Degradation mechanism phosphates/phosphonates

Oximes, which are valuable intermediates for the conversion of oxoalkyl phosphonic diesters into those of aminoalkylphosphonic acids (Chapter 4, Section IV.C. 1. d), are also readily available, although it is necessary to prepare them with some care. Nevertheless, the feature of interest here is their ready degradability, particularly under aqueous conditions, and which has been intensively investigated by Breuer and coworkers. The necessity for care in the preparation of oximes of acylphosphonic diesters, is illustrated by the synthesis of dimethyl [a-(hydroxyimino)benzyl]phosphonate this compound exists in the thermodynamically more stable ( ) form which, under the influence of acid is converted into the less stable (Z) form, and both forms have been separately characterized by X-ray crystallography. The geometric isomers of the oxime differ in their behaviour under basic conditions with NaOH-MeOH, the ( ) form undergoes monodealkylation, whereas the (Z) isomer decomposes to dimethyl phosphate and benzonitrile. In aqueous solution, ( )-[a-(hydroxyimino)benzyl]phosphonic acid also decomposes into benzonitrile together with phosphoric acid, in a manner which is pH dependent, and consistent with a dissociative mechanism that involves the early formation of monomeric metaphosphate. ... 

Wanner, 1994). The other probably involves a redox mechanism for the oxidation of organophosphonates not readily hydrolysed to phosphate (Avila and Frost, 1989). A phosphonate-degrading pathway independent of phosphate starvation has been identified in Pseudomonas fluorescens... 

In a study of the flame retardance of styrene-methyl methacrylate copolymer with covalently bound pyrocatechol-vinyl phosphate, diethyl p-vinyl benzyl phosphonate, or di(2-phenyl ethyl phosphonate) groups. Ebdon and co-workers [23] obtained data on their decomposition behaviour. This was achieved by reducing the rate of liberation of flammable methyl methacrylate monomer during combustion. Possible mechanisms for these processes are suggested. Other methacrylate copolymers which have been the subject of thermal degradation studies include PMMA-N-methylmaleimide-styrene [24] and PMMA-ethylene vinyl acetate [25-27]. 

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