- Fluorinated phosphorus compounds: Part 11. The reactions of some fluorinated amines with dialkyl and bis(fluoroalkyl) phosphorochloridates
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Dimethyl phosphorochloridate reacted with RFCH 2NH2 in ether in the presence of Et3N to afford (MeO)2P(O)NHCH2RF, where RF = CF3 and C2F5, in 39 and 47% yield, respectively. Similar reactions with di-n-propyl and diisopropyl phosphorochloridates could be effected only with H2NCH 2CF3 when 4-dimethylaminopyridine catalyst was added and (n-PrO)2P(O)NHCH2CF3 and (i-PrO) 2P(O)NHCH2CF3 were isolated in 49 and 25% yield, respectively. Treatment of POCl3 with one molar equivalent each of H2NCH2CF3 and Et3N permitted the synthesis of Cl2P(O)NHCH2CF3 in 43% yield. Bis(fluoroalkyl) phosphorochloridates (RFO)2P(O)Cl, where RF = C2F5CH2, C3F 7CH2 and (CF3)2CH, reacted with 2,2,2-trifluoroethylamine and 2,2,3,3,3-pentafluoropropylamine to furnish phosphoramidates (RFO)2P(O)NHCH2R, where R = CF3 or C2F5, in yields of 32-67%.
- Timperley, Christopher M.,Waters, Matthew
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Read Online
- Synthesis and in vitro cytotoxicity and antibacterial activity of novel1,2,3-triazol-5-yl-phosphonates
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Novel1,2,3-triazol-5-yl-phosphonates were prepared by the copper(I)-catalyzed domino reaction of phenylacetylene, organic azides and dialkyl phosphites. The process was optimized on the synthesis of the dibutyl (1-benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)phosphonate in respect of the catalyst, the base and the solvent, as well as of the reaction parameters (molar ratio of the starting materials, atmosphere, temperature and reaction time). The method elaborated could be applied to a range of organic azides and dialkyl phosphites, which confirmed the large scope and the functional group tolerance. The in vitro cytotoxicity on different cell lines and the antibacterial activity of the synthesized1,2,3-triazol-5-yl-phosphonates was explored. According to the IC50 values determined, only modest antibacterial effect was detected, while some derivatives showed moderate activity against human promyelocytic leukemia HL-60 cells.
- Bálint, Erika,Hackler, László,Kari, Beáta,Puskás, László G.,Szabó, Pál Tamás,Tóth, Emese,Tripolszky, Anna
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- Method for preparing phosphite diester by transesterification
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The invention discloses a method for preparing phosphite diester by transesterification. Dimethyl phosphite and monohydric alcohol which are used as raw materials are stirred, reacted and rectified under the action of a basic catalyst to prepare the phosphite diester, so the problems of high deice requirements and large amount of acid-containing three wastes in the process of producing the phosphite diester by reacting phosphorus trichloride with alcohol are avoided. The method has the advantages of low raw material toxicity, simple process, mild reaction conditions, low device requirements, low pollution, high raw material conversion rate, high product selectivity, stable supply of the raw materials, provision of the phosphite diester used for fine chemical engineering or medical intermediates by dimethyl phosphite production enterprises, high added values of the product, and provision of a new way for the synthesis of the phosphite diester.
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Paragraph 0026
(2020/01/25)
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- Continuous flow alcoholysis of dialkyl h-phosphonates with aliphatic alcohols
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The continuous flow alcoholysis of dialkyl H-phosphonates by aliphatic alcohols in the absence of a catalyst was elaborated using a microwave (MW) reactor equipped with a flow cell. By the precise control of the reaction conditions, the synthesis could be fine-tuned towards dialkyl H-phosphonates with two different and with two identical alkyl groups. In contrast to the “traditional” batch alcoholysis, flow approaches required shorter reaction times, and the products became available at a larger scale.
- Bálint, Erika,Tajti, ádám,Tóth, Nóra,Keglevich, Gy rgy
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- Electrophilic trifluoromethylation of S-hydrogen phosphorothioates
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A series of S-hydrogen phosphorothioates have been converted to the corresponding S-trifluoromethyl derivatives upon reaction with the electrophilic trifluoromethylation reagent 1 (trifluoromethyl 1,3-dihydro-3,3-dimethyl-1,2- benziodoxole). Relative rate data were obtained by 19F NMR monitoring of competition experiments and were evaluated by means of the Taft equation. A high positive polar sensitivity factor of 2.55 was found for electron-rich substrates and a negative one of -0.37 for electron-poor ones, implying the involvement of two different rate-determining steps. Furthermore, the reaction was found to be unaffected by steric factors.
- Santschi, Nico,Togni, Antonio
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experimental part
p. 4189 - 4193
(2011/07/31)
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- Diastereoselective synthesis of new dialkylphosphorylhydrazones
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A series of 22 dialkylphosphorylydrazones (dialkyl ester, N′-[(1E)-(R1 phenyl)methylene]-phosphorohydrazidic acid), 20 of them new, along with three new N,N′-bis (diisobutylphosphorylthioamide)diamines (bis-[diisobutyl ester), N-thioxomethylene]-, diamine)phosphora-midic acid, were prepared and characterized by IR, 1H NMR, 13C NMR, 31P NMR, and mass spectrometry. The analysis of 1H NMR, 13C NMR, 31P NMR, and NOE spectra confirmed the observation of the single diastereoisomer E in the synthesis of dialkylphosphorylydrazones. The results of a molecular modeling study performed in order to investigate the mechanism of the synthesis of dialkylphosphorylydrazones are in agreement with the experimental results, i.e., the favored formation of diastereoisomer E over Z.
- Rodrigues, Janaina Marques,Sant'anna, Carlos Mauricio R.,Rumjanek, Victor Marcos,Dacosta, Joao Batista Neves
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experimental part
p. 40 - 56
(2010/04/26)
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- Synthesis of O,O-dialkyl 2-oxo-2-(4-(selenomorpho-linosulfonyl)phenylamino) ethylphosphonate
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A series of O,O-dialkyl 2-oxo-2-(4-(seleomorpholinosulfonyl)phenylamino) ethy lphosphonate were synthesized by reactions of 2-chloro-N-(4- (seleomorpholino sulfonyl)phenyl)acetamide with dialkylphosphite in the presence of sodium hydride. The structure of all new compounds has been confirmed by 1H NMR,31P NMR, IR, Mass spectroscopy and elemental analyses. Copyright Taylor & Francis Group, LLC.
- Wang, Fang,Hu, Liming,Li, Xiaopeng,Xu, Xuemei,Du, Hongguang
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scheme or table
p. 610 - 616
(2009/04/11)
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- An efficient synthesis of O,O- di propyl (E)-2-[1-methyl 2-oxopropylidene]phosphorohydrazidothiolate (E) oxime and its analogues: A potential marine toxin
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An efficient method for the synthesis of Ptychodiscus brevis toxin O,O- di n-propyl (E)-2-[1-methyl 2-oxopropylidene]phosphorohydrazidothiolate (E) oxime (TG-1) and its analogues has been developed using thermally stable and recyclable silica gel and Na2SO4 as a condensing agent and water scavenger, respectively. The compounds were evaluated against fish Rasbora daniconius by determining the LC50 and LC90 values. The results of biological evaluation showed that these compounds have high degree of toxicity. Copyright Taylor & Francis Group, LLC.
- Gupta, Arvind K.,Dubey,Parashar,Kaushik
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scheme or table
p. 1892 - 1910
(2009/08/07)
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- Synthesis of dialkyl phosphites and trialkyl phosphates by oxidation of sodium hypophosphite by copper(II) chloride
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Sodium hypophosphite oxidazies in alcoholic solution of CuCl2 at 50-80 deg C to give dialkyl phosphite and trialkyl phosphate.The yield of trialkyl phosphate increases with decreasing molecular weight of the alcohol and reaches ca. 100percent for MeOH and EtOH.The optimal conditions were found, and the mechanism of oxidation of NaPH2O2 to (RO)2PHO and (RO)3PO by copper(II) chloride was studied.The reaction proceeds via the formation of alkyl hypophosphite and copper(II) complexes with alkyl hypophosphite and dialkyl phosphite, which undergo inner-sphere two-electron redox decomposition with the liberation of dialkyl phosphite and trialkyl phosphate, respectively.
- Dorfman, Ya. A.,Aleshkova. M. M.
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p. 515 - 520
(2007/10/03)
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- Phosphino Sulphonates, a Type of PIII-anhydride and Their Isomerisation into Phosphinoyl Sulphinates: a Novel Rearrangement in Phosphorus-Sulphur Chemistry
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The imidazolides (1) react smoothly with RSO3H to afford a novel class of trico-ordinate phosphorus anhydride, the phosphino sulphonates (2); under suitable structural circumstances the compounds (2) undergo a novel type of rearrangement, (2) -> (6), which provides the first example of a phosphinoyl sulphinate structure (6).
- Dabkowski, Wojciech,Michalski, Jan,Skrzypczynski, Zbigniew
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p. 1260 - 1261
(2007/10/02)
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