Diketopyrrolopyrrole Bis-Phosphonate Conjugate: A New Fluorescent Probe for In Vitro Bone Imaging

The synthesis of a conjugate molecule between an unusual red-fluorescent diketopyrrolopyrrole (DPP) unit and a bis-phosphonate (BP) precursor by a click-chemistry strategy to target bone tissue and monitor the interaction is reported. After thorough investigation, conjugation through a triazole unit between a γ-azido rather than a β-azido BP and an alkyne-functionalized DPP fluorophore group turned out to be the winning strategy. Visualization of the DPP-BP conjugate on osteoclasts and specific antiresorption activity were successfully demonstrated.     

Convenient synthesis of α,β-unsaturated phosphonates via a Mizoroki-Heck reaction of arylboronic acids with diethyl vinylphosphonate

Palladium acetate catalyzed Mizoroki-Heck reactions of arylboronic acids with diethyl vinylphosphonates afford α,β-unsaturated phosphonates in good yields.     

Reactions of dialkyl phosphonates and phosphonates with bis(benzylideneimino)toluene

Dialkyl phosphonates bind to the C=N bond of bis(benzylideneimino)toluene, with formation of dialkyl (benzylideneimino)benzylaminobenzyl phosphonates. The complicated character of IR spectra of these compounds is connected with the possibility of formation of dimeric cyclic associates and intramolecular hydrogen bonding. Phosphinic acid reacts with bis(benzylidenimino)toluene in a 2: 1 ratio to affordN,N-benzylidenebis(-amino-benzytphosphonic) acid.Translated fromIzvestiya Akademii Nouk. Seriya Khimicheskaya, No. 5, pp. 1303–1305, May, 1996.     

Chemistry of organophosphonate scale growth inhibitors: two-dimensional, layered polymeric networks in the structure of tetrasodium 2-hydroxyethyl-amino-bis(methylenephosphonate)

Aminomethylene phosphonates are important scale inhibitors applied in diverse areas of technology. This study adds to the existing body of information on this subject and reports the crystal and molecular structures of tetrasodium 2-hydroxyethylamino-bis(methylene-phosphonate) decahydrate ([Na₄(HOCH₂CH₂N(CH₂PO₃)₂)]·10H₂O, 1). The crystal structure of 1 could be described as two-dimensional polymeric layered structure hydrogen bonded into a 3D supramolecular polymeric network. The structure of the tetraanion consists of a “three-arm” backbone stemming from the N atom. Two “arms” are deprotonated methylene phosphonate (-CH₂PO₃²⁻) moieties and the third is a hydroxyethyl (-CH₂CH₂OH) moiety. One Na cation forms an intramolecular complex with two oxygens from separate phosphonate groups, a hydroxyl oxygen, the nitrogen and two lattice water molecules. The position of this Na cation points to a possible coordination site for Ca in a proposed Ca-HEABMP complex (HEABMP=2-hydroxyethylamino-bis(methylene-phosphonate).     

The influence of varying reaction conditions on the coordination behavior of the phosphonoformate anion

Abstract

In medical and pharmaceutical science phosphonic acids and phosphonates play an important role with regard to their wide application in various drugs as medicines against osteoporosis or antiviral agents. In the course of the investigations on the coordination chemistry of biologically active phosphonates different salts of the phosphonoformate anion were prepared via hydrolysis of corresponding esters under basic conditions. Depending on the reaction and crystallization conditions, different sodium salts with the phosphonoformate moiety were obtained and structurally characterized.     

<Emphasis Type="Italic">O,O</Emphasis>-diphenyl <Emphasis Type="Italic">N</Emphasis>-sulfonylbenzimidoylphosphonates,a novel type of C-phosphorylated imines

A preparative method for the synthesis of first representatives of O,O-diphenyl N-sulfonylbenzimidoylphosphonates was proposed. The method involves oxidation of the corresponding α-(sulfonylamino)benzylphosphonates. The σ-constants of the N-sulfonylbenzimidoylphosphonate group were estimated by ¹⁹F NMR spectroscopy. The imidoylphosphonates obtained easily formed stable adducts at the C=N bond with P-and O-nucleophiles. Dedicated to the Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2567–2570, November, 2005.     

Concise Synthesis of P-Glycosyl Alkenylphosphonates and P,C-di and P,P,C tri-Glycosyl Phosphonates

A direct access to P-glycosyl-, P, P-di-glycosyl alkenylphosphonates and P, C-glycosyl phosphonates is described. The method involves the Horner reaction of an anion derived from P-monoglycosyl and P ¹, P′-diglycosyl methylenediphosphonates either on the exocyclic aldehyde group of carbohydrates or on the masked aldehydic form of the furanose hemiacetals. In this last case, the carbonyl olefination, followed by an intramolecular cyclization, leads to P,C-di and P,P,C-triglycosyl phosphonates.     

Efficient Synthesis of Modified Sulfamides and Cyclosulfamides Containing Phosphonate Moieties

Abstract

The synthesis of two new series of functionalized phosphonates is described. A new entry for the synthesis of 5-phosphonoalkyl cyclosulfamides and bis(phosphonoalkyl) sulfamides starting from dihalogeno bis(amino) sulfone has been developed. These compounds have been synthesized in good yields. Triethylphosphite has been used to introduce the phosphonate moiety into sulfamides and cyclosulfamides via Arbuzov reaction.     

The Nucleophile-Catalyzed Atherton-Todd Reaction

Two examples of nucleophile catalyzed Atherton-Todd reaction was reported. In the presence of triethylamine α-sulfonyl group stabilized carbanions gave directly carbon-phosphorus compounds, e.g. 1-halo-1-arylsulfonylmethylphosphonate. The reaction of carbohydrates with thiophosphite was catalyzed by KI to give carbohydrate thiophosphates in good yield.     

The Hydrolysis of Phosphinates and Phosphonates: A Review

Phosphinic and phosphonic acids are useful intermediates and biologically active compounds which may be prepared from their esters, phosphinates and phosphonates, respectively, by hydrolysis or dealkylation. The hydrolysis may take place both under acidic and basic conditions, but the C-O bond may also be cleaved by trimethylsilyl halides. The hydrolysis of P-esters is a challenging task because, in most cases, the optimized reaction conditions have not yet been explored. Despite the importance of the hydrolysis of P-esters, this field has not yet been fully surveyed. In order to fill this gap, examples of acidic and alkaline hydrolysis, as well as the dealkylation of phosphinates and phosphonates, are summarized in this review.