction. High-vacuum sublimation of the crystalline part yields the already known compound (CH3N)4P3F7, the new spiro-isomer F3P(CH3N)2PF(CH3N)2PF3 and the spiro-compound F3P(CH3N)2PF(CH3N)2PF(CH3N)2PF3, an isomer of the known compound (CH3N)6P4F8.

Fluordiazadiphosphetidine, 16. Mitt.

The reaction of (CH3NPF3)2 with NH3 and primary aliphatic and aromatic amines in the molar ratio 3:2 yields (CH4NPF4)2 and the monoamino substituted fluordiaza-diphosphetidines. These react with N-Trimethylsilyl-methylamine to the mixed diamino substituted compounds.With 1,4-Diazabicyclo[2.2.2]octan as HF-acceptor a second step of nucleophilic substitution with NH3 and primary amines is possible. In the case of ammonia a by- product has been identified as the 1:1 adduct of (CH3NPF2NH2)2 with 1,4-diazabicyclo[2.2.2]octan.

Fluordiazadiphosphetidine, 11. Mitt.: Eine neue Methode zur Herstellung der doppelt zwitterionischen Verbindung (CH3N)6P4F8

A new synthetic route for the preparation of the betain-like compound (CH3N)6P4F8 from (CH3NPF3)2,N-methyl-hexamethyldisilazane andN,N′-dimethyl-urea has been found. The steps of this multi-stage reaction could be rationalized to a far extent.