REACTION DES O,O-DIETHYL OXO-1 ALKANEPHOSPHONATES AVEC LES DERIVES DE L'HYDRAZINE: UNE VOIE DE SYNTHESE DES HYDRAZONES α-PHOSPHONATEES ET DES HYDRAZIDES

Abstract

Under the normal conditions, the reaction of hydrazine and methylhydrazine with OO-diethyl 1 oxoalkane phosphonates 1 proceeds by cleavage of the phosphorus-carbon bond and leads to the formation of diethylphosphite 2 and N-acylhydrazide 3 . A procedure has been developed for the synthesis of new primary hydrazone of OO-diethyl 1-oxoalkane phosphonates 4 . A mechanism is proposed. The structure of those compounds 4 was confirmed by NMR and IR spectroscopy.     

Nano catalytic synthesis of flavanone phosphonates using domino Knoevenagel-phospha-Michael route

Abstract

Novel derivatives of diethyl (4-oxo-2-phenylchroman-3-yl) methyl phosphonate have been synthesized under optimal conditions using domino-Knoevenagel-phospha-Michael reaction catalyzed by nano-zinc oxide. The combination of recovery and reusability of catalyst, simple and applicable approach, good reaction time and good yields of products make this method as a suitable route for this purpose. The structures of the products were determined by FT-IR, ¹H-, ¹³C- and ³¹P- Nuclear Magnetic Resonance spectroscopies, and elemental analysis.     

Simple and Advantageneous Stereoselective Synthesis of (Z)-Allyl Phosphonates Starting from Baylis–Hillman Adducts

Baylis–Hillman adducts 3-hydroxyl-2-methylene alkanoates have been converted in one pot into the corresponding (Z)-allyl phosphonates by treatment with FeCl₃ and trialkyl phosphites in toluene under reflux. The products are formed in excellent yields (88–98%) within 1–1.5 h. The process is highly convenient and efficient, cost-effective, and remarkably stereoselective.     

三维介孔氨基三亚甲基膦酸锆的合成及其担载铁催化剂的甲醛催化氧化活性

以氧氯化锆和氨基三亚甲基膦酸(ATMP)为原料合成了一种新型介孔材料氨基三亚甲基膦酸锆(NTAZP)。使用XRD、FTIR、TG-DTA和SEM等手段对所合成的介孔材料进行了结构表征和形貌分析。然后以NTAZP为载体,用Fe(NO3)3水溶液处理,得到担载Fe3+的氨基三亚甲基膦酸锆。研究结果表明,Fe3+被吸附到载体孔道中后,NTAZP结构未被破坏,Fe3+离子与NTAZP孔壁骨架上的N发生了配位作用。铁担载NTAZP(NTAZP-Fe3+)对甲醛氧化具有良好的催化活性,催化反应条件温和,催化剂稳定性良好。以载体NTAZP担载铁还避免了Fe3+进入水体,催化剂得以回收利用,避免造成二次污染。NTAZP-Fe3+是一种高效绿色的新型小分子醛类化合物氧化催化剂。     

Selected Thoughts on Hydrophobicity in Drug Design

The fundamental aim of drug design in research and development is to invent molecules with selective affinity towards desired disease-associated targets. At the atomic loci of binding surfaces, systematic structural variations can define affinities between drug candidates and biomolecules, and thereby guide the optimization of safety, efficacy and pharmacologic properties. Hydrophobic interaction between biomolecules and drugs is integral to binding affinity and specificity. Examples of antiviral drug discovery are discussed.     

Catalytic,Asymmetric Synthesis of Phosphonic γ‐(Hydroxyalkyl)butenolides with Contiguous Quaternary and Tertiary Stereogenic Centers

A procedure that enables high yielding access to phosphonic γ‐(hydroxyalkyl)butenolides with excellent regio‐, diastereo‐ and enantiocontrol is reported. The simultaneous construction of up to two adjacent quaternary stereogenic centers by a catalytic asymmetric vinylogous Mukaiyama aldol reaction unites biologically and medicinally relevant entities, namely α‐hydroxy phosphonates and γ‐(hydroxyalkyl)butenolides. This is achieved by utilizing a readily available chiral copper‐sulfoximine catalyst showing a broad functional group tolerance for both the electrophilic and nucleophilic reactants. A discussion about potential factors affecting the observed level of enantioselectivity, which stems from the enantiopure sulfoximine ligand, is also included.     

Rational Synthesis of Amorphous Iron‐Nickel Phosphonates for Highly Efficient Photocatalytic Water Oxidation with Almost 100 % Yield

A simple solvent ligation effect was successfully used to disrupt the growth of a model compound, Fe[(OH)(O₃P(CH₂)₂CO₂H)]?H₂O (MIL‐37), into an extended 2D structure by replacing water with dimethylformamide (DMF) as the solvent during the synthesis. Owing to the lack of ?OH group, which provides the corner‐sharing (binding) oxygen atoms for the octahedra, an amorphous and porous structure is formed. When Fe³⁺ is partially replaced by Ni²⁺, the amorphous structure remains and the resultant binary metal catalyst displays excellent photocatalytic oxygen evolution activity with almost 100 % yield achieved under visible light irradiation using [Ru(bpy)₃]²⁺ as the photosensitizer. This study opens up new possibilities of using the simple solvent effect to synthesize high surface area metal phosphonates for catalytic and other applications.     

Phosphonate‐Modified UiO‐66 Brønsted Acid Catalyst and Its Use in Dehydra‐Decyclization of 2‐Methyltetrahydrofuran to Pentadienes

Phosphorus‐modified all‐silica zeolites exhibit activity and selectivity in certain Brønsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well‐defined sites, we report the incorporation of Brønsted acidity to metal–organic frameworks with the UiO‐66 topology, achieved by attaching phosphonic acid to the 1,4‐benzenedicarboxylate ligand and using it to form UiO‐66‐PO₃H₂ by post‐synthesis modification. Characterization reveals that UiO‐66‐PO₃H₂ retains stability similar to UiO‐66, and exhibits weak Brønsted acidity, as demonstrated by titrations, alcohol dehydration, and dehydra‐decyclization of 2‐methyltetrahydrofuran (2‐MTHF). For the later reaction, the reported catalyst exhibits site‐time yields and selectivity approaching that of phosphoric acid on all‐silica zeolites. Using solid‐state NMR and deprotonation energy calculations, the chemical environments of P and the corresponding acidities are determined.     

MgCl2/Et3N Base System as a New Catalyst for the Synthesis of α‐Hydroxyphosphonate

An efficient and simple synthesis of α‐hydroxyphosphonates via reaction of aldehydes and ketones with dimethylphosphite in the presence of MgCl₂/Et₃N base system is reported. The use of readily available and easy to handle reagent MgCl₂/Et₃N makes this method simple, convenient, and practical.