Derivate des Phosphorsäure-o-phenylenesters. XVI. o-Phenylendioxyphosphonium-hexahalogenoantimonate

Derivatives of o-Phenylenphosphates. XVI. o-Phenylendioxyphosphonium-hexahalogenoantimonates Pentacoordinated o-phenylen-orthophosphate-trihalogenides 1 resp. bis-o-phenylenorthophosphate-chloride 3 can be transformed to stable quasiphosphoniumsalts 2 resp. 4 by reaction with SbCl₅ or SbBr₃/Br₂. The structures of 2 and 4 are confirmed by ³¹P-n.m.r.     

Derivate des Phosphorsäure-o-phenylenesters. XIX. Zum Ablauf der Bromierung von Phenyl-o-phenylenphosphit

Derivatives of o-Phenylene Phosphates. XIX. Bromination of Phenyl o-Phenylene Phosphite The bromination of phenyl o-phenylene phosphite does not yield the expected penta-coordinated phosphorus dibromide 3 but phosphorus tribromide, phenoxy-bis-(o-phenylendioxy)-phosphorane and tetraphenoxyphosphonium bromide. The mechanism of the reaction is discussed.     

Derivate des Phosphorsäure-o-phenylenesters. XII[1]. Reaktion von Orthosäurechloriden mit Äthylenoxid

Derivatives of o-Phenylene Phosphate. XII. Reaction of Ortho-acid Chlorides with Ethylene Oxide Ortho-acid chlorides react with ethylene oxide in dependence of their structure either to ortho-acid β-chloroethylester or by splitting off 1,2-dichloroethane to the corresponding carbonyl- and phosphoryl derivatives, respectively. Using this method i. a. pentacovalent P-derivatives (pentaoxyphosphoranes 14, 16 ) are available.     

Derivate des Phosphorsäure-o-phenylenesters. 23. Verhalten von Brenzkatechylphosphortrichlorid gegenüber O-funktionellen P(III)-Verbindungen

Derivatives of o-Phenylene Phosphates. 23. Behaviour of Catechyl Phosphorus Trichloride towards Phosphites and Phosphinites Catechyl phosphorus trichloride ( 1 ) reacts with triethyl phosphite ( 4 ), triphenyl phosphite ( 9 ), and the o-phenylene phosphites ( 16a–d ) by ligand exchange and with isopropyl diphenyl-phosphinite ( 21 ) by ligand exchange and oxidation.     

Derivate des Phosphorsäure-o-phenylenesters. XV [1]. Synthese von Tris-(o-phenylendioxy)-phosphorat(V)

Derivatives of o-Phenylenephosphate. XV. Synthesis of Tris-(o-phenylenedioxy)-phosphorate(V) The structure of an orthophosphate which had been supposed earlier to represent type 1 , has been proven to be a compound having only one P-nucleus in the molecule, with a penta( 4 ) resp. hexacoordinated ( 5 ) structure depending on the solvent. The triethyl-ammonium salt 8 of this first example of a hexacoordinated phosphoric acid with 6 P O-bonds ( 5 ) is formed simply from tri- als well as from tetra- and pentacoordinated derivatives of phosphorous resp. phosphoric or thiophosphoric acid.     

Analytik von Phosphorsäurepartialestern

Analytic of Phosphoric Acid Partial Esters Phosphoric acid partial esters are best synthesized by reaction of fatty alcohol with P₂O₅. The chosen mol ratio of fatty alcohol and P₂O₅ determines the amounts of mono-, di- and trialkylester, of oligomeric esters, of free fatty alcohol and of phosphoric acid. Several methods are used for the characterisation and determination of the individual components, the potentiometric titration, the ³¹P-nuclear magnetic resonance, the gel permeation chromatography, the ion chromatography and the supercritical fluid chromatography. The combination of all the results of the applied methods provides the key to the composition of the phosphoric acid ester. The results of the analysis are checked by a phosphorus calculation. This analytical procedure can be applied to phosphoric acid partial esters in the acid and salt form. The analysis of alkylethoxyphosphoric esters is done with the exclusion of the chromatographic methods.