Notes. Unsymmetrical bis(phosphorus) compounds: synthesis of unsymmetrical ditertiary phosphines, phosphine oxides, and diquaternary phosphonium salts

1984 ◽  
pp. 293 ◽  
Author(s):  
F. Roger Benn ◽  
Josie C. Briggs ◽  
Charles A. McAuliffe
Keyword(s):  
Phosphorus Compounds ◽  
Phosphine Oxides ◽  
Phosphonium Salts

Organophosphorverbindungen mit tertiären Alkylsubstituenten. III*: Synthese und Reaktionen Di-1-adamantylsubstituierter Phosphorverbindungen; Kristallstruktur von Di-1-Adamantylphosphinsäurechlorid / Organophosphorus Compounds with Tertiary Alkyl Substituents. Ill: Synthesis and Reactions of Di-1-adam antyl-Substituted Phosphorus Compounds; Crystal Structure of Di-1-adam antylphosphinic Chloride

1994 ◽  
Vol 49 (6) ◽  
pp. 801-811 ◽  
Author(s):  
Jens R. Goerlich ◽  
Axel Fischer ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Organophosphorus Compounds ◽  
Phosphorus Compounds ◽  
Secondary Phosphine ◽  
Phosphine Oxides ◽  
X Ray ◽  
Dry Air ◽  
Nmr Data ◽  
Standard Procedures ◽  
Hydrolysis Of ◽  
Tertiary Alkyl

The reaction of adamantane with PCl3/A1Cl3, followed by hydrolysis, gave (1-Ad)2P(:O)Cl 1, which was converted to (1-Ad)2P(:O)F 2 and (1-Ad)2P(:S)Cl 3 by standard procedures. The structure of 1 was confirmed by a single crystal X-ray structure determination; despite the bulky substituents the P-C bond lengths are normal (184.0(3), 185.0(3) pm). Whereas chlorine-fluorine exchange in 3 with AsF3 furnished (1-Ad)2P(:S)F 4, desulfuration of 3 with Ph3P to give (1-Ad)2PCl 5 failed. The secondary phosphine oxides R 1R2P(:O)H (R1, R2 = 1-Ad: 6; R1 = 1-Ad, R2 = tBu: 7; R1, R2 = tBu: 8) were synthesized by reaction of 1, 1-AdP(:O)Cl2 and tBuP(:0)Cl2 with tBuLi. 6 and 8 reacted readily with chloral to give the adducts R2P(:O)CH(OH)CCl3 (R = 1-Ad: 9; R = tBu: 10). Silylation of 6 with Me2NSiMe3 in the presence of dry air led to (1-Ad)2P(:O)OSiMe3 11, which was hydrolyzed to give (1-Ad)2P(:O)OH 12. (1-Ad)2POSiMe3 13 was obtained by the reaction of 6 with n-BuLi, followed by Me3SiCl. No reaction took place upon heating 6 with Mo(CO)6. (1-Ad)2PCl 5 was synthesized in low yield by the reaction of 6 with PCl3. The action of tetrachloro-obenzoquinone (TOB) upon 6 furnished (1-Ad)2P(:O)(o-OH)C6Cl4 15, whereas the tbutyl analogue of 15, 16, was synthesized by hydrolysis of the TOB-adduct of di-tbutylfluorophosphine. Analogous 1-adamantyl- and tbutyl-phosphorus compounds are compared with regard to their 31P NMR data

Preparation and Nuclear Magnetic Resonance Study of Phosphorus Compounds Containing Alkenyl Functional Groups

1974 ◽  
Vol 52 (9) ◽  
pp. 1714-1720 ◽  
Author(s):  
Peter W. Clark ◽  
John L. S. Curtis ◽  
Philip E. Garrou ◽  
George E. Hartwell
Keyword(s):  
Magnetic Resonance ◽  
Nuclear Magnetic Resonance Study ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Phosphorus Compounds ◽  
Proton Spectrum ◽  
Phosphine Oxides ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
Proton Decoupling

The phosphines PPhn(CH2CH2CH=CH2)3−n, n = 2–0, PPhn(CH2CH2CH2CH=CH2)3−n, n = 1 or 2, and PPh2CH2CH = CH2 have been synthesized and studied by 1H and 31P magnetic resonance. The n.m.r. spectra of PPh2(OCH2CH=CH2), its oxide, O=PPh2(OCH2CH=CH2), and its Arbuzov rearrangement product, O=PPh2(CH2CH=CH2), have been investigated by 31P decoupling of the proton spectrum, selective proton decoupling of the 31P spectrum, and comparison with computer-simulated spectra to determine the spin–spin coupling constants. The n.m.r. spectra of the related oxides O=PPh2CH2CH2CH=CH2, O=P(CH2CH2CH=CH2)3, and O=P(OCH2CH=CH2)3 are also assigned. The data indicate that 3JPH > 2JPH for alkenylphosphines, 2JPH is larger for phosphine oxides than for phosphines, and 3JPH is little changed in comparing phosphorus(III) with phosphorus(V) compounds.

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.

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