- Reaction of N-(benzyloxycarbonyl)aminobenzylphosphonous acid with ethyl orthoformate
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Reaction of N-(benzyloxycarbonyl)aminobenzylphosphonous acid with ethyl orthoformate afforded two major products diethyl N(benzyloxycarbonyl)aminobenzylphosphinite and ethyl (diethoxymethyl)[N- (benzyloxy-carbonyl)aminobenzyl]phosphinate, a product of addition of phosphonous acid to orthoformate.
- Stano, Adrian,Mucha, Artur,Kafarski, Pawel
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- Synthesis of Pyridiniumboranephosphonate Diesters and Related Compounds using Trityl Cation as a Borane Hydride Acceptor
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Boranephosphonate diesters react with pyridine and some tertiary amines in the presence of dimethoxytrityl chloride used as a borane hydride acceptor, to afford the boron-modified phosphodiester analogues containing a P-B-N structural motif. The reaction provides a convenient entry to pyridinium- and ammoniumboranephosphonates derived from the corresponding alkyl, aryl, or nucleoside boranephosphonate diesters. Some aspects of the synthetic protocol, mechanistic features related to a possible intermediate involved, and the role of the solvents used, are discussed.
- Rachwalak, Marta,Go??biewska, Justyna,Jakubowski, Tomasz,Stawinski, Jacek
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- Access to α-aminophosphonic acid derivatives and phosphonopeptides by [Rh(P-OP)]-catalyzed stereoselective hydrogenation
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The hydrogenation of N-substituted vinylphosphonates using rhodium complexes derived from P-OP ligands L1, ent-L1, or (R,R)-Me-DuPHOS as catalysts has been successfully accomplished, achieving very high levels of stereoselectivity (up to 99% ee or de). Th
- Fernández-Pérez, Héctor,Lenartowicz, Pawe?,Carreras, Lucas,Grabulosa, Arnald,Kafarski, Pawe?,Vidal-Ferran, Anton
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- Electrochemical synthesis of phosphorus esters from white phosphorus in the presence of copper complexes and ethanol
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In the presence of white phosphorus the redox potentials of the copper ions change and the potential of the reduction wave of CuI/Cu 0 shifts noticeably toward more positive values. The Cu I-P4 complex is characterized by a lower value of the electrochemical gap, that is, higher polarizability and reactivity compared to those of the free CuI cation. Phosphorus esters can be synthesized from P4 and ethanol. The latter is in the composition of the copper(II) complexes, which act as a catalyst-charge mediator.
- Budnikom,Kafiyatullina,Sinyashin,Abdreimova
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- Reaction of diethyl butane-1-phosphonate with the surface of tin dioxide
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Reaction of diethyl butane-1-phosphonate with the surface of tin dioxide was studied. The reaction involves grafting of the phosphonate residue onto the oxide surface; in the process, one or both ethoxy groups are eliminated. The resulting grafted layer exhibits fairly high resistance to hydrolysis and heat.
- Ikaev,Polezhaeva,Mingalev,Lisichkin
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- Novel synthetic method of diethyl phosphite
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The invention relates to a synthetic method of diethyl phosphite. The method comprises the following steps: adding triethyl phosphite into a stirring reactor and heating to 30 - 60 in 70 - 80 °C minutes; carrying out chromatographic analysis by adding water to the stirring reactor for 60 minutes; and controlling the triethyl phosphite ≤ 0.3% to open the receiving bottle to carry out pressure reduction and rectification. The method is prepared by direct reaction of triethyl phosphite and water, and a solvent is not needed in the traditional process. No catalyst is needed, the reaction is mild, the yield is high, and the yield can reach ≥ 99%. Raw materials are easy to obtain, and the production cost can be effectively reduced. The method has the advantages of simple operation, no side reaction in the reaction process, good product purity, less 99% or more product purity, low cost, safety and environmental protection, and is suitable for industrial production.
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Paragraph 0022-0032
(2021/09/15)
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- Preparation method of important chemical raw material
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The invention provides a preparation method of diethyl phosphite, which is characterized by comprising the following steps: at room temperature, adding phosphorous acid, a silver catalyst and water into a reaction container with stirring until the reactants are dissolved; then slowly dropwise adding ethanol into the reaction container, simultaneously heating the system to 50-100 DEG C, reacting for 1-4 hours, stopping stirring after the reaction is finished, standing the system; collecting an organic layer, and performing reduced pressure distillation to obtain a product. As the soluble silver salt is adopted as the catalyst, the reaction can be quickly and efficiently catalyzed in water, compared with the prior art, the reaction condition is milder, the water is adopted as the solvent to be more environment-friendly, and as water is generated in the reaction and is consistent with the reaction solvent, the content of water is increased after the reaction; therefore, the method provided by the invention is more beneficial to the rapid separation of water-insoluble diethyl phosphite from the system, so that the post-treatment is simpler and more efficient, the reaction time is saved, and the yield and purity of the product are improved.
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Paragraph 0036-0051
(2021/06/06)
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- Photochemical Radical C–H Halogenation of Benzyl N-Methyliminodiacetyl (MIDA) Boronates: Synthesis of α-Functionalized Alkyl Boronates
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α-Haloboronates are useful organic synthons that can be converted to a diverse array of α-substituted alkyl borons. Methods to α-haloboronates are limiting and often suffer from harsh reaction conditions. Reported herein is a photochemical radical C-H halogenation of benzyl N-methyliminodiacetyl (MIDA) boronates. Fluorination, chlorination, and bromination reactions were effective by using this protocol. Upon reaction with different nucleophiles, the C?Br bond in the brominated product could be readily transformed to a series of C?C, C?O, C?N, C?S, C?P, and C?I bonds, some of which are difficult to forge with α-halo sp2-B boronate esters. An activation effect of B(MIDA) moiety was found.
- Yang, Ling,Tan, Dong-Hang,Fan, Wen-Xin,Liu, Xu-Ge,Wu, Jia-Qiang,Huang, Zhi-Shu,Li, Qingjiang,Wang, Honggen
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supporting information
p. 3454 - 3458
(2020/12/17)
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- A greener protocol for the synthesis of phosphorochalcogenoates: Antioxidant and free radical scavenging activities
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In this contribution, a metal- and base-free protocol has been developed for the synthesis of phosphorochalcogenoates (Se and Te) by using DMSO as solvent at 50 °C. A variety of phosphorochalcogenoates were prepared from diorganyl dichalcogenides and H-phosphonates, leading to the formation of a Chal-P(O) bond, in a rapid procedure with good to excellent yields. A full structural elucidation of products was accessed by 1D and 2D NMR, IR, CGMS, and HRMS analyses, and a stability evaluation of the phosphorochalcogenoates was performed for an effective operational description of this simple and feasible method. Typical 77Se{1H} (δSe = 866.0 ppm), 125Te{1H} (δTe = 422.0 ppm) and 31P{1H} (δP = ?1.0, ?13.0 and ?15.0 ppm) NMR chemical shifts were imperative to confirm the byproducts, in which this stability study was also important to select some products for pharmacological screening. The phosphorochalcogenoates were screened in vitro and ex vivo tests for the antioxidant potential and free radical scavenging activity, as well as to investigation toxicity in mice through of the plasma levels of markers of renal and hepatic damage. The pharmacological screening of phosphorochalcogenoates indicated that compounds have antioxidant propriety in different assays and not changes plasma levels of markers of renal and hepatic damage, with excision of 3g compound that increased plasma creatinine levels and decreased plasma urea levels when compared to control group in the blood mice. Thus, these compounds can be promising synthetic antioxidants that provide protection against oxidative diseases.
- Mailahn, Daniela H.,Iarocz, Lucas E.B.,Nobre, Patrick C.,Perin, Gelson,Sinott, Airton,Pesarico, Ana Paula,Birmann, Paloma T.,Savegnago, Lucielli,Silva, Márcio S.
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- Reaction of sodium N-benzylideneglycinate with dialkyl chlorophosphites in the presence of water
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The outcome of reaction of sodium N-benzylideneglycinate containing water in its crystal lattice with dialkyl chlorophosphites depends on the mode of addition of the latter. Upon the simultaneous mixing of the reactants, 1,4-bis[α-(dialkoxyphosphoryl)benz
- Dimukhametov, Mudaris N.,Mironov, Vladimir F.,Islamov, Daut R.,Litvinov, Igor A.,Gnezdilov, Oleg I.,Danilova, Yuliya V.
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p. 107 - 109
(2021/02/16)
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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 0025
(2020/01/25)
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- METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing an organophosphorus compound which has excellent energy efficiency without containing a halogenated alkyl or a by-product derived from a halogenated alkyl. SOLUTION: There is provided a method for producing an organophosphorus compound by reacting a trivalent organophosphorus compound represented by the following general formula (1) in the presence of a super strong acid and/or at least one acid catalyst containing a solid superstrong acid catalyst to generate a pentavalent organophosphorus compound represented by the following general formula. (where Z1 represents OR2 or R2; Z2 represents OR3 or R3; R1, R2 and R3 represent an alkyl group, an alkenyl group or the like; when R2 and R3 are an alkyl group or the like, R2 and R3 may be bonded to each other to form a cyclic structure; and R1 may be a hydrogen atom.) SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0084; 0094
(2020/05/02)
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- Sulfur phosphate compound, non-aqueous lithium ion battery electrolyte containing sulfur phosphate compound and lithium ion battery
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The invention discloses a thiophosphate compound, a synthesis method and a non-aqueous electrolyte. After the compound is applied to a battery with the non-aqueous electrolyte, even if the battery isunder high voltage, an electrode/electrolyte interface of a lithium ion battery is effectively improved, so that an electrode surface film is stabilized, side reactions are reduced, the stability of the battery under high temperature and high voltage is improved, and the cycling stability of the battery is improved, and meanwhile, the self-extinguishing time of the non-aqueous electrolyte after combustion is shortened, the flame retardance is improved, and the safety performance of the battery is improved.
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Paragraph 0040-0042; 0048-0050; 0054-0056; 0098; 0102-0112
(2020/12/14)
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- Phosphate compound and synthetic method thereof, and non-aqueous electrolyte
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The invention relates to a phosphate compound, a method for synthesizing the phosphate compound, and a non-aqueous electrolyte; the main means for suppressing side reactions on the surface of an electrode comprises coating an electrode active material and adding an effective film-forming additive to an electrolyte to form a passivation film having sufficient thickness and density on the surface ofthe electrode; the two means are undoubtedly used for preventing the electrolyte from contacting the surface of the electrode to obtain and lose electrons and preventing the surface of the electrodefrom being corroded by decomposition byproducts of the electrolyte. The phosphate compound disclosed by the invention has the beneficial effects that the phosphate compound is easy to prepare and purify, high in thermal stability, convenient to store, strong in compatibility with other components of an electrolyte and other components in a battery, moderate in viscosity, high in dielectric constant, capable of dissolving a lithium salt, has certain wetting capacity, and has flame-retardant and positive and negative electrode surface film-forming functions.
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Paragraph 0009; 0035; 0039; 0043
(2020/12/31)
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- Disulfide Promoted C?P Bond Cleavage of Phosphoramide: “P” Surrogates to Synthesize Phosphonates and Phosphinates
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A metal-free C?P bond cleavage reaction is described herein. Phosphoramides, a phosphine source, can react with alcohols to produce phosphonate and phosphinate derivatives in the presence of a disulfide. P?H2, P-alkyl, and P,P-dialkyl phosphoramides can be used as substrates to obtain the corresponding pentavalent phosphine products. (Figure presented.).
- Hou, Fei,Du, Xing-Peng,Alduma, Anwar I.,Li, Zhi-Feng,Huo, Cong-De,Wang, Xi-Cun,Wu, Xiao-Feng,Quan, Zheng-Jun
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p. 4755 - 4760
(2020/10/06)
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- Rhodium-catalyzed phosphorylation reaction of water-soluble disulfides using hypodiphosphoric acid tetraalkyl esters in water
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RhCl3 catalyzed the exchange reaction of disulfides and hypodiphosphoric acid tetraalkyl esters in water under homogeneous conditions, which indicated the hypodiphosphoric acid tetraalkyl esters to be novel and efficient phosphorylation reagent
- Arisawa, Mieko,Fukumoto, Kohei,Yamaguchi, Masahiko
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p. 13820 - 13823
(2020/04/23)
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- Water determines the products: An unexpected Br?nsted acid-catalyzed PO-R cleavage of P(iii) esters selectively producing P(O)-H and P(O)-R compounds
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Water is found able to determine the selectivity of Br?nsted acid-catalyzed C-O cleavage reactions of trialkyl phosphites: with water, the reaction quickly takes place at room temperature to afford quantitative yields of H-phosphonates; without water, the reaction selectively affords alkylphosphonates in high yields, providing a novel halide-free alternative to the famous Michaelis-Arbuzov reaction. This method is general as it can be readily extended to phosphonites and phosphinites and a large scale reaction with much lower loading of the catalyst, enabling a simple, efficient, and practical preparation of the corresponding organophosphorus compounds. Experimental findings in control reactions and substrate extension as well as preliminary theoretical calculation of the possible transition states all suggest that the monomolecular mechanism is preferred.
- Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
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supporting information
p. 2916 - 2922
(2019/06/18)
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- New synthesis of trimethylsilyl esters of phosphorus(III) acids
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Abstract: A novel synthetically important reaction has been developed for the quick, convenient, and high-yield preparation of trimethylsilyl esters of phosphorus(III) acids, synthetically valuable Michaelis–Arbuzov reaction precursors. Commercially and synthetically available initial compounds used are derivatives of propan-2-ol phosphorylated in the second position capable of long-term storage and available silylating reagents: hexamethyldisilazane, bis(trimethylsilyl)acetamide, and diethyl(trimethylsilyl)amine. Also, a stepwise reaction scheme of the starting compounds with silylating reagents has been proposed. Graphic abstract: [Figure not available: see fulltext.].
- Morgalyuk, Vasily,Strelkova, Tatyana,Brel, Valery
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p. 1993 - 1997
(2019/11/13)
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- Synthesis and Selected Reactions of 2(3)-Furoyl Phosphonates Functionalyzed at the Neighbor Position of the Furan Ring
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Reactions of 2-and 3-furoyl chlorides having chloromethyl or butylthiomethyl group in the adjacent position of the furan ring as well as of analogous N-morpholinomethylfuroyl chloride hydrochlorides with triethyl phosphite have been studied. The synthesized chloromethylfuroyl phosphonates have given the corresponding products of nucleophilic substitution in the reactions with sodium azide and potassium thiocyanate in the case of 4-chloromethyl-3-furoyl phosphonate. In the reaction of 3-chloromethyl-2-furoyl phosphonate with sodium azide, cleavage of the P-C bond takes place simultaneously with nucleophilic substitution. Potassium thiocyanate forms 3-thiocyanatomethyl-2-furoyl phosphonate in the reaction with this substance. The synthesized stable furoyl phosphonates enter the Wittig reaction with resonance-stabilized phosphoranes to give phosphorylated furylalkenes. If these compounds carry a chloromethyl group in the furan ring, they react with sodium azide and potassium thiocyanate to give the corresponding products of nucleophilic substitution. Analogously, aminomethyl derivatives have been obtained in the reaction with morpholine at room temperature.
- Pevzner,Sokolova
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p. 1604 - 1619
(2019/10/14)
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- Catalytic Phosphite Hydrolysis under Neutral Reaction Conditions
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Cationic phosphametallocene-based platinum(II) aqua complexes were used as efficient precatalysts for the hydrolysis of aromatic and aliphatic tertiary phosphites under neutral reaction conditions at room temperature, leading to the selective cleavage of one P-O bond of the phosphite. NMR labeling experiments combined with stoichiometric model reactions and theoretical density functional theory calculations, performed with the appropriate model compounds, shed light on the operative catalytic cycle, which comprises intramolecular water molecule transfer to the cis-coordinated phosphite molecule.
- Oberhauser, Werner,Manca, Gabriele
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supporting information
p. 4824 - 4827
(2018/05/17)
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- Method for continuously synthesizing diethyl phosphite in microchannel reactor
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The invention discloses a method for continuously synthesizing diethyl phosphite in a microchannel reactor, and belongs to the technical field of organic synthesis processes. More specifically, the method is a method for generating diethyl phosphite by a continuous reaction in a microchannel continuous flow reactor using anhydrous ethanol and phosphorus trichloride as a substrate and chloroform asa solvent, wherein the mixed solution of the chloroform and the phosphorus trichloride is a material A, the anhydrous ethanol solution is a material B, and the material A and the material B simultaneously enter a microchannel through a metering pump. According to the method, the efficient mass transfer and heat transfer efficiency of the microchannel reactor are utilized to effectively strengthenthe mass transfer rate between two-phase materials, and the safety and operability of an experiment are greatly improved.
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Paragraph 0029-0046
(2019/01/15)
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- SUPPORTED MOLYBDENUM PEROXO COMPLEXES FOR TRANSFORMING ORGANO PHOSPHATE NEUROTOXINS TO A VALUE-ADDED, COMMODITY PHOSPHORUS CHEMICAL
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The invention relates to degradation of organophosphate neurotoxins with molybdenum complexes. In particular, the degradation of phosphate ester neurotoxins can be performed with molybdenum peroxo complexes resulting in recoverable phosphorus-containing compounds.
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Paragraph 0022
(2018/10/21)
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- Reinvestigation of the iodine-mediated phosphoramidation reaction of amines and P(OR)3 and its synthetic applications
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A systematic study on the iodine-mediated phosphoramidation reaction of amines and trialkyl phosphites was conducted, which not only disclosed the factors affecting the reaction but also revealed that it could proceed smoothly in CH2Cl2 at room temperature in open air. Using this method, various phosphoramidates with different aliphatic amines and aromatic amines were synthesized in good to excellent yields. Our present investigation shows that this underused method is actually a mild, practical and general way to synthesize phosphoramidates and will have wide applications.
- Chen, Xunwei,Xiao, Zecai,Chu, Hanyu,Wang, Bo,Peng, Ai-Yun
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p. 6783 - 6790
(2018/09/29)
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- Diethyl phosphite production from phosphorothioate degradation with molybdenum peroxides and hydrogen peroxide in ethanol
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A polystyrene-supported molybdate-peroxide polymer (Mo-Y(s)) destroys phosphorothioate pesticides of the form (ArO)P(=S)(OEt)2 in EtOH under mild oxidative (H2O2) conditions and produces a commodity organophosphate. This is the first report of a metal-based system that successfully degrades the “live” pesticides parathion, diazinon and coumaphos. In addition to the operational advantages of heterogeneous reaction chemistry, the Mo-Y(s) support degrades multiple equivalents of the pesticide in H2O2(aq). Of particular importance is the predominant production of diethyl phosphite, a commodity chemical, from diazinon degradation over Mo-Y(s) in EtOH; no toxic oxon is found. Coumaphos and parathion produce the corresponding oxon which have ΔH? (kcal/mol) of 15.4 (0.5) and 21.7 (0.8), respectively; these activation parameters are consistent with key observations found in the relative amount of coumoxon and paraoxon produced. Finally, a discrete molybdate-peroxide complex is presented as a possible solution model for this heterogeneous reaction.
- Kuo, Louis Y.,Miao, Qianli,Bright, Emily,Inoue, Kei,Phillips, Owen,Seaman, Joe,Ng, Megan,Kang, Lauren
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supporting information
p. 229 - 234
(2018/09/05)
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- Reaction of Boranephosphonate Diesters with Amines in the Presence of Iodine: The Case for the Intermediacy of H-Phosphonate Derivatives
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Mechanistic and stereochemical aspects of the reaction of boranephosphonate diesters with amines promoted by iodine were investigated. This is a complex, multistep reaction that ultimately produces the corresponding phosphoramidate diesters via a formal replacement of the borane group by an amine moiety. We found by a stereochemical correlation analysis that, contrary to a literature report, the whole transformation proceeded with total inversion of the configuration at the phosphorus center. Our study also showed that instead of the postulated nucleophilic substitution by iodide at the phosphorus center of the initially formed intermediate, the corresponding iodoboranephosphonate, the crucial step of the reaction involved intermediacy of H-phosphonate derivatives that reacted with iodine to afford ultimately phosphoramidate diesters. The reaction of the iodoboranephosphonate with the amine to produce an aminoboranephosphonate diester that rapidly dissociated into the corresponding H-phosphonate and the borane parts was apparently instrumental to the formation of an H-phosphonate diester intermediate.
- Go??biewska, Justyna,Rachwalak, Marta,Jakubowski, Tomasz,Romanowska, Joanna,Stawinski, Jacek
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p. 5496 - 5505
(2018/05/28)
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- Synthesis and structure-activity relationships study of α-aminophosphonate derivatives containing a quinoline moiety
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Two series of α-aminophosphonate derivatives containing a quinoline moiety have been designed and synthesized by introducing bioactive quinoline scaffold to α-aminophosphonate. The in vitro cytotoxic activities of target compounds were first investigated against two human cancer cell lines including Eca109 and Huh7 by MTT assay. Results revealed that most of target compounds exhibited moderate to high antitumor activities against the tested cancer cell lines and some demonstrated more potent inhibitory activities compared with Sunitinib. Among them, compounds 4b2 and 4b4 containing methyl-substituted aniline group were found to be more active than Sunitinib against both of two cancer cell lines, with IC50 in the range of 2.26?μmol/L–7.46?μmol/L.
- Zhu, Xi-Feng,Zhang, Jing,Sun, Shuo,Guo, Yan-Chun,Cao, Shu-Xia,Zhao, Yu-Fen
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p. 1514 - 1518
(2017/07/17)
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- Preparation method of adefovir dipivoxil crystals
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The invention belongs to the technical field of drug preparation and in particular relates to a preparation method of adefovir dipivoxil crystals. The preparation method comprises the following steps: synthesizing diethyl phosphite; synthesizing diethyl (p-phenylsulfonyloxy)methylphosphonate; synthesizing 9-(2-hydroxyethyl) adenine; synthesizing 4,9-[2-(diethylphosphonomethoxy)ethyl]adenine; synthesizing adefovir; synthesizing adefovir dipivoxil. Compared with the prior art, the preparation method of the adefovir dipivoxil crystals, provided by the invention, takes acetonitrile as a water-soluble organic medium, and the difficulty that DMF (Dimethyl Formamide) is difficult to remove is overcome; ethyl acetate is used for replacing isopropyl acetate in a previous process, isopropyl ether is used for replacing ethyl ether and ethanol is used for replacing acetone; the preparation method is simple to operate; the obtained product has good purity and high yield; the industrialized production is easy to realize and the production cost is reduced.
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Paragraph 0014-0016
(2017/07/21)
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- Synthesis and herbicidal activity of α-[(substituted phenoxybutyryloxy or valeryoxy)]alkylphosphonates and 2-(substituted phenoxybutyryloxy)alkyl-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one containing fluorine
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Based on our previous work on the structural modification of the lead compound I, three series of novel fluorine-containing phosphonates derivatives (II, III and IV) were designed and synthesized. Their post-emergence herbicidal activities against some species of weeds were evaluated in a green house. The compounds II were synthesized by introducing of two methylene into the structure I. Compared with the commercial herbicidal clacyfos, compounds II showed moderate herbicidal activity with 60–85% inhibition effect against chingma abutilon (Abutilon theophrasti), common amaranth (Amaranthus retroflexus) and white eclipta (Eclipta prostrate) at a rate of 150 g ai/ha. The compounds III were designed by introducing open-chain phosphonates, which displayed notable herbicidal activity. Especially, the compounds III-1–III-4, III-6, III-8, III-11 and III-12 exhibited significant herbicidal activity (80–100%) comparing to the clacyfos against all tested broadleaf weeds, while compounds IV with five carbon atoms in the carboxylic acid chain were inactive against all of the tested weeds. Structure-activity relationship analyses indicated that the length of the carbon chain had a great effect on the herbicidal activity. Furthermore, a broad spectrum test confirmed that compounds III-4 and III-8 were comparable with glyphosate against all of the tested weeds at a rate of 75 g ai/ha.
- Wang, Wei,Zhou, Yuan,Peng, Hao,He, Hong-Wu,Lu, Xing-Tao
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- Hydrophosphonylation of Alkynes with Trialkyl Phosphites Catalyzed by Nickel
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The use of simple and inexpensive NiCl2?6 H2O as a catalyst precursor for C?P bond formation in the presence of commercially available trialkyl phosphites (P(OR)3, R=Et, iPr, Bu, SiMe3) along with several alkynes is presented. Control experiments showed the in situ formation of (RO)2P(O)H as the species that undergo the addition into the C≡C bond at the alkynes to yield the product of P?H addition. The hydrophosphonylation of diphenylacetylene with P(OEt)3, P(OiPr)3, and P(OSiMe3)3 proceeds in high yields (>92 %) without the need of a specific solvent or ligand. This method is useful for the preparation of organophosphonates for both phenylacetylene as a terminal alkyne model and internal alkynes in yields that range from good to modest.
- Islas, Rosa E.,García, Juventino J.
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p. 4125 - 4131
(2017/10/09)
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- Synthesis and Herbicidal Activity of α-(Substituted Phenoxybutyryloxy or Valeryloxy)alkylphosphonates and 2-(Substituted Phenoxybutyryloxy)alkyl-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one
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On the basis of our work on the modification of alkylphosphonates 1, a series of α-(substituted phenoxybutyryloxy or valeryloxy)alkylphosphonates (4-5) and 2-(substituted phenoxybutyryloxy)alkyl-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one (6) were designed and synthesized. The bioassay results indicated that 14 of title compounds 4 exhibited significant postemergence herbicidal activity against velvetleaf, common amaranth, and false daisy at 150 g ai/ha. Compounds 5 were inactive against all tested weeds. Compounds 6 exhibited moderate to good inhibitory effect against the tested dicotyledonous weeds. Structure-activity relationship (SAR) analyses showed that the length of the carbon chain as linking bridge had a great effect on the herbicidal activity. Broad-spectrum tests of compounds 4-1, 4-2, 4-9, 4-30, and 4-36 were carried out at 75 g ai/ha. Especially, 4-1 exhibited 100% inhibition activity against the tested dicotyledonous weeds, which was higher than that of glyphosate.
- Wang, Wei,Zhang, Sha-Sha,Zhou, Yuan,Peng, Hao,He, Hong-Wu,Lu, Xing-Tao
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p. 6911 - 6915
(2016/10/03)
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- Synthesis of α-Aminophosphonate Derivatives by Microwave-Assisted Kabachnik-Fields Reaction
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The synthesis of aminophosphonates was studied in aqueous solution using triethyl phosphite and under solvent-free and microwave-assisted conditions using >P(O)H species and starting from primary amines or α-, β- and γ-amino acid derivatives. The synthesis of bisaminophosphonates from suitable bifunctional compounds was also investigated in the presence of the T3P reagent.
- Bálint, Erika,Fazekas, Eszter,Tripolszky, Anna,Kangyal, Réka,Milen, Mátyás,Keglevich, Gy?rgy
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p. 655 - 659
(2016/01/15)
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- Synthesis and antitumor activity of α-aminophosphonate derivatives containing thieno[2,3-d]pyrimidines
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Abstract Two series of thieno[2,3-d]pyrimidine derivatives were designed and synthesized, in which bioactive α-aminophosphonate subunits were introduced at the N3 position through an NN bond connection. The in vitro cytotoxic activity of the novel compounds was tested against human esophageal carcinoma cells (EC109), human hepatocarcinoma cells (HepG2), human gastric carcinoma cells (MGC-803), respectively, by the MTT method. The evaluation results revealed that compounds 6mb, 6mf, 6mg, 6nd and 6nh exerted the most potent inhibition against HepG2, MGC-803 and EC109 cells, respectively. In particular, compound 6mg presented excellent inhibitory effect against HepG2 (91.2%) and MGC-803 (94.4%) cells.
- Guo, Yan-Chun,Li, Jing,Ma, Jiao-Li,Yu, Zhi-Ran,Wang, Hai-Wei,Zhu, Wen-Juan,Liao, Xin-Cheng,Zhao, Yu-Fen
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p. 755 - 758
(2015/08/03)
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- Novel dialkylphosphorylhydrazones: Synthesis, leishmanicidal evaluation and theoretical investigation of the proposed mechanism of action
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As part of a program to develop new drugs for the treatment of neglected diseases, new dialkylphosphorylhydrazones were synthesized and evaluated against the trypanosomatid parasites Leishmania braziliensis and Leishmania amazonensis. The synthesis of these compounds proved satisfactory with yields ranging from moderate to good. The most active compounds against L. braziliensis presented IC50 values in the 10-2 μM range, similar to that of the reference drug pentamidine. Two compounds, 4m and 4n, showed a significant dose dependent decrease in the infection index of L. amazonensis infected macrophages and caused a complete healing of nodules and ulcers when tested in vivo against L. amazonensis-infected mice, but the control of parasite burden at the inoculation site was statistically significant only in the case of treatment with 4n. A target fishing (reverse docking) approach using molecular docking with 15 enzymes of L. braziliensis indicated that the probable target of the active compounds was hexokinase, the first enzyme of the glycolytic pathway.
- Da Matta, Carolina Barbosa Brito,De Queiroz, Aline Cavalcanti,Santos, Mariana Silva,Alexandre-Moreira, Magna Suzana,Gon?alves, Vinicius Tomaz,Del Cistia, Catarina De Nigris,Sant'Anna, Carlos Mauricio R.,DaCosta, Jo?o Batista N.
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- N-cycloalkyl- and N-arylimidoylphosphonates
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Reaction of acetyl- and fluorobenzoylphosphonates with 2- and 3-trifluoromethyl-substituted cyclohexylamines or 2- and 3-trifluoromethylanilines has resulted in the formation of the corresponding iminophosphonates and/or in the cleavage of the C-P bond yielding the dialkyl phosphites. The σ constants of N-[(trifluoromethyl)cyclohexyl]- and N-[(trifluoromethyl)phenyl]-substituted imidoylphosphoryl group have been determined by means of 19F NMR spectroscopy.
- Onys'Ko,Klyukovskii,Bezludnyi
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p. 2065 - 2070
(2015/10/29)
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- Tamiphosphor monoesters as effective anti-influenza agents
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Oseltamivir is a potent neuraminidase inhibitor for influenza treatment. By replacing the carboxylate group in oseltamivir with phosphonate monoalkyl ester, a series of tamiphosphor derivatives were synthesized and shown to exhibit high inhibitory activities against influenza viruses. Our molecular modeling experiments revealed that influenza virus neuraminidase contains a 371-cavity near the S1-site to accommodate the alkyl substituents of tamiphosphor monoesters to render appreciable hydrophobic interactions for enhanced affinity. Furthermore, guanidino-tamiphosphor (TPG) monoesters are active to the oseltamivir-resistant mutant. TPG monohexyl ester 4e having a more lipophilic alkyl substituent showed better cell permeability and intestinal absorption than the corresponding monoethyl ester 4c, but both compounds showed similar bioavailability. Intranasal administration of TPG monoesters at low dose greatly improved the survival rate of mice infected with lethal dose of H1N1 influenza virus, whereas 4c provided better protection of the infected mice than oseltamivir and other phosphonate congeners by oral administration.
- Chen, Chun-Lin,Lin, Tzu-Chen,Wang, Shi-Yun,Shie, Jiun-Jie,Tsai, Keng-Chang,Cheng, Yih-Shyun E.,Jan, Jia-Tsrong,Lin, Chun-Jung,Fang, Jim-Min,Wong, Chi-Huey
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p. 106 - 118
(2014/06/09)
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- Synthesis of α-hydroxy(polyprenyl) bisphosphonates
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Bisphosphonates derived from natural terpenes were synthesized by phosphonylation of corresponding aldehydes. The general strategy of introduction of the phosphonate groups into the polyprenol molecule involves successive treatment of a hydroxyl compound by Swern reagent to oxidize the C-OH group into C=O and a (EtO)3P/[PyH]+ClO - 4 mixture to phosphylate the resulting carbonyl compound.
- Kolodyazhnaya,Kolodyazhnyi,Cherkasov,Garifzyanov,Davletshina,Koshkin
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p. 647 - 653
(2014/06/09)
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- A critical overview of the kabachnik-fields reactions utilizing trialkyl phosphites in water as the reaction medium: A study of the benzaldehyde- benzylamine triethyl phosphite/diethyl phosphite models
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α-Aminophosphonates may be synthesized by the three-component condensation of oxo-compounds, amines, and dialkyl phosphites or trialkyl phosphites. In the latter case, mostly water is the reaction medium and a catalyst is also needed. This approach has been studied critically by us, exploring the background of this version of the Kabachnik-Fields condensation. The possibilities for the Kabachnik-Fields condensation of benzaldehyde, benzylamine, and triethyl phosphite or diethyl phosphite including the accomplishment in water were studied in detail.
- Keglevich, Gyoergy,Balint, Erika,Kangyal, Reka,Balint, Maria,Milen, Matyas
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p. 282 - 289
(2014/07/22)
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- Synthesis of H-Phosphonate Intermediates and Their Use in Preparing the Herbicide Glyphosate
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The esterfication of hypophosphorous acid is followed by reaction with another molecule of alcohol under the action of a nickel catalyst to provide a green method for the preparation of H-phosphonate diesters. This method avoids the need for any stoichiometric chlorine unlike those based on phosphorous trichloride.
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Paragraph 0045
(2014/10/16)
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- Stability of phosphite coordinated to ruthenium(II) in aqueous media
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Changes in the reactivity of phosphorus(III) esters, which are promoted by coordination to the ruthenium(II) metal centre, were the focus of this study. Nuclear magnetic resonance data, which were acquired as a function of time, suggest that the phosphite coordination to the ruthenium(II) centre stabilises these molecules in terms of hydrolysis. This stabilisation is greater when the coordination occurs to the trans-[Ru(H2O)(NH3) 4]2+ rather than to the trans-[Ru(NO)(NH3) 4]3+ fragment, and these results are interpreted considering the 4dπ(RuII) → 3dπ(P(III)) back-bonding interactions. The correlation between the data on alkyl phosphite hydrolysis constants in trans-[Ru(NO)(NH3)4P(III)]n + (P(III) = P(OEt)3, P(O)(OEt)2, P(O iPr)3 and P(OBu)3) complexes and the δ13C data show that the hydrolysis of phosphites that are coordinated to Ru(II) preferably occurs via the Michaelis-Arbuzov mechanism. Only the nitrosyl complex, where P(III) = P(OMe)3, did not exhibit this correlation, which suggests that the hydrolysis likely occurs via the Aksnes mechanism in this case.
- Truzzi, Daniela R.,Franco, Douglas W.
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p. 238 - 244
(2014/07/21)
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- Trans-[Ru(NO)(NH3)P(O-)(OEt)2] 2+: A new and robust NO/HNO-donor in aqueous media
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This study describes the synthesis and reactivity in aqueous media of a new potential NO/HNO-donor: trans-[Ru(NO)(NH3)4P(O -)(OEt)2](PF6)2. This compound exhibits a remarkable robustness over a wide range of pH relative to other similar ruthenium phosphorus nitrosyl complexes. At pH 3.0 and 25 °C, trans-[Ru(NO)(NH3)4P(O-)(OEt) 2](PF6)2 decays, yielding free diethyl phosphite with a half-life of 9 days (k = 8.9 × 10-7 s -1). At pH 7.5 and 25 °C, this complex is competitively consumed by diethyl phosphite dissociation (k = 5.15 × 10-5 s -1) and nucleophilic attack at the nitrosyl group (k = 7.25 × 10-5 s-1). Nevertheless, the trans-[Ru(NO)(NH 3)4P(O-)(OEt)2](PF6) 2 exhibits a half-life of 1.5 h (pH 7.5 and 25 °C) for delivering NO/HNO by electrochemical activation at potentials of -0.50 and -0.80 V versus SCE. The NO liberation from trans-[Ru(NO)(NH3)4P(O -)(OEt)2]+ ion occurs with k- NO = 0.24 ± 0.01 s-1, and electrochemical data indicate that k-HNO ? k-NO.
- Truzzi, Daniela R.,Franco, Douglas W.
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- Catalytic enantioselective hydrophosphonylation of aldehydes using the iron complex of a camphor-based tridentate Schiff base [FeCl(SBAIB-d)]2
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An iron(III)-Schiff base-catalyzed, highly enantioselective hydrophosphonylation of various aldehydes is described. Under the optimized reaction conditions, 5 mol% of the iron/camphor-based tridentate Schiff base complex [FeCl(SBAIB-d)]2 produces high yields (up to 99%) of α-hydroxy phosphonates in excellent enantioselectivities (up to 99%). The merits of this catalytic system are an easily synthesizable catalyst, inexpensive starting materials, practically simple aerobic reaction conditions, and low catalyst loading (5 mol%). Copyright
- Boobalan, Ramalingam,Chen, Chinpiao
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supporting information
p. 3443 - 3450
(2013/12/04)
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- Acyloxy derivatives of trivalent phosphorus in amidoalkylation of hydrophosphoryl compounds
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In order to model the previously suggested mechanism of the P-C bond formation via the Arbuzov reaction, we have studied the interaction of diethylacylphosphite (prepared beforehand as well as generated in situ from tetraethylpyrophosphite) with the in situ generated acyliminium cation. Various conditions of in situ generation of acylphosphite derivatives of P(III) from hydrophosphoryl compounds and acyliminium ions from N,N′- alkylidenebiscarbamates have been investigated: solvent nature, acid catalyst, and the reagents mixing order). The results obtained have confirmed the suggested mechanism of three-component reaction of amidoalkylation of hydrophosphoryl compounds with the formation of P-C bond via the Arbuzov reaction of in situ formed intermediates.
- Dmitriev,Ragulin
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p. 1888 - 1894
(2014/01/06)
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- [1-Hydroxy-1-(2-hydroxyphenyl)ethyl]phosphonates and -phosphinates: Convenient synthesis through intramolecular Abramov reaction and protective activity against influenza A
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A combination of intramolecularization and tandem reaction methodologies has been applied to the synthesis of diethylammonium[1-hydroxy-1-(2- hydroxyphenyl)ethyl]phosphonates and -phosphinates, which were found to be unavailable through a standard intermolecular hydrophosphonylation/hydrolysis sequence. A mild hydrolysis of amidophosphites and -phosphonites, bearing 2-acetylphenoxy-fragment and a hydrolytically labile diethylamino-group at the same trivalent phosphorus atom, directly afforded the title compounds. The overall process probably consists of three steps: (i) selective hydrolysis of the P(III)-N bond to generate the hydrophosphoryl-type intermediates; (ii) formation of the strained 2-substituted 3-hydroxy-2-oxo-2,3-dihydro-1,2- benzoxaphospholes through intramolecular Abramov reaction; (iii) hydrolysis of the endocyclic P(IV)-O bond in the 1,2-benzoxaphospholes to give the acyclic products. Being only modestly active in vitro, at high dosage non-toxic water-soluble title α,γ-dihydroxyphosphonates and -phosphinates exhibited beneficial, but short-lasting effect against experimental influenza A infection (H3N2) in mice.
- Korshin, Edward E.,Pozdeev, Oskar K.
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p. 11109 - 11115
(2014/01/06)
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- Photocatalytic degradation and intermediates characteristics of chlopyrifos by nano-TiO2
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The photocatalytic degradation and characteristics of corresponding intermediates of pesticide chlopyrifos have been investigated in aqueous solution with TiO2 as photocatalyst. A series of mixed-solution with different chlopyrifos-TiO2 ratios were prepared and then illuminated by high pressure mercury lamp. After the reaction for 30 and 60 min, the samples were taken for further analysis. The determination of the concentration of chlopyrifos by HPLC shows the degradation rate of chlopyrifos increases with the increase of initial concentration in lower range (5-20 mg/L) but decreases in higher range (20-80 mg/L). The highest degradation rate is 51.3% after 30 min photocatalytic degradation with the initial concentration of 20 mg/L. Then after the degradation for 60 min, the highest degradation rate reaches 89.0%. Three kinds of intermediates 3,5,6-trichloro-2-pyridinyl ester, 3,5,6-trichloro-Pyr and diethyl phosphite were identified after GC/MS analysis. According to toxicity database, we found that the toxicity of intermediate diethyl phosphate is much less than that of chlopyrifos, and the toxicity of former two intermediates is slightly higher than that of chlopyrifos but could be neglected due to their low concentration in reaction system. The nano-TiO2 is proved to be an excellent photocatalyst for degradation of chlopyrifos.
- Liu, Xiang-Ying,Wang, Lifeng,Bai, Lian-Yang,Zhou, Xiao-Mao,Luo, Kun
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p. 469 - 476
(2013/11/06)
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- Organophosphorus chemistry without PCl3: A bridge from hypophosphorous acid to H-phosphonate diesters
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A process for the conversion of hypophosphorous acid (H3PO 2, HPA) and alcohols into various H-phosphonate diesters [(RO) 2P(O)H] is described. The new reaction provides a missing bridge between HPA and important H-phosphonates, completely avoiding the use of PCl3. Nickel chloride or nickel on silica catalyze the oxidative phosphorylation of alkyl phosphinates with various alcohols or water. The reaction is atom economic and avoids the formation of waste products. The previous need for both chlorine and base is completely avoided. Esterification of hypophosphorous acid followed by reaction with another molecule of alcohol under the action of a nickel catalyst provides a green method for the preparation of H-phosphonates. This method entirely avoids the need for any stoichiometric chloride unlike those based on phosphorus trichloride. Copyright
- Fisher, Henry C.,Prost, Lucie,Montchamp, Jean-Luc
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p. 7973 - 7978
(2014/01/06)
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- Method for the esterification of P-O components
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The present invention is directed to a new method for esterification of P-O components. More specifically, the present invention relates to a new method for esterification of P-O components containing at least one P-O-H functional group, whereby the P-O-H functional group(s) is converted into P-O-R functional group(s). The method according to the invention may find particular use in the manufacture of diesters of phosphorous acid.
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Paragraph 0038; 0039; 0043
(2013/04/25)
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- Flame retardant properties of phosphorylated derivatives of malonic ester
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Thermal stability of the phosphorylated derivatives of malonic ester synthesized by the Michaelis-Becker reaction was studied. The flame-retardant efficiency of the phosphonomalonic ester was assessed by the flame-tube technique measuring the weight loss of wood samples impregnated with the studied compound.
- Sal'Keeva,Taishibekova,Minaeva,Shibaeva,Kasenov,Sal'Keeva,Muratbekova
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p. 659 - 662
(2013/07/27)
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- H-transfer reaction during decomposition of N-(2-methylpropyl)- N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1)-based alkoxyamines
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Thermal decomposition of four tertiary N-(2-methylpropyl)-N-(1- diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1)-based alkoxyamines (SG1-C(Me)2-C(O)-OR, R = Me, tBu, Et, H) has been studied at different experimental conditions using 1/su
- Edeleva, Mariya,Marque, Sylvain R.A.,Kabytaev, Kuanish,Guillaneuf, Yohann,Gigmes, Didier,Bagryanskaya, Elena
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p. 1323 - 1336
(2013/04/10)
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- Multicomponent reactions in a one-pot synthesis of α- aminophosphonates and α-aminophosphonic diamides with anti-inflammatory properties
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Schiff-base Kabachnik-Fields intermediates generated in situ from substituted pyrazole-4-carbaldehyde and 2-aminothiophene derivatives were trapped by dialkyl phosphites to produce the corresponding α- aminophosphonates in moderate yields. The latter products could be also obtained in excellent yields (≥75%) by directly applying the phosphorus reagents to the Schiff bases. Next, dialkyl phosphites were applied to one of the parent aldehydes to give the expected α-hydroxyphosphonate derivatives. Applying hexaalkyl triamidophosphites to the Schiff base in ethanol afforded methylphosphonic diamide derivatives, whereas ring attack on the pyrazole ring occurred when the same amidophosphites were applied to the parent aldehyde to give the corresponding alkylidenephosphorane ylides in an open structure form in good yields. Some of the new compounds exhibited considerable anti-inflammatory properties.
- Abdou, Wafaa M.,Barghash, Reham F.,Bekheit, Mohamed S.
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experimental part
p. 649 - 656
(2012/02/03)
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- Synthesis of new bisphosphonate and bisphosphonic acid derivatives and heterocyclic and dialkylcarbamoyl oxazolone derivatives with anticancer and antischistosomal activity
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The reaction of 5(4H)-oxazolones with tetraethyl methanediylbis(phosphonate) afforded new 1,1-bisphosphonate and 1,1-bisphosphonic acid derivatives. Moreover, 5(4H)-oxazolones reacted with Wittig reagents to give the corresponding heterocyclic products. Treatment of 5(4H)-oxazolones with trisdialkylaminophosphanes gave the corresponding N-(1-dialkylcarbamoyl)-2-phenylvinylbenzamides. Mechanisms accounting for the formation of the new products are discussed. The biological activity of the newly synthesized compounds was also examined.
- Boulos, Leila S.,Ewies, Ewies F.,Fahmy, Amin F.M.
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experimental part
p. 1056 - 1068
(2011/12/13)
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- Protonation and alkylation of organophosphorus compounds with trifluoromethanesulfonic acid derivatives
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Protonation (alkylation) of triphenylphosphine, triethylphosphite, triphenylphosphine oxide, triethylphosphate, hexamethylphosporamide, and dimethylphosphite with trifluoromethanesulfonic acid, its bisimide, and methyl ester was studied and the corresponding 1H, 13C, 19F, 31P NMR spectra were analyzed.
- Tolstikova,Bel'Skikh,Shainyan
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scheme or table
p. 474 - 480
(2011/06/23)
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- Alteration of the course of the Michaelis-Arbuzov reaction in imidazolium ionic liquids
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Room-temperature imidazolium ionic liquids [Rmim][X] (X = Br, BF 4, NTf2) as a reaction medium change the reaction course of phosphorus(III) acid esters with primary alkyl halides, aryl bromides, and propargyl bromide to afford hydrophosphoryl compounds, products of oxidation of the starting phosphorus substrates, and 2,3-bis(phosphoryl)prop-1-enes, respectively.
- Matveeva, Ekaterina V.,Kozlov, Vladimir A.,Odinets, Irina L.
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body text
p. 145 - 147
(2011/07/30)
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