- Reductive Rearrangement of Tetraphenyldiphosphine Disulfide To Trigger the Bisthiophosphinylation of Alkenes and Alkynes
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The facile synthesis of organophosphorus compounds is of great importance for the development of new synthetic methods by using air-stable sources of phosphorus. In this respect, a synthetic method that is based on a reductive rearrangement and is capable of converting air-stable pentavalent phosphorus compounds into reactive trivalent phosphorus compounds is a powerful tool. Tetraphenyldiphosphine disulfide, which is a shelf-stable solid, was the focus of this study, and it was shown to undergo reductive rearrangement to trigger the bisthiophosphinylation of a variety of alkenes, such as terminal, cyclic, internal, and branched alkenes, 1,3-dienes, and terminal alkynes when exposed to light without any catalyst, base, or additive.
- Sato, Yuki,Nishimura, Misaki,Kawaguchi, Shin-ichi,Nomoto, Akihiro,Ogawa, Akiya
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- Room-temperature reduction of sulfur hexafluoride with metal phosphides
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Upon treatment with sulfur hexafluoride, alkali metal diphenyl or dicyclohexyl phosphides are oxidized within seconds to tetraphenyl or tetracyclohexyl diphosphines. When bulky di-tert-butylphosphide is employed, fluorophosphine intermediates are detected. This is the first reported reaction of sulfur hexafluoride with metal phosphides, and a rare example of reactivity of sulfur hexafluoride at ambient temperature. This journal is
- Huchenski, Blake S. N.,Speed, Alexander W. H.
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supporting information
p. 7128 - 7131
(2021/07/28)
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- Preparation method of phosphinate, phosphinate and non-aqueous electrolyte
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The present invention provides a method for preparing phosphinate, the phosphinate and a non-aqueous electrolyte. The method for preparing the phosphinate comprises the following steps: (1) reaction of Grignard reagent R1MgX with thiophosphoryl halide X3P=S in a solvent to obtain a first intermediate; (2) reaction of halogenating agent M' Xa and the first intermediate to obtian a second intermediate; and (3) reaction of the second intermediate with R2OH and water to obtain the phosphinate; wherein R1 and R2 are each selected from the group consisting of hydrocarbon groups or an organic group containing at least one element of boron, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine, and iodine; X represents a halogen; M' represents a metal element; and a representsa valence of the metal element M'. The electrolyte prepared by from the phosphinate can improve the high-temperature cycle stability of a secondary battery, also has non-flammable, flame-retardant orself-extinguishing characteristics, and can improve the safety performance of the secondary battery.
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Paragraph 0087-0088
(2020/08/09)
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- Asymmetric synthesis of P -stereogenic diarylphosphinites by palladium-catalyzed enantioselective addition of diarylphosphines to benzoquinones
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The reaction of phenyl(2,4,6-trimethylphenyl)phosphine with a substituted benzoquinone in the presence of a chiral phosphapalladacycle complex as a catalyst and triethylamine in chloroform at -45 °C proceeded in a new type of addition manner to give a high yield of a 4-hydroxyphenyl phenyl(2,4,6-trimethylphenyl)phosphinite with 98% enantioselectivity, which is a versatile intermediate readily convertible into various phosphines and their derivatives with high enantiomeric purity.
- Huang, Yinhua,Li, Yongxin,Leung, Pak-Hing,Hayashi, Tamio
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supporting information
p. 4865 - 4868
(2014/04/17)
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- Preparation of organohalosilanes
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In an industrial process for preparing organohalosilanes by reacting metallic silicon particles with an organohalide in the presence of a copper catalyst, a contact mass composed of the metallic silicon and the catalyst further contains an effective amount of a phosphine chalcogenide compound. The invention drastically increases the silane formation rate and the utilization of silicon without lowering the selectivity of useful silane.
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- The 'one-pot' syntheses of α,α′-diphosphino-substituted imines: A unique reaction of bulky bis(dialkylamino)chlorophosphines
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The reaction between various bis(dialkylamino)chlorophosphines and N-isopropyl-substituted lithium amides afforded bis(α,α′-phosphino)imines in a 'one-pot' procedure. These compounds react with sulfur to generate intramolecularly hydrogen-bonded ylide derivatives. The molecular structure of (Pr2iN)2PCH2C(=NBut) CH2P(NPri)2 has been determined by X-ray crystallography.
- Baceiredo,Bertrand,Dyer,Fawcett,Griep-Raming,Guerret,Hanton,Russell,Williamson
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p. 591 - 596
(2007/10/03)
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- ELECTROCHEMICAL REACTIONS OF PHOSPHORIC ACID DERIVATIVES. II. REDUCTION OF DIORGANYLPHOSPHINOUS DERIVATIVES
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The mechanism of the heterogenous reduction of diorganylphosphinous derivatives includes the stages of electron transfer, breakage of the P-El (El = S, C) bond in the radical anion, and subsequent chemical reaction between the phosphide anion and the original molecule.Examination of the homogeneous reduction of diorganylphosphinous derivatives with help of electrochemically generated radical anions as mediators shows that the kinetic characteristics of the separate stages of the process depend strongly on the nature of the mediator, and in some cases the mediator affects the nature of the product.Thus, the reduction of Ph2PSBu by the radical anion of anthracene gives the diphosphide, while the radical anion of bipyridine leads to the isomerization product Ph2P(S)Bu.It is suggested that the electron transfer has inner-sphere character, that between the mediator and the substrate a complex is formed, and that this determines the whole mechanism of the reduction.
- Budnikova, Yu. G.,Novoselova, T. R.,Kargin, Yu. M.
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p. 1267 - 1273
(2007/10/02)
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