Manfred Spahn

DIE REAKTION VON 1,1,3,3-TETRAKIS-(DIMETHYLAMINO)-DIPHOSPHET MIT SCHWEFELKOHLENSTOFF, I

Abstract 1,1,3,3-Tetrakis(dimethylamino)-diphosphete, 1, reacts with CS2 to give 1,1,3,3-tetrakis(dimethylamino)-1-phospha-3-phosphonium-2-dithio-carboxylato-cyclobutene-1, 2. The new compound is characterized by its nmr-, mass-, and ir-spectra. 1,1,3,3-Tetrakis(dimethylamino)-diphosphet, 1, reagiert mit CS2 zu 1,1,3,3-Tetrakis(dimethylamino)-1-phospha-3-phosphonium-2-dithio-carboxylato-cyclobuten-1, 2. Die neue Verbindung ist durch ihre NMR-, Massen- und IR-Spektren charakterisiert.

Neue Carbodiphosphorane. Notiz zur Reaktion zwischen Bis(dimethylamino)fluormethylidenphosphoran und n-Butyllithium / New Carbodiphosphoranes. Note on the Reaction between Bis(dimethylamino)fluoromethylidene-phosphorane and n-Butyllithium

The main product from the reaction between bis(dimethylamino)fluoromethylidene-phosphorane (1) and n-butyllithium in the presence of tetramethylethylenediamine is n-butyl-dimethylamino-methyl-{[tris(dimethylamino)phosphoranylidene]methylene}-phosphorane (7). As a by-product from the reaction between methyl-bis(dimethylamino)difluorophosphorane and n-butyllithium bis(dimethylamino)-methyl-{[n-butyl-bis(dimethylamino)phosphoranylidene]methylene}-phosphorane (9) was isolated in small yield. The new carbodiphosphoranes 7 and 9 are characterized by their 1H, 13C, and 31P NMR and mass spectra.

The first 1λ5,3λ5,5λ5-triphosphabenzene derivative

The synthesis, NMR data and an X-ray structural analysis of 1,1,3,3,5,5-hexakis(dimethylamino)- 1λ5,3λ5,5λ5-triphosphabenzene (3) are described.

Neue 1-Aza-2 λ5, 4 λ5-diphosphirine (2 λ5, 4 λ5-Diphosphapyridine) / New 1 -Aza-2λ5, 4λ5-diphosphirines (2λ5, 4λ5-Diphosphapyridines)

6-(Furan-2-yl)-2,4-tetrakis(dimethylamino)-1-aza-2λ5, 4λ5-diphosphirine (2) and 6-(N-pyrrolidinyl)-2,4-tetrakis(dimethylamino)-1-aza-2λ5, 45-diphosphirine (3) were prepared by reacting 1,1,3,3-tetrakis(dimethylamino)-1 λ5,3 λ5-diphosphete with 2-cyanofuran, and N-cyanopyrrolidine, respectively. 2 and 3 are characterized by their physical properties, NMR, IR, and mass spectra. In 2 two 6J(PH) long range coupling constants could be identified.

λ5-Diphosphacyclobutadienes and Their Reactions

Abstract In earlier work the synthesis of λ5-diphosphacyclo-butadienes (diphosphetes) has been described:1,2 They can be conceived as twofold cyclic ylides with highly cabanionic carbon atoms3 and their chemical behaviour can best be interpreted on this basis. With R-C-P (R=t-bu), the lλ5, 3λ5,5λ3-triphosphinine I is formed4, while reaction with acetylenedialkoxycarboxylates yields the first 1λ5,3λ5-diphosphinines5: Reactions of diphosphetes with HC-C-COOR, (FgCg)-C=N and ROOC-C-N also yield new heterocyclic systems.