Monomers phosphorus compounds

Many other aliphatic or aromatic amines produce the same reaction. However if N-alkyl (or aryl)2-aniline is made to react with tris-dimethylaminophosphine, tricoordinated phosphorus compounds are obtained. Their analyses and mass spectra show that they are tetramers (5) when the energy of the ionizing electron beam is nearly 70 eV the mass spectra of the oligomers show an intense [M] peak which corresponds to the monomer ion (n = 1) but when the spectra are obtained by field desorption m.s. the molecular ion peak corresponds to a tetramer (n = 4) one sees also smaller peaks for ions n = 3, 2 or 1. 

These oligomers, when heated in various solvents are in equilibrium with the monomer a dicoordinated phosphorus compound ... 

Some P-containing monomers can be self-condensed to form homo-polymers, while others can be co-polymerised with a non-phosphorus-containing monomer. Desirable commercial properties are sought in polymers of the latter type, which employ a minimal amonnt of the usually more expensive phosphorus compound. 

Several recent papers refer to the effects of phosphorus compounds upon radical polymerizations. Various chlorophosphines act as degradative transfer agents. - Some compounds of quinquevalent phosphorus, notably phosphorus oxychloride (POClj), have quite pronounced and complicated effects on polymerizations initiated by AIBN they act as transfer agents, although to a lesser extent than say phosphorus trichloride. They also increase the overall rate probably by complexing with the monomer and modifying its reactivity. For styrene, AIBN, and phosphorus oxychloride, there is a contribution from a cationic polymerization initiated by the oxychloride, ... 

Spontaneous alternating copolymerizations of two cyclic phosphorus compounds, 2-phenyl-l,3,2-dloxaphospholane 11 and 2-phenoxy-1,3,2-dloxaphospholane 20, with several electrophilic monomers were discussed. As the electrophilic monomers, /3-proplolactone 13, 3-hydroxypropanesulfonlc acid lactone (propane-sultone) 15, acrylic acid 16, acrylamide 17, acrylate were sucessfully copolymerized with 11. At temperatures lower than those of copolymerization, the combinations of 11—13, 11—16, 11—-17 and 11—acrylate produced trioxyphosphorane derivatives having spiro-ring structures, which were significant in two... 

Reaction of these phosphorus compounds and of those covered earlier lead to intermediates of interest such as monomers, insecticides, fungicides, and pharmaceutical products. Their chemistry and potential is far from being fully exploited. 

Saegusa studied a very broad spectrum of cyclic and acyclic trivalent phosphorus compounds as the M components in combination with many Me monomers. Some of investigated cyclic P-containing monomers are shown in Table 4. 

Although most of the macrocycles that contain phosphorus or arsenic which have thus far been prepared, are primarily transition metals binders, two compounds have been prepared which are essentially crown ethers containing phosphorus. Kudrya, Shtepanek and Kirsanovhave prepared two compounds which are essentially polyoxygen macrocycles but which contain one or two methylphosphonic acid esters as part of the ring. These two macrocycles are shown below as 7d and 17 and are both prepared by the reaction of 2,2 [oxybis(ethyleneoxy)] bisphenolate with methylphosphonic dichloride in a mixture of acetonitrile and benzene. The crystalline monomer 16) and dimer 17) were isolated in 17% and 11% yields respectively as indicated in Eq. (6.13). 

Peptidomimetics in which one amide bond is replaced by a phosphinic acid (R-P(0H)(=0)-R phosphinic peptides ) are of interest as potential protease inhibitors [17-19]. These compounds have been prepared either from orthogonally protected phosphorus-containing monomers [17,18,20], or by forming the phosphorus-containing fragments on solid phase, as sketched in Figure 11.4 [19,21], Phosphinic acids have been prepared on solid phase mainly by reaction of carbon electrophiles with monoalkylphosphinates. As carbon electrophiles, acrylates, aldehydes, reactive alkyl halides, or a, 3-unsaturated ketones can be used. 

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