54057-96-4

Upstream product

• 24262-31-5 acetone enolate ion 
• 608-28-6 2,6-dimethyliodobenzene 
• 29800-93-9 diethyl phosphite 
• 108-38-3 m-xylene 
• 762-04-9 phosphonic acid diethyl ester 
• 122-52-1 triethyl phosphite 
• 762-04-9 Diethyl phosphonate 
• 89620-99-5 silver diethyl phosphonate 
• 814-49-3 diethyl chlorophosphate 
• 576-26-1 2.6-dimethylphenol 
• 64-17-5 ethanol 
• 85320-25-8 (2,6-diphenylphenyl)phosphinous dichloride 

Downstream Products

• 85320-18-9 2,6-dimethylphenylphosphonic acid monoethyl ester 
• 1610675-58-5 P-(1,3-dimethylphenyl)phosphonamidic acid ethyl ester 

Relevant academic research and scientific papers

Palladium-catalyzed one-pot phosphorylation of phenols mediated by sulfuryl fluoride

We report a general palladium-catalyzed one-pot procedure for the synthesis of phosphonates, phosphinates and phosphine oxides from phenols mediated by sulfuryl fluoride. It features mild conditions, broad substrate scope, high functionality tolerance and water insensitivity. The utility of this procedure has been well demonstrated by gram-scale synthesis, sequential synthesis of click chemistry building blocks, late-stage decoration of drugs and natural products and on-DNA synthesis of phosphine oxide for a DNA-encoded library (DEL).

Metal-free azaphosphaannulation of phosphonamides through intramolecular oxidative C-N bond formation

We report an efficient metal-free azaphosphaannulation of a myriad of phosphonamides through intramolecular oxidative C-N bond formation using PhI(OAc)2 and iodine in acetonitrile under air, thus leading to the formation of benzazaphosphol-3-on

Manganese(III)-mediated direct phosphonylation of arenes

Manganese (III)-promoted direct phosphonylation of mono- and disubstituted arenes with dialkylphosphite afforded regioselective dialkylphosphonates in good yields. The reactions can apply to arenes bearing electron-donating groups and electron-withdrawing

Development of a room temperature Hirao reaction

Arylphosphonates were prepared at 25 °C through the palladium-catalyzed coupling of aryl iodides with a silver phosphonate. A wide range of aryl iodides were successfully employed including phenolic substrates as well as those containing an ortho substitu

Oxidative Phoshonylation of Aromatics with Ammonium Cerium(IV) Nitrate

Arylphosphonates 5 and 6 can be prepared in good yields in a one-step synthesis starting from arenes with tri- or diethylphosphites and cerium ammonium nitrate (CAN) as oxidant.The seletivity of the oxidative phosphonylation is relatively low; the reactive species is a phosphite radical cation.

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.

THE EFFECT OF ORTHO SUBSTITUENTS IN SRN1 REACTIONS. SOME SYNTHETIC APPLICATIONS.

Several ortho-substituted iodobenzenes were allowed to react, via the SRNl mechanism, with mixtures of diethyl phosphite ion and pinacolone enolate ion.From product composition data, the relative reactivities of the two nucleophiles were reckoned.They represent relative reactivities in attachment to aryl radical intermediates.Most of the ortho effects are slight, but there is evidence that large ortho substituents hinder attachment of the phosphite more than the enolate nucleophile.The methoxy and diethoxyphosphoryl substituents, when para to the site of substitution, respectively favour and disfavour the phosphite with respect to the enolate ion.SRNl reactions of ortho-substituted halobenzenes are, for some substituents, followed by other reactions which afford products of synthetic interest.

OXIDATION REACTIONS OF PHOSPHAALKENES.

Phosphaalkenes such as left bracket (2,6-dimethylphenyl) (diphenylmethylene)phosphine right bracket are quite reactive in many respects but are rather sluggish in their reaction with oxygen and sulfur. Primary intermediates in the reactions are the oxide, the phosphene and the phosphinidene oxide which together with (thio)benzophenone is formed by oxidative cleavage of the P equals C bond. The occurrence of these unstable intermediates is concluded from their interception by ethanol or water in the oxygen reactions and by ethanol in the sulfur reaction. The mechanism of these reactions and the competition between various reactants are discussed. The structure of the reaction products is determined from their spectral properties and by alternative synthesis along unequivocal routes.