46475-48-3

Upstream product

• 108-90-7 chlorobenzene 
• 122-52-1 triethyl phosphite 
• 66003-76-7 Diphenyliodonium triflate 
• 1754-49-0 diethyl phenylphosphonate 
• 368-39-8 triethyloxonium fluoroborate 
• 71-43-2 benzene 

Downstream Products

• 1638-86-4 diethyl phenylphosphonite 
• 1754-49-0 diethyl phenylphosphonate 
• 1394286-72-6 C₁₀H₁₈BO₂P 

Relevant academic research and scientific papers

Visible-Light-Mediated Metal-Free Synthesis of Aryl Phosphonates: Synthetic and Mechanistic Investigations

This work describes a straightforward access to a large variety of aryl phosphonates by the simple combination of diaryliodonium salts with phosphites in the presence of a base and under visible-light illumination. The reaction proceeds smoothly, tolerates various functionalities, and was applied for the synthesis of pharmaceutically relevant compounds. Mechanistic investigations, including EPR, NMR, and DFT calculations, support the postulated reaction mechanism.

PROCESSES FOR THE STEREOSELECTIVE PREPARATION OF P-CHIRAL FOUR -COORDINATED PHOSPHORUS BORANE COMPOUNDS AND P-CHIRAL THREE-COORDINATED PHOSPHORUS COMPOUNDS

Processes for the stereoselective preparation of P-chiral four-coordinated phosphorus borane compounds and P-chiral three-coordinated phosphorus compounds.

Kinetics and Mechanism of the Hydrolysis of Acyclic Oxyphosphonium Salts

A kinetic study is reported of the hydrolysis of seven acyclic alkoxyphosphonium ions and two alkoxyaryloxyphosphonium ions .First-order rate constants follow the relationship kobsd=k0+kOH+kA, showing a reaction with water, hydroxide, and the base component of the buffer.The last two reactions are shown or argued to involve only P-O cleavage in the hydrolysis.The water reaction occurs with some C-O cleavage as well.The mixed phosphonium ions hydrolyze over a range of acidities to produce 4-methoxyphenol and the methyl phosphinate ester.The P-O cleavage reaction in all cases is argued to involve rate-limiting formation of a pentavalent hydroxyphosphorane intermediate.The buffer reaction represents general base catalysis of the addition of water, the base assisting the water attack by simultaneously removing a proton.Broensted coefficients are large, ranging from 0.6 to 0.85.This implies a transition state with a considerable amount of proton transfer.A comparison is presented with the general base-catalyzed hydration reactions of carbocations, which show significantly smaller β values.The water rates for the phosphonium ions lie close to the Broensted plots, suggesting that this reaction is also occuring with general base catalysis.Large rate decreases are observed with added acids and salts.These effects are explained by the general base mechanism with considerable hydronium ion character in the transition state.A comparison is also presented of the effects of sulfuric acid on the rates of hydrolysis of an alkoxyphosphonium ion and an analogous hydroxyphosphonium ion or protonated phosphinate ester.

OXIDATIVE PHOSPHONYLATION OF AROMATIC COMPOUNDS

Aryl phosphonates can be prepared in good yield from the respective arenes and tri- or dialkylphosphites by either chemical or anodic oxidation.The anodic oxidation proceeds either via phosphinium radical cations, which then attack the arenes electrophilically, or via arene radical cations, which add the trialkylphosphite as nucleophile.Aryl phosphonates are also obtained in good yield by chemical oxidation with peroxodisulfate/AgNO3 in acetonitrile/water or glacial acetic acid.The diethylphosphinium radical cation, formed from diethylphosphite by oxidation with Ag(II), is supposed to be the reactive species in this process.Raising the silver salt concentration leads to an increase in polyphosphonylation.Selectivity ratios were determined for the oxidative phosphonylation process.