Compounds of Phosphorus

M. Halmann, Analytical Chemistry of Phosphorus Compounds, Wiley-Interscience, New York, 1972. 

Phosphorus and Silicon in Waters, Effluents and Sludges [e.g. Phosphorus in Waters, Effluents and Sludges by Spectrophotometry-phosphomolybdenum blue method. Phosphorus in Waters and Acidic Digests by Spectrophotometry-phosphovanadomolybdate method. Ion Chromatographic Methods for the Determination of Phosphorus Compound, Pretreatment Methods for Phosphorus Determinations, Determination of silicon by Spectrophotometric Determination of Molybdate Reactive Silicon-1 -amino-2-naphthol-4, sulphonic acid (ANSA) or Metol reduction methods or ascorbic acid reduction method. Pretreatment Methods to Convert Other Eorms of Silicon to Soluble Molybdate Reactive Silicon, Determination of Phosphorus and Silicon Emission Spectrophotometry], 1992... 

Speziale and his co-workers have carried out comprehensive studies of the reactions of phosphorus compounds. It has been shown 108) that the reaction of N,N-dialkyl-a-trichloroacetamides (127) with phosphites and phosphines gives trichlorovinylamines (128). In general the trialkyl-phosphines gave somewhat higher yields (60 to 83%) and purer products... 

Within the wide range of phosphorus compounds described as activating agents for polyesterification reactions,2,310 triphenylphosphine dichloride and diphenylchlorophosphate (DPCP) were found to be the most effective and convenient ones. In pyridine solution, DPCP forms a A-phosphonium salt which reacts with the carboxylic acid giving the activated acyloxy A -phosphonium salt. A favorable effect of LiBr on reaction rate and molar masses has been reported and assumed to originate from the formation of a complex with the A-phosphonium salt. This decreases the electron density of the phosphorus atom... 

Previous syntheses of terminal alkynes from aldehydes employed Wittig methodology with phosphonium ylides and phosphonates. 6 7 The DuPont procedure circumvents the use of phosphorus compounds by using lithiated dichloromethane as the source of the terminal carbon. The intermediate lithioalkyne 4 can be quenched with water to provide the terminal alkyne or with various electrophiles, as in the present case, to yield propargylic alcohols, alkynylsilanes, or internal alkynes. Enantioenriched terminal alkynylcarbinols can also be prepared from allylic alcohols by Sharpless epoxidation and subsequent basic elimination of the derived chloro- or bromomethyl epoxide (eq 5). A related method entails Sharpless asymmetric dihydroxylation of an allylic chloride and base treatment of the acetonide derivative.8 In these approaches the product and starting material contain the same number of carbons. 

The mode of action of phosphorus-based flame retardants is believed to take place in either the condensed or the vapor phase (refs. 1,2) depending on the type of phosphorus compound and the chemical composition of the polymer. Phosphorus has been reported to be 3 to 8 times more effective than bromine depending on the polymer type (ref. 3). 

Analysis of the Murchison meteorite led to a completely different type of phosphorus compound the only phosphorus-containing compounds found were alkanephos-phonic acids. Spurred on by these results, de Graaf et al. (1995) irradiated mixtures of o-phosphorous acid in the presence of formaldehyde, primary alcohols or acetone with UV light (low pressure Hg lamp, 254 nm with a 185-nm component) and obtained phosphonic acids, including hydroxymethyl and hydroxyethyl phosphonic acids, which had been found in the Murchison meteorite. Alkanephosphonic acids can be derived from phosphorous acid, with a P-H bond being replaced by a P-C bond. 

CHEC-II(1996) comprehensively outlines the most commonly used synthetic approaches applied to these types of bicyclic compounds of phosphorus, arsenic, antimony, and bismuth <1996CHEC-II(8)863>. The six classes of compounds listed in this section have received considerable attention over the review period and as such the principal synthetic methods for these compounds are discussed. Schoth et al. <2000CCR101> have reviewed the use of fluorinated 1,3-diketones, 2-trifluoroacetylphenols, and their derivatives in the synthesis of phosphorus compounds. Included in this review is the use of these reagents for the synthesis of various [3.3.1] nonfused and [3.3.0] fused phosphorus bridgehead bicyclic systems. 

Soley S (2010) Interaction between macrophytes and phytoplankton compartments for the uptake and decomposition of phosphorus compounds, the case of the Ebro river (NE Spain). Master thesis. University of Girona, Spain... 

Topics in Phosphorus Chemistry, Vols. 1-11, Grayson, M. and Griffith, E.J., Eds., Wiley-InterScience, New York, 1964-1983 — This series has contributed chapters concerned with individual types of reactions, mechanisms, and spectroscopy of phosphorus compounds. 

Fluck, E. and Lorenz, J., Nuclear magnetic resonance of phosphorus compounds. XIV. Chemical shifts of phosphines, phosphonium salts, and diphos-phinonickel(II) chlorides, Z. Naturforsch., 22B, 1095, 1967. 

We begin, however, with a brief consideration of a group of phosphorus compounds of significance for their utility in the formation of carbon-phosphorus bonds via reaction with organometallic reagents in displacement reactions. 

Altoff, W., Fild, M., Rieck, H.-R, and Schmutzler, R., Synthesis and NMR spectroscopic studies of phosphorus compounds with vinyl and ethynyl groups, Chem. Ber., Ill, 1845, 1978. 

In 1969, Fiaud and Kagan[U1 tested ephedrine boranes but achieved only 3.6-5% enantiomeric excess in the reduction of acetophenone. Itsuno et a/.[121 reported in 1981 an interesting enantioselective reduction of a ketone using an amino alcohol-borane complex as a catalyst. Buono[131 investigated and developed the reactivity of phosphorus compounds as ligands in borane complexes for asymmetric hydrogenation. 

When magnesium sulphate was omitted from distilled water samples of phosphorus compounds, recovery was variable. Table 12.11 shows yields of a series of standards with and without the magnesium sulphate addition and with and without the final hydrolysis. The magnesium sulphate is used as an acidic solution (after addition to the seawater sample, the pH was about 3) to minimize silicate leaching from the glassware during evaporation. The acid and heating are necessary to hydrolyse any condensed phosphates in the final mixture. 

It should be emphasized that the phosphorus oxydichlorofluoride method for preparing esters of phosphorofluoridic acid cannot compare in speed with the hydrogen phosphite method already described (p. 46). Furthermore, it is not very suitable for very large-scale work. On the other hand, once the apparatus is set up and a supply of POCl2F is obtained, one has a simple, clear-cut, method for producing a large variety of phosphorus compounds, not only esters but amino compounds (p. 87) and mixed compounds (p. 90). In other words, the method is extremely valuable for exploratory purposes and where an unequivocal synthesis is required. 

Fortunato, B., Munari, A. and Manaresi, P., Inhibiting effect of phosphorus compounds on model transesterification and direct esterification reactions catalysed by titanium tetrabutylate, Polymer, 35, 4006 (1994). 

The e.s.r. spectra of phosphorus compounds have been reviewed.101 The phosphorus hyperfine splitting (ap 33.5 G) of the radical anion (77) is within the 25—36 G range of phosphorin radical anions.102 The cis- and fra/w-isomers of 1,2-bisdiphenylphos-phinoethylene gave the same radical anion (78). The unpaired electron is coupled to all the protons in the molecule as well as to the two phosphorus atoms, and shows that the electron is completely delocalized. Only when caesium was used as the gegenion in THF could a metal interaction be detected. The spectrum in this case corresponded to the association of two caesium ions with the radical anion, the third... 

The use of phosphorus compounds as flame retardants has been reviewed by Lyons and others (1, 2, 3, 4 5). The mechanism of the action of this element is generally accepted to involve decomposition to produce acids which function as char promoters. Phosphorus compounds are particularly effective flame retardants for polyesters where they function to increase the char yields. 

While the jr-conjugation ability of phosphorus compounds does not seem to depend on the size of... 

The author hopes that this chapter has convinced the readers of the value of homogeneous catalysis for the synthesis of organophosphorus compounds and for organo-heteroatom compounds in a broader sense. Hydrosilylation and hydroboration are indispensable modern synthetic reactions in this category. The H-P addition reactions herein described joins them as a third member. Although this chapter does not cover, the addition reactions of the S-P and Se-P bonds in thiophosphates [39] and selenophosphates [40] to alkynes also proceed in the presence of transition metal catalysts. In view of the wide use of phosphorus compounds, the new procedures will find practical applications. 

Group V has also been an area of interest, the mass spectrometry of phosphorus compounds having recently been reviewed (162). The mass spectra of phosphorus-containing pesticides have attracted interest... 

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