- Hydrolysis and alcoholysis of phosphinates and phosphonates
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Phosphinic and phosphonic acids useful intermediates and biologically active compounds may be prepared from their esters: phosphinates and phosphonates, respectively, by acid-catalyzed hydrolysis either on conventional heating or on MW irradiation. The transesterification of alkyl phosphinates took place only in the presence of suitable ionic liquids as the catalysts. In the cases of phenylphosphonates, depending on the nature of the ionic liquid, the formation of the ester was accompanied by the fission of the C–O bond.
- Harsági, Nikoletta,Keglevich, Gy?rgy,Sz?ll?si, Betti,Varga, Petra Regina
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- Optimization and a Kinetic Study on the Acidic Hydrolysis of Dialkyl α-Hydroxybenzylphosphonates
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The two-step acidic hydrolysis of α-hydroxybenzylphosphonates and a few related derivatives was monitored in order to determine the kinetics and to map the reactivity of the differently substituted phosphonates in hydrolysis. Electron-withdrawing substituents increased the rate, while electron-releasing ones slowed down the reaction. Both hydrolysis steps were characterized by pseudo-first-order rate constants. The fission of the second P-O-C bond was found to be the rate-determining step.
- Harsági, Nikoletta,Rádai, Zita,Szigetvári, áron,Kóti, János,Keglevich, Gy?rgy
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- Synthesis and inhibitory activity of acetamidophosphonic acids against metallo-β-lactamases
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Metallo-β-lactamases (MβLs) are the target enzymes of antibiotic resistance and the phosphonic drugs make great influence to the development of contemporary medicine. Eleven acetamidophosphonic compounds were prepared and evaluated as inhibitors of the MβLs. Compounds 4, 5, 7, 9, and 10 exhibited specific inhibitory activity against the MβL NDM-1 and CcrA with an IC50 value range of 17 to 354 μM. Analysis of the structure–activity relationship showed that both the acetamido linker and the position of the substituent on the phenyl ring played an important role in the inhibitory abilities of the inhibitors against MβLs.
- Zhang, Yi-Lin,Zhang, Yue-Juan,Wang, Wen-Ming,Yang, Ke-Wu
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- HIV-1 non-nucleoside reverse transcriptase inhibitors: Incorporation of benzylphosphonate moiety for solubility improvement
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Benzylphosphonates of 5'-norcarbocyclic analogue of 2',3'-dideoxy-2',3'-didehydrouridine and its N3-benzyl derivatives with different substituents at the phosphorus atom were designed and synthesized in attempt to improve solubility of potentia
- Matyugina, Elena S.,Valuev-Elliston, Vladimir T.,Chizhov, Alexander O.,Kochetkov, Sergei N.,Khandazhinskaya, Anastasia L.
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p. 114 - 116
(2016/04/10)
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- Crystal structures of the apo form and a complex of human LMW-PTP with a phosphonic acid provide new evidence of a secondary site potentially related to the anchorage of natural substrates
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Low molecular weight protein tyrosine phosphatases (LMW-PTP, EC 3.1.3.48) are a family of single-domain enzymes with molecular weight up to 18 kDa, expressed in different tissues and considered attractive pharmacological targets for cancer chemotherapy. Despite this, few LMW-PTP inhibitors have been described to date, and the structural information on LMW-PTP druggable binding sites is scarce. In this study, a small series of phosphonic acids were designed based on a new crystallographic structure of LMW-PTP complexed with benzylsulfonic acid, determined at 2.1 ?. In silico docking was used as a tool to interpret the structural and enzyme kinetics data, as well as to design new analogs. From the synthesized series, two compounds were found to act as competitive inhibitors, with inhibition constants of 0.124 and 0.047 mM. We also report the 2.4 ? structure of another complex in which LMW-PTP is bound to benzylphosphonic acid, and a structure of apo LMW-PTP determined at 2.3 ? resolution. Although no appreciable conformation changes were observed, in the latter structures, amino acid residues from an expression tag were found bound to a hydrophobic region at the protein surface. This regions is neighbored by positively charged residues, adjacent to the active site pocket, suggesting that this region might be not a mere artefact of crystal contacts but an indication of a possible anchoring region for the natural substrate - which is a phosphorylated protein.
- Fonseca, Emanuella M.B.,Trivella, Daniela B.B.,Scorsato, Valéria,Dias, Mariana P.,Bazzo, Natália L.,Mandapati, Kishore R.,De Oliveira, Fábio L.,Ferreira-Halder, Carmen V.,Pilli, Ronaldo A.,Miranda, Paulo C.M.L.,Aparicio, Ricardo
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p. 4462 - 4471
(2015/08/03)
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- METHODS FOR THE PREPARATION OF PHOSPHONIC ACID DERIVATIVES
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The present invention provides methods for the preparation of aralkyl phosphonic acids and aryl phosphonic acids. In a first method of the invention, an aralkyl dialkyl phosphonate is contacted with an aqueous acidic solution under reflux conditions. Upon cooling, solid crystals of the corresponding aralkyl phosphonic acid are obtained, which can be collected via filtration. In a second method of the invention, an aryl phosphorous dihalide is added to a pot containing an aqueous nitric acid solution while maintaining the pot temperature below about 50° C. and then allowing the reactants to self-reflux. Upon cooling, crystals of the corresponding aryl phosphonic acid are obtained, which can be collected via filtration.
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Page/Page column 3
(2008/06/13)
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- Reactions of elemental phoshorus and phosphine with electrophiles in superbasic systems: XIX. Formation of the C-P bond with participation of elemental phosphorus under microwave assistance
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Microwave irradiation facilitates phosphorylation of aryl methyl chlorides and styrene with red phosphorus in the presence of strong bases and increases the yield of the main products, tertiary phosphine oxides. Nauka/Interperiodica 2007.
- Malysheva,Gusarova,Kuimov,Sukhov,Kudryavtsev,Sinyashin,Budnikova,Pai,Tolstikov,Trofimov
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p. 415 - 420
(2008/02/11)
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- Reactions of elemental phosphorus and phosphine with electrophiles in superbasic systems: XVI. Phosphorylation of benzyl chloride with elemental phosphorus and phosphine
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The major product of the reaction of benzyl chloride with red phosphorus in the system concentrated aqueous KOH-dioxane-phase-transfer catalyst (43-95°C, Ar) is tribenzylphosphine oxide (yield up to 61%). Under similar conditions, phosphorylation of benzy
- Trofimov,Gusarova,Malysheva,Shaikhudinova,Belogorlova,Kazantseva,Sukhov,Plotnikova
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p. 684 - 688
(2007/10/03)
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- SAR directed design and synthesis of novel β(1-4)-glucosyltransferase inhibitors and their in vitro inhibition studies
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This paper describes SAR directed design and synthesis of novel β (1-4)-glucosyltransferase (BGT) inhibitors. The designed inhibitors 1 5 provide conformational mimicry of the transition-state in glucosyltransfer reactions. The compounds were tested for i
- Bhattacharya, Asish K,Stolz, Florian,Kurzeck, Juergen,Rueger, Wolfgang,Schmidt, Richard R
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p. 1129 - 1136
(2007/10/03)
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- Dealkylation of dialkyl phosphonates with boron tribromide
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Boron tribromide cleanly and quantitatively converts dimethyl-, diethyl-, diisopropyl-, and ditertiobutyl phosphonates RP(O)(OR')2 into the corresponding phosphonic acids RP(O)(OH)2 via methanolysis. The use of boron tribromide is compatible with a variety of functionalities in the R group.
- Gauvry,Mortier
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p. 553 - 554
(2007/10/03)
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- Dealkylation of phosphonate esters with chlorotrimethylsilane
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Chlorotrimethylsilane completely dealkylates phosphonate esters at elevated temperature in a sealed reaction vessel. These conditions are tolerated by a variety of functional groups and lead to high conversions of dimethyl, diethyl and diisopropyl phosphonates to their corresponding phosphonic acids.
- Gutierrez,Prisbe,Rohloff
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p. 1299 - 1302
(2007/10/03)
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- Anilide derivative, production and use thereof
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This invention is to provide a compound of the formula: wherein R1 is an optionally substituted 5- to 6-membered ring: C is a divalent group of the formula: wherein the ring A is an optionally substituted 5- to 6-membered aromatic ring, X is an optionally substituted C, N or O atom, and the ring B is an optionally substituted 5- to 7-membered ring; Z is a chemical bond or a divalent group; R2 is (1) an optionally substituted amino group in which a nitrogen atom may form a quaternary ammonium, etc., or a salt thereof, which is useful for antagonizing MCP-1 receptor.
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- Preparation of chiral α-monofluoroalkylphosphonic acids and their evaluation as inhibitors of protein tyrosine phosphatase 1B
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Enantiomerically pure α-monofluoroalkylphosphonic acids 4-9 were synthesized by diastereoselective electrophilic fluorination of α-carbanions of asymmetric phosphonamidates bearing (-)-ephedrine as a chiral auxiliary. The diastereomeric excess of the fluo
- Kotoris, Christopher C.,Wen, Wcndy,Lough, Alan,Taylor, Scott D.
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p. 1271 - 1281
(2007/10/03)
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- Reactions of phosphonates with organohaloboranes: New route to molecular borophosphonates
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Phosphonates RPO(OR′)2 (R = Me, R′ = Et (1); R = CH2Ph, R′ = Et (2); R = CH double bond CH2, R′ = Et (3); R = CH2-CH double bond CH2, R′ = Me (4); R = CH2N3, R′ = Et (5)) react with CyBCl2 (6; Cy = C6H11) in a 1:1 molar ratio in toluene at -30 °C to form the primary adducts CyBCl2·O double bond PR(OR′)2 (7-11). These products undergo a thermally induced bis-chlorodealkylation with the formation of mixtures of oligomers [-O-PR(O-)-O-BCy(O-)]n (22-26) having isovalent P-O-B groupings. Under electron impact mass spectral conditions, the ions [RPO3BCy]4-Cy, which may be attributed to tetramers [RPO3BCy]4 (22′-26′), are detected. Compounds 22′-26′ presumably possess a central cubic M4O12P4 framework that is analogous to those found in alumino- and gallophosphate materials. NMR monitoring shows that [CyBCl(μ2-O)2PR(OR′)]2 (12-16) are formed as intermediates in these reactions. These unstable dimers 12-16 possess a cyclic core analogous to the single-four-ring (4R) secondary building units (SBUs) found in zeolites and phosphate molecular sieves. Hydrolysis of 12-16 and 22-26 with methanol at 30 °C gave respectively RPO(OH)(OR′) (17-21) and RPO(OH)2 (27-31). NMR monitoring reveals that the cyclic dimer [Me2B(μ2-O)2P(CH2Ph)(OEt)]2 (35a) is the primary adduct in the reaction of PhCH2PO(OEt)2 (2) with Me2BBr (34). Heating or prolonged storage at room temperature leads to a mixture of 35a, cyclic borophosphonate Me2BC(μ2-O)2P(CH2Ph)(OEt) (35b), and the mixed anhydride of benzylphosphonic acid and dimethylborinic acid (35c).
- Mortier, Jacques
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p. 4266 - 4275
(2008/10/08)
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- Phosphorylating power of red phosphorus towards aldehydes in basic and in acidic media
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The reactivity of red phosphorus towards aldehydes was investigated under basic and acidic media. It was demonstrated that the real phosphorylating agent involved in the reaction was phosphane (PH3) in basic media, and hypophosphorous acid (H3PO2) in acidic media. A convenient one- pot synthesis of (α-hydroxyalkyl)phosphinic acids from red phosphorus and aldehydes in basic media was realized under sonication. The same reaction under acidic media in the presence of hydriodic acid led to the corresponding phosphonic acids. The (α-hydroxyalkyl) phosphinic acids were readily prepared under sonication from hypophosphorous acid and aldehydes in the presence of catalytic amounts of hydrochloric acid. The mechanism of the addition reaction of PH3 to benzaldehyde was elucidated and shows the complexity of the reaction as a function of the experimental conditions.
- Albouy, Dominique,Etemad-Moghadam, Guita,Koenig, Max
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p. 861 - 868
(2007/10/03)
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- Benzylphosphonic acid inhibitors of human prostatic acid phosphatase
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A series of α-substituted benzylphosphonic acids is described as inhibitors of human prostatic acid phosphatase, an enzyme has been used as a model to study aryl phosphatases. The most potent inhibitors in this series are 2-trifluoromethylbenzhydrylphosphonic acid (9 μM), and α-(2-phenylethyl)benzylphosphonic acid (14 μM). The structure-activity studies suggest that bulk tolerance beyond the phosphate binding area limits the steric or hydrophobic contribution to inhibitor potency achieved through α-carbon substitution.
- Schwender,Beers,Malloy,Cinicola,Wustrow,Demarest,Jordan
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p. 311 - 314
(2007/10/03)
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- (o-Hydroxyphenyl)methylphosphonic acids: Synthesis and Potentiometric Determinations of their pKa Values
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(o-Hydroxyphenyl)methylphosphonic acids are readily obtained from o-(bromomethyl)- or o-(hydroxymethyl)phenols and trialkyl phosphites.Subsequent hydrolysis leads to the corresponding phosphonic acids.For a series of such compounds, the pKa val
- Boehmer, Volker,Vogt, Walter,Chafaa, Salah,Meullemeestre, Jean,Schwing, Marie-Jose,Vierling, Francois
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p. 139 - 149
(2007/10/02)
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- PHOTOLYSIS OF ARYL ESTERS OF TRI- AND TETRACOORDINATED PHOSPHORUS COMPOUNDS
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Upon UV excitation in methanol, some diaryl esters of alkly- or alkenyl phosphonates underwent an elimination of two aryl groups to give biaryls and the corresponding alkyl- or alkenylphosphonic acids.Tris(4-methoxyphenyl) phosphite also underwent a similar elimination to give 4,4'-dimethoxybiphenyl and 4-methoxyphenyl phosphonate.This interesting biaryl elimination was confirmed to proceed via a singlet intramolecular excimer by means of fluorescence spectra and Stern-Volmer analysis.
- Shi, Min,Yamamoto, Kiichi,Okamoto, Yoshiki,Takamuku, Setsuo
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- Plant growth regulators
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New agents for regulating plant growth, especially for reducing the height of plants, containing a mixture of a quaternary substituted thianium or ammonium salt and a phosphonic acid derivative.
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- Dealkylation Reaction of Acetals, Phosphonate, and Phosphate Esters with Chlorotrimethylsilane/Metal Halide Reagent in Acetonitrile, and Its Application to the Synthesis of Phosphonic Acids and Vinyl Phosphates
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A mild and efficient method has been developed for carbon-oxygen bond cleavage using chlorotrimethylsilane/sodium iodide in acetonitrile.It was applied to synthetic transformation under nonaqueous and neutral conditions, such as acetal deprotection and the synthesis of phosphonic acids from the corresponding dialkyl phosphonates via methanolysis of their silyl esters.Effectiveness of various kinds of metal or ammonium iodides for this type of dealkylation was examined in the acetonitrile solution by 1H NMR.Satisfactory results were also obtained with lithium or potassium iodide in place of sodium iodide.However, copper(I) or quarternary ammonium iodide was ineffective.Chlorotrimethylsilane/lithium bromide in acetonitrile is effective for selective dealkylation of multifunctional phosphonic esters or dialkyl vinyl phosphates.
- Morita, Tsuyoshi,Okamoto, Yoshiki,Sakurai, Hiroshi
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p. 267 - 273
(2007/10/02)
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- The Dealkylation of Phosphate and Phosphonate Esters by Iodotrimethylsilane: A Mild and Selective Procedure
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Iodotrimethylsilane transforms alkyl esters of phosphorus oxyacids into their corresponding trimethylsilyl esters and alkyl iodide.The reaction is rapid and quantitative at room temperature.The reagent has no effect on aryl phosphate ester functions or upon alkyl carboxylate, ether, bromoalkane, vinyl, and ethynyl functions under the conditions employed for transesterification.The trimethylsilyl esters can be isolated by distillation or solvolysed without purification using methanol or water to afford dealkylated phosphate and phosphonate species.Selective monodealkylation of dialkyl phosphonates cannot be achieved using only one equivalent of the reagent, wich leads to the formation of mixed products.
- Blackburn, G. Michael,Ingleson, David
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p. 1150 - 1153
(2007/10/02)
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- Insecticidal compositions and methods of combatting insects using 3-phenoxybenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate insecticide with a synergistic compound of mono (alkyl and alkenyl)mono omega-alkynyl arylphosphonates
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Synergistic insecticidal combinations of esters of certain cyclopropanecarboxylic acids, e.g. pyrethrins, allethrin, and related compounds, with mono(alkyl and alkenyl) mono-ω-alkynyl aryl- and aralkylphosphonates are described. The preparation and proper
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