Synthesis of the P-sulfide derivatives of 3-phosphabicyclo[3.1.0]hexanes and 1,2-dihydrophosphinines

Several 3-phosphabicyclo[3.1.0]hexane 3-oxides have been transformed into the corresponding sulfides by reaction with phosphorus pentasulfide. The 3-phenyl derivative could also be prepared by deoxygenation of the oxide followed by reaction with elemental sulfur. Opening of the cyclopropane ring in phosphabicyclohexane sulfides afforded mixtures of 3- and 5-methyl-1,2-dihydro-phosphinine-1-sulfides. Because of better yields, preparation of these products by thionation of the dihydrophosphinine oxides is more appropriate. The new phosphorus heterocycles have been characterized by 31P, 13C, and 1H NMR and mass spectral data.

[1]  G. Keglevich,et al.  P-Substituted 3-phosphabicyclo [3.1.0] hexane 3-oxides from diastereoselective substitution at phosphorus , 1993 .

[2]  L. D. Quin,et al.  Photochemical fragmentation of the 2‐phosphabicyclo[2.2.2]octa‐5,7‐diene ring system as a versatile method for generating 3‐coordinate methylene phosphine oxides and sulfides , 1993 .

[3]  K. Újszászy,et al.  Convenient synthesis of 1‐alkoxy‐di‐ and tetrahydrophosphinine 1‐oxides by ring enlargement , 1993 .

[4]  C. Reese,et al.  Dibenzoyl tetrasulphide - A rapid sulphur transfer agent in the synthesis of phosphorothioate analogues of oligonucleotides , 1992 .

[5]  L. Ricard,et al.  Reaction of phosphole sulfides with diazoalkanes as a new route to phosphinines , 1991 .

[6]  G. Keglevich,et al.  Convenient synthesis of 1‐alkoxy‐1,2‐dihydrophosphinine 1‐oxides by ring enlargement , 1990 .

[7]  V. Fülöp,et al.  THE STEREOCHEMISTRY OF THE DICHLOROCYCLOPROPANATION REACTION OF 2,5-DIHYDRO-LH-PHOSPHOLE1-OXIDES , 1990 .

[8]  L. D. Quin,et al.  Thionation Studies on a 2,3-Oxaphosphabicyclo(2.2.2)octene Derivative. O-C Bond Cleavage with Incorporation of the Species ArPS2. , 1989 .

[9]  G. Keglevich,et al.  Synthesis of dihydrophosphorins by the thermal transformation of phosphole-dichlorocarbene adducts , 1988 .

[10]  L. D. Quin,et al.  Ring expansion in the addition of dichlorocarbene to 2,5-dihydro-1H-phosphole 1-oxides , 1987 .

[11]  F. Mathey,et al.  DONNEES COMPLEMENTAIRES SUR LA CONVERSION DES PHOSPHOLES EN PHOSPHORINES , 1984 .

[12]  C. Santini,et al.  Phosphole [2 + 2] and [4 + 2] dimerizations around metal carbonyl moieties. Structure and chemistry of a new type of exo [4 + 2] dimers , 1980 .

[13]  G. Märkl,et al.  4‐Methylen‐phosphacyclohexa‐2,5‐diene , 1966 .

[14]  H. Olbrich,et al.  Derivatives of Phospha‐2,5‐cyclohexadien‐4‐one and 4,4′‐Diphosphabi‐(2,5‐cyclohexadienylidene) , 1966 .

[15]  L. Horner,et al.  Phosphororganische Verbindungen, XIX. Reduktion von Phosphorverbindungen mit Alkalimetallen , 1959 .

[16]  L. Ricard,et al.  Persulfuration of phosphinines: Synthesis and X‐ray crystal structure analysis of a P2S3 derivative , 1990 .

[17]  F. Mathey,et al.  Generation anf trapping of a C-unsubstituted methylenephosphine sulphide , 1984 .

[18]  F. Mathey,et al.  Acces aux [pyridyl-2′]-2 phosphorines , 1982 .

[19]  L. Horner,et al.  Phosphororganische Verbindungen 1001 Thiophosphylverbindungen Durch-Austausch , 1982 .

[20]  F. Mathey.  Synthese de la phenyl-2-dimethyl-4,5-phosphorine a partir du benzyl-1-dimethyl-3,4-phosphole , 1979 .

[21]  G. Märkl,et al.  Synthese und reaktionen eines phospha-cyclohexadienons , 1968 .