- Stereospecific Deoxygenation of Aliphatic Epoxides to Alkenes under Rhenium Catalysis
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The combination of a catalytic amount of Re2O7 and triphenyl phosphite as a reductant is effective for the deoxygenation of unactivated aliphatic epoxides to alkenes. The reaction proceeds stereospecifically with variously substituted epoxides under neutral conditions and is compatible with various functional groups. Protection and deprotection of a double bond functionality using an epoxide are shown as an example of the current rhenium-catalyzed deoxygenation protocol. The effect of reductants for the stereoselectivity has also been studied, indicating that the use of electron-deficient phosphines or phosphites is the key for the stereospecific deoxygenation. (Chemical Equation Presented).
- Nakagiri, Takuya,Murai, Masahito,Takai, Kazuhiko
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- CHEMILUMINESCENCE UPON DECOMPOSITION OF THE OZONIDE OF TRIPHENYLPHOSPHITE
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We have studied the spectral composition of luminescence and the kinetics of attenuation of chemiluminescence upon thermal decomposition of the ozonide of triphenylphosphite.We have established that the emitter of chemiluminescence in the IR region is singlet oxygen, and the emitter of chemiluminescence in the visible region is triphenylphosphate.
- Shereshovets, V. V.,Ostakhov, S. S.,Korotaeva, N. M.,Sharipov, G.L.,Kazakov, V. P.,et al.
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- PROPERTIES OF TRIPHENYLPHOSPHITE-MODIFIED RHODIUM CARBONYL CATALYSTS FOR THE HYDROFORMYLATION OF 2-BUTENES
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The factor responsible for the deactivation of a carbonyl triphenylphosphite rhodium hydroformylation catalyst appears to be the formation of a chelate-structure complex with diphenylphosphite, which is the product of partial hydrolysis of the organophosphorus ligand.The deactivating effect of diphenylphosphite can be supressed upon interaction of the H(O)P(OPh)2 and P(OPh)3-modified complex with 2-butenes under hydroformylation reaction conditions.
- Slivinskii, E. V.,Markova, N. A.,Teleshev, A. T.,Korneeva, G. A.,Butkova, O. L.,et al.
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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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- VOLTAMMETRIC STUDY OF REACTIONS OF TRIPHENYLPHOSPHITE OZONIDE
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The electrochemical characteristics of reduction of triphenylphosphite ozonide at a stationary platinum electrode were determined in acetonitrile at between -30 and -11 deg C.The feasibility of employing voltammetric methods to investigate the reactions of phosphite ozonides was demonstrated in a model study of the kinetics of the thermal decomposition of (C6H5O)3PO3 and its reaction with triphenylphosphite. Keywords: kinetics, decomposition, ozonide, triphenylphosphite, ozonation, voltammetry.
- Rusakov, I. A.,Shereshovets, V. V.,Abramova, N. A.,Maistrenko, V. N.,Murinov, Yu. I.
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- Tellurium tetrachloride as an efficient chlorinating agent for di- or trialkyl phosphites: Novel synthesis of dialkyl chlorophosphates
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Various dialkyl chlorophosphates are prepared by the reaction of TeCl4 with di- or trialkyl phosphites in good yields.
- Koh,Oh
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- Iodosobenzene and iodoxybenzene as reagents for oxygen transfer in organophosphorus chemistry
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The application of iodosobenzene (1) and iodoxybenzene (2) for the oxidation reaction of phosphorous, phosphorothiono and phosphoroseleno compounds into the corresponding ≡P(O) analogs is demonstrated. Retention of configuration at the phosphorus atom and full stereoselectivity of these reactions in model diastereoisomeric cis- and trans-2-phenylamino-2-thiono-4-methyl-1.3.2-dioxaphosphorinans (30) as well cis- and trans-2-phenylamino-2-seleno-4-methyl-1.3.2-dioxaphosphorinans (31) systems, are demonstrated.
- Mielniczak,Lopusiński
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- A Reexamination of the Ozone-Triphenyl Phosphite System. The Origin of Triphenyl Phosphate at Low Temperatures
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The reaction of ozone with triphenyl phosphite (P) at -78°C affords a labile 1:1 complex (PO3) together with small amounts of triphenyl phosphate (PO) (Q. E. Thompson, J. Am. Chem. Soc. 1961, 83, 845). In this work we found that the amount of PO present initially after complete ozonation of P in toluene was 12 ± 2% at -78°C and 11 ± 2% at -95°C. Partial ozonation of solutions of P in toluene at -78°C gave mixtures of P, PO, and PO3 whose composition changed with time as a result of the reaction of P with PO3 to give additional PO. Between -25 and -60 °C, the rate constant of the latter reaction is given by the expression log k (M-1 s-1) = (8.64 ± 0.04) - (11.44 ± 0.74) kcal/AT. This reaction at -78°C is too slow to account for the PO formed during the ozonation, which is proposed to arise instead by competitive reactions of an intermediate. The solubility of PO in toluene at -78°C was measured as 0.06 M, and that of PO3 about 6 times greater.
- David Mendenhall,Priddy, Duane B.
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- Preparation of Flame-Resistant Liquids Based on Mixed Tri(phenyl, p-tert-butylphenyl) Phosphates by Transesterification of Triphenyl Phosphate with p-tert-Butylphenol
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Abstract: The possibility of controlling the composition of a mixture of triphenyl phosphate, p-tert-butylphenyl diphenyl phosphate, di(p-tert-butylphenyl)phenyl phosphate, and tri(p-tert-butylphenyl) phosphate, formed by transesterification of triphenyl phosphate with p-tert-butylphenol, was demonstrated. The amount of p-tert-butylphenol necessary for transesterification of triphenyl phosphate to yield a mixture of phosphates of required composition was determined. If necessary, the composition of the phosphates can be adjusted by selective distillation of triphenyl phosphate in a vacuum.
- Karchevskaya, O. G.,Korneeva, G. A.,Kron, T. E.,Noskov, Yu. G.
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- Zero-Valent Amino-Olefin Cobalt Complexes as Catalysts for Oxygen Atom Transfer Reactions from Nitrous Oxide
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The synthesis and characterization of several zero-valent cobalt complexes with a bis(olefin)-amino ligand is presented. Some of these complexes proved to be efficient catalysts for the selective oxidation of secondary and allylic phosphanes, as well as diphosphanes, even with a direct P?P bond. With 5 mol % catalyst loadings the oxidations proceed under mild conditions (25–70 °C, 7–22 h, 2 bar N2O) and afford good to excellent yields (65–98 %). In this process, the greenhouse gas N2O is catalytically converted into benign N2and added-value organophosphorus compounds, some of which are difficult to obtain otherwise.
- Gianetti, Thomas L.,Rodríguez-Lugo, Rafael E.,Harmer, Jeffrey R.,Trincado, Monica,Vogt, Matthias,Santiso-Quinones, Gustavo,Grützmacher, Hansj?rg
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- Pyridine catalyzed decomposition of triphenylphosphine ozonide
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Pyridine accelerated the decomposition of triphenylphospite ozonide in CH2Cl2.The addition of ethanol to the (PhO)3PO3-C5H5N-CH2Cl2 system increases the rate of the process.The kinetic regularities of the decomposition of (PhO3)PO3 in the presence of pyri
- Kazakov, D. V.,Kabal'nova, N. N.,Shereshovets, V. V.
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- Evaluation of kinetic parameters from the synthesis of triaryl phosphates using reaction calorimetry
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Triaryl phosphates were prepared by a "one-pot" methodology through the reaction of sodium phenoxides with phosphorus oxychloride. This system can be described as a semi-batch reaction, where the phenoxides were synthesized inside the reactor anda solution of phosphorus oxychloride in toluene was added continuously through a pump. These highly exothermic reactions were performed in a Mettler RC-1 reaction calorimeter. The aim of this work was to evaluate the reaction rate and the reaction rate constant through the study of the rate of heat release. Although the phenoxides react almost immediately with phosphorus oxychloride, it was possible to notice the slight differences among the sodium phenoxides studied. The phenoxide bearing an electron-donating group (methoxy) was the most reactive, and the one bearing an electron-withdrawing group (nitro) was the least reactive one. The reactions could be considered to be feed-controlled. It was demonstrated that the reaction temperature does not affect the reaction rate and reaction rate constant in the same way that the feed rate of the phosphorus oxychloride does.
- Machado e Silva, Carlos F. Pinto,Da Silva, Joao F. Cajaiba
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- Rapid and high yield oxidation of phosphine, phosphite and phosphinite compounds to phosphine oxides, phosphates and phosphinates using hypofluorous acid-acetonitrile complex
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The hypofluorous acid acetonitrile complex was used as a mild, rapid, and effective agent to oxidize a wide variety of phosphines, phosphites and phosphinites to the corresponding phosphine oxide, phosphate and phosphinate compounds.
- Peng, Weimin,Shreeve, Jean'Ne M.
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- Reductive cleavage of the halogen-phosphorus, oxygen-phosphorus and phosphorus-phosphorus bonds with alkali metals
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The reduction of phosphorus acid chlorides as well as hypophosphates, pyrophosphates and mixed P(III)-P(V) anhydrides with alkali metals (Li, Na, K) in NH3 liq. / THF solution and potassium naphthalenide was investigated. It was found that this type of phosphorus compounds easily undergo reduction: a) >P(O)Cl to >P(O)H; b) >P(O)P(O)P(O)H; c) >P(O)-O-P(O)P(O)OH and >P(O)H; d) >P(O)-O-PP(O)O- and >P-. The results of our experiments strongly suggest that the mixed P(III)-P(V) anhydride is reduced by potassium naphthalenide in THF with the cleavage of the P(III)-oxygen bond.
- Nycz, Jacek,Rachon, Janusz
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- Quenching of a photosensitized dye through single-electron transfer from trivalent phosphorus compounds
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Various types of trivalent phosphorus compounds 1 undergo single-electron transfer (SET) to the photoexcited state of rhodamine 6G (Rho+(*)) in aqueous acetonitrile to quench the fluorescence from Rho+(*). The rate constants k(p) for the overall SET process were determined by the Stern-Volmer method. The rate is nearly constant at a diffusion-controlled limit in the region of E( 1/2 )(1) +), whereas log k(p) depends linearly on E( 1/2 )(1) in the region of E( 1/2 )(1) > 1.3 V, the slope of the correlation line being -αF/RT with α = 0.2. The potential at which the change in dependence of log k(p) on E( 1/2 )(1) occurs (1.3 V) is in accordance with the value of E( 1/2 )(Rho+(*)) (1.22 V) that has been obtained experimentally. Thus, the SET step is exothermic when E( 1/2 )(1) 1.3 V. The α-value (0.2) obtained in the endothermic region shows that the SET step from 1 to Rho+(*)is irreversible in this region. Trivalent phosphorus radical cation 1(·+) generated in the SET step undergoes an ionic reaction with water in the solvent rapidly enough to make the SET step irreversible. In contrast, the SET from amines 2 and alkoxybenzenes 3 to Rho+(*) is reversible when the SET step is endothermic, meaning that the radical cations 2(·+) and 3(·+) generated in the SET step undergo rapid 'back SET' in the ground state to regenerate 2 and 3.
- Yasui, Shinro,Tsujimoto, Munekazu,Itoh, Kenji,Ohno, Atsuyoshi
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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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- Synthesis of diaryl phosphates using orthophosphoric acid as a phosphorus source
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This paper presents a new synthetic route for diaryl phosphate esters, which are traditionally synthesized from phosphorus oxychloride. Specifically, we report the synthesis of diaryl phosphates by the dehydrative condensation of orthophosphoric acid, a phosphorus source, with aromatic alcohols.
- Tran, Cong Chi,Asao, Kazuya,Sasaki, Takeshi,Hayakawa, Yasuyuki,Kawaguchi, Shin-ichi
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supporting information
(2022/04/09)
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- 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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- Method for preparing phosphate ester derivatives from white phosphorus
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A method for preparing phosphate ester derivatives from white phosphorus relates to the field of chemical engineering, and comprises the following steps: adding alkali, a catalyst, a white phosphorus solution, ROH or RSH (R represents alkyl or aromatic group) into a reaction container in an inert atmosphere, and heating and stirring the mixture in a mixed solvent of toluene and DMSO (dimethyl sulfoxide) to react for a certain time, so as to obtain three-coordinated phosphate ester derivatives; and 2) continuing to add H2O2, air or sulfur powder until the oxidation is completed, thereby obtaining the tetra-coordinated phosphate ester derivative. According to the method, chlorine, phosphorus trichloride and halogen are not needed, phosphite ester is directly prepared from elementary white phosphorus in an efficient, green and environment-friendly manner, and phosphate and thiophosphate can be directly prepared after oxidation. High pollution and high corrosivity of a traditional method are avoided in the whole process; meanwhile, white phosphorus is completely converted in the whole process, white phosphorus residues are avoided, and the post-reaction treatment process is safe.
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- Flash production of organophosphorus compounds in flow
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Flow synthesis techniques have received a significant amount of attention due to their high productivity. However, when reaction condition is heterogeneous, it is usually difficult to adapt it to flow synthesis. Herein, by selecting appropriate reagents, the synthesis of phosphate esters, which is commonly heterogeneous, was made homogeneous, enabling synthesis in flow systems. In addition, reaction rate was accelerated compared to the batch system. It was demonstrated that not only can the high productivity of flow synthesis be achieved in flow, but also high productivity can be achieved by accelerating the reaction. Finally, we demonstrated the synthesis of the Akiyama-Terada catalyst, a chiral organocatalysts, in a short period.
- Nagaki, Aiichiro,Tamaki, Takashi
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supporting information
(2021/09/09)
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- Zinc-catalyzed transformation of diarylphosphoryl azides to diarylphosphate esters and amides
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We have developed a facile and efficient procedure for the synthesis of diarylphosphate esters and amides. Using Zn(acac)2 as the catalyst, the reaction of diarylphosphoryl azides with aliphatic alcohols and phenols through an unusual P?N bond cleavage provided a number of diarylphosphate esters in good yields (22 examples, up to 94%). Additionally, various diarylphosphate amides were obtained from the corresponding amines in excellent yields as well (8 examples, up to 96%).
- Ying, Jun,Gao, Qian,Wu, Xiao-Feng
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p. 1540 - 1543
(2020/04/15)
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- Metal-free synthesis of biarenes via photoextrusion in di(tri)aryl phosphates
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A metal-free route for the synthesis of biarenes has been developed. The approach is based on the photoextrusion of a phosphate moiety occurring upon irradiation of biaryl- A nd triaryl phosphates. The reaction involves an exciplex as the intermediate and it is especially suitable for the preparation of electron-rich biarenes.
- Qrareya, Hisham,Meazza, Lorenzo,Protti, Stefano,Fagnoni, Maurizio
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supporting information
p. 3008 - 3014
(2021/01/18)
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- Characterizing the thermal degradation mechanism of two bisphosphoramidates by TGA, DSC, mass spectrometry and first-principle theoretical protocols
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The present investigation describes a combined experimental-theoretical strategy to assess the thermal resistance features of two symmetric bisphosphoramidates, tetraphenyl ethane-1,2-diylbis (phosphoramidate) 1 and tetraphenyl propane-1,3-diylbis (phosphoramidate) 5. Therefore, their structural reluctance to thermal decomposition through differential scan calorimetric (DSC) and thermogravimetric (TGA) experiments was evaluated. Then, their molecular degradation path was followed by analysing recorded data from mass spectrometry measurements performed at different temperature conditions. Their corresponding thermal degradation mechanism was then established by searching plausible transition states interconnecting the intermediaries found in our mass spectrometry records using a quantum theoretical protocol based on Coupled-Cluster calculations. Through this strategy, key intermediaries of the two bisphosphoramidates studied during their molecular degradation mechanism were identified, although compound 5 displayed the highest resistance to heat decomposition.
- Castrejón-Flores, José Luis,Flores-Martinez, Yazmin M.,Franco-Pérez, Marco,García-Ventura, María Isabel,Reyna-Luna, Julieta,Zamudio-Medina, Angel
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- Exploration of chiral Lewis acid Mg2+ catalysts in the synthesis of aryl organophosphate triesters from phosphorus oxychloride through a three-step, two-pot substitution sequence
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A variety of nucleophilic and Lewis acid catalysts were examined for use in promoting the synthesis of organophosphate triesters. Eight novel organophosphate triesters are reported here for the first time. MgSO4 was discovered as an inexpensive catalyst capable of improving the synthesis of a variety of aryl organophosphate triesters from the readily available and low cost precursor phosphorus oxychloride in a three-step, two-pot sequence. Yields for this method improve upon the uncatalyzed method by 8–36%. Several chiral catalysts were tested, but none were able to induce enantioselectivity in the reaction.
- Granger, Emily,Solomianko, Katarzyna,Young, Cori,Erb, Jeremy
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p. 1404 - 1408
(2018/03/13)
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- Method for compounding organphosphorus by using black phosphorus
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The invention discloses a method for compounding organphosphorus by using black phosphorus. The method takes the black phosphorus as a reaction raw material, safely and efficiently compounds organic phosphate, sulpho-phosphite ester, amino phosphite ester, alkylphosphine, alkylphosphine oxide and other organphosphorus with wide usages, a conventional synthsis route by using phosphorus halide and phosphate to compound the organphosphorus is avoided, the synthesis steps are simple and short, the production technology is operated simply and easily, the reproducibility is good, the reaction is simple and green, the use of a phosphorus halide reagent is avoided, the range of the synthetic organphosphorus is wider, the method satisfies the requirements of green chemical development, and the large-scale production can be achieved.
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Paragraph 0103; 0104; 0105
(2018/10/19)
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- DCC-assisted direct esterification of phosphinic and phosphoric acids with O-nucleophiles
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A novel and efficient dicyclohexylcarbodiimide-promoted protocol for the selective and controllable esterification of P(O)OH compounds using O-nucleophiles (alcohols and phenols) as efficient esterification reagents is described. This method features a high efficiency and good functional-group tolerance, meaning a simple way to synthesize a broad spectrum of phosphinic and phosphoric acid esters from basic starting materials with moderate to excellent yields.
- Xiong, Biquan,Wang, Gang,Zhou, Congshan,Liu, Yu,Li, Jiandong,Zhang, Pangliang,Tang, Kewen
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supporting information
p. 239 - 244
(2017/11/20)
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- PROCESS FOR THE PREPARATION OF A TRIARYL PHOSPHATE ESTER COMPOSITION
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The invention relates to a process for the preparation of a triaryl phosphate ester composition comprising a. reacting a phosphorous oxyhalide with a (C1-C15-alkyl)phenol to obtain a first product; b. reacting the first product with phenol to obtain a triaryl phosphate ester composition; wherein in step a., for every mol of phosphorous oxyhalide 1.3 to 1.6 mols of (C1-C15-alkyl)phenol are used. The invention also relates to a triaryl phosphate ester composition obtainable according to the process of the invention.
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Page/Page column 14
(2017/09/08)
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- CDI-promoted direct esterification of P(O)-OH compounds with phenols
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A novel and efficient N,N′-carbonyl diimidazole-catalyzed protocol for the direct esterification of P(O)-OH compounds using phenols as efficient esterification reagents is illustrated. It is a simple way to synthesis a broad spectrum of functionalized O-aryl phosphinates, phosphonates, and phosphates from basic starting materials with moderate to excellent yields.
- Xiong, Biquan,Hu, Chenghong,Li, Haotian,Zhou, Congshan,Zhang, Pangliang,Liu, Yu,Tang, Kewen
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supporting information
p. 2482 - 2486
(2017/05/31)
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- Method for preparing phosphinic acid ester/phosphorous acid ester/phosphoric acid ester from P(O)-OH compound and aryl boronic acid
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The invention provides a method for high-selectivity synthesis of phosphinic acid ester/phosphorous acid ester/phosphoric acid ester derivatives containing different substituted functional groups; a metal salt is used as a catalyst, a P(O)-OH-containing compound and aryl boronic acid are used as reactants, and an alkali, an additive and an organic solvent are added into the reaction system. The method has the advantages that the catalyst is cheap and easy to obtain; the reaction conditions are mild, and the method is safe and reliable; the selectivity of the obtained target product is close to 100%, and the yield is as high as 90% or more. The method solves the deficiency that traditional synthetic phosphinic acid ester/phosphorous acid ester/phosphoric acid ester compounds have poor reaction selectivity, complex reaction steps and low yield and need to use reagents harmful to the environment, and has a good prospect in industrial application. The invention also provides the corresponding phosphinic acid ester/phosphorous acid ester/phosphoric acid ester derivatives correspondingly containing different substituted functional groups.
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Paragraph 0022; 0023
(2016/10/10)
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- FLAME RETARDANT COMPRISING AROMATIC PHOSPHATE ESTER-BASED COMPOUND, AND METHOD FOR PREPARING SAME
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A method for preparing a novel aromatic phosphate ester-based compound, including: (a) reacting a compound expressed by chemical formula 1 (i) and a C6-10 aryl compound substituted with hydroxy or C1-6 alkoxy, or a C6-20 arylalkyl compound substituted with hydroxy or C1-6 alkoxy (ii), which are used as reaction materials by gradually heating to the temperature levels of 90-125° C., 125-180° C., 180-210° C. and 210-240° C.; (b) separating an aromatic phosphate ester-based compound from the resultant product in step (a) under the condition of a pressure of 0.01 mmHg-50 mmHg and a temperature of 50° C.-300° C. using fractional distillation; and (c) reacting the aromatic phosphate ester-based compound separated in step (b) (i) and C1-10 alcohol or a nitrogen compound (ii) at a temperature of 10-70° C.
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Paragraph 0149-0158
(2015/11/10)
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- Direct aerobic oxidative esterification and arylation of P(O)-OH compounds with alcohols and diaryliodonium triflates
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Copper-catalyzed aerobic oxidative esterification of P(O)-OH compounds is achieved using alcohols as efficient esterification reagents, giving the expected products with good to moderate yields. Furthermore, it is shown that the arylation of P(O)-OH compounds proceeds efficiently to produce the corresponding products via the treatment of diaryliodonium triflates under mild reaction conditions. It is a simple way to produce a broad spectrum of functionalized phosphinates, phosphonates, and phosphates from basic starting materials with good to excellent yields. The protocol is convenient for practical application. A plausible mechanism has been proposed for the reaction.
- Xiong, Biquan,Feng, Xiaofeng,Zhu, Longzhi,Chen, Tieqiao,Zhou, Yongbo,Au, Chak-Tong,Yin, Shuang-Feng
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p. 537 - 543
(2015/04/14)
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- Copper-catalyzed direct esterification of P(O)-OH compounds with phenols
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A novel copper-catalyzed method for the direct esterification of P(O)-OH compounds using phenols as efficient esterification reagents is illustrated. It is a simple way to generate a broad spectrum of functionalized O-aryl phosphinates, phosphonates, and phosphates from basic starting materials with moderate to excellent yields.
- Xiong, Biquan,Zeng, Kui,Zhang, Shanshan,Zhou, Yongbo,Au, Chak-Tong,Yin, Shuang-Feng
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supporting information
p. 9293 - 9298
(2015/11/27)
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- Interaction of 1,3,2,4-benzodithiadiazines with aromatic phosphines and phosphites
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Although an interaction between hydrocarbon and fluorocarbon 1,3,2,4-benzodithiadiazines (1) and P(C6H5)3 continuously produces chiral 1,2,3-benzodithiadiazol-2-yl iminophosporanes (2; in this work, 5,7-difluoro derivative 2a ) via 1:1 condensation, an interaction between 1 and other PR3 reagents gives different products. With R = OC6H5 and both hydrocarbon and fluorocarbon 1, only X=P(OC6H5)3 (X = S, O) were identified in the complex reaction mixtures by 13C and 31P NMR and GC-MS. With R = C6F5, no interaction with the archetypal 1 was observed but catalytic addition of atmospheric water to the heterocycle afforded 2-amino-N-sulfinylbenzenesulfenamide (4). With electrophilic B(C6F5)3 instead of nucleophilic P(C6F5)3, only adduct H3N→B(C6F5)3 and a new polymorph of C6F5B(OH)2 were isolated and identified by X-ray diffraction (XRD). A molecular structure of 2a was confirmed by XRD, and the π-stacked orientation of one of phenyl groups and heterocyclic moiety was observed. This structure is in general agreement with that calculated at the RI-MP2 level of theory, as well as at three different levels of DFT theory with the PBE and B3LYP functionals. Mild thermolysis of 2a in a dilute decane solution gave persistent 5,7-difluoro-1,2,3-benzodithiazolyl (3a) identified by EPR in combination with DFT calculations.
- Grayfer, Tatiana D.,Makarov, Alexander Yu,Bagryanskaya, Irina Yu,Irtegova, Irina G.,Gatilov, Yuri V.,Zibarev, Andrey V.
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- METHOD OF PREPARING BIPHENYL-4-YL DIPHENYL PHOSPHATE COMPOSITION
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Provided is a method of preparing a biphenyl-4-yl diphenyl phosphate composition for use as a flame retardant or a plasticizer for resin, including mixing phosphoryl chloride (POCl3), 4-phenylphenol, and a catalyst, so that first dehydrochlorination occurs; and further adding phenol, so that second dehydrochlorination occurs.
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Paragraph 0019
(2013/07/19)
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- Synthesis and coordination properties of new preorganized ligand on the triphenylphosphine oxide platform
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Tris(2-cyanomethoxyphenyl)phosphine oxide was synthesized by the reaction of tris-(2-hydroxyphenyl)phosphine oxide with chloroacetonitrile. Its coordination properties were studied for the complexation with neodymium(III) and copper(ii) nitrates using vibrational spectroscopy, NMR, and quantum chemical calculations.
- Kudryavtsev,Baulina,Pasechnik,Aisin,Matveev,Petrovskii,Nifant'Ev
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p. 1086 - 1090
(2014/03/21)
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- METHOD OF PREPARING BIPHENYL-4-YL DIPHENYL PHOSPHATE COMPOSITION
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Provided is a method of preparing a biphenyl-4-yl diphenyl phosphate composition for use as a flame retardant or a plasticizer for resin, including mixing phosphoryl chloride (POCl3), 4-phenylphenol, and a catalyst, so that first dehydrochlorination occurs; and further adding phenol, so that second dehydrochlorination occurs.
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Page/Page column 5; 6
(2012/02/02)
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- Low Triphenylphosphate, High Phosphorous Content Isopropyl Phenyl Phosphates With High Ortho Alkylation
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The present invention relates to low triphenyl phosphate, high phosphorous content aryl phosphates with high ortho alkylation that are suitable for use as flame retardant compositions, processes for their preparation, and their use as flame retardants.
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- Catalytic synthesis of triaryl phosphates from white phosphorus
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Triaryl phosphates were synthesized from white phosphorus and phenols under aerobic conditions and in the presence of iron catalysts and iodine. Full conversion to phosphates was achieved without the use of chlorine, and the reactions do not produce acid waste. Triphenyl phosphate, tritolyl phosphate and tris(2,4-di-tert-butyl)phenyl phosphate were synthesized by this method with high selectivities. Various iron(III) diketonates were used to catalyze the conversion. Mechanistic studies showed that the reaction proceeds by formation of PI3, then O=PI(OPh)2 before the final formation of the phosphate. The nucleophilic substitution of O=PI(OPh)2 with phenol to form O=P(OPh)3 was found to be the rate-limiting step.
- Armstrong, Kenneth M.,Kilian, Petr
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experimental part
p. 2138 - 2147
(2011/06/28)
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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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- Substitution- and elimination-free phosphorylation of functionalized alcohols catalyzed by oxidomolybdenum tetrachloride
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Among 14 oxidometallic species examined for catalytic phosphorylation of the tested alcohols, oxidomolybdenum tetrachloride (MoOCl4) was found to be the most efficient with a negligible background reaction mediated by triethylamine (Et3N). The new catalytic protocol can be applied to the chemoselective phosphorylations of primary, secondary and tertiary alcohols as well as the substitution-free phosphorylations of allylic, propargylic, and benzylic alcohols. Functionalized alcohols bearing acetonide, tetrahydropyranyl ether, tert-butyldimethylsilyl ether, or ester group are also amenable to the new catalytic protocol. The most difficult scenarios involve substitution-free phosphorylations of 1-phenylethanol and 1-(2-naphthyl)ethanol which can be effected in 95 and 90% yields, respectively. ESI-MS, IR, 1H, and 31P NMR spectroscopic analyses of the reaction progress suggest the intermediacy of an alkoxyoxidomolybdenum trichloride-triethylamine adduct such as [(RO)Mo(O)Cl3-Et3N] to be responsible for the catalytic turnover.
- Liu, Cheng-Yuan,Pawar, Vijay D.,Kao, Jun-Qi,Chen, Chien-Tien
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experimental part
p. 188 - 194
(2010/07/03)
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- A flash photolysis and theoretical study of the reaction of arylnitroso oxides with phosphorus(III) compounds
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The kinetic features of the reaction of aromatic nitroso oxides (ArNOO) with tri-n-butyl phosphite and substituted phosphines were studied by flash photolysis. It was shown that the trans-isomers of nitroso oxides enter into the reaction. The mechanism of the reaction was studied by theoretical methods, and the inertness of the cis-form of ArNOO was explained.
- Khursan,Kovaleva,Chainikova,Talipov,Safiullin
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experimental part
p. 284 - 289
(2011/11/12)
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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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body text
p. 1879 - 1881
(2009/10/10)
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- DIARYL ALKYLPHOSPHONATES AND METHODS FOR PREPARING SAME
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A method for preparing substantially pure optionally substituted diaryl alkylphosphonates from an optionally substituted triarylphosphite and an optionally substituted trialkylphosphite or an optionally substituted alkanol under special reaction conditions is described.
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Page/Page column 25-26
(2010/11/28)
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- Efficient aerobic oxidation of phosphines, phosphites, and sulfides by using trialkylborane
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Treatment of phosphines, phosphites, or sulfides with trialkylborane under air afforded the corresponding oxides in good yields.
- Motoshima, Kosuke,Sato, Akinori,Yorimitsu, Hideki,Oshima, Koichiro
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experimental part
p. 2229 - 2231
(2009/08/08)
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- Surface-mediated solid phase reactions: A simple, efficient and base-free synthesis of phosphonates and phosphates on Al2O3
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Al2O3-supported solvent free condensation of alkylphosphonic dichlorides with alcohols at room temperature yielded phosphorus esters in excellent yields.
- Acharya, Jyotiranjan,Shakya, Purushottam D.,Pardasani, Deepak,Palit, Meehir,Dubey, Devendra K.,Gupta, Arvind K.
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p. 194 - 196
(2007/10/03)
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- Anti-inflammatory and psoriasis treatment and protein kinase inhibition by hydroxy stilbenes and novel stilbene derivatives and analogues
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The present invention provides novel diphenyl ethene compounds and pharmaceutically-acceptable salts thereof. Also provided are methods for making the compounds of the invention as well as methods for the use thereof in the treatment of immune, inflammatory, and auto-immune diseases.
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- PROCESS FOR PREPARATION OF PHOSPHORIC ESTERS
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A process for preparing a phosphoric ester, comprising: Step (1) of reacting naphthol with phosphorus oxychloride in a molar ratio of 1:1.3 or more in the presence of a metallic halide and removing unreacted phosphorus oxychloride and Step (2) of reacting the reaction product of Step (1) with phenol in a molar ratio (molar ratio of chlorine contained in the reaction product to phenol) of 1:1-1.5 and removing hydrogen chloride produced as a by-product to thereby obtain a phosphoric ester represented by the general formula (I): wherein n is 1 or 2.
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- Synthesis of phosphorus derivatives from 1,3-dioxolan-2-one
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A new route for the synthesis of some mixed organic phosphorus compounds from 1,3-dioxolan-2-one is reported. By heating a mixture of phosphorus-chlorine derivatives and 1,3-dioxolan-2-one in the presence of a catalyst, mixed phosphorus derivatives having 2-chloroethyl ester groups could be obtained. A wide range of phosphorus derivatives can be obtained using this method.
- Ilia, Gheorghe,Bora, Alina,Iliescu, Smaranda,Popa, Adriana,Dehelean, Gheorghe
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p. 2491 - 2496
(2007/10/03)
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- An improved method for Lewis acid catalyzed phosphoryl transfer with Ti(t-BuO)4
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Several inorganic esters have been evaluated as phosphoryl transfer catalysts. Of these, Ti(t-BuO)4 was found to be the most effective catalyst giving excellent yields of the desired phosphate esters. The loading of the catalyst could be reduced to a little as 5 mol % for a majority of substrates with no loss in the yield of product. This methodology is significantly more versatile than using TiCl4 and is suitable for the phosphorylation of more complex carbohydrates and molecules of biological interest.
- Jones, Simon,Selitsianos, Dimitrios,Thompson, Kate J.,Toms, Steven M.
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p. 5211 - 5216
(2007/10/03)
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- A simple, general and improved procedure for phosphorylation of alcohols catalyzed by indium(III) chloride
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A general and efficient procedure has been developed for the preparation of dialkyl phosphate esters by indium(III) chloride catalyzed phosphoryl transfer from diethyl and diphenyl chlorophosphate to a variety of alcohols and phenols in THF in presence of triethylamine.
- Ranu, Brindaban C.,Das, Arijit
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p. 1063 - 1064
(2007/10/03)
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- Anti-inflammatory and psoriasis treatment and protein kinase inhibition by hydroxyltilbenes and novel stilbene derivatives and analogues
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Disclosed herein are compositions containing hydroxylstilbenes or their derivatives or analogues. The compositions are useful to inhibit protein kinease, and for the treatment of inflammatory diseases, including psoriasis, multiple sclerosis, rhumatoid arthritis, restinosis, inflammatory bowel disease, and inflammatory lung disease. They are also useful to treat surgical adhesions and graft rejection. Novel derivatives and analogues are also disclosed.
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- A simple and effective method for phosphoryl transfer using TiCl4 catalysis
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(graph presented) A number of Lewis acids have been evaluated as catalysts for the phosphoryl transfer, the most efficient being TiCl4. Application of this methodology to the phosphorylation of a number of representative target alcohols is presented.
- Jones, Simon,Selitsianos, Dimitrios
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p. 3671 - 3673
(2007/10/03)
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- Regioselective oxygenations of s-trans dienes, silyl dienol ethers (SDEs), by triphenyl phosphite ozonide (TPPO) and its mechanistic study
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The direct oxygenation of s-trans dienes, silyl dienol ethers (SDEs) 2, by triphenyl phosphite ozonide (TPPO) has been examined in detail. The regioselective oxygenation was found to give hydroperoxide 3, alcohol 4, ketone 5, dimer 6, and peroxy phosphate 7 with concomitant formation of triphenyl phosphate 8 and diphenyl trimethylsilyl phosphate 10. The formation of peroxy phosphate 7 was found for the first time in TPPO oxygenation reactions. The low temperature31P and1H NMR spectroscopic analyses proved the direct reaction of SDEs with TPPO without generation of singlet oxygen. The formation of the oxygenated products 3-7 is reasonably explained by the intervention of the zwitterion ZI, which can be formed by the nucleophilic attack of SDE to the central oxygen of the ozonide. The regioselective attack of SDE to the central oxygen of the ozonide was supported by the quantum chemical calculation (B3LYP/6-31G*).
- Mori,Abe,Nojima
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p. 3548 - 3553
(2007/10/03)
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- Diisocyanates containing hydantoin groups and polyurethanes in which they are present
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Diisocyanates of the formula (I) where R1is a C1-C10-hydrocarbon radical and R3is a C1-Cl2-hydrocarbon group and n is an integer from 1 to 10, are described.
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- Electrochemical Functionalization of White Phosphorus
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An electrochemical method, based on the joint action of nucleophilic and electrophilic reagents on P4, is proposed in order to utylize white phosphorus in the formation of the esters of phosphorus acids.
- Budnikova, Y. H.,Kargin, Y. M.,Sinyashin, O. G.
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p. 565 - 568
(2007/10/03)
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