14143-01-2

Upstream product

• 814-49-3 diethyl chlorophosphate 
• 108-39-4 3-methyl-phenol 
• 762-04-9 phosphonic acid diethyl ester 
• 78-40-0 triethyl phosphate 
• 125320-80-1 Dicyclohexyl-amine; compound with 3-methyl-phenol 
• 32578-31-7 3-tolyl triflate 
• 54058-00-3 diethyl phosphite potassium salt 

Downstream Products

• 17171-17-4 4'-methoxy-3-methylbiphenyl 
• 7025-91-4 4-m-tolylmorpholine 
• 253342-48-2 4,4,5,5-tetramethyl-2-m-tolyl-1,3,2-dioxaborolane 
• 129529-19-7 2-(Diethyl-phosphinoyl)-5-methyl-phenol 
• 80615-39-0 (2-Hydroxy-4-methyl-phenyl)-phosphonic acid diethyl ester 

Relevant academic research and scientific papers

Electrochemical phosphorylation of arenols and anilines leading to organophosphates and phosphoramidates

A practical phosphorylation for generating organophosphates and phosphoramidatesviaelectrochemical dehydrogenative cross-coupling of P(O)H compounds with arenols and anilines is disclosed. This method involves using inorganic iodide salts as both redox catalysts and electrolytes in an undivided cell without the addition of oxidants or bases. A preliminary mechanistic study suggests that radicals are not involved in this process. This method is green and eco-friendly and has good functional group tolerance, high yields and broad substrate scope, with the potential for practical synthesis.

LiI/TBHP Mediated Oxidative Cross-Coupling of P(O)–H Compounds with Phenols and Various Nucleophiles: Direct Access to the Synthesis of Organophosphates

An efficient and mild method for the direct phosphorylation of phenols, alcohols, and amines with P(O)–H has been reported by LiI/TBHP mediated oxidative cross-coupling reaction. Moreover, this protocol extended to β-keto esters for the synthesis of enol phosphates using H-phosphonates. Notably, this developed method applied for the synthesis of organopesticides such as paraoxon, cyanophos, and methyl parathion. The key features of this protocol are mild conditions, short reaction time, good functional group tolerance, and broad substrate scope.

Tf2O-Promoted Activating Strategy of Phosphate Analogues: Synthesis of Mixed Phosphates and Phosphinate

A metal-, toxic chloride reagent-free activating strategy of various phosphates has been developed. This method enables the facile synthesis of functional phosphates such as alkyl phosphates, aza phosphates, thiophosphate, and mixed diaryl phosphates. A transient phosphorylpyridin-1-ium species in situ generated from phosphates with Tf2O/pyridine readily undergoes a substitution reaction with diverse nucleophiles to form versatile phosphate compounds.

Enantioselective and Regioselective Hydroetherification of Alkynes by Gold-Catalyzed Desymmetrization of Prochiral Phenols with P-Stereogenic Centers

The gold(I)-catalyzed enantioselective hydroetherification of alkynes was achieved via desymmetrization of prochiral bisphenols bearing P-stereogenic centers. (S)-DTBM-Segphos(AuCl)2/AgNTf2 proved to be a highly efficient catalyst system for this transformation, affording P-chiral cyclic phosphine oxides in good yields with high enantioselectivities (with up to 99% ee). The same catalyst system allowed for the enantioselective desymmetrization of dialkynes. Synthetic transformations of the cyclization products afforded other P-chiral molecules with high enantiospecificity.

Pd(II)-catalyzed ortho-arylation of aryl phosphates and aryl hydrogen phosphates with diaryliodonium triflates

Functionalized biaryl compounds were successfully synthesized using phosphates as the ortho-directing group in the Pd(II)/Pd(IV) catalytic cycle.

Triethylphosphate/phosphorus pentoxide as an efficient reagent for the phosphorylation of phenols

A simple, efficient, and novel method has been developed for the phosphorylation of phenols. Treatment of phenols with a mixture of triethylphosphate/phosphorus pentoxide gives the corresponding phosphate derivatives in good yields. This method is easy, rapid, and offers good yields for the phosphorylation of phenols. The reaction of triethylphosphate with phosphorus pentoxide was also studied by variable-temperature 31P-NMR spectroscopy. Copyright

Nickel-catalyzed amination of aryl phosphates through cleaving aryl C-O bonds

The amination of triaryl phosphates was achieved using a Ni(II)-(σ-Aryl) complex/NHC catalyst system in dioxane at 110 °C in the presence of NaH as base. Electron-neutral, -rich, and -deficient triaryl phosphates were coupled with a wider range of amine partners including cyclic and acyclic secondary amines, aliphatic primary amines, and anilines in good to excellent yields.

Phosphorylation of phenols with diethyl chlorophosphonate on the surface of magnesia

Phosphorylation of phenols with diethyl chlorophosphonate on the surface of magnesia is an easy, rapid, safe and high-yielding reaction.

A CONVENIENT SYNTHETIC ROUTE TO PHOSPHATE ESTERS FROM PHOSPHITES

Dialkyl arylphosphate esters have been synthesized in improved yields by the reaction of dicyclohexylamine salts of substituted phenols with dialkyl hydrogen phosphite and carbon tetrachloride.The reaction proceeds through the corresponding phosphorochloridates.

Reaction of Triflates with Potassium Diethyl Phosphite. Formation of Phosphate Esters

Phenyl triflate and substituted analogues react with potassium diethyl phosphite in liquid ammonia to form aryl diethyl phosphate esters.The reaction formally involves loss of trifluoromethanesulfinate ion from the triflate and concomitant oxidation of phosphorus to the phosphate stage.Preliminary data suggest that, in a series of triflates, reactivity follows the order aryl > cyclohexenyl > cyclopropyl > alkyl.Studies on aryl triflates with added labeled phenoxide rule out a mechanism involving free phenoxide ion, i.e., displacement of phenoxide by nucleophilic attack of diethyl phosphite ion on sulfur followed by phosphorylation of displaced phenoxide.Three potential mechanisms, including one involving initial attack of phosphorus at sulfur, a biphilic insertion mechanism, and one involving nucleophilic attack on oxygen, are suggested, all of which could account for these observations.