Phosphorus acid derivatives

Haloacetyl groups have also a synthetic potential. Thus, pesticidal (alkylthio)-vinyl esters of phosphorus acid derivatives have been prepared by the introduction and subsequent displacement of two chlorine atoms in the acetyl moiety attached to the furazan ring (Scheme 69) [73GEP(0)2144393]. 

A review (91 references) on electrophilic and nucleophilic reactions of trivalent phosphorus acid derivatives, reactions of two-coordinate phosphorus compounds, and miscellaneous reactions has appeared.228 Earlier in this review we looked at the heavy-atom isotope effects on reactions of Co(III)-bound /vnitrophenyl phosphate,186 the uranyl ion hydrolysis of /vnitrophcnyl phosphodiesters (218)-(220),190 and the Th(IV) hydrolysis of these.191... 

To get a broader concept of the nucleophilic reactivity of phosphorus acid derivatives towards organosilanes we studied mechanism of reactions of triorganosilyl halides with esters of tricoordinate and tetracoordinate phosphorus having the general formulae ... 

Lebduskova, P., Kotek, J., Hermann, P., Vander Elst, L., Muller, R.N., Lukes I., and Peters, J.A., A gadolin-ium(III) complex of a carboxylic-phosphorus acid derivative of diethylenetriamine covalently bound to inulin, a potential macromolecular MRI contrast agent, Bioconjugate Chem., 15, 881-889, 2004. 

Quasiphosphonium ions involving oxygen directly bound to the positive phosphorus site are generated as intermediates in numerous other reactions. For example, the Michaelis-Arbuzov reaction (see Section 3.5) produces a quasiphosphonium ion as an intermediate that undergoes attack by the associated amon at the carbon end of the C T P linkage. The reaction follows a different course when aryl ester linkages are present on the starting trivalent phosphorus acid derivative. In such instances, a quasiphosphomum ion is... 

The main area of activity this year has again been the use of tervalent phosphorus acid derivatives for preparation of phosphates or modified phosphates of biochemical interest. Most of this work is reported in part 3.3 of this chapter. 

As this area was not covered in Volume 31, the present chapter provides an overview of the literature published over the two years between July 1998 and June 2000. The report is structured in terms of the principal classes of tervalent phosphorus acid derivatives, viz halogenophosphines, tervalent phosphorus esters, and amides. Attempts have been made to minimise the extent of overlap with other chapters, in particular those concerned with the synthesis of nucleic acids and nucleotides to which the chemistry of tervalent phosphorus esters and amides contributes significantly (see Chapter 4), the use of known halogenophosphines as reagents for the synthesis of phosphines (see Chapter 1), and the reactions of dialkyl- and diaryl-phosphite esters, in which the contribution of the phosphonate tautomer, (R0)2P(0)H, is the dominant aspect. 

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