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Activations phosphorus compounds

Liquid Chromatography. - Diasteriomeric phosphonodipeptides have been separated by ion exchange column chromatography.267 H.p.l.c. has been used for the analysis of a variety of biologically active phosphorus compounds, such as aminoacid phosphate esters,26 phosphinothrycin,269 inositol triphosphate,270 fructose diphosphate,271 pyridoxal phosphate,272 and ATP.273... [Pg.416]

Stereochemical evidence for the mechanism of nucleophilic substitution at a tetracovalent phosphorus atom has been mainly forthcoming from the experiments of Michalski et a/.48-50 with esters containing thiophosphoryl centers. Until recently, the inaccessibility of suitable optically active phosphorus compounds precluded stereochemical investigations on the mechanisms of their hydrolysis. [Pg.12]

The earliest method of preparation of an optically active phosphorus compound was by resolution of a phosphine oxide Meisenheimer resolved ethyl-... [Pg.93]

Mono- and diphosphonium halides have been found to be flame retardants for plastic materials. Their effectiveness can be related to the formation of various active phosphorus compounds, as well as to many of the postulated mechanisms for flame retardant action. The compounds are postulated to be effective because they decompose on ignition to thermally stable phosphine oxides or phosphonic acids which, in turn, are decomposed to continuous films of phosphate glass. In addition, the phosphonium halides form alkyl halides which cool the flame and/or form halogen acids which are fame retardants. [Pg.333]

Martin, D., and Niclas, H.-J., Cyanic acid esters. Part 11. Reactions of bromocyanogen and cyanic acid aryl esters with carbanion-active phosphorus compounds, Chem. Ber, 100, 187, 1967. [Pg.300]

The ester fluorides of phosphoric acid and phosphonic adds were the earliest known examples of biologically active phosphorus compounds. Sarin (2) and soman (3), previously mentioned, did not attain practical importance because of their high toxicity, but they were the starting point for the development of other derivatives more suitable for agricultural purposes. Within this framework Schrader developed N,N,N, N -tetramethyl phosphorodiamidofluoridate (14), which is used under the name dimefox. It is produced by the reaction of phosphoryl chloride with dimethylamine and the subsequent interaction of the phosphoro-chloridate formed with sodium fluoride (Schrader, 1947). [Pg.121]

J. Michalski, Optically active phosphorus compounds, Colloq. Int. Cent. Nat. Rech. Sci., 285,1970. W.E. McEwen, Stereochemistry of reactions of organophosphorus compounds. Topics Phos. Chem., 2,1, 1965. [Pg.1325]

In view of the low activity of desoxyribonucleic acid it is of great importance to purify very carefully the sample from other, more active phosphorus compounds present. Such a purification can be obtained by repeated solution in an alkaline medium and precipitation with a solution of hydrogen chloride in methanol (9). [Pg.177]

FIGURE 2.29 Examples of configuration of optically active phosphorus compounds. [Pg.37]

Optically active phosphonium salts were also reported [80]. Methods of obtaining them are described in literature [81 ]. An interesting example of optically active phosphorus compound is its complex with ethioporphyrin [82] (Figure 2.31). [Pg.37]

Organophosphorus compounds. Phosphorus-carbon bond fonnation takes place by the reaction of various phosphorus compounds containing a P—H bond with halides or tritlates. Alkylaryl- or alkenylalkylphosphinates are prepared from alkylphosphinate[638]. The optically active isopropyl alkenyl-methylphosphinate 778 is prepared from isopropyl methylphosphinate with retention[639]. The monoaryl and symmetrical and asymmetric diarylphosphi-nates 780, 781, and 782 are prepared by the reaction of the unstable methyl phosphinate 779 with different amounts of aryl iodides. Tnmethyl orthoformate is added to stabilize the methyl phosphinate[640]. [Pg.243]

Phosphorus is m the same group of the periodic table as nitrogen and tricoordi nate phosphorus compounds (phosphines) like amines are trigonal pyramidal Phos phmes however undergo pyramidal inversion much more slowly than amines and a number of optically active phosphines have been prepared... [Pg.314]

Although unsynunetrically substituted amines are chiral, the configuration is not stable because of rapid inversion at nitrogen. The activation energy for pyramidal inversion at phosphorus is much higher than at nitrogen, and many optically active phosphines have been prepared. The barrier to inversion is usually in the range of 30-3S kcal/mol so that enantiomerically pure phosphines are stable at room temperature but racemize by inversion at elevated tempeiatuies. Asymmetrically substituted tetracoordinate phosphorus compounds such as phosphonium salts and phosphine oxides are also chiral. Scheme 2.1 includes some examples of chiral phosphorus compounds. [Pg.79]

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... [Pg.78]

The toxic organic phosphorus compounds act as powerful inhibitors of cholinesterase, an enzyme found predominantly in the nervous tissue of animals, including insects. This enzyme hydrolyzes acetylcholine, which plays an essential role in the transmission of nerve impulses. The toxicity of compounds in this series can be largely accounted for on the basis of their anticholinesterase activity (7,8,12,14, SI). [Pg.150]

The enormous importance of phosphorus for the living cell was not realized until the twentieth century. Phosphorus compounds are active ... [Pg.115]

The often posed question as to whether phosphorus compounds were active in the initial phases of the development of life, or intervened only at a later stage in the evolutionary process, remains unanswered. However, de Duve (1991) was completely right when he stated that life is basically organized around phosphorus . [Pg.121]

As recently as 1965, Thoma and Stewart predicted that alterations in reaction rates [in the presence of the cycloamyloses] should be anticipated whose magnitude and sign will fluctuate with the reaction type, and added that at the present juncture, it is impossible to sort out confidently. . . which factors may contribute importantly to raising or lowering the activation energy of the reaction. In the short interval between 1965 and the present, a wide variety of cycloamylose-induced rate accelerations and decelerations have, indeed, been revealed. More importantly, rate alterations imposed by the cycloamyloses can now be explained with substantially more confidence. The reactions of derivatives of carboxylic acids and organo-phosphorus compounds with the cycloamyloses, for example, proceed to form covalent intermediates. Other types of reactions appear to be influenced by the dielectric properties of the microscopic cycloamylose cavity. Still other reactions may be affected by the geometrical requirements of the inclusion process. [Pg.258]

Aaron, H.S., Uyeda, R.T., Frack, H.F., and Miller, J.I., The stereochemistry of asymmetric phosphorus compounds. IV. The synthesis and stereochemistry of displacement reactions of optically active isopropyl methylphosphonochlo-ridate, /. Am. Chem. Soc., 84, 617, 1962. [Pg.141]

Just as O.M.P.A. is oxidized enzymically to a cholinesterase inhibitor of greatly enhanced activity (p. 173), so also are systox (p. 179), thimet and certain related sulphur organo-phosphorus compounds. [Pg.195]

We must stress that organo-phosphorus compounds are not specific inhibitors for the cholinesterases, but are rather inhibitors for enzymes possessing carboxylic esterase activity. All the enzymes mentioned below will hydrolyse carboxylic esters. However, not all esterases are inhibited, for example, A-esterase which hydrolyses phenyl acetate is not inhibited by organo-phosphorus compounds. [Pg.200]

It is not wise to assert categorically that the initiating reaction is actually the hydrogen bonding between the fluorine atom (or oxygen atom in T.E.P.P., see below) of the phosphorus compound and the active hydrogen. It should be noted in support,... [Pg.202]

The stereochemistry of optically active phosphorus thio-acids has been reviewed2 and published lectures have covered such topics as phosphate and phosphonate compounds based on adamantane3 and AW-dihalogeno-amides of phosphoric acids.4... [Pg.102]

The optically active thiones (4), readily obtainable from (—)-ephedrine, undergo P—N bond fission, with inversion of configuration at phosphorus, when treated with ethanolic HC1 this provides a highly recommendable method for the preparation of valuable amounts of optically active acyclic compounds (5), isolable as the 5-methyl esters (6).9... [Pg.103]

Rantala, P.-R. Wirola, H. Solid, slightly soluble phosphorus compounds as nutrient source in activated sludge treatment of forest industry wastewaters. Water Sci. Technol. 1997, 55 (2-5), 131-138. [Pg.495]

There have been efforts to form aromatic polyamides directly from diacids at moderate temperatures by using various phosphorus compounds for in situ activation of the carboxyl groups [Arai et al., 1985 Higashi and Kohayashi, 1989 Krigbaum et al., 1985]. A useful agent is diphenyl(2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate, which probably activates the carboxyl group by forming a mixed carboxylic-phosphoric anhydride [Ueda, 1999 Ueda et al., 1991]. [Pg.100]


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Phosphorus compounds

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