- 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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- 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 0106-0110
(2019/10/17)
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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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- P-Toluenesulfonic acid-Celite as a reagent for synthesis of esters of alkylphosphonic acids under solvent-free conditions
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The coupling reaction of alkylphosphonic acids and alcohols on the surface of p-toluenesulfonic acid-Celite under mild and solvent-free conditions gave the corresponding phosphonates in excellent yields. This method provides a useful rapid synthesis of phosphonates for use in the unambiguous identification of chemical warfare agents.
- Gupta, Arvind K.,Kumar, Rajesh,Dubey, Devendra K.,Kaushik
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p. 328 - 331
(2008/02/10)
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- 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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p. 3403 - 3407
(2008/02/13)
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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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- Reaction of pyrimidyl esters of some phosphorus acids with isomeric butyl alcohols
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A series of pyrimidyl esters of some phosphorus acids was prepared with the purpose of investigation of their reaction with isomeric butyl alcohols. According to31P NMR data, the obtained phosphates all are capable of phosphorylating isomeric butyl alcohols. The reactions with diphenyl (4-oxo-3,4-dihydro-2-pyrimidyl) phosphate and diphenyl (2-pyrimidyl) phosphate occur in quantitative yield under mild conditions, and the reactions with diphenyl (4,6-dimethyl-2-pyrimidyl) phosphate and dibutyl (4,6-dimethyl-2-pyrimidyl) phosphate require severe conditions to occur. In the latter two cases, certain reaction selectivity was observed, depending on the nature of the solvent and some other factors. Pyrimidyl esters of sulfur-containing phosphorus acids do not react with isomeric butyl alcohols under the studied conditions.
- Semenov,Akamsin,Enikeev,Reznik
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p. 1386 - 1388
(2007/10/03)
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- ELECTROCHEMICAL REDUCTION OF TRIPHENYL PHOSPHATE
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The electrolytic reduction of triphenyl phosphate proceeds with the participation of tetrabutylammonium cations with the formation of butyl diphenyl phosphate in DMF.It was concluded that the step involving electron transfer to the triphenyl phosphate molecule has retarded character.
- Yanilkin, V. V.,Budnikova, Yu. G.,Kargin, Yu. M.,Gritsenko, E. I.,Strelets, V. V.
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p. 1149 - 1152
(2007/10/02)
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- Catalytic Hydrolysis of Phosphate Esters in Microemulsions. 3. Analysis of the Hydrolysis Products of p-Nitrophenyl Diphenyl Phosphate via 31P NMR
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An analysis of the hydrolysis products of p-nitrophenyl diphenyl phosphate (PNDP) in three different microemulsions via 31P NMR has proven that diphenyl phosphate is the major product and that p-nitrophenyl phenyl phosphate is the second most abundant product in each of the three media.For the media containing butanol, butyl diphenyl phosphate is observed as a third primary product.Numerous secondary products result from the hydrolysis of butyl diphenyl phosphate.
- Burnside, Beth A.,Szafraniec, Linda L.,Knier, Barry L.,Durst, H. Dupont,Mackay, Raymond A.,Longo, F.R.
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p. 2009 - 2011
(2007/10/02)
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- NEW PHOSPHORYLATING AGENTS FOR GENERAL SYNTHESIS OF MIXED PHOSPHATE ESTERS
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An effective procedure has been developed for the general synthesis of mixed alkyl or aryl phosphate esters by metal-catalyzed phosphorylation of alcohols with aryl bis(2-oxo-3-oxazolinyl)phosphinate.Among metallic acetylacetonates examined as catalysts, the zirconium complex was the most effective as in activity order of Zr(IV)> Ce(III)> Zn(II)> Mn(III)> Mn(II)-complexes.
- Nagamatsu, Tomohisa,Kunieda, Takehisa
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p. 2375 - 2378
(2007/10/02)
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- PHOSPHORORGANISCHE VERBINDUNGEN 96. DIE SELECTIVE VERKNUEPFUNG BIOLOGISCH WICHTIGER FUNKTIONELLER GRUPPEN MIT PHOSPHORORGANISCHEN SAEUREN
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Derivatives of phosphinic, phosphonic, and phosphoric acids of the general type R1R2P(O)X show selectivity in their reactions with nucleophiles RYH (R = n-C4H9; Y = O, NR or S) according the Eq. (1); the selectivity depends on the nature of the leaving group (X = Cl, F, CN, N3 or OC6H4NO2(p)) and the base used.The nature of the ligands R1 and R2, exert a comparatively minor influence on the reaction.Method: (a) The phosphylating agent R1R2P(O)X was allowed to react with mixture of two nucleophiles RYH and RY'H in competition (Reagent ratio 1:1:1).The product mixture (R1R2P(O)YR + R1R2P(O)Y'R was then analyzed. (b) Compounds of the type HY-CH2-CH2-Y'H (serine-n-butylamide L-cysteinmethylester) were reacted with the phosphylating agent R1R2P(O)X (reagent ratio 1:1) according the Eqs. (3) and (4) respectively.The products were isolated, identified and the yields quantitatively determined.Results: For X = F, CN, OC6H4NO2 (p), the O-ester is formed virtually exclusively.For X = Cl, only amides are formed.Azides (X = N3) show no selectivity.In competition reactions using n-butylamine and n-butylthiol, the organophosphorus chlorides (X = Cl) were found to be N-selective,, whereas the corresponding cyanides (X = CN) were S-selective.In competition reactions using n-butanol and n-butylthiol, the organophosphorus fluorides (X = F) p-nitrophenylesters (X = OC6H4NO2(p)) and cyanides (X = CN) were all O-selective.
- Horner, L,Gehring, R.
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p. 157 - 176
(2007/10/02)
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