Phosphorus compounds, organic, table

Quite often, we find nonsystematic nomenclature used in the literature dealing with organophosphorus compounds. This results in unnecessary confusion, as systematic nomenclature is easy to use and understand. Nomenclature based on the oxidation state of the phosphorus center eliminates the confusion and helps to promote understanding of the chemistry as well as to facilitate communication. Table 1.1 shows structures for tricoordinate and tetracoordinate phosphorus compounds related to oxyacids with their English general names. Also noted are the names for simple esters of the parent acids. They are organized based on oxidation state and the number of bonds of the carbon-phosphorus type. 

Table 22.8 Low Moleculor Weight Organic Phosphorus Compounds Indentified or Likely to Be Present in Seawater. ... 

Table I. AIBN-Initiated Oxidation of Organic Phosphorus Compounds in ferf-Butylbenzene at 70°C.

Table II. Rate of Thermal Decomposition of AIBN (0.3 Mole per Liter) in the Presence of Organic Phosphorus Compounds (0.1 Mole per Liter) at 70°C.

The OH radical reactions with a number of nitrogen-, sulfur- and phosphorus-containing organic compounds appear to proceed, at least in part, by an initial addition reaction (Atkinson, 1989,1994 Kwok et al., 1996), although the products observed may in some cases be those expected from H-atom abstraction. Note that the recent study of Talukdar et al. (1997) indicates that the reactions of the OH radical with alkyl nitrates proceed only by H-atom abstraction, and Table 14.1 gives the applicable substituent group factors for alkyl nitrates. 

Similarly, phosphorus occurs directly beneath nitrogen in the periodic table and therefore often exhibits a valence of three. Again, structures with an expanded valence, having five bonds to the phosphorus, are common, especially when the extra bonds are to oxygen. This book is not concerned with all the possible sulfur and phosphorus compounds, nor does it spend much time on their nomenclature. Instead, it concentrates on those of most importance in organic chemistry and biochemistry. Let s begin with a discussion of some common sulfur compounds. 

Inhibition of the cholinesterase activity of the blood is the most sensitive means now available, with the possible exception of the inhibition of the esterase activity of the liver, for detecting the absorption of an organic phosphorus compound that is known to be capable of inducing this effect. The values indicative of cholinesterase activity are shown in Tables III and V. All subjects were exposed to the recommended dosage (one Vaporizer per 1000 cubic feet) except subjects 15 and 16, who were exposed to resin strips that contained no dichlorvos. 

Table 7 Selected organic phosphorus compounds identified or likely to be present in seawater.

Table 9. Organic phosphorus compounds from nucleophilic attack on phosphorus... 

Table 8. Conversion yields obtained from organic phosphorus compounds...

Both an automatic peak-picking routine in the processing software and visual inspection are used to identify peaks. Chemical shifts are then compared with literature reports. Table 2.1 shows some of the biological phosphorus compounds identihed in NMR studies of environmental samples, while Table 2.2 shows peak shifts for phosphorus minerals determined by solid-state spectroscopy. Although this chapter focuses on organic phosphorus, the overlap of peak shifts for biological and mineral phosphorus compounds must be noted. This may complicate the identification of phosphorus species in solid-state spectroscopy, because both biological and mineral phosphorus forms may be present. To further confirm peak shifts, standards such as methylene diphosphonic acid may be added directly to the sample or included as capillary tube inserts in solution NMR (e.g. Koopmans et aL, 2003). 

In addition to the compounds listed in Table 3.5, there were a number of additional organic phosphorus compounds found only in water from the ENR outflow, and these are listed in Table 3.6. It might be reasonable to assume that these were compounds formed within the treatment areas, although further quantitative experiments would be needed to verify this. 

Table 9.1. Summary characteristics of various processes for uptake of phosphate and seiected dissoived organic phosphorus compounds, inciuding genetic controi and cataboiic repression. Genetic terms refer to structures and processes in Escherichia coii. (ATPase = adenosine 5 -triphosphatase.)... 

Although aquatic biochemical ecologists have focused nearly exclusively on lytic processes for dissolved organic phosphorus utilization, heterotrophic bacteria can directly take up certain organic phosphorus compounds from their surrounding environment without prior hydrolysis (Table 9.2). E. coli is known to have two different processes by which glycerol 3-phosphate can be taken up without prior hydrolysis... 

The structural chemical formulae of flame-retardant organic phosphorus compounds is given in Table 5.7. They can act either by an additive or a reactive mechanism. 

Since polyphosphorus species are far more common than polynitrogen compounds, in contrast to their order of appearance in the periodic table (N, P, As, Sb, Bi), here we discuss the neutral homopolyatomic phosphorus compounds first. As stated above, phosphorus occurs in three main forms white, black, and red. White phosphorus consists of tetrahedral P4 molecules (Fig. 1) and forms a molecular lattice that melts already at 44°C, and even the boiling point is rather low at 280°C. In accord with its molecular structure, P4 is soluble in many organic nonpolar solvents but is insoluble in water—indeed, P4 is usually stored under water because it is spontaneously flammable in air. 

Table 17.1 Organic phosphorus compounds. (The data given are. except where stated, for condensed phase spectra, i.e, liquids or solids, measured in nujol or as discs)...

Biologically active components of the organic soil fraction include polysaccharides, amino sugars, nucleotides, and organic sulfur and phosphorus compounds. Humus, a water-insoluble material that biodegrades very slowly, makes up (he bulk of soil organic matter. The organic compounds in soil are summarized in Table 18.1. 

Historically organic phosphorus agrochemicals meant insecticides. Today that is not the case. Organic phosphorus agrochemicals (Table 29.10) now include most applications. Just as organic carboxylic acids are vital to various life processes, so too are phosphorus compounds. Thus it is not surprising that phosphorous compounds find their place as versatile agrochemicals. 

In catalytic incineration, there are limitations concerning the effluent streams to be treated. Waste gases with organic compound contents higher than 20% of LET (lower explosion limit) are not suitable, as the heat content released in the oxidation process increases the catalyst bed temperature above 650 °C. This is normally the maximum permissible temperature to which a catalyst bed can be continuously exposed. The problem is solved by dilution-, this method increases the furnace volume and hence the investment and operation costs. Concentrations between 2% and 20% of LET are optimal, The catalytic incinerator is not recommended without prefiltration for waste gases containing particulate matter or liquids which cannot be vaporized. The waste gas must not contain catalyst poisons, such as phosphorus, arsenic, antimony, lead, zinc, mercury, tin, sulfur, or iron oxide.(see Table 1.3.111... 

The primary function of this section is to organize data to faalitate NMR structure elucidation of organofluonne compounds Selectively fluonnated aliphatics are emphasized, whereas fluonnated aromatics are covered m less detail Inorganic nitrogen, phosphorus, silicon, and sulfur fluondes are not included, although compounds containing these and other heteroatoms attached to CF3 are the focus of multmuclear data presented later (see Table 16)... 

To be useful as CVD precursors, a metallo-organic compound should be stable at room temperature so that its storage and transfer are not a problem. It should also decompose readily at low temperature, i.e., below 500°C. The compounds listed in Table 4.1 meet these conditions with the exception of the alkyls of arsenic and phosphorus, which decompose at higher temperatures. For that reason, the hydrides of arsenic and phosphorus are often preferred as CVD precursors (see Ch. 3). These hydrides however are extremely toxic and environmental considerations may restrict their use. 

Some research groups have investigated effects of substituents less common in organic chemistry. Quin and co-workers (127,128) determined a-SCSs of tri-and tetravalent phosphorus substituents in n-alkyl and cyclohexyl derivatives (Tables 5 and 6). The difference between -PH2 and -P(CH3)2 effects is easily explained by 3-SCS(CH3) (about 10 ppm for each methyl) this approach, however, is not satisfactory for P(OCH3)2 and PC12, since it would suggest a-SCS values of ca. 16 (found 21.4) and ca. 22 (found 32.5), respectively, for those two substituents. A stereochemical dependence similar to that of X = CH3 and OH seems to exist only for the primary phosphine (X = PH2) and the compounds with tetravalent phosphorus substituents, whereas the a-SCS values of the tri-valent functions are quite similar in many cases, regardless of their stereochemical position. 

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