6303-30-6Relevant articles and documents
Reactivity of an electrophilic hypervalent iodine trifluoromethylation reagent with hydrogen phosphates - A mechanistic study
Santschi, Nico,Geissbühler, Patrik,Togni, Antonio
experimental part, p. 83 - 86 (2012/03/27)
The electrophilic trifluoromethylation of hydrogen phosphates with the reagent trifluoromethyl-1,3-dihydro-3,3-dimethyl-1,2-benziodoxole (1) was studied by means of initial rates determined for pseudo first order setups and subsequent Taft analysis of the calculated relative rates. A positive polar sensitivity factor, indicative of a negative charge forming during the rate-determining step, was found for the whole data set.
Determination of phosphoric acid mono- and diesters in municipal wastewater by solid-phase extraction and ion-pair liquid chromatography-tandem mass spectrometry
Quintana, Jose Benito,Rodil, Rosario,Reemtsma, Thorsten
, p. 1644 - 1650 (2008/02/05)
The first analytical method for the determination of 13 phosphoric acid mono- and diesters from aqueous samples is presented. The method consists of solid-phase extraction (SPE) and ion-pair liquid chromatographic separation with tri-n-butylamine coupled to electrospray ionization tandem mass spectrometry in the negative ion mode. Due to a lack of pure standards, only 3 of the 13 esters could be quantified. SPE recoveries ranged from 71 to 112% for di-n-butyl phosphate, diphenyl phosphate, and di-(2-ethylhexyl) phosphate (DEHP) with limits of quantification from 7 to 14 ng/L for 100-mL samples. At analyte concentrations ≥1 μg/L, aqueous samples can be analyzed by direct injection without extraction. In municipal wastewater, six diesters and one monoester were unambiguously identified by comparison with synthesized reference material. DEHP showed highest concentrations of 60 and 5 μg/L in raw and treated wastewater, respectively. The detection of monoethylhexyl phosphate was confirmed by LC-Q-TOF-MS analysis, and it was found at a concentration level comparable to DEHP. Laboratory degradation tests show that phosphoric acid diesters can be formed as intermediates in the microbial degradation of trialkyl phosphates that are being used as flame retardants and plasticizers.
Oxidative alkoxylation of zinc phosphide in alcoholic solutions of copper(II) chloride
Dorfman,Ibraimova,Polimbetova
, p. 50 - 55 (2007/10/03)
Oxidative alkoxylation of Zn3P2 with the formation of valuable phosphoric and phosphorous acid esters occurred at a high rate and with a high selectivity in alcoholic solutions of CuCl2 under the action of oxygen at 30-60°C. Depending on the nature of the alcohol, two products were formed, namely, trialkyl phosphates (RO)3PO and dialkyl phosphites (RO)2HPO. Water favored the formation of dialkyl phosphates (RO)2(HO)PO. The kinetics and mechanism of the new catalytic reaction were studied, and the optimal conditions for conducting this reaction were found. The reaction proceeded in a topochemical mode by a separate redox mechanism.
Oxidative cleavage of o-hydroxyphenyl phosphate by iodobenzene diacetate
Wu, Pei-Lin,Chen, Jhy-Hong,Huang, Ded-Shih
, p. 967 - 970 (2007/10/03)
The protecting o-hydroxyphenyl group in the synthesis of mono- or dialkyl phosphates (6 or 8) could be removed by oxidative cleavage of mono- or dialkyl o-hydroxyphenyl phosphates (3 or 7) using iodobenzene diacetate.
Synthesis of dialkyl phosphites and trialkyl phosphates by oxidation of sodium hypophosphite by copper(II) chloride
Dorfman, Ya. A.,Aleshkova. M. M.
, p. 515 - 520 (2007/10/03)
Sodium hypophosphite oxidazies in alcoholic solution of CuCl2 at 50-80 deg C to give dialkyl phosphite and trialkyl phosphate.The yield of trialkyl phosphate increases with decreasing molecular weight of the alcohol and reaches ca. 100percent for MeOH and EtOH.The optimal conditions were found, and the mechanism of oxidation of NaPH2O2 to (RO)2PHO and (RO)3PO by copper(II) chloride was studied.The reaction proceeds via the formation of alkyl hypophosphite and copper(II) complexes with alkyl hypophosphite and dialkyl phosphite, which undergo inner-sphere two-electron redox decomposition with the liberation of dialkyl phosphite and trialkyl phosphate, respectively.
CONVENIENT SYNTHETIC ROUTE TO MONO- OR DIAKLYL PHOSPHATE FROM INORGANIC PHOSPHORUS ACIDS
Okamoto, Yoshiki,Kusano, Tetuya,Takamuku, Setsuo
, p. 195 - 200 (2007/10/02)
Mono- or dialkyl phosphate was synthesized in a favorable yield by oxidation of phosphonic or phosphinic acid in alcohol with oxygen at the presence of a catalytic amount of copper(II)chloride.The reaction may proceed via the formation of corresponding phosphorochloridate or phosphorochloridite.
