35Cl NQR spectra, structure, and mutual influence of substituents in the series of chlorine-containing organic compounds of pentavalent phosphorus

Regularities of transmission of the effect of equatorial and axial substituents were established for a number of chlorine-containing organic compounds of pentatalent phosphorus using³⁵Cl NQR spectra. The field constants of³⁵Cl NQR frequencies of the chlorine atoms participating in the P−Cl bond were estimated for a series of tetrahedral phosphorus ions. The³⁵Cl NQR frequencies of chlorine atoms in tetracoordinated ions of pentavalent phosphorus and in analogous isoelectronic silicon compounds are related by a linear dependence. Deceased Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 915–922, May, 1999.     

Muon Spin Rotation/Resonance (μSR) for Studying Radical Reactivity of Unsaturated Organophosphorus Compounds

The positive muon (μ⁺) can be regarded as a light isotope of proton and has been an important tool to study radical reactions of organic compounds. Recently, muons have been applied to produce short-lived paramagnetic species from the heavier unsaturated organic molecules including the p-block elements. This article overviews recent muon spin rotation/resonance (μSR) studies on the phosphorus analogs of alkenes, anthracenes, and cyclobutane-1,3-diyls together with the fundamentals of μSR. The acyclic phosphaalkene of P=C and phosphasilenes of P=Si can accept muonium (Mu=[μ⁺e⁻]) at the heavier double bonds, and the corresponding radicals have been characterized. The phosphorus atom in 9-phosphaanthracene, whose P=C double bond is stabilized by the peri-substituted CF₃ groups, predominantly captures muonium to provide the corresponding paramagnetic fused heterocyclic system. The peri-trifluoromethyl groups are functional to promote the unprecedented light isotope effect of muon providing the planar three-cyclic molecular structure to consume the increased zero-point energy. The formally open-shell singlet 1,3-diphosphacyclobutane-2,4-diyl unit can accept muonium at the (ylidic) phosphorus or the skeletal radicalic carbon, and the corresponding paramagnetic phosphorus heterocycles can be characterized by μSR. The findings on these muoniation processes to the unsaturated phosphorus-containing compounds will contribute not only to development of novel paramagnetic functional species but also to progress on muon science.     

C-phosphorylation of formaldehyde and crotonaldehydeN,N-dimethylhydrazones

The first representatives of hydrazones having trivalent phosphorus at the azomethine carbon atom or the carbon atom vinylogous to it were synthesized by reactions of formaldehyde and crotonaldehydeN,N-dimethylhydrazones with PBr₃ and diphenylchlorophosphine in the presence of organic bases. Some properties of the compounds synthesized were studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1797–1801, September, 1998.     

磷氯化物(PCl_3,PCl_5,POCl_3)作为氯化试剂在有机合成中应用的研究进展

综述了近十几年来磷氯化物 (PCl3,PCl5,POCl3)作为氯化试剂在有机合成中应用的新进展 ,主要包括磷氯化物与羟基化合物、羧酸、羰基化合物、烯烃、含孤对电子基团化合物、磺酸及其盐、硅化合物、磷化合物的氯化反应 ,以及氢氯交换反应。     

充满生机和科学机遇的磷化学研究所

简要地综述了第十五届国际磷化学会议的报告内容，介绍了目前磷化学的主要 研究领域，包括不对称合成、配合化学，生物碱化学，药物化学，农业化学等相关 领域的研究动态及新进展。     

Controlled defect formation in elemental phosphorus as method for its chemical activation

The reveiw surveys and systematizes data on the role of defect formation in activation of red phosphorus. The reactivities of different modifications of elemental phosphorus (viz., white phosphorus, commercial red phosphorus, and red phosphorus containing high concentrations of biographical and induced defects) in inorganic and organic reactions were comparatively analyzed.     

Mass spectrometry of natural organic phosphorus

This article provides a review of the use of modern mass spectrometry (MS) for quantitative and qualitative measurements of organic phosphorus compounds in nature. Included is a brief discussion of recent developments in large molecule mass spectrometry, focusing on time-of-flight (TOF) and ion cyclotron resonance (ICR) mass analysis techniques, as well as electrospray (ESI) and inductively coupled plasma (ICP) ionization. The use of ICP with high-resolution mass spectrometry for quantitative measurements of total phosphorus and as a detector coupled to HPLC and CE for defining organic phosphorus speciation is demonstrated using results from a study of phosphorus cycling in a treatment wetland. Qualitative identifications of individual phosphorus compounds by ultrahigh resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is demonstrated using dissolved organic phosphorus isolated from this same wetland.     

Reduced inorganic phosphorus in the natural environment: significance, speciation and determination

It is commonly assumed that phosphorus occurs almost exclusively in the environment as fully oxidized phosphate (primarily H₂PO₄⁻ and HPO₄²⁻, where the oxidation state of phosphorus is +V). Recent developments in the field of microbiology and research on the origin of life have suggested a possibly significant role for reduced, inorganic forms of phosphorus in bacterial metabolism and as evolutionary precursors of biological phosphate compounds. Reduced inorganic forms of phosphorus include phosphorus acid (H₃PO₃, P(+III)), hypophosphorus acid (H₃PO₂, P(+I)) and various forms of phosphides (P(−III)). Reduced phosphorus has been detected in anaerobic sediments, sewage treatment facilities and in industrial and agricultural processes.Microbiological evidence suggests a significant role for reduced phosphorus species in metabolic processes and raises interesting questions regarding the biogeochemistry of this nutrient in the environment. However, the paucity of data on the presence and cycling of reduced phosphorus compounds in the environment requires attention in order to elucidate the role of these compounds in natural systems. This paper discusses the significance of reduced phosphorus in the natural environment, its speciation and methods of detection.     

Nukleophile Substanzen zur Entgiftung von Phosphorestern

A series of N-substituted hydroxylamine derivatives was synthesized as a potential substitute for calcium hypochlorite. Like calcium hypochlorite, these compounds are highly P(V)-nucleophilic with respect to toxic phosphorus esters.Incorporating surface-active structural elements into the compounds can enhance their reactivity to phosphorus esters on the one hand (micelle catalysis); on the other hand aqueous solutions of these compounds wet polymer surfaces easily, thus ensuring that they can be well applied. The effectiveness of the compounds in the detoxification of phosphorus esters was examined using diisopropyl fluorophosphate (DFP) as a model substance.

     

catena‐Phosphorus Cations

Recent advances towards a systematic development of catena‐phosphorus cations are reviewed. The cations represented in this new and developing chapter in fundamental phosphorus chemistry complement the series of neutral and anionic polyphosphorus compounds.     

NMR investigation of chlorophosphorylation products of N‐vinylazoles

The structure of novel phosphorus‐containing N‐vinylazoles prepared by action of phosphorus pentachloride has been studied by multinuclear ¹H, ¹³C, ¹⁵N, ³¹P and two‐dimensional (2D) NMR spectroscopy. N‐vinyl‐substituted 1,2‐diazoles and 1,2,3‐triazoles have undergone phosphorylation, exclusively, on double bond. N‐vinylazoles‐based hexa‐coordinated phosphorus compounds have been synthesized for the first time. ³¹P NMR spectroscopy provides the most convenient and unambiguous method for the investigation of E—Z‐isomeric structures of phosphorylated enamines. Copyright © 2008 John Wiley & Sons, Ltd.     

Highly Selective 1,4‐ and 1,6‐Addition of P(O)?H Compounds to p‐Quinones: A Divergent Method for the Synthesis of C‐ and O‐Phosphoryl Hydroquinone Derivatives

The reaction of P(O)? H compounds with p‐quinones could proceed through either 1,4‐ or 1,6‐addition pathways by employing different additives to selectively give the corresponding C‐ and O‐phosphoryl hydroquinone derivatives in good yields. Oxidative double 1,4‐addition of P(O)? H compounds to p‐quinones was also achieved by tuning the solvent, affording a facile synthesis of bis‐substituted hydroquinones with phosphorus functionality. Further studies on these reactions by using optically active H‐phosphinates showed that all addition reactions took place stereospecifically with retention of configuration at the phosphorus center. The findings lead to the establishment of a divergent method for the synthesis of C‐ and O‐phosphoryl hydroquinone derivatives from easily available P(O)? H compounds.     

SYNTHESES AND BIOLOGICAL ACTIVITIES OF 1,2,4-TRIAZOLO-[3,4-B][1,3,4]THIADIAZOLE DITHIOPHOSPHATES

In this article, we incorporated the organic phosphorus group on to a triazolothiadiazole ring to prepare the title compounds fused 1,2,4-triazolo[3,4-b][1,3,4]thiadiazole heterocyclic compounds. From the results on biological activities, we found that most compounds showed weak activities, and thus the structures need to be further optimized for improved activity.     

TiO2光催化氧化-分光光度法测定总磷的研究

借助自行设计并制作的微型高效光催化氧化反应器,采用超细TiO2光催化氧化法对有机磷样品进行氧化处理,测定了有机磷水处理剂及循环冷却水中总磷量。以2-磷酸基丁烷-1,2,4-三羧酸(PBTC)为样本,研究了多种催化反应条件对降解率的影响。本法加标回收率为95.4%~99.1%,相对标准偏差(RSD)0.93%。将测定结果与国标法进行比较,证明此法是一种适宜的总磷分析方法。     

Synthesis and Molluscicidal Activity of Phosphorus-Containing Heterocyclic Compounds Derived from 5,6-Bis (4-bromophenyl)-3-hydrazino-1,2,4-triazine

Novel N¹-(phosphoryl moiety)-N²-(1,2,4-triazin-3-yl)hydrazines 4, 6, 8, 9 and 12, iminophosphorane 3, iminophosphane 5, 1,2,4-triazinyldiazaphospholine 7, 1,2,4,3-triazaphospholinotriazines 2, 10, 11, and 1,2,4-triazino[3,2-c][1,2,4,5] triazaphosphine 13 have been obtained via treatment 5,6-bis(4-bromophenyl)-3-hydrazino-1,2,4-triazine (1) with various polyfunctional phosphorus reagents by stirring at room temperature or refluxing for long time in tetrahydrofuran. Structures of these compounds have been deduced upon the basis of elemental and spectral data. Molluscicidal activity of the prepared compounds against Biomphalaria Alexandrina snails (the intermediate host of Schistosoma mansoni) showed considerable activities.     

A multi-pumping flow system with on-line photochemical conversion and improved sensitivity for phosphorus fractionation in freshwaters

A flow-based procedure with solenoid micro-pumps was developed for phosphorus fractionation (dissolved organic and inorganic phosphorus) in freshwaters. The spectrophotometric detection was based on the formation of molybdenum blue and the organic species were on-line photo-converted to orthophosphate. The analytical response was linear within 10 and 75?µg?L^?1 with a detection limit of 2.0?µg?L^?1 (99.7% confidence level). Coefficient of variation of 1.8% (50?µg?L^?1 P, n?=?20) and sampling rate of 40 determinations per hour were achieved. Per determination, 160?µg (NH₄)₆Mo₇O₂₄, 10?µg SnCl₂, 640?µg K₂S₂O₈ and 10?mg NaOH were consumed, generating 2.0?mL of waste. Slopes of analytical curves obtained for four different organic phosphorus species agreed with those obtained for orthophosphate, indicating quantitative conversion. The results for freshwater samples agreed with those obtained by the AOAC reference procedure at 95% confidence level. The organic matter did not interfere in the photo-oxidative process. The proposed procedure is a fast and environmentally friendly alternative for the phosphorus fractionation in freshwaters.     

REACTIONS OF DERIVATIVES OF PHOSPHORUS ACIDS WITH CARBONYL COMPOUNDS ACTIVATED BY ELECTRONEGATIVE GROUPS

Abstract

The Arbuzov reaction results in the synthesis of various phosphonic esters and is of great importance for the further development of the chemistry of organophosphorus compounds. Investigations of recent decades have shown that, besides halogen-containing organic compounds, different types of organic compounds of the electrophilic type which do not contain halogen atoms are capable of entering this reaction. Reactions with carbonyl compounds are especially interesting. This report presents the results of reactions of derivatives of tricoordinated phosphorus (trialkyl phosphites, amidophosphites, ester anhydrides, isocyanate phosphites) with carbonyl compounds. Special emphasis was placed on studying the reactions with carbonyl compounds activated by some electronegative groups. The regularities and mechanisms of these reactions were investigated depending on the structure of the carbonyl compounds, the derivatives of tricoordinated phosphorus and the reaction conditions.     

The influence of the sacrificial anode nature on the mechanism of electrochemical arylation and alkylation of white phosphorus

The material of the sacrificial anode has a substantial effect on the nature and yield of the target products of electrochemical phosphorylation of organic halides by white phosphorus in the presence of the nickel complexes with 2,2"-bipyridine. The use of the zinc anode results in the products with tricoordinated phosphorus, viz., triorganylphosphines, the reaction on the aluminum anode affords triorganylphosphine oxides, and the presence of Mg²⁺ ions in the reaction mixture provides the transformation of white phosphorus into cyclic phosphines (PhP)₅.     

A Facile,One-Pot Synthesis of Azoic Compounds and Anthraquinone Derivatives Containing Dialkyl Phosphoryl Moieties in Multicomponent Reactions

Protonation of the reactive 1:1 intermediates produced in the reactions between triphenylphosphine and dialkyl acetylenedicarboxylates by 1-amino-anthraquinone or 1,5-diphenylcarbazone as a core dye leads to vinyl phosphonium salts, which undergo Michael addition with conjugate base of NH compounds to produce stable phosphorus ylides as novel dyes in fairly good yields. These ylides can exist in two geometrical isomers (Z) and (E) for 3, because the negative charge of the ylide moiety of these compounds are strongly conjugated with the adjacent carbonyl group. Rotation around the carbon–carbon double bond is slow in the (Z) and (E) geometrical isomers on the NMR time scale at ambient temperature. These compounds are assigned by their IR, ¹H, ¹³C NMR spectral data as well as their mass spectroscopic data.     

Functionalization of P4 Using a Lewis Acid Stabilized Bicyclo[1.1.0]tetraphosphabutane Anion

Reacting white phosphorus (P₄) with sterically encumbered aryl lithium reagents (aryl=2,6‐dimesitylphenyl or 2,4,6‐tBu₃C₆H₂) and B(C₆F₅)₃ gives the unique, isolable Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutane anion. Subsequent alkylation of the nucleophilic site of the RP₄ anion gives access to non‐symmetrical disubstituted bicyclic tetraphosphorus compounds. This novel method enables P? C bond formation in a controlled fashion using white phosphorus as starting material.