Polyphosphorus compounds

Although this monograph is concerned primarily with compounds containing one phosphorus atom, some account has already been given of esters of pyrophosphoric acid (p. 103) attention must also be drawn to some recent important contributions to the organic chemistry of polyphosphorus compounds made by M. Tolkmith. He has prepared decamethyltriphosphor-amide (XX) by the action  

This is of course a modified Arbusov reaction. Compound (XVIII) had been prepared by Schrader and our preparation of compound (XIX) is referred to on p. 89. 

Using similar techniques, isomeric dodecamethylphosphor-amides were prepared as follows  

The linear compound (XXI) is twice as active as the pyramidal compound (XXII) against Aphis fabae. 

As is pointed out later (p. 172), O.M.P.A. or the octa-methylamide of pyrophosphoric acid (XXIII) has been developed, more particularly in England, as a selective systemic insecticide which does not kill predatory insects. Furthermore, it has a rather greater safety margin than other cholinergic organo-phosphorus insecticides. A satisfactory method for the large-scale preparation of O.M.P.A. is given on p. 172. 

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Peroxide-Initiated Reaction of Strained-Ring Polyphosphorus Compounds with Olefins... 

M. Baudler, Angew. Chem. Int. Ed. Engl. 1987, 26, 419 (polyphosphorus compounds). 

Reaction of (r-C4Hj )3 with PCI5 (molar ratio 1 2) yields the diphos-phane Cl(r-C4H9)P— P(r-C4H9)C1, which is an excellent synthon for three-membered phosphorus heterocycles of the type (r-C4H9P)2ER (E = hetero atom, n = 0-2) as well as for polyphosphorus compounds. ... 

Trilithium heptaphosphide, dilithium hexadecaphosphide, and trisodium henicosaphosphide are polyphosphides with isolated anions in the solid state as well as in solution. These metalated poly phosphorus compounds are of interest because of their structural relationship to the phosphorus hydrides (phosphanes) and organophosphanes P.R and particularly because of their potential use as building blocks for the syntheses of polyphosphorus compounds. 

These names are very useful for indexes. The names are in use in British literature and will be used more and more in the ACS journals. European chemists have diflBculty in converting the names into their languages, and have made some counter proposals. It will take time to solve all the problems in the nomenclature of phosphorus compounds, especially for polyphosphorus compounds. 

Baudler s group, and others, continue to employ metallophosphide reagents in the development of the chemistry of cyclic polyphosphorus compounds. 

J. Hahn, Higher-order P NMR spectroscopy of polyphosphorus compounds In Phosphorus-31 NMR Spectroscopy in Stereochemical Analysis (Eds. J.G. Verkade and L.D. Quin) VCH, Florida, 1987, pp. 331-364. 

P4S10 + 14KSCN K6(Pi2S,2N,4) + I4CS2 + 4K2S 9.10.8 Polyphosphorus Compounds with P-S and P-C Linkages [1-3]... 

For three-coordinate phosphorus, the best correlations of 5(P) with ring size concern the polyphosphorus compounds, (RP) . The phosphorus chemical shift is approximately linearly correlated with average endocyclic P-P-P bond angles and definite ranges can be established for /i = 5, -1-30 to — lOppm, n = 4, —50 to —80ppm, and = 3, —130 to —180 ppm. The rapid increase in... 

The chemistry of polyphosphorus compounds has developed impressively over the last four decades. The development of several preparative techniques and above all the progress made in P NMR spectroscopy has enabled systematic studies of the structures and reactivity of this class of compounds. Thus, a great number of cyclic and catenated polyphosphanes (both as hydrides and as organic derivatives) have been synthesised and successfully characterised [1-8]. The chemistry of these... 

Baudler M (1987) Polyphosphorus compounds—new results and perspectives. Angew Chem Int Ed Engl 26 419-441... 

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