60705-73-9

Upstream product

• 150-78-7 1,4-dimethoxybezene 
• 676-97-1 methylphosphonic acid dichloroanhydride 
• 150-76-5 4-methoxy-phenol 

Downstream Products

• 2132-80-1 4,4'-Dimethoxybiphenyl 
• 16391-06-3 methyl hypophosphorous acid methyl ester 
• 27983-20-6 2,6-Dimethoxydibenzodioxin 
• 756-79-6 dimethyl methane phosphonate 
• 993-13-5 methylphosphonic acid 
• 66731-04-2 2,4',5-trimethoxy-1,1'-biphenyl 

Relevant academic research and scientific papers

New feature of Friedel-Crafts phosphonation of anisoles: Unexpected in situ methylphosphorylation reaction

Anisoles 1, reacting with AlCl3 and PCl3 with appropriate reagent ratios, give, in good yields, the corresponding diaryl methylphosphonates 2 or the methylphoshinates 3b,c and the methylphosphine oxides 4b,c. This unexpected in situ methylphosphorylation explains the reported limited and conflicting results to obtain methoxy-substituted arylphosphonous dichloride with the same reagents. A suggested mechanism is also reported.

Photolysis of 4-Methoxyphenyl Aryl Alkylphosphonates

UV irradiation of bis(4-methoxyphenyl) methylphosphonate 1a in methanol gave 4,4'-dimethoxybiphenyl 2a as the main product through an intramolecular excimer.With 4-cyanophenyl-4-methoxyphenyl methylphosphonate 1b 4-cyano-4'-methoxybiphenyl 2c and 4-cyano-2-(4'-methoxyphenyl)phenyl methylphosphonate 4b were obtained through an intramolecular exciplex. 3-Cyanophenyl-4-methoxyphenyl methyl phosphonate 1c gave only 3-cyano-4'-methoxybiphenyl 2f.Methyl 4-methoxyphenyl 4-chlorobenzylphosphonate 5a gave dimethyl 4-chlorobenzyl 2-(4'-methoxyphenyl)phosphonate and dimethyl 2-(4'-methoxyphenyl)benzylphosphonate.

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.

Photolysis of bis(methoxyphenyl) methylphosphonates. Their emission spectra and formation of dimethoxybiphenyl and dimethoxy-9,10-dioxaanthracene

Upon UV-irradiation in methanol, bis(methoxyphenyl) methylphosphonates underwent an intramolecular coupling of two methoxyphenyl groups to give dimethoxybiphenyls and dimethoxy-9,10-dioxaanthracenes. The reactivities and fluorescence spectra of the phosphonates were sensitive to the position of the methoxy group. These photo-induced couplings proceed probably through the formation of the two types of singlet intramolecular excimers.

Process for preparing diaryl methylphosphonate and derivatives thereof

A process is provided for the preparation of diaryl methylphosphonates through the reaction of triaryl phosphites with methanol in the presence of a catalytic quantity of methyl iodide. The reaction is conducted at a temperature of from about 170° C. to about 250° C. New and useful derivatives are produced by reaction of the diaryl methylphosphonates with polyols or amines.