γ-strahlenchemische Reaktionen des weißen Phosphors in Cyclohexan- und Cyclohexan-Tetrachlorkohlenstoff-Lösung

1964 ◽  
Vol 19 (7) ◽  
pp. 549-557 ◽  
Author(s):  
K.-D. Asmus ◽  
A. Henglein ◽  
G. Meissner ◽  
D. Perner
Keyword(s):  
Organic Phosphorus ◽  
Phosphinic Acid ◽  
Reaction Scheme ◽  
White Phosphorus ◽  
Phosphorus Compounds ◽  
Reaction Products ◽  
Red Phosphorus ◽  
Γ Irradiation ◽  
Polymeric Form ◽  
Chain Reactions

Red phosphorus, soluble phosphorus organic compounds and small amounts of phosphine are formed when white phosphorus in cyclohexane solution is exposed to γ-rays. The red phosphorus contains one C6H11-group per 4 — 5 P-atoms. It reacts with chlorine to give cyclohexylphosphorusdichloride. Its reactivity towards oxygen can be decreased by high temperatures during irradiation or by high γ-doses. It is concluded from quantitative studies of this “annealing” process that phosphorus atoms carrying C6H11-endgroups are especially reactive in the polymeric form of phosphorus. The low molecular weight products of the reaction between white phosphorus and cyclohexane undergo typical reactions of tertiary phosphines. They can readily be oxidized and chlorinated to yield cyclohexyl-phosphinic-acid or cyclohexyl-phosphorus-dichloride, respectively. White phosphorus acts as a scavenger for free H-atoms and C6H11-radicals from the radiolysis of cyclohexane. This reaction, however, does generally not lead to the complete cracking of all PP-bonds of the P4-molecule.The following products are formed in the γ-irradiation of white phosphorus in cyclohexane in the presence of carbon tetrachloride: Red phosphorus containing C6H11- and CCl3-endgroups, cyclohexylphosphorus-dichloride, trichloromethyl-phosphorus-dichloride, chloroform, cyclohexyl-chloride, hexachloroethane and trichloromethyl-cyclohexane. The yields of these products at various doses, dose rates, temperatures and compositions of the solutions are described. Several products such as C6H11PCl2 are produced with high G-values at temperatures above 100°C. The results are explained by a reaction scheme in which three chain reactions simultaneously occur. They are linked together since they have a common intermediate in the form of the CCl3-radical. At high doses, the reaction products of phosphorus mentioned above (including the red phosphorus) are transformed into soluble organic phosphorus compounds of high boiling points the structure of which has not yet been recognized.

scholarly journals Free Radical Chemistry of White Phosphorus: γ-Irradiation of P4 in Bromoform

1968 ◽  
Vol 23 (7) ◽  
pp. 916-921 ◽  
Author(s):  
P. Airey ◽  
H. Drawe ◽  
A. Henglein
Keyword(s):  
Free Radicals ◽  
White Phosphorus ◽  
High Yield ◽  
Red Phosphorus ◽  
Γ Irradiation ◽  
Γ Radiation ◽  
Chain Reactions ◽  
Phosphorus Containing ◽  
High Yields ◽  
Free Radical Chemistry

CHBr2PBr2 and (CHBr2)2PBr are formed in high yields and in preparatively useful amounts when solutions of white phosphorus in bromoform are exposed to γ-radiation. In the first stages of irradiation, a red phosphorus containing many groups from the solvent is the only reaction product. About 1000 molecules of P4 are consumed per 100 eV of energy absorbed. In the later stages of irradiation, free radicals from the solvent attack this red phosphorus and lead to the formation of bromophosphines in high yield. Chain reactions are formulated for the formation of both the red phosphorus and the bromophosphines.

scholarly journals REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS

2020 ◽  
Vol 86 (7) ◽  
Author(s):  
Anatolii Popov ◽  
Illia Kapitanov ◽  
Anna Serdyuk ◽  
Aleksandr Sumeiko
Keyword(s):  
Organic Phosphorus ◽  
Organophosphorus Pesticides ◽  
Reaction Rates ◽  
Hydroxamic Acids ◽  
Phosphorus Compounds ◽  
Reaction Products ◽  
Electron Pairs ◽  
Alkyl Derivatives ◽  
Solvent Type ◽  
Electron Deficiency

The review analyzes issues related to the reactivity of nucleophiles and the manifestation of the α-effect in substitution processes at electron-deficient centers. The fundamental aspects of this phenomenon, as well as the possibilities and prospects of using α-nucleophiles in systems for the highly efficient degradation of substrates - ecotoxicants of various natures, are discussed. In the first part of the review such aspects were observed: inorganic α-nucleophiles as the most effective class of reagents for the decomposition of organic phosphorus compounds, hydroxylamine, its N-alkyl derivatives, oximes, and hydroxamic acids, reactivity of the НОО– anion in the processes of acyl group transfer, reactivity of oximate ions, inorganic α-nucleophiles as the basis of formulations for the degradation of neurotoxins, vesicants, and organophosphorus pesticides, design of inhibited acetylcholinesterase reactivators based on hydroxylamine derivatives, ways of structural modification of α-nucleophiles and systems based on them. The data on the reactivity of typical inorganic α-nucleophiles in the cleavage of acyl-containing substrates, including phosphorus acid esters, which provide abnormally high reaction rates in comparison with other supernucleophiles, are analyzed. Various types of such α-nucleophiles, features of their structure and reactivity are considered. It was shown that an important feature of hydroxylamine, oximes, and hydroxamic acids is the presence of a fragment with adjacent O and N (–N – O – H) atoms containing one or more lone electron pairs, which determines their belonging to the class of α-nucleophiles. It has been shown that a many of factors can be responsible for the manifestation of the α-effect and its magnitude, the main of which is the destabilization of the ground state of the nucleophile due to repulsion of lone electron pairs, stabilization of the transition state, the unusual thermodynamic stability of reaction products, solvation effects of the solvent, type of hybridization of the electrophilic center, etc.

Biodegradation of a phosphorus compounds by the culture of black aspergill

2019 ◽  
Vol 60 (12) ◽  
pp. 1-24
Author(s):  
Anton Z. Mindubaev ◽  
◽  
Elena K. Badeeva ◽  
Salima T. Minzanova ◽  
Lubov G. Mironova ◽  
...  
Keyword(s):  
Culture Medium ◽  
Phosphomolybdic Acid ◽  
White Phosphorus ◽  
Industrial Wastes ◽  
Practical Significance ◽  
Phosphorus Compounds ◽  
Biological Degradation ◽  
Red Phosphorus ◽  
Yellow Phosphorus ◽  
Intermediate Oxidation

The biological degradation of white phosphorus, which is being studied by our team is without a doubt a phenomenon of scientific novelty and practical significance. In a decade of studying this phenomenon, we have achieved significant results. However, the field of application of white and yellow phosphorus is rather a narrow one, and this imposes a limitation on the applicability of our method for the neutralization of industrial wastes. Accordingly, an interesting and important path of focus is to expand the spectrum of substances neutralized by the microbial cultures studied by our team. It is thus logical to commence such a major study with phosphorus compounds, since fungal cultures were adapted for the biodegradation of substances containing this element. In this regard, it should be pointed out that, white phosphorus cannot be metabolized to phosphate in one stage; metabolites are formed with intermediate oxidation states of phosphorus. Therefore, it can be assumed that microorganisms that neutralize white phosphorus should be capable of biodegradation of a whole spectrum of phosphorus compounds. We tested this hypothesis experimentally. It was uncovered that Aspergillus niger AM1 posseses the ability to use red phosphorus, triamide of phosphoric acid, phosphomolybdic acid, substituted dithiophosphate and organophosphorus matter as sources of phosphorus. In addition, in the present work, we describe attempts made to increase the concentration of white phosphorus in the culture medium to values above 1%. To do this, we added olive oil (a solvent in which white phosphorus is relatively soluble) to the culture medium. It turned out that in the presence of this component, the minimum inhibitory concentration of white phosphorus drops abruptly.

CHARACTERIZATION OF MODEL AND SOIL ORGANIC MATTER METAL-PHOSPHATE COMPLEXES

1969 ◽  
Vol 49 (3) ◽  
pp. 365-373 ◽  
Author(s):  
M. Lévesque
Keyword(s):  
Organic Matter ◽  
Fulvic Acid ◽  
Organic Phosphorus ◽  
Inorganic Phosphorus ◽  
Chelating Resin ◽  
Alkaline Media ◽  
Phosphorus Compounds ◽  
Metal Phosphate ◽  
Reaction Products ◽  
Soil Extracts

Fulvic acid–metal–phosphate complexes prepared in the laboratory and corresponding complexes extracted (0.1 N NaOH and chelating resin) from a soil were characterized by means of electrophoresis, Sephadex gel filtration, and methods for differentiation of organic and inorganic phosphorus. The findings can be summarized as follows:(1) The prepared material in aqueous solution (after purification by dialysis) comprised three different entities: a fulvic acid–metal–phosphate complex, a fulvic acid–metal complex, and unbonded inorganic phosphate. These entities were reaction products obtained during the formation of fulvic acid–metal–phosphate complexes.(2) Upon hydrolysis in mild alkaline media, the metal–phosphate bonds of the fulvic acid–metal–phosphate complexes were broken; the fulvic acid–metal complexes, freed from the phosphate, remained intact.(3) While metal ions were necessary for bridging phosphorus and fulvic acid, phosphorus in turn may have bridged the fulvic acid–metal units.(4) Significant amounts of complexed inorganic phosphorus were found intermixed with organic phosphorus compounds in soil extracts; this suggested the existence of organic matter metal–phosphate complexes in soil.

scholarly journals REACTIVITY OF NUCLEOPHILES AND α-EFFECT IN SUBSTITUTION PROCESSES AT ELECTRON - DEFICIENCY CENTERS (Part 2)

2020 ◽  
Vol 86 (8) ◽  
pp. 77-100
Author(s):  
Anatolii Popov ◽  
Illia Kapitanov ◽  
Anna Serdyuk ◽  
Aleksandr Sumeiko
Keyword(s):  
Organic Phosphorus ◽  
Organophosphorus Pesticides ◽  
Reaction Rates ◽  
Hydroxamic Acids ◽  
Phosphorus Compounds ◽  
Reaction Products ◽  
Electron Pairs ◽  
Alkyl Derivatives ◽  
Solvent Type ◽  
Electron Deficiency

The review analyzes issues related to the reactivity of nucleophiles and the manifestation of the α-effect in substitution processes at electron-deficient centers. The fundamental aspects of this phenomenon, as well as the possibilities and prospects of using α-nucleophiles in systems for the highly efficient degradation of substrates - ecotoxicants of various natures, are discussed. In the first part of the review such aspects were observed: inorganic α-nucleophiles as the most effective class of reagents for the decomposition of organic phosphorus compounds, hydroxylamine, its N-alkyl derivatives, oximes, and hydroxamic acids, reactivity of the НОО– anion in the processes of acyl group transfer, reactivity of oximate ions, inorganic α-nucleophiles as the basis of formulations for the degradation of neurotoxins, vesicants, and organophosphorus pesticides, design of inhibited acetylcholinesterase reactivators based on hydroxylamine derivatives, ways of structural modification of α-nucleophiles and systems based on them. The data on the reactivity of typical inorganic α-nucleophiles in the cleavage of acyl-containing substrates, including phosphorus acid esters, which provide abnormally high reaction rates in comparison with other supernucleophiles, are analyzed. Various types of such α-nucleophiles, features of their structure and reactivity are considered. It was shown that an important feature of hydroxylamine, oximes, and hydroxamic acids is the presence of a fragment with adjacent O and N (–N – O – H) atoms containing one or more lone electron pairs, which determines their belonging to the class of α-nucleophiles. It has been shown that a many of factors can be responsible for the manifestation of the α-effect and its magnitude, the main of which is the destabilization of the ground state of the nucleophile due to repulsion of lone electron pairs, stabilization of the transition state, the unusual thermodynamic stability of reaction products, solvation effects of the solvent, type of hybridization of the electrophilic center, etc.

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