- Efficient and convenient one-pot synthesis of phosphoramidates and phosphates
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A simple and efficient one-pot method is described for the synthesis of phosphoramidates/phosphates in excellent yields from dialkylphosphites and trichloroisocyanuric acid in acetonitrile and subsequent treatment with dialkyl amines/alcohols. The procedure is operationally simple, has reduced reaction times, and uses a one-pot procedure. Copyright Taylor & Francis Group, LLC.
- Gupta,Acharya,Dubey,Kaushik
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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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- Recyclable copper catalyst on chitosan for facile preparation of alkyl/aryl mixed phosphates via deaminated esterification between diphenylphosphoryl azides and aliphatic alcohols
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An efficient methodology was established for the preparation of alkyl/aryl mixed phosphates under aerobic conditions promoted by a easily recoverable heterogeneous catalyst. This highly active copper catalyst was obtained by directly mixing of copper precursor with chitosan solution, followed by a simple work-up process. In this catalytic system, different phosphoryl azides and aliphatic alcohols were employed to generate desired products in moderate to excellent yields with good functional group tolerance. This protocol provided a practical application of the chitosan supported heterogeneous copper catalyst towards a novel P–O bond formation.
- Hao, Qingqing,Hong, Qian,Jiao, Lin-Yu,Li, Zhuo,Liu, Shanshan,Ma, Xiao-Xun,Ning, Zi-Hui,Sun, Ming,Xu, Long,Zhang, Ze
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- Method for catalytically synthesizing phosphoric acid mixed ester compound by using chitosan-loaded copper
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The invention relates to a method for synthesizing a phosphoric acid mixed ester compound under the catalysis of chitosan-loaded copper. The preparation method comprises the following steps of: sequentially adding an azido phosphate compound, a chitosan-l
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Paragraph 0061-0065
(2020/10/19)
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- Copper catalyzed synthesis of aryl/alkyl mixed phosphates from diphenylphosphoryl azides and aliphatic alcohols under mild conditions
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An efficient and convenient one-pot protocol is developed to prepare aryl/alkyl mixed phosphates in the presence of copper catalyst under exceptionally mild conditions. A series of versatile, ubiquitous, and inexpensive phosphoryl azides and aliphatic alcohols are combined for the first time ever. Diphenylphosphoryl azide is employed as novel phosphors reagent through an unexpected cleavage of P[sbnd]N bond. The transformation is advantageous with respect to a broad of functional group compatibility and different esterification products are isolated in good to excellent results. This new catalytic system represents a superior platform towards a mild, operationally simple, practical, and scalability alternative to access target molecules. Furthermore, a plausible mechanism is proposed based on insightful mechanistic studies.
- Jiao, Lin-Yu,Zhang, Ze,Yin, Xiao-Mei,Li, Zhuo,Ma, Xiao-Xun
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- Synthesis method of copper-catalyzed phosphate mixed ester compound
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The invention provides a synthesis method of a copper-catalyzed phosphate mixed ester compound. The synthesis method comprises the steps that a phosphate ester azide compound and fatty alcohol are mixed, then a copper catalyst is added, alkali is added, reaction is conducted at the temperature of 20-100 DEG C for 3-24 h, and the phosphate mixed ester compound is obtained through aftertreatment. According to the synthesis method, the phosphate ester azide compound and the fatty alcohol are adopted to synthesize the phosphate mixed ester compound for the first time, in the synthesis process, only the copper catalyst and the alkali with the catalytic dosage are needed to be added, operation is easy, the defect of needing inert gas protection is overcome, and the synthesis method is novel andefficient.
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Paragraph 0036-0038
(2019/10/17)
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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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- 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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- Simple and compelling biomimetic metal-organic framework catalyst for the degradation of nerve agent simulants
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Inspired by biology, in which a bimetallic hydroxide-bridged zinc(II)-containing enzyme is utilized to catalytically hydrolyze phosphate ester bonds, the utility of a zirconium(IV)-cluster-containing metal-organic framework as a catalyst for the methanolysis and hydrolysis of phosphate-based nerve agent simulants was examined. The combination of the strong Lewis-acidic ZrIV and bridging hydroxide anions led to ultrafast half-lives for these solvolysis reactions. This is especially remarkable considering that the actual catalyst loading was a mere 0.045 % as a result of the surface-only catalysis observed. Nervous breakdown: UiO-66, a biomimetic metal-organic framework based on a zirconium oxo cluster, is capable of rapidly catalyzing the breakdown of phosphate-based nerve agent simulants. UiO-66 catalyzes both methanolysis and hydrolysis of the nerve agent simulant methyl paraoxon (shown in the graphic, R=CH3) with high catalytic efficiency.
- Katz, Michael J.,Mondloch, Joseph E.,Totten, Ryan K.,Park, Jin K.,Nguyen, Sonbinh T.,Farha, Omar K.,Hupp, Joseph T.
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p. 497 - 501
(2014/01/23)
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- Enhanced catalytic decomposition of a phosphate triester by modularly accessible bimetallic porphyrin dyads and dimers
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A series of metalloporphyrin dimers were modularly prepared and shown to catalyze the methanolysis of a phosphate triester, yielding rates that are large compared to the rate of the uncatalyzed reaction. Up to 1300-fold rate acceleration can be achieved v
- Totten, Ryan K.,Ryan, Patrick,Kang, Byungman,Lee, Suk Joong,Broadbelt, Linda J.,Snurr, Randall Q.,Hupp, Joseph T.,Nguyen, Sonbinh T.
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supporting information; experimental part
p. 4178 - 4180
(2012/05/05)
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- Hydrolysis of organophosphate esters: Phosphotriesterase activity of metallo-ss-lactamase and its functional mimics
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The phosphotriesterase (PTE) activity of a series of binuclear and mononuclear zinc(II) complexes and metallo-β-lactamase (mβl) from Bacillus cereus was studied. The binuclear complex 1, which exhibits good mβl activity, shows poor PTE activity. In contrast, complex 2, a poor mimic of mβl, exhibits much higher activity than 1. The replacement of Cl - ligands by OH- is important for the high PTE activity of complex 2 because this complex does not show any catalytic activi-ty in methanol. The natural enzyme mssl from B. cereus is also found to be an inefficient catalyst in the hydrolysis of phosphotriesters. These observations indicate that the binding of -lactam substrates at the binuclear zinc(II) center is different from that of phosphotriesters. Furthermore, phospho diesters, the products from the hydrolysis of triesters, significantly inhibit the PTE activity of mβl and its functional mimics. Although the mononuclear complexes 3 and 4 exhibited significant mβl activity, these complexes are found to be almost inactive in the hydrolysis of phosphotriesters. These observations indicate that the elimination of phosphodiesters from the reaction site is important for the PTE activity of zinc(II) complexes.
- Tamilselvi,Mugesh, Govindasamy
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experimental part
p. 8878 - 8886
(2010/11/02)
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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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- An efficient method for the esterification of phosphonic and phosphoric acids using silica chloride
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Silica chloride is used as an effective heterogeneous catalyst for the rapid esterification of alkyl/aryl phosphonic/phosphoric acids to their corresponding alkyl/aryl phosphonates/phosphates under mild conditions with quantitative yields.
- Sathe, Manisha,Gupta, Arvind K.,Kaushik
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p. 3107 - 3109
(2007/10/03)
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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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- Alpha- haloenamine reagents
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The present invention describes immobilized haloenamine reagents, immobilized tertiary amides, methods for their preparation, and methods of use.
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- THE NATURE AND CONSEQUENCES OF THE INTERACTION OF PHOSPHORYL NUCLEOPHILES WITH A TRIORGANOSILYL CHLORIDE
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In order to throw light on the possible role of positively charged tetra-coordinate silicon intermediates in the racemization of α-NpPhMeSiCl (1) induced by uncharged nucleophiles two sets of kinetic studies have been carried out.In the first the rates of two reactions namely racemization of 1 catalysed by (PhO)2(Me3SiO)P=O (2) and transsilylation of 2 with 1, which take place together and are believed to involve the same intermediate were determined; the transsilylation was found to be faster than the racemization, and involved transient formation of an optically active product.In the second the racemization of 1 catalysed by HMPT in various CCl4/CH2Cl2 mixtures was studied; the rate was found to increase markedly with increase in the dielectric constant of the medium.The results of both sets of experiments were consistent with a mechanism involving a silyloxyphosphonium cation intermediate.
- Chojnowski, J.,Cypryk, M.,Michalski J.,Wozniak, L.
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p. 275 - 282
(2007/10/02)
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- Successive Displacements of Phenoxy by Methoxy Groups in Triphenyl Phosphite Ozonide: Mechanism of the Accelerated Singlet Oxygen Formation with Pyridine and Methanol
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The ozonides from triphenyl phosphite, methyl diphenyl phosphite, and phenyl dimethyl phosphite form a series (1-3) which liberate singlet thermally at rates incresing by an order of magnitude for each substitution of methoxy for phenoxy.Trimethyl phosphite ozonide (4) fits in this series, although the very low temperature limit of its stability has not been determined.When triphenyl phosphite ozonide (1) is treated with methanol and pyridine in methylene chloride and yields singlet oxygen at an accelerated rate, the phenyl methyl phosphates 6 and 7 and trimethyl phosphate (8) are produced in a total amount corresponding to the singlet oxygen evolved.The lower the temperature, the greater the predominance of trimethyl phosphate (8) in the product.Each of the mixed phosphite ozonides 2 and 3 is in turn subject to accelerated singlet oxygen formation by the action of methanol and pyridine; in each case the phosphates formed contain at least one more methoxy group than the starting ozonide.These facts establish the mechanism of the accelerated singlet oxygen liberation as a successive displacement of phenoxy by methoxy groups on the initial phosphite ozonide, each newly formed aliphatic-aromatic phosphite ozonide decomposing thermally at its own increased rate.
- Bartlett, Paul D.,Lonzetta, Charles M.
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p. 1984 - 1988
(2007/10/02)
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- ACTIVATION OF CARBOXYL GROUPS BY DIPHENYL 2-OXO-3-OXAZOLINYLPHOSPHONATE. FACILE PREPARATION OF VERSATILE REAGENTS, 3-ACYL-2-OXAZOLONES
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Synthetic utility of the 2-oxazolone moiety as an excellent new leaving group is described.Based on such a function of the heterocycles, diphenyl 2-oxo-3-oxazolinylphosphonate has been newly introduced as a carboxyl-activating reagent which permits a facile direct preparation of 3-acyl-2-oxazolones and amides including peptides from a wide variety of carboxylic acids.The 3-acyl-2-oxazolides also serve as versatile reactive agents for highly chemoselective acyl-transfer to the nucleophilic species such as amines, alcohols and thiols, providing convenient and high-yield routes to amides, esters and thiol esters under mild conditions.They are also useful intermediates for ketones and alcohols.
- Kunieda, Takehisa,Higuchi, Tsunehiko,Abe, Yoshihiro,Hirobe, Masaaki
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p. 3253 - 3260
(2007/10/02)
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- Nouvelle methode de preparation d'esters phosphoriques, renfermant un groupe β-mercaptoethyle, utilisables en synthese nucleotidique
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The 2-alkoxy-2-oxo-1,3,2-dioxaphospholanes are easy to prepare and react with thiolate anions, giving in good yields phosphodiesters carrying a β-mercaptoethyl group used as a protecting group.Application of this reaction to 5'-o-monomethoxytritylthymidine easily leads to the nucleoside 3'-phosphodiester from which fully protected TpT and TpTp have been prepared.
- Thuong, Nguyen Thanh,Chassignol, Marcel,Asseline, Ulysse,Chabrier, Pierre
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