- A Direct Catalytic Synthesis of Sodium Diarylphosphinates and Their Corresponding Acids from Sodium Phosphinate
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In this contribution we present the direct conversion of sodium phosphinate (NaH2PO2·H2O) to symmetrical sodium diarylphosphinates and their corresponding acids by using palladium catalysis. This route eliminates the need for chlorinated precursors, such as PCl3and intermediate alkyl- or ammoniumphosphinates.
- Botez, Laurian,de Jong, G. Bas,Slootweg, J. Chris,Deelman, Berth-Jan
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p. 434 - 437
(2017/02/05)
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- Solvent effects on reactions of hydroxide ion with phosphorus (V) esters. A quantitative treatment
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Second-order rate constants of reactions of HO- with phosphate, phosphinate and thiophosphinate esters, (PhO)2PO.OC6H4NO2-p, Ph2PO.OC6H4NO2-p, Ph2PO.SPh, Ph2PO.SC6H4NO2-p and Ph2PO.SEt, go through minima with decreasing water content of H2O-MeCN or H2O-t-BuOH. The rate decrease is due to stabilization of the non-ionic ester on addition of organic solvent to H2O. This inhibition is partially offset by stabilization of the anionic transition states and in the drier solvents partial desolvation of HO- increases rates.
- Bunton, Clifford A.,Gillitt, Nicholas D.,Kumar, Anurag
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p. 145 - 151
(2007/10/03)
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- ZUR KENNTNIS DES NATRIUMDIPHENYLPHOSPHINOFORMIATS Ph2PCOONa
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Ph2PCOONa 2, prepared from Ph2PNa and CO2, is readily hydrolyzed in protic media with formation of Ph2PH and CO2.Hydrolysis is much slower in NaOH and small quantities of Ph2P(O)O- and HCOO- are additionally formed.Reactions of 2 with RI in stoichiometrical amounts gave tertiary phosphines Ph2PR (R=Me, Et) while the phosphonium compound I resulted from 2 and MeI in excess.Ph2PCOOMe, Ph2PCOOSiMe3 or Ph2PCSSNa were obtained from 2 and (MeO)2SO2, Me3SiCl or CS2.Ph2P(O)ONa and Ph2P(S)SNa were isolated when 2 was reacted with O2 or S8 in benzene.
- Diemert, Klaus,Hahn, Thomas,Kuchen, Wilhelm
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p. 287 - 294
(2007/10/02)
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- OPTICALLY ACTIVE SILYL ESTERS OF PHOSPHOROUS. II. STEREOCHEMISTRY OF REACTIONS WITH NUCLEOPHILES
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We report the stereochemistry of reactions of various nucleophiles with optically active silyl esters of phosphorus of general formula: tBuPhP(X)OSiMePhNp X= -(1), Oxygen (2), Sulfur (3), Selenium (4).The list of nucleophiles includes O,S,N,C nucleophiles as well as halides.The nucleophilic attack is essentially directed towards silicon.The phosphinuos and phosphonic acid esters react with predominant retention of configuration at silicon atom, whereas the thiono and seleno crossover is explained in terms of possible interaction of the electrophilic part of the nucleophile with the oxyphosphoryl group or tricoordinate phosphorous.
- Wozniak, Lucyna,Cypryk, Marek,Chojnowski, Julian
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p. 4403 - 4414
(2007/10/02)
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- Preparation of anhydrous organic acid salts
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One-step process for preparing anhydrous, organic acid alkali or alkaline earth metal salts by contacting and reacting an organic or polymeric acid fluoride, anhydride or ester and an organic alkali or alkaline earth metal silanolate.
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