Cyclopolymerization of Diallyldiphenylphosphonium Salts. Polymeric Phosphonium Salts, Phosphine Oxides, and Phosphorus Ylides

1995 ◽  
Vol 28 (9) ◽  
pp. 3055-3066 ◽  
Author(s):  
Dietmar Seyferth ◽  
T. Craig Masterman
Keyword(s):  
Phosphine Oxides ◽  
Phosphonium Salts ◽  
Phosphorus Ylides

scholarly journals Reactivity of allenylphosphonates/allenylphosphine oxides – some new addition/cycloaddition and cyclization pathways

2019 ◽  
Vol 91 (5) ◽  
pp. 773-784 ◽  
Author(s):  
K. C. Kumara Swamy ◽  
Mandala Anitha ◽  
Shubham Debnath ◽  
Mallepalli Shankar
Keyword(s):  
Nmr Spectra ◽  
Electrophilic Addition ◽  
Cycloaddition Reactions ◽  
Phosphine Oxides ◽  
Iodine Monochloride ◽  
Phosphonium Salts ◽  
Hydroxymethyl Group ◽  
X Ray ◽  
Cycloaddition Product ◽  
Work Done

Abstract In this paper, we highlight some addition/cycloaddition reactions of allenylphosphonates and allenylphosphine oxides, mostly based on the work done in our laboratory. Thus the electrophilic addition of iodine monochloride (ICl) with allenylphosphine oxides affords cyclic phosphonium salts rather than γ-chloro-β-iodovinylphosphine oxides (NMR, HRMS, X-ray) that exhibit rather unusual downfield shifts in the 31P NMR spectra. These compounds undergo hydrolysis to afford γ-hydroxy-β-iodovinylphosphine oxides; the hydroxymethyl group in these compounds can be oxidized by Dess-Martin periodinane to afford the corresponding aldehyde-substituted vinylphosphine oxides. A [2+2] cycloaddition product of an allenylphosphonate has also been structurally characterized. Other reactions that are highlighted include those leading to (Z)/(E)-β-aminovinylphosphonates, β-ketophosphonates (and their utility in Horner-Wadsworth-Emmons reaction), indolyl/furanyl/isocoumaranyl/naphthyl phosphine oxides, thiophosphorylated phosphonates and azo-substituted coumarin phosphonates.

Mercury(II) complexes of new bidentate phosphorus ylides: synthesis, spectra and crystal structures

2014 ◽  
Vol 68 (5) ◽  
Author(s):  
Seyyed Sabounchei ◽  
Mohammad Panahimehr ◽  
Hamid Khavasi ◽  
Fateme Bagherjeri ◽  
Collete Boscovic
Keyword(s):  
Single Crystal ◽  
Nmr Spectra ◽  
Mononuclear Complex ◽  
13C Nmr Spectra ◽  
Phosphonium Salts ◽  
X Ray Diffraction ◽  
Phosphorus Ylides ◽  
X Ray ◽  
Mononuclear Complexes ◽  
Tetrahedral Environment

AbstractThe reaction of dppm (1,1-bis(diphenylphosphino)methane) with 2-bromo-4-phenylacetophenone and benzyl bromoacetate in chloroform produces new phosphonium salts, [Ph2PCH2PPh2CH2C(O) C6H4Ph]Br (I) and [Ph2PCH2PPh2CH2COOCH2Ph]Br (II). By allowing the phosphonium salts to react with the appropriate base, the bidentate phosphorus ylides, Ph2PCH2PPh2=C(H)C(O)C6H4Ph (III) and Ph2PCH2PPh2=C(H)C(O)OCH2Ph (IV), were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes {HgX2[(Ph2PCH2PPh2C(H)C(O)C6H4Ph)]} (X = Cl (V); X = Br (VI); X = I (VII)) and {HgX2[(Ph2PCH2PPh2C(H)COOCH2Ph)]} (X = Cl (VIII); X = Br (IX); X = I (X)). The FTIR and 1H, 31P and 13C NMR spectra were studied. The structure of compound III was unequivocally determined by the single-crystal X-ray diffraction technique. Single-crystal X-ray analysis of the {HgBr2[(Ph2PCH2PPh2C(H)C(O)C6H4Me)]} complex (XI) revealed the presence of a mononuclear complex containing the Hg atom in a distorted tetrahedral environment. In all complexes, the ylides referred to above were coordinated through the ylidic carbon and the phosphine atom.

Ein- und Zweielektronen-Oxidation von Phosphor-Yliden mit Kupfer(II)-Salzen / One- and Twoelectron Oxidation of Phosphorus Ylides Using Copper(II) Salts

1984 ◽  
Vol 39 (5) ◽  
pp. 618-622 ◽  
Author(s):  
Graham A. Bowmaker ◽  
Cornelia Dörzbach ◽  
Hubert Schmidbaur
Keyword(s):  
Electron Transfer ◽  
Oxidative Coupling ◽  
Radical Cations ◽  
High Yield ◽  
Phosphonium Salts ◽  
Analogous Reaction ◽  
Phosphorus Ylides ◽  
Radical Trapping ◽  
Anhydrous Tetrahydrofuran ◽  
Plausible Mechanism

The reaction of CuCl2 with equimolar quantities of an ylide R3P=CH2 (1a-c, R=CH3, C2H5, C6H5) in anhydrous tetrahydrofuran at low temperature leads to oxidative coupling, with ethylidene-1,2-bis-phosphonium salts R3P⊕-CH2-CH2-P⊕R3 2X⊖ (2, 3a-c) as high- yield products. The process is interpreted as a one-electron transfer to give radical cations R3P⊕-ĊH2 (II) which subsequently undergo dimerization. The initial counterions CuCl2⊖ (in 2a-c) can be replaced by PF6⊖ (as in 3a-c). (C2H5)3P=CHCH3 (1d) yields the cation (C2H5)3P⊕-*CH(CH3)-*CH(CH3)P⊕(C2H5)3 with two chiral centers as a mixture of diasteromers RR/SS, RS. The ratio of the components is 2,8:1. as evaluated by NMR spectroscopy.The analogous reaction with (C6H5)3P=CHCH3 and (C6H5)3P=C(CH3)2 (1e, f) takes a very different course. Along with minor quantities of (C6H5)3P⊕CH2CH3/(C6H5)3P⊕CH(CH3)2 species, mainly 1-chloroalkyl-phosphonium cations are formed, which were again isolated as the hexafluorophosphates (4a, 4b: [(C6H5)3P⊕CH(CI)CH3]PF6⊕, [(C6H5)3P⊕C(Cl)(CH3)2]Pf6⊖). H-radical trapping from the medium by II ist proposed for the formation of the former, while a two- electron oxidation followed by addition of Cl⊖ is the most plausible mechanism for the generation of the latter

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