Cyclization of protected N-acylhydroxyguanidine to 3-amino-1,2,4-oxadiazole

The acid mediated cyclization of a protected N-acylhydroxyguanidine into the corresponding 3-amino-1,2,4-oxadiazole and confirmation of its structure by single crystal X-ray crystallography is reported herein. The yield of the cyclization is comparable to literature reports utilizing alternative procedures. Importantly, these new conditions provide complementary chemoselectivity to current synthetic procedures which may be useful for the synthesis of 3-amino-1,2,4-oxadiazoles in general.     

Rate enhancement of PFP sulfonate ester aminolysis by chloride salts in organic and aqueous media

We report here, a method of accelerating the rate of aminolysis of PFP sulfonates to yield sulfonamides using tetrabutylammonium salts. We have previously explored the utility of employing PFP sulfonates in the formation of sulfonamides; however we demonstrate here the advantages of combining the existing methodology with a revised protocol which allows the diversity within both the sulfonate ester and the amine to be extended.     

Future of low-x forward physics at RHIC

Comparisons of particle production from high-energy ion collisions with next-to-leading order perturbative QCD calculations show good agreement down to moderate transverse momentum values. Distributions of azimuthal angle differences between coincident hadrons in these collisions support a partonic origin to the particle production, again down to moderate transverse momentum values. The rapidity dependence of inclusive and coincident particle production can therefore be used to probe parton distribution functions down to small momentum fractions where theory anticipates that parton saturation could be present. This paper describes how such experiments could be completed.Arrival of the final proofs: 27 July 2005PACS: 12.38 Qk, 13.88. + e, 24.85. + p     

Correlation dimension: A pivotal statistic for non-constrained realizations of composite hypotheses in surrogate data analysis

Currently surrogate data analysis can be used to determine if data is consistent with various linear systems, or something else (a nonlinear system). In this paper we propose an extension of these methods in an attempt to make more specific classifications within the class of nonlinear systems.

In the method of surrogate data one estimates the probability distribution of values of a test statistic for a set of experimental data under the assumption that the data is consistent with a given hypothesis. If the probability distribution of the test statistic is different for different dynamical systems consistent with the hypothesis, one must ensure that the surrogate generation technique generates surrogate data that are a good approximation to the data. This is often achieved with a careful choice of surrogate generation method and for noise driven linear surrogates such methods are commonly used.

This paper argues that, in many cases (particularly for nonlinear hypotheses), it is easier to select a test statistic for which the probability distribution of test statistic values is the same for all systems consistent with the hypothesis. For most linear hypotheses one can use a reliable estimator of a dynamic invariant of the underlying class of processes. For more complex, nonlinear hypothesis it requires suitable restatement (or cautious statement) of the hypothesis. Using such statistics one can build nonlinear models of the data and apply the methods of surrogate data to determine if the data is consistent with a simulation from a broad class of models. These ideas are illustrated with estimates of probability distribution functions for correlation dimension estimates of experimental and artificial data, and linear and nonlinear hypotheses.     

Solid phase synthesis of 5-aminopyrazoles and derivatives

The development of a novel solid phase synthesis of some 5-aminopyrazoles and derivatives is described. Reaction of hydrazines with solid supported β-keto-nitrile (1) affords 5-aminopyrazoles (2) the amino group of which is readily acylated or sulphonylated. Generation of the solid supported β-keto-nitrile (1) is non trivial and represents a key step in the overall synthesis.     

A concise total synthesis of (+)-FR900482 and (+)-FR66979

The concise, enantioselective total synthesis of the potent antitumor antibiotics (+)-FR900482 and (+)-FR66979 are described. Sharpless asymmetric epoxidation technology has been deployed to construct the optically active aziridine-containing fragment that is joined to the aromatic moiety in a highly convergent manner. Dimethyldioxirane effects the remarkable one-step deprotection/oxidative cyclization of an eight-membered ring amino-ketone to the unique hydroxylamine hemiketal ring system that is a distinctive structural motif of FR900482. This reaction has been exploited in a concise 33-step enantioselective total synthesis of FR900482.     

The structures and thermal decomposition of cupric mono,di and trichloracetates

Magnetic moment measurements and ultra-violet diffuse reflectance spectroscopy have been used to investigate the structure of the chloroacetates of copper(II). These studies indicate that cupric monochloroacetate dihydrate is dimeric and cupric trichloracetate tetrahydrate is monomeric. Cupric dichloracetate tetrahydrate forms an intermediate case. The thermal decomposition of these compounds under nitrogen has been studied using thermogravimetry and differential thermal analysis, together with analysis of the products of the decomposition. The major organic product formed in the thermal decomposition of the mono- and dichloracetates is the corresponding chlorinated acetic acid; the solid inorganic product is cuprous chloride. Thermal decomposition of the trichloracetate yields cupric chloride and a mixture of trichloracetic acid and trichloracetyl chloride.

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Zusammenfassung Messungen des magnetischen Momentes sowie diffuse UV-Remissionspektroskopie wurden zur Untersuchung der Struktur der Kupfer(II)-chloracetate eingesetzt. Die Ergebnisse deuten darauf hin, daß Kupfermonochloracetat-Dihydrat dimer und Kupfertrichloracetat-Tetrahydrat monomer ist. Das Kupferdichloracetat-Tetrahydrat bildet hierbei eine Zwischenstufe. Die thermische Zersetzung dieser Verbindungen wurde in Stickstoffatmosphäre unter Anwendung der Thermogravimetrie und Differentialthermoanalyse untersucht, bei gleichzeitiger Analyse der Zersetzungsprodukte. Das bei der thermischen Zersetzung des Mono- und Dichloracetats gebildete organische Hauptprodukt ist die entsprechende chlorierte Essigsäure; der feste anorganische Rückstands das Kupfer(I)-chlorid. Die thermische Zersetzung des Trichloracetats ergibt Kupfer(II)-chlorid sowie eine Mischung von Trichloressigsäure und Trichloracetylchlorid.

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Résumé La mesure du moment magnétique et la spectroscopie de réflexion diffuse dans l'U. V. sont utilisées pour étudier la structure des chloroacétates de cuivre (II). Les résultats indiquent que le monochloroacétate de cuivre (II) dihydraté est dimère et que le trichloroacétate de cuivre (II) tétrahydraté est monomère. Le dichloroacétate de cuivre (II) tétrahydraté représente un cas intermédiaire. La décomposition de ces composés dans l'azote a été suivie par thermogravimétrie et analyse thermique différentielle, en analysant simultanément les produits de décomposition. Le principal produit organique formé lors de la décomposition thermique des mono et dichloroacétates est l'acide chloroacétique correspondant; le produit solide inorganique est le chlorure de cuivre (I). La décomposition thermique du trichloroacétate fournit le chlorure de cuivre (II) et un mélange d'acide trichloracétique et de chlorure trichloroacétylique.

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(II). , (II) , (II) - . (II) . , , . , - , , (I). (II) (II) .

     

Optimisation of dead-end filtration conditions for an immersed anoxic membrane bioreactor

The optimisation of the energy demand in the application of dead-end filtration in an immersed membrane bioreactor applied to groundwater denitrification has been studied. Filtration cycle length was varied at a set flux to control the amount of foulant deposited at the membrane surface. Physical cleans comprising a simultaneous backflush and gas injection were subsequently instigated and the reversibility of the deposit determined by the residual resistance, R_res. Examination of R_res versus flux and cycle length variation indicated an operational envelope where limited fouling occurred. The transition from limited fouling to extensive fouling was indicated by a parameter based on the critical accumulated mass, indicating incipient deposit consolidation. The transition between regions became less severe when the solids retention time was increased from 10 to 25 and 40 days. This was apparently related to a shift in bulk physical characteristics. Nevertheless, low residual fouling was observed during long-term filtration when operating below the critical mass, resulting in a 20× reduction in energy demand over that of constant gas injection.