20464-82-8

Upstream product

• 150-76-5 4-methoxy-phenol 

Downstream Products

• 135263-39-7 bis(4-methoxyphenyl) 4-tolyl phosphate 
• 58544-30-2 ethyl bis(4-methoxyphenyl) phosphate 
• 139301-33-0 (S)-3-[Bis-(4-methoxy-phenoxy)-phosphoryloxy]-2-tert-butoxycarbonylamino-propionic acid benzyl ester 
• 144426-68-6 Acetic acid (3R,4aR,5S,6S,6aR,10R,10aS,11aS)-6-hydroxy-3,4a,7,7,10-pentamethyl-1-oxo-3-vinyl-decahydro-4,11-dioxa-cyclopropa[e]phenanthren-5-yl ester 
• 144426-67-5 7β-acetoxy-8,13-epoxy-6β-hydroxy-11-oxolabd-14-ene-1,9-diyl p-(methoxyphenyl)-phosphate 
• 144426-67-5 7β-acetoxy-8,13-epoxy-6β-hydroxy-11-oxolabd-14-ene-1,9-diyl p-(methoxyphenyl)-phosphate 
• 29138-97-4 bis(4-methoxyphenyl) phosphate 
• 74178-22-6 di-p-methoxyphenyl amidophosphate 
• 76628-14-3 Bis(4-methoxyphenyl)-phosphorofluoridat 
• 70138-26-0 Phenyl-phosphoramidic acid bis-(4-methoxy-phenyl) ester 
• 70160-21-3 di-p-methoxyphenyl N-methylamidophosphate 
• 417708-19-1 4-cyanophenyl bis(4-methoxyphenyl) phosphate 
• 417708-20-4 4-nitrophenyl bis(4-methoxyphenyl) phosphate 
• 417708-17-9 3-chlorophenyl bis(4-methoxyphenyl) phosphate 

Relevant academic research and scientific papers

Polyethers with phosphate pendant groups by monomer activated anionic ring opening polymerization: Syntheses, characterization and their lithium-ion conductivities

This paper describes the preparations and lithium-ion conductivities of various solid polymer electrolytes for potential use in high-energy density lithium-ion batteries. The ring opening polymerization of epoxides (M1-M6), catalyzed by Zn(II), Cu(II) and Cd(II) complexes in the presence of tetrabutylammonium bromide (TBAB), yielded polyethers (P1-P6) in which phosphates were attached as pendant groups. A reaction condition where Zn(II) catalyst used slightly excess to TBAB increased the polymerization rate remarkably and yielded the polyethers with higher molar masses in a short time. These polymerizations proceeded following a "monomer activated anionic ring opening polymerization" mechanism. These living like polymerizations also progressed according to "formation of polymer chain per initiator" model. The solid-state lithium-ion conductivities of these polymers were examined using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The conductivity of one of the solid polymer electrolytes with 40 wt% of LiTFSI was 5.2 × 10-5 S cm-1 at room temperature and 2.9 × 10-4 S cm-1 at 80 C.

Synthesis of phosphoramidates: A facile approach based on the C-N bond formation via Ir-catalyzed direct C-H amidation

A new synthetic route to phosphoramidates by intermolecular C-H amidation is presented. Substrates with assorted directing groups were activated by an iridium-based catalyst system and reacted with a number of phosphoryl azides, executing efficient phosphoramidate synthesis via C-N bond formations. (Chemical Equation Presented).

Hydrogen phosphates: Self initiated organocatalysts for the controlled ring-opening polymerization of cyclic esters

A series of arylhydrogenphosphates and aryldihydrogenphosphates was synthesized and characterized using spectroscopic methods and single crystal X-ray diffraction. These compounds were assessed as catalysts towards the ring-opening polymerization and proved to be potent organocatalysts for the ring-opening polymerization of cyclic esters. The bulk polymerizations were performed in the absence of external initiator. The polymerization proceeds in a controlled fashion which leads to well defined polyesters with narrow molecular weight distributions. In the post polymerization experiments, kinetics, mechanism and monomer concentration effects were investigated. The kinetic results have confirmed the pseudo-living character of the polymerizations and mechanistic studies suggest that the polymerization operates through a cationic mechanism.

Highly Z-selective synthesis of a,b-unsaturated nitriles using the Horner-Wadsworth-Emmons reaction

A new HWE reagent, (o-tBuC6H4O)2P(O)CH2CN (2e), reacts with various types of aldehydes to give Z-a,bunsaturated nitriles with 86% to >99% Z-selectivity. Especially, the reaction of 2e with bulkier aldehydes, both aromatic and aliphatic, gave the Z-olefins with extremely high selectivity. The combination of t-BuOK and 18-crown-6 (1 equiv) is the base of choice for aromatic aldehydes and t-BuOK is generally the base of choice for aliphatic aldehydes.

Kinetics and mechanism of the anilinolysis of bis(aryl) chlorophosphates in acetonitrile

The nucleophilic substitution reactions of bis(Y-aryl) chlorophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 35.0 °C. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorophosphates (2). The substrate 1 has one more identical substituent Y compared to substrate 2. The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of cross-interaction constant (CIC) from negative ρXY = -1.31 (2) to positive ρXY = +1.91 (1), indicating the change of reaction mechanism from a concerted SN2 (2) to a stepwise mechanism with a rate-limiting leaving group departure from the intermediate (1). The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines (XC6H4ND2) show secondary inverse, k H/kD = 0.61-0.87. The DKIEs invariably increase as substituent X changes from electron-donating to electron-withdrawing, while invariably decrease as substituent Y changes from electron-donating to electron-withdrawing. A stepwise mechanism with a rate-limiting bond breaking involving a predominant backside attack is proposed on the basis of positive sign of ρXY and secondary inverse DKIEs.

Transition-state variation in the nucleophilic substitution reactions of aryl bis(4-methoxyphenyl) phosphates with pyridines in acetonitrile

The kinetics and mechanism of the reactions of Z-aryl bis(4-methoxyphenyl) phosphates, (4-MeOC6H4O)2P(=O) OC6H4Z, with pyridines (XC5H4N) are investigated in acetonitrile at 55.0 °C. In the case of more basic phenolate leaving groups (Z = 4-Cl, 3-CN), the magnitudes of βx (βnuc) and βz (βlg) indicate that mechanism changes from a concerted process (βx = 0.22-0.36, βz = -0.42 to -0.56) for the weakly basic pyridines (X = 3-Cl, 4-CN) to a stepwise process with rate-limiting formation of a trigonal bipyramidal pentacoordinate (TBP-5C) intermediate (βx = 0.09-0.14, βz = -0.08 to -0.28) for the more basic pyridines (X = 4-NH2, 3-CH3). This proposal is supported by a large negative cross-interaction constant (ρxz = -1.98) for the former and a positive ρxz(+0.97) for the latter processes. In the case of less basic phenolate leaving groups (Z = 3-CN, 4-NO2), the unusually small magnitude of βz values is indicative of a direct backside attack TBP-5C TS in which the two apical sites are occupied by the nucleophile and leaving group, ap(NX)-ap(LZ). The instability of the putative TBP-5C intermediate leading to a concerted displacement is considered to result from relatively strong proximate charge transfer interactions between the π-lone pairs on the directly bonded equatorial oxygen atoms and the apical bond (no(eq) - ?*(ap)). These are supported by the results of natural bond orbital (NBO) analyses at the NBO-HF/6-311+G**//B3LYP/6-311+G** level of theory.

Improved protective groups for phosphate of o-phosphoserine useful for the solid-phase peptide synthesis

2-Methylphenyl and 2,6-dimethylphenyl groups on phosphate moiety of O-phosphoserine were more stable in HF treatment than phenyl group and could be effectively removed by hydrogenolysis. They were shown to be protective groups for phosphoserine practicall

PHOTOLYSIS OF ARYL ESTERS OF TRI- AND TETRACOORDINATED PHOSPHORUS COMPOUNDS

Upon UV excitation in methanol, some diaryl esters of alkly- or alkenyl phosphonates underwent an elimination of two aryl groups to give biaryls and the corresponding alkyl- or alkenylphosphonic acids.Tris(4-methoxyphenyl) phosphite also underwent a similar elimination to give 4,4'-dimethoxybiphenyl and 4-methoxyphenyl phosphonate.This interesting biaryl elimination was confirmed to proceed via a singlet intramolecular excimer by means of fluorescence spectra and Stern-Volmer analysis.

Metalation-Induced Double Migration of Phosphorus from O-->C. Convenient Preparation of Bis(2-hydroxyaryl)phosphinic Acids

Treatment of diaryl ethyl phosphates 8 with lithium diisopropylamide in tetrahydrofuran yields ethyl bis(2-hydroxyaryl)phosphinates 9.The reaction involves the double migration of phophorus from O-->C and is probably intramolecular.These phosphinate esters 9 on treatment with trimethylsilyl chloride and sodium iodide in acetonitrile undergo transesterification to give trimethylsilyl esters that yield the corresponding phosphinic acids 15 on treatment with water.