- Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus
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Industrially important triaryl phosphites, traditionally prepared from PCl3, have been synthesized by a diphenyl diselenide-catalyzed one-step procedure involving white phosphorus and phenols, which provides a halogen- and transition metal-free way to these compounds. Subsequent oxidation of triaryl phosphites produces triaryl phosphates and triaryl thiophosphates. Phosphorotrithioates are also prepared efficiently from aromatic thiols and aliphatic thiols.
- Zhang, Yue,Cai, Ziman,Chi, Yangyang,Zeng, Xiangzhe,Chen, Shuanghui,Liu, Yan,Tang, Guo,Zhao, Yufen
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p. 5158 - 5163
(2021/07/20)
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- Aerobic Oxidation of Phosphite Esters to Phosphate Esters by Using an Ionic-Liquid-Supported Organotelluride Reusable Catalyst
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We describe the synthesis of an ionic-liquid (IL)-supported organotelluride catalyst and its application as a recyclable catalyst for the aerobic oxidation of phosphite esters to phosphate esters. This method shows high conversion rates, allows the ready isolation and purification of the resulting products, and exhibits good reusability of the catalyst.
- Mihoya, Aya,Shibuya, Yuga,Ito, Akane,Toyoda, Anna,Oba, Makoto,Koguchi, Shinichi
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supporting information
p. 2043 - 2045
(2020/11/10)
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- Nickel-catalyzed amination of aryl phosphates through cleaving aryl C-O bonds
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The amination of triaryl phosphates was achieved using a Ni(II)-(σ-Aryl) complex/NHC catalyst system in dioxane at 110 °C in the presence of NaH as base. Electron-neutral, -rich, and -deficient triaryl phosphates were coupled with a wider range of amine partners including cyclic and acyclic secondary amines, aliphatic primary amines, and anilines in good to excellent yields.
- Huang, Jin-Hua,Yang, Lian-Ming
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supporting information; experimental part
p. 3750 - 3753
(2011/09/14)
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- Reaction kinetics on hydrolysis of substituted di-phenyl phosphate ester in different borate buffers
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The reaction of hydroxide ion with di-4-methyl phenyl phosphate has been studied in the presence of micelles of cationic detergent. It has been investigated at pH 8.0 to 10.0 at 40 ± 0.10°C in aqueous dioxane di-phosphate esters. Pseudo-first order rate constants kψ and k′w have been measured spectrophotometrically by rate of appearance of inorganic phosphate during hydrolysis. kψ and k′w were rate constants with and without CTAB, which varied in between 0.02 × 10-3 to 2 × 10-3 mol dm -3 and the concentration of phosphate was restricted to 5.0 × 10-3 s-1. Rate constants increase with concentrations of CTAB, giving at rate maximum, kψ = 67.03 × 10-5 s-1 at 18 × 10-3 mol dm-3 CTAB and k ψ = 52.43 × 10-5 s-1 at 16 × 10-3 mol dm-3 CTAB respectively at pH 8.0 and 9.0 for di-anions of 4-mpp. The values of ion exchange parameter calculated at pH 8.0 and 9.0 by using various ion exchange equations have been summarized. The activation energy is 25.08 kcal/mol and entropy is 52.07 [-ΔS(eu)], which bas been found at pH 8.0 and used borate buffer 3.9 × 10-3 mol dm-3 [OH-].
- Kumar, Adesh,Yadav
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body text
p. 863 - 867
(2011/04/25)
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- Aerobic photooxidation of phosphite esters using diorganotelluride catalysts
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Diorganotellurides containing bulky aromatic substituents are found to catalyze the photooxidation of phosphite esters using aerobic oxygen as a terminal oxidant. A Hammett plot with substituted triaryl phosphites yielding p = 2.88 agrees with a nucleophilic oxygen transfer from telluroxide to phosphite.2009 American Chemical Society.
- Oba, Makoto,Okada, Yasunori,Nishiyama, Kozaburo,Ando, Wataru
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supporting information; experimental part
p. 1879 - 1881
(2009/10/10)
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- Effects of triaryl phosphates on mouse and human nuclear receptors
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The constitutively active receptor (CAR) is a crucial regulator of genes encoding for enzymes active in drug/steroid oxidation, conjugation, and transport. In our attempt to isolate the endogenous inhibitory ligand(s) for the mouse CAR, we found surprisingly that the inhibitory activity was associated with di- and tri-isopropylated phenyl phosphates that were present in livers of untreated mice. Trans-activation experiments in mammalian cells with synthetic compounds verified that mouse CAR was inhibited by various isopropylated phenyl phosphates (40-80%). Such triaryl phosphates are widely used as fire retardants, lubricants, and plasticizers, and some of them are known to disturb reproduction by currently unknown mechanisms. Equipped with the finding that these compounds could interact with mouse CAR, we proceeded to determine their functional effects on other nuclear receptors. Human CAR and pregnane X receptor (PXR) were variably activated (2-5-fold) by triaryl phosphates while mouse PXR, peroxisome proliferator-activated receptor-α, and vitamin D receptor were refractory. Among steroid hormone receptors, the human androgen receptor was inhibited by triphenyl phosphate and di-ortho-isopropylated phenyl phosphate (40-50%) and activated by di- and tri-para-substituted phenyl phosphates (2-fold). Our results add to the list of CAR and PXR activators and suggest steroid-dependent biological pathways that may contribute to the reproductive effects of triaryl phosphates.
- Honkakoski, Paavo,Palvimo, Jorma J.,Penttilae, Leena,Vepsaelaeinen, Jouko,Auriola, Seppo
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- Absolute viscosity and density of trisubstituted phosphoric esters
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This paper presents measurements on the absolute viscosity (η) and density (ρ) of trisubstituted phosphoric esters which are useful in understanding their flow mechanism necessary for accessing their role as plasticizers. The effect of chain length and branching has been examined on the η and ρ trends. From η data, by using the Vogel-Tammann-Fulchur (VTF) equation, the VTF temperature (To) has been obtained which also represents the ideal glass transition temperature. To is related to the flexibility of the molecules. It is observed that To initially decreases with molecular weight, reaches a minimum, and increases thereafter. The initial decrease in To has been attributed to the enhanced flexibility of the phosphate esters. Reversal of flexibility with relative molar mass beyond 400 is due to the gentle collision of the arms of the trisubstituted phosphoric esters. This has been further corroborated from the molar mass exponent as exhibited in the η-molar mass plot. The isomeric effect on η has also been investigated in tricresyl phosphates, hitherto for the first time. The ortho isomer has highest η among the isomers. The para isomer was found to have lowest To and hence highest flexibility compared to the ortho and meta isomers.
- Kannan,Kishore
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p. 649 - 655
(2007/10/03)
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- "One-pot" Synthesis of Triaryl Phosphates a Reaction Calorimetry Approach
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Triaryl phosphates were obtained in yields ranging from 85-96percent in a "one-pot" synthesis via an alkaline route: an ethanolic solution of sodium hydroxide was added to a solution of substituted phenol in toluene.The mixture was distilled until all ethanol was removed.Phosphorus oxychloride was then added and the toluene was distilled.The triaryl phosphates were characterized by NMR (1H and 31P), MS and FTIR.The heat capacity (Cp), the total heat transfer coefficient (U) and the reaction enthalpy (ΔH) were determined for the synthesis of tris(4-chloro-3-methylphenyl), tris(p-cresyl), tris(o-methoxyphenyl) and tris(p-nitrophenyl) phosphates. - Keywords: Phosphate; NMR spectra; heat capacity; phosphorus oxychloride
- Silva, J. F. Cajaiba da,Nakayama, H. T.,Neto, C. Costa
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- Polymer supported reagents: An efficiant and simple method for the synthesis of triaryl phosphates
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The reaction of phosphoryl chloride with insoluble polymer-supported phenoxide ion reagents in benzene at room temperature, produced triaryl phosphates in excellent yields. The isolation of pure products by simple filtration and evaporation is an important feature of this method.
- Sagar,Thorat,Salunkhe
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p. 2029 - 2033
(2007/10/02)
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- THIONO COMPOUNDS. 10. STRUCTURES AND REACTIONS OF INTERMEDIAATES FROM THE OXIDATION OF PHOSPHOROTHIOATES
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Intermediates from the oxidation of phosphorothioates, (RO)3PS, were studied previously at low temperature using 31P NMR, UV and Raman spectra.Now reported is further information about the structure of intermediates and about their reactions, both of which afford significant clues as to how phosphorothioates may produce adverse biological reactions after they have ben oxidized biologically.Mass spectra identified intermediates corresponding to (RO)3PSn with n up to 7 (although presence of some equivalent masses with two oxygens in place of a sulfur atom is possible).HPLC separated unstable intermediates for which UV and MS evidence again was consistent with the structure (RO)3PSn.That intermediates can react as nucleophiles is illustrated by reactions with Ellman's Reagent, which produced a maximum of thiolate ion at about the time 31P NMR and UV indicated a maximum of intermediates.A second illustration of nucleophilicity was reaction with N-ethylmaleimide (and other Michael acceptors), which led to thiiranes and thiirane 1-oxides.That the intermediates can react also as electrophiles is illustrated by reactions (followed by UV and 31P NMR) with trimethyl phosphite, hydroxyl ion, and water (perhaps to some extent); use of H2(18)O did not introduce (18)O into phosphate products, but exchange reactions with H2(18)O did indicate presence of oxygenated species among the intermadiates.Keywords: Ellman's Reagent; N-ethylmaleimide; 31P NMR spectra; Phosphorothioates; Thiiranes; UV spectra.
- Swinson, Joel,Field, Lamar,Heimer, Norman E.,Stone, Michael P.,Wazer, John R. Van
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- THIONO COMPOUNDS. 9. USE OF SPECTRA TO STUDY INTERMEDIATES IN THE OXIDATION OF THIONO PHOSPHORUS COMPOUNDS
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Intermediates in the oxidation by m-chloroperoxybenzoic acid (MCPBA) of 13 structurally different thiophosphoramides and phosphorothioates were studied at -25 deg C to 0 deg C using NMR, EPR, UV, IR and Raman spectra.The lifetimes of intermediates ascertained by NMR varied from a few minutes to many hours at the same temperature and were longer for thiono esters than for amides, for aryl than for alkyl constituents, and for electron-donating substituents on aryl groups than for electron-withdrawing groups.The major 31P NMR peaks for all intermediates appeared in the same region, about midway between the resonances of the P(S) starting materials and the P(O) products, indicating close structural similarly to one another for the intermediates; the range of 13-33 ppm for the major peaks indicates that the intermediates are tetracoordinate and supports phosphonium polysulfide structures for them of the type R3PSx (26, Scheme 1), or perhaps R3POSx.UV spectra also afforded support for polysulfide structures, since typical absorption develops and then disappears.Raman, 31P NMR, and UV spectra are consistent with longer-term presence of bisphosphonium species (e.g. 25, from reactions of 26; Scheme 1).EPR spectra gave no indication of homolysis. - Key words: Phosphorothioates, Raman Spectra, Infrared Spectra, Thionophosphorus, NMR Spectra, Thiophosphoramides
- Swinson, Joel,Field Lamar,Heimer, Norman E.,Michalska, Danuta,Muccio, Donald D.,et al.
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p. 159 - 172
(2007/10/02)
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- Metalation-Induced Double Migration of Phosphorus from O-->C. Convenient Preparation of Bis(2-hydroxyaryl)phosphinic Acids
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Treatment of diaryl ethyl phosphates 8 with lithium diisopropylamide in tetrahydrofuran yields ethyl bis(2-hydroxyaryl)phosphinates 9.The reaction involves the double migration of phophorus from O-->C and is probably intramolecular.These phosphinate esters 9 on treatment with trimethylsilyl chloride and sodium iodide in acetonitrile undergo transesterification to give trimethylsilyl esters that yield the corresponding phosphinic acids 15 on treatment with water.
- Dhawan, Balram,Redmore, Derek
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p. 179 - 183
(2007/10/02)
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- Cycloadditions of N-Aryl-C-(Trifluoromethyl)nitrilimines with Dimethyl Fumarate and Maleate
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The cycloadditions of N-aryl-C-(trifluoromethyl)nitrilimines 1, generated in situ from various precursors, with dimethyl fumarate and maleate are described.N-Aryltrifluoroacetohydrazonoyl bromides 2 reacted with fumarate in the presence of triethylamine to give the trans-4,5-dimethoxycarbonylpyrazolines 4 whereas the reactions with maleate afforded the 4,5-dimethoxycarbonylpyrazoles 5 as well as 4.In the reactions with the chloride 6 under the more drastic conditions, both fumarate and maleate gave the pyrazole 5a.From thermolysis of the oxadiazaphosphole 8, thetrans-pyrazoline 4a was formed in both cases of fumarate and maleate.The preparation of the cis-pyrazoline 9 was attempted from 8 and maleic anhydride but 9 was found to be so unstable as to be epimerized under the mild conditions.
- Tanaka, Kiyoshi,Maeno, Seiji,Mitsuhashi, Keiryo
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p. 565 - 568
(2007/10/02)
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- Chewing insect toxicant compositions
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This invention relates to chewing insect toxicant compositions comprising (1) a 1-(mono-substituted phenyl)-3-benzoyl urea compound in admixture with (2) an amount sufficient to enhance the chewing insect toxicity of said urea compound of a phosphorous-containing compound. This invention is also directed to chewing insect toxicant compositions comprising an acceptable carrier and as the active toxicant an effective amount of the composition of this invention as well as to a method of controlling insects by subjecting them to an effective amount of the composition of this invention.
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- SYNTHESIS OF TRIARYL PHOSPHATES CATALYZED BY POLYETHYLENE GLYCOLS IN A TWO-PHASE SYSTEM: PHASE TRANSFER CATALYSIS
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The synthesis of triaryl phosphates has been accomplished, at room temperature, in nearly quantitative yields in a two-phase system with poly(ethylene glycol) as a phase transfer catalyst.
- Krishnakumar, V. K.
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p. 189 - 196
(2007/10/02)
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- SYNTHESIS OF 2,2,2-TRISUBSTITUTED 5-TRIFLUOROMETHYL-Δ4-1,3,4,2-OXADIAZAPHOSPHOLINES AND THEIR POTENTIALITY AS PRECURSORS OF TRIFLUOROACETONITRILE IMINES
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N'-Phenyl- and methyltrifluoroacetohydrazides react with phosphorus pentachloride to give the corresponding 2,2,2-trichloro-3-phenyl- and methyl-Δ4-1,3,4,2-oxadiazaphospholines, from which various 2,2,2-trisubstituted derivatives are further synthesized.Heating 3-phenyl-2,2,2-tris(p-tolyloxy) analog with an excess of styrene affords 1,5-diphenyl-3-trifluoromethyl-2-pyrazoline, which indicates that the phospholine behaves as a precursor of trifluoroacetonitrile phenylimine.
- Tanaka, Kiyoshi,Igarashi, Toh-ru,Mitsuhashi, Keiryo
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p. 507 - 510
(2007/10/02)
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