Phosphorus compounds, solvent effects

Chemical Shifts and Shielding ElSects.—Phosphorus-31. In this section, positive P chemical shifts (dp) are upheld from 85% phosphoric acid. A linear relationship between dp and vapour pressure for elemental phosphorus in the gas phase has been reported. Solvent effects have also been examined. dp compounds. The n.m.r. parameters of various protic and deuteriated... 

The chemical shifts of the Esters of Phosphonic and Phosphoric Acid are similar to those of the carboxylic acids, however, their spectra are distinguished by the spin-spin coupling interactions of the nearby hydrocarbon groups with the Phosphorus nucleus. As noted, many of these couplings and their associated coupling constants are quite sensitive to structural and substituent differences. Both groups of compounds are quite soluble in carbon tetrachloride and deuterochloroform and no unusual solvent effects have been noted for these two solvents. 

Studies of Equilibria, Reactions, and Solvent Effects.—Lanthanide shift reagents have been found to be effective for phosphines and phosphoryl compounds, but not for thiophosphoryl compounds. - In a comparison of various shift reagents, europium nitrate hexadeuterium oxide (26) was found to give large shifts of 8 for phosphates and phosphonates. A contact contribution to the Sp shifts was established. When there are two possible sites for co-ordination, as in the aminophosphine (27), steric effects play an important role. Co-ordination occurs at nitrogen in (27 R = H) but at phosphorus in (27 R = Me). The n.m.r. parameters... 

Phosphorus compounds give resonances in characteristic ranges depending primarily on the oxidation state and coordination munber of the phosphorus atoms present (Table 1). Chemical shifts also depend on the pH, concentration, and salt content of the solution, solvent effects, and the electronegativity of any substituents. Since the phosphorus atom is a comparatively reactive center, it can usually... 

Isomer and conformer ratios in dichlorocyclohexane mixtures can be successfully found from n.m.r. data. The conformational equilibria in cyclohexylamines and their protonated analogues have been determined from chemical shift data with an accuracy of 2%. This was shown to be sufficient to allow the effects of ionization and solvent on the conformation to be deduced. A detailed conformational study of a number of cis- and trans-t-butylcyclohexyl phosphorus compounds (15) has been made. In this the n.m.r. data of the trans-isomers are consistent with... 

In the past, many variations of the sol-gel process have been developed and used to produce powders with different Ca/P ratios, by altering not only the quantity and composition of precursors but also the processing variables. As the synthesis of HA requires a calcium to phosphorus molar ratio of 1.67 1 in the final product, a number of caldum/phosphorus precursor combinations have been used in the preparation of HA powders. For example, calcium nitrate or different calcium alkoxides and 2-ethyl-hexyl phosphate, triethyl phosphate or orthophos-phoric acid, have been used as the calcium and phosphoras precursors, respectively. The major limitation for appUcation of the sol-gel process was shown to be the very poor solubility of the calcium alkoxides in organic solvents, and the poor reactivity of the phosphorous compounds. The effective control of stoichiometry due to the volatility of the phosphorous compounds used also represented a challenge. 

The stereoselectivity of the Wittig reaction is believed to be the result of steric effects that develop as the ylide and carbonyl compound approach one another. The three phenyl substituents on phosphorus impose large steric demands that govern the formation of the diastereomeric adducts.240 Reactions of unstabilized phosphoranes are believed to proceed through an early TS, and steric factors usually make these reactions selective for the d.v-alkcnc.241 Ultimately, however, the precise stereoselectivity is dependent on a number of variables, including reactant structure, the base used for ylide formation, the presence of other ions, solvent, and temperature.242... 

The pure compound is a pale yellow, nearly odourless oil, soluble in organic solvents, but almost insoluble in water. Averell and Norris2 describe the detection of minute quantities of parathion (20 /ig.) in spray and dust, by reduction with zinc, diazotization and coupling with an amine to give an intense magenta colour. It is effective (at concentrations of 25-600 p.p.m.) against many insect species, but of course, like the majority of organo-phosphorus insecticides, it is toxic to man and to animals. 

Solvent and temperature effects have been especially studied in simple compounds—white phosphorus,(1969 180) PH3, (1967>43> PFS, (1968,51) phosphorus acid, phosphines, phosphonium compounds etc. (1965> 39 1967,169 1968,155 1969,53) phosphorus chemical shifts or line-widths,... 

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