SPIROPHOSPHORANES – STRUCTURE REACTIVITY

Abstract

The first part of this article will deal with the reactions of spirophosphoranes with a P[sbnd]H bond. These compounds contain two five-membered rings and have four oxygen atoms, or three oxygen atoms and one nitrogen atom, or two oxygen and two nitrogen atoms directly bonded to the phosphorus atom, which in all cases bears an hydrogen atom (Scheme 1). The most remarkable property of these compounds is undoubtedly their ability to give rise to a tautomeric equilibrium between the tri- and penta-coordinated structures P_III→P_V.     

CATALYSE INTRAMOLECULAIRE DE L'AMINOLYSE DES HETEROCYCLES PHOSPHORES DERIVES DES α AMINOAMIDES. II: ETUDE DE LA CYCLISATION DES PHOSPHORDIAMIDES INCORPORANT UN RESIDU DE β AMINOACIDE,REACTIVITE VIS A VIS DE NUCLEOPHILES DES HETEROCYCLES FORMES

Abstract

Derivatives of β aminoacids in form of esters 1 or nitrile 4 (table I) undergo in an alcohol-ate/alcohol medium a rearrangement (Fig. 2), with formation of a β peptide link, resulting in the formation of esters 6 (table II). According to the experimental conditions the six membered ring heterocycles 5 are detected or isolated. They are also synthetized by cyclisation of acids 2 or hydrazide 3 (Fig. 5). While phosphorus easily reacts with alcohols and water, leading respectively to esters 6 and acids 9 (Fig. 7), it remains unaffected by amines. These results are discussed in term of mechanisms of the phosphorylation. The applications for β peptide synthesis and the participation of the p amide group in phosphorylation are limited.     

REAKTIONEN DES PYRIDINIUM-FLUOR-DITHIOPHOSPHORSÄURE-BETAINS

Abstract

Pyridinium-fluor-dithiophosphorsäure-betain (1) reagiert mit Hydrazin unter Bildung von Pyridinium-hydrazin-bis(fluor-dithiophosphate) (3), mit Phenylhydrazin unter Bildung von Pyridinium-phenylhydrazido-fluordithiophosphat (5). 3 und 5 können mit Methyljodid in die entsprechenden S-Methylester 7 und 8 überführt werden. Die Umsetzung der Titelverbindung 1 mit H₂S führt zu Pyridinium-difluor-pentathiodiphosphat (9). Das primäre Hydrolyseprodukt von 1 ist nicht stabil. Mercaptane und 1 reagieren zu den Pyridiniumsalzen der Fluor-trithiophosphorsäure-monoester (10), die durch Umsetzung mit Methyljodid in die Fluor-trithiophosphorsäure-diester (12) umgewandelt werden können. Die Reaktion von Phenyl-t-butyl-phosphan mit 1 hat eine P–P-Verknüpfung zur Folge. Reaktionsprodukt ist Pyridinium-phenyl-t-butyl-phosphido-fluor-dithiophosphat (13).

Pyridinium-fluoro-dithiophosphoric betaine (1) reacts with hydrazine to give pyridinium hydrazine bis(fluoro-dithiophosphate) (3), with phenylhydrazine to give pyridinium phenylhydrazido fluoro-dithiophosphate (5). 3 and 5 can be converted into the corresponding S-methyl esters 7 and 8 by methyl iodide. Reaction of the title compound 1 with H₂S yields pyridinium difluoro pentathiodiphosphate (9). The primary hydrolysis product of 1 is not stable. Mercaptanes and 1 yield pyridinium salts of fluoro trithiophosphoric monoesters (10) which by reaction with methyl iodide can be converted into fluoro trithiophosphoric diesters (12). The reaction of phenyl t-butyl phosphane with 1 results in the formation of a P–P bond. Reaction product is pyridinium phenyl t-butyl phosphido fluoro dithiophosphate (13).     

REACTIVITE DES N 1-TOSYLAMIDRAZONES VIS-À-VIS DU TRICHLORURE DE THIOPHOSPHORYLE ET DU DISULFURE DE CARBONE: OBTENTION DES TRIAZAPHOSPHOLINES ET DES TRIAZOLETHIONES

The condensation of N ¹ -tosylamidrazones with thiophosphorus trichloride and carbone disulfide forms a new synthetic method for access to new phosphorus or sulfur heterocycles such as triazaphospholines and triazolethiones.     

REACTION DES O,O-DIETHYL OXO-1 ALKANEPHOSPHONATES AVEC LES DERIVES DE L'HYDRAZINE: UNE VOIE DE SYNTHESE DES HYDRAZONES α-PHOSPHONATEES ET DES HYDRAZIDES

Abstract

Under the normal conditions, the reaction of hydrazine and methylhydrazine with OO-diethyl 1 oxoalkane phosphonates 1 proceeds by cleavage of the phosphorus-carbon bond and leads to the formation of diethylphosphite 2 and N-acylhydrazide 3 . A procedure has been developed for the synthesis of new primary hydrazone of OO-diethyl 1-oxoalkane phosphonates 4 . A mechanism is proposed. The structure of those compounds 4 was confirmed by NMR and IR spectroscopy.     

Toward faster and higher resolution LA–ICPMS imaging: on the co-evolution of LA cell design and ICPMS instrumentation

We describe trends in fast, high resolution elemental imaging by laser ablation–inductively coupled plasma mass spectrometry (LA–ICPMS). Recently developed low dispersion LA cells deliver quantitative transport of ablated aerosols within 10 ms and also provide enhanced sensitivity compared to conventional LA cells because the analyte ion signal becomes less diluted during aerosol transport. When connected to simultaneous ICPMS instruments, these low dispersion LA cells offer a platform for high speed and high lateral resolution shot-resolved LA–ICPMS imaging. Here, we examine the current paradigms of LA–ICPMS imaging and discuss how newly developed LA cell technology combined with simultaneous ICPMS instrumentation is poised to overcome current instrumental limitations to deliver faster, higher resolution elemental imaging.     

用LA催化预处理粘胶纤维的炭化活化过程研究

粘胶纤维毡由化学药品ＬＡ催化预处理，然后经高温８２０～８５０℃下水蒸汽活化来制备粘胶活性炭纤维，其孔结构受热解炭化和活化过程的影响。本文研究了不同升温速率、不同温度下通入水蒸汽以及不同空速对活化结果的影响；同时考察了粘胶炭纤维与水蒸汽反应的动力学以及粘胶活性炭纤维的吸附性能。     

ACTION DU REACTIF DE LA WESSON SUR LES HYDRAZONES γ-PHOSPHONATEES: SYNTHESE DE NOUVEAUX DERIVES DE LA Δ5-3-THIOXO-1,2,3-DIAZAPHOSPHOLINE

Abstract

The Lawesson reagent (L.R) reacts with phenylhydrazones of ketones γ-disubstituted phosphonates and phosphine oxide 1 to give 1,2,3-diazaphospholine derivatives 2 and 2′. Two diastereomers were obtained in some cases. The structure of the products 2 and 2′ is confirmed by NMR and IR spectroscopy.     

Trace analysis of high-purity graphite by LA–ICP–MS

Laser-ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) has been established as a very efficient and sensitive technique for the direct analysis of solids. In this work the capability of LA–ICP–MS was investigated for determination of trace elements in high-purity graphite. Synthetic laboratory standards with a graphite matrix were prepared for the purpose of quantifying the analytical results. Doped trace elements, concentration 0.5 μg g^–1, in a laboratory standard were determined with an accuracy of 1% to ± 7% and a relative standard deviation (RSD) of 2–13%. Solution-based calibration was also used for quantitative analysis of high-purity graphite. It was found that such calibration led to analytical results for trace-element determination in graphite with accuracy similar to that obtained by use of synthetic laboratory standards for quantification of analytical results. Results from quantitative determination of trace impurities in a real reactor-graphite sample, using both quantification approaches, were in good agreement. Detection limits for all elements of interest were determined in the low ng g^–1 concentration range. Improvement of detection limits by a factor of 10 was achieved for analyses of high-purity graphite with LA–ICP–MS under wet plasma conditions, because the lower background signal and increased element sensitivity. Received: 4 January 2001 / Revised: 27 March 2001 / Accepted: 28 March 2001     

Application of LA–ICP–MS in polar ice core studies

The direct determination of element signatures in polar ice core samples from Greenland by laser ablation with subsequent inductively coupled plasma mass spectrometry analysis has been investigated. A cryogenic sample chamber enables the element determination in ice directly from the solid (frozen) state. A procedure was developed to analyse up to 38 elements (traces: Mg, Al, Fe, Zn, Cd, Pb and rare earth elements; minor constituents: Na) in ice samples from Greenland with a previously unachievable spatial resolution of 4 mm along the core axis. This resolution is helpful to detect seasonal variations of element concentration in thin annual layers of deep ice. We report operating conditions and analytical performance of the experimental set up, the improvement of signal stability by (17)OH internal standardisation and application of a desolvation unit. Calibration of the system was performed with frozen multielement standard solutions along a special preparation procedure. Detection limits for the tracers Na, Mg (sea salt), Al (mineral dust) and Zn (anthropogenic source) are 0.1-1 microg kg(-1). Best detection limits in the range of 0.001-0.01 microg kg(-1 )were reached for Co, Pb and all rare earth elements. To validate the method, frozen standard reference materials were measured. The recovery is about +/-10%. Greenland ice core samples from different ages were analysed with the new technique. The results obtained by laser ablation were compared with values from solution analysis, available published data and the particle content. Most elements have shown good correlation with the particle content in the Greenland samples; however, differences could be seen between the values obtained by laser ablation and solution bulk analysis after a tri-acid digestion. The influence of particles is discussed. The high spatially resolved 2D mapping of element concentrations shows strong inhomogeneities along the core axis most probably due to seasonal variations of element deposition.     

9443对LA—795肺腺癌的放射增敏作用

为观察含锗药物９４４３的放射增敏作用，以小鼠实体肿瘤ＬＡ－７９５肺腺癌研究９４４３的放射增敏效果。采用肿瘤生长延缓法评价，测得平均放射增敏比为１．２，药物ＬＤ５０毒性为５００ｍｇ／ｋｇ体重。     

有机金属催化剂与丙交酯(LA)开环聚合反应

聚乳酸等聚酯是一类重要的新型生物可降解高分子材料,可替代传统石油基塑料,从而解决"白色污染"问题,减少化石资源的消耗,同时在许多生物医用材料和器件领域也有着广泛的应用.聚乳酸通常是在催化剂的作用下,通过丙交酯单体的开环聚合而得到.本文基于本课题组前期的研究结果对丙交酯单体开环聚合催化剂进行了评述,其中主要介绍了有机金属催化剂,包括基于取代基、手性、中心金属等不同设计的单核有机金属催化剂;另外也对双核和三核金属催化剂的进展进行了总结,讨论了催化剂结构及其聚合反应中心的金属原子间相互作用对开环聚合性能的影响.     

ACTION DESIMINES SUR LES MONOCHLOROPHOSPHINES: NOUVELLE VOIE D'ACCES A DES CETONES β-PHOSPHORYLEES

Abstract

The reaction of imines 1 with monochlorophosphines leads to β-phosphorylketones obtained in the ketonic 2 or enolic forms 2′. The structure of all obtained products is confirmed by NMR and IR spectroscopy.     

SYNTHESE DE NOUVEAUX MACROCYCLES DéRIVéS DE LA 1-PYRAZOLYLBENZIMIDAZOLE-2-THIONE

Abstract

De nouveaux macrocycles de structures variées, renfermant une ou deux unités pyrazolylbenzimidazoles au sein d'une cha[icaron]ne polyéthylèneglyco1 ont été préparés par condensation, en catalyse par transfert de phase solide-liquide, de la 1-[3(5)-phénylpyrazol-5(3)-yl] benzimidazole-2-thione 1 avec le dichlorotétraéthylèneglycol 4 d'une part, et du 1,8(1,11)bis-[1-[3(5)-phtnylpyrazol-5(3)-yl] benzimidazol-2-yl]mercapto tri (tétra) glycol 9(10) avec les dichloropolyéthylèneglycols 3 et 4, d'autre part.     

A convenient method to prepare random LA/CL copolymers from poly(L-lactide) and ε-caprolactone

Sequential addition of L-lactide(LA) followed by ε-caprolactone(CL), and simultaneous addition of both monomers, afforded random LA/CL copolymers in the presence of lanthanide aryloxides under mild conditions. Transesterification was proved to play a predominant role in random copolymer formation. Moreover, treatment of poly(L-lactide) with ε-CL led to random copolymer formation, which provides a new strategy not only to prepare random LA/CL copolymers, but also to directly modify PLLA.     

ACTION DES HYDRAZINES ET DE L'HYDROXYLAMINE SUR QUELQUES PHOSPHONATES β, β-BIFONCTIONNALISES: SYNTHESE DE PHOSPHONOAMINOPYRAZOLES ET ISOXAZOLES

Abstract

Reaction of hydrazines and hydroxylamine with β, β-bifunctionalized phosphonates 1 and 1′ leads to phosphoaminopyrazoles and isoxazoles 2 3, 4 and 5. The structure of all obtained products was confirmed by NMR and IR spectroscopy.     

GC/MS法测定肉类食品中残留激素——DES、Zeranol、Trenbolone、Dianabol的研究

本课题研究了对肉类食品中四种残留激素——DES、Zeranol、Trenbolone,Dianabol的检测方法。按其性质分为类固醇和非类固醇二类,并作不同的前处理,然后分别注入GC/MS,以柱上衍生、电子轰击源电离、MID扫描、内标法定量检测;同时研究了用MS/MS方法对这四种激素作定性检测。     

Tree ring microanalysis by LA–ICP–MS for environmental monitoring: validation or refutation? Two case histories

An empirical approach is presented for validating trace metal profiles in tree rings for use as environmental archives. Concentration profiles of Zn, Cd, Cu, Pb and U in tree rings and lake sediments are compared for assessing the reliability of the former as an environmental proxy. Laser ablation sampling in conjunction with inductively coupled plasma mass spectrometry (LA–ICP–MS) is used for the direct analysis of tree rings. An optimised analytical protocol is devised with particular emphasis on sample preparation and quantification strategy. Significant correlations in the two environmental archives were found for zinc, copper and uranium, while cadmium and lead temporal trends, although showing enrichment in recent years, do not agree with the concentration profiles in lacustrine sediment cores. A chemical model based on metal affinity for hard type ligands present in wood is proposed to explain these results. Moreover, spring and winter wood are analysed separately thanks to the high spatial resolution of laser ablation sampling. As a result, enhanced metal loadings are shown to lead to intraring differences in trace metal concentrations.     

Hydrophobically modified polyelectrolytes Ⅲ. Reactivity ratio determination of FX14/AA, LA/AA and SA/AA

The reactivity ratios of three hydrophobia monomers, FX14, LA and SA, to a hydrophilic monomer, acrylic acid (AA), were determined. For the fluorocarbon containing hydropho-bic monomer FX14, elemental analysis was adopted to obtain the relative content of FX14 to AA. For two hydrocarbon monomers, 13C NMR was used. FR, KT linear method and EVM nonlinear method were applied in calculating reactivity ratios. It is found that the reactivity of LA and SA is lower than that of AA, for solution polymerization in cyclohexane. Whereas FX14 is more reactive than AA in benzene. Finally, the distribution of small amounts of these hydrophobic monomers along the polymeric chain is discussed and a random sequence is confirmed.