Other phosphorus containing compounds

Gates M and Renshaw BC (1946). Fluorophosphates and other phosphorus-containing compounds. In Summary Technical Report of Division 9, Vol. 1, Parts I, n, pp. 131, 155. Washington, DC, USA Office of Scientific Research and Development. 

P NMR spectroscopy is the method of choice for phospholipids or any other phosphorus-containing compound. Most phospholipids contain only one phosphorus atom, so the P NMR spectrum of lecithin reads like an HPLC chromatogram. There are some advantages in eomparison with HPLC specific detection of the phosphorus nucleus, high dispersion and hi dynamics. The role of P NMR spectroscopy will be discussed later in detail. 

The reaction between ozone and arsine leads to an emission continuum in the visible region and a discrete emission in the UV. The hydrides of arsenic, antimony, and tin can be determined down to sub-ppb levels. The chemiluminescent reaction between ozone and phosphine has been employed to determine phosphate and other phosphorus-containing compounds after reduction. The chemiluminescent oxidation of silane was used to determine silicate in natural waters. A variety of applications involving ozone as a reagent gas have been included in Table 2. 

Coleman and Gadian (1976) studied developing frog (Xenopus laevis) embryos. They deduced that the ATP molecules are liganded to divalent cations other than Mn, probably Ca or Mg. The internal pH of the embryo was found to be 6.8. Changes in Pj levels and levels of other phosphorus-containing compounds occurred during development of the embryo. 

Not only do heavy-metal ions catalyze the destruction of peroxide compounds but they also catalyze other chemical processes caused by oxygen and air. Sequestering these metal ions by phosphorus-containing compounds will decrease their undesired effects. 

Where the target analyte contains heteroatoms such as nitrogen, phosphorus and sulfur, atom-selective detectors can provide an ideal detection method. A number of examples appear in the literature of the use of a detector called a thermal energy analyser (TEA) for the measurement of A-nitroso compounds [14-17] and aromatic nitro compounds [18]. This has also been used as an HPLC detector [19, 20], and a modified TEA has been reported to be useful for analysis of amines and other nitrogen-containing compounds [17]. Unfortunately, this technique appears not to have gained in popularity, since no reports have appeared in the literature for over two decades. 

Figure 13.19 Examples of other phosphorus-containing hydrolyzable functionalities. In these compounds, carbons are directly bonded to phosphorus. Note that if-0-R3 is replaced by -S-Rj one obtains the corresponding thioesters.

A modified INDO model that is not entirely obsolete is the symmetric orthogonal-ized INDO (SINDOl) model of Jug and co-workers, first described in 1980 (Nanda and Jug 1980). The various conventions employed by SINDOl represent slightly different modifications to INDO theory than those adopted in the MINDO/3 model, but the more fundamental difference is the inclusion of d functions for atoms of the second row in the periodic table. Inclusion of such functions in the atomic valence basis set proves critical for handling hyper-valent molecules containing these atoms, and thus SINDOl performs considerably better for phosphorus-containing compounds, for instance, than do other semiempirical models that lack d functions (Jug and Schulz Chem. 1988). 

However, two other areas are of interest (Fig. 9) namely, a) derivatisation of phenols or amines to phosphorus-containing compounds and b) on-column methylation. In the former, phosphorylation of 7 alcohols and 12 phenols with diethyl chlorophosphate in the presence of triethylamine at 60-70 C in benzene has been reported (35). Aliphatic alcohols, such as methanol, butanol or isoamyl alcohol react instantaneously while phenol and cresols require ca 1-1 1/2 hrs. and xylenols 3-4 hrs. for best results. 

Ishizu has reported on the toxicity towards mice of these compounds and their acyclic precursors (75MI1). They appear to be somewhat less toxic than other phosphorus-containing flame retardants. 

For the sensitive and selective detection of trace amounts of low-molecular-weight alcohols and other hydroxyl-containing compounds by means of the alkali FID, Vilceanu and Schulz [43] prepared phosphorus-containing derivatives. Derivatives 5.1 and 5.2 were prepared by the reaction with 2-chloro-l, 3,2-dioxaphosphorinane (5.3) and 2-chloro-1,3,2-dioxaphospholane (5.4), respectively, in the presence of triethylamine in benzene, which proceeds very quickly, and were particularly suitable for the determination of trace amounts of alcohols in non-alcoholic and anhydrous media. Retention indices of these derivatives of alcohols up to C5 are listed in Table 5.4. 

Flame retardants—Whereas halogen-containing Mannich bases arc mainly used as modifiers of macromolccular materials, as mentioned before, phosphorus derivatives arc employed as additives. These products arc obtained from phosphorous acid or phosphites 584 " and from other analogous phosphorus-containing compounds. N-Heterocyclcs, after reaction with melamine and formaldehyde (585), are also used as (lame retardants. -... 

Other types of phosphorus-containing compounds, e.g., organophos-phates, might be present hi small amounts on the surfaces of hydrotreating... 

To identify the phosphorus-containing compounds described in the previous sections and the related species containing aluminum, molybdenum, cobalt, or nickel which might be present in hydrotreating catalysts, it is convenient to use techniques such as NMR, IR, UV. and Raman spectroscopies and XRD. XRD is useful for characterizing crystalline bulk compounds, and other techniques are appropriate for well-dispersed species and amorphous phases. Typical IR, Raman, and NMR data presented in Tables VI, VII, and VIII, respectively, could be the basis for such identifications. 

Extrusion of cyclo-P3 to form [(triphos)M(r23-P3)]n+ takes place from a variety of phosphorus containing compounds other than P4. This list include Pred, P 4S3, P 4S5, P 4S7, P4Se3, P2Te3, cyclo-P5Me5 Peruzzini M, Stoppioni P (unpublished results)... 

Other important GC detectors include the thermionic detector, the electrolytic conductivity or Hall detector, and the photoionization detector. The thermionic detector is similar in construction to the FID. With the thermionic detector, nitrogen- and phosphorus-containing compounds produce increased currents in a flame in which an alkali metal salt is vaporized. The thermionic detector is widely used for organophosphorus pesticides and pharmaceutical compounds. 

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