Palladium complexes of a chiral P,C-chelating phosphino-(sulfinylmethyl)phosphonium ylide ligand

A new type of phosphino-phosphonium ylide ligand bearing a chiral sulfinyl center affords a P,C-chelated palladium(II) complex with a resolved asymmetric ylidic carbon atom. According to ³¹P NMR analysis of the crude material, the diastereoselectivity of the complexation at room temperature is ca. 7:1. In the crystal state, an X-ray diffraction analysis of one epimer reveals a quasi C₂-symmetric chloro-bridged dinuclear structure, where the (S) configuration of the sulfur atom induces a (S) configuration of the ylidic carbon atom. A in situ Pd(0) catalyst generated from the phosphino-ylide and Pd(PPh₃)₄ promotes allylic substitution of 3-acetoxy-1,3-diphenylpropene by sodium malonate in 70% yield and 5% e.e.     

一类非线性退化方程混合问题解的渐进性态

本文利用比较原理以及一种特殊变换研究了一类非线性退化方程的混合问题，得到了这类复杂问题解的渐进性质。     

Preparation and catalytic applications of partially fluorinated binaphthol ligands

New partially fluorinated binaphthols were obtained using a copper-catalyzed oxidative coupling. The corresponding enantiomerically pure compounds were prepared by fractional crystallization of the corresponding bis(menthyl)carbamates. Nucleophilic aromatic substitution using oxygen- and carbon-based nucleophiles resulted in functionalized derivatives without concomitant racemization. The titanium(IV) complexes of these ligands are catalytically active in the asymmetric oxidation of sulfides.     

Synthesis,characterization and properties of methylaminocellulose

Homogeneously prepared tosylcelluloses (TC) with degrees of substitution (DS) of DS_Tos 0.1–1.8 were used as intermediates for the synthesis of methylaminocelluloses (MAC) by nucleophilic substitution with methylamine. TC with DS_Tos up to 1.1 were shown to be valuable intermediates for selective synthesis of MAC with DS_MA varying from 0.1 to approximately 1. No nucleophilic substitution was observed at higher DS_Tos. At the chosen reaction conditions (60 °C, 48 h) residual tosyl moieties remained unchanged and little hydrolysis took place. The samples obtained were characterized by means of elemental analysis, FTIR and ¹³C CP/MAS NMR spectroscopy. ¹³C CP/MAS NMR spectroscopy was found to be an efficient tool for quantification of DS_MA. Furthermore, the swelling behaviour in water was investigated and preliminary tests concerning the bilirubin adsorption capacity of MAC were carried out.     

57Fe Mössbauer spectroscopic study of (25−x)MnO–xZnO–15Fe2O3–60B2O3 glasses

The ⁵⁷Fe Mössbauer technique has been used to investigate the effect of zinc oxide substitution in (25???x)MnO–xZnO–15Fe₂O₃–60B₂O₃ glass system (x?=?0, 5, 10, 15 and 20 mol% of ZnO ). Mössbauer absorption spectra for all the samples recorded at room temperature suggest the existence of the two paramagnetic quadrupole doublets. The observed variations in hyperfine parameters have been explained on the basis of cations distribution and exchange interaction at the lattice sites and it is concluded that B–B interaction increases while the metal–metal interaction decreases due to replacement of manganese oxide by zinc oxide. These results suggest that the present glass system exhibits a paramagnetic behaviour that changes towards the weak paramagnetic when manganese oxide was replaced with zinc oxide.     

Single-period Two-product Inventory Model with Reorder and Substitution

In market, excess demands for many products can be met by reorder even during one period, and retailers usually adopt substitution strategy for more benefit. Under the retailer's substitution strategy and permission of reorder, we develop the profits maximization model for the two-substitutable-product inventory problem with stochastic demands and proportional costs and revenues. We show that the objective function is concave and submodular, and therefore the optimal policy exists. We present the optimal conditions for order quantity and provide some properties of the optimal order quantities. Comparing our model with Netessine and Rudi's, we prove that reorder and adoption of the substitution strategy can raise the general profits and adjust down the general stock level.     

Reaction of pentafluorobenzoylpyruvic acid with amines

Reactions of pentafluorobenzoylpyruvic acid with amines afford the respective enamines. The intramolecular cyclization of the latter results inN-substituted 4-quinolone-2-carboxylic acids. Ammonia and triethylamine favor the cyclization of pentafluorobenzoylpyruvic acid to 2-carboxychromone.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 299–302, February, 1994.     

Mechanism of Interaction of γ-Halogenated Salts of Pyrylium and Benzopyrylium with Aromatic Amines

Stoichiometry and kinetics of reactions of 2,6-diphenyl-4-chloropyrylium, 4-chloroflavylium, 4-bromoflavylium, and 4-iodoflavylium perchlorates with nucleophiles N,N-dimethylaniline and n-phenylenediamine are studied using cyclic voltammetry and spectroscopy. Nucleophilic substitution in these compounds proceeds via the formation of a charge-transfer complex, which converts into a radical ion pair as a result of the electron transfer. Heterolytic clevage of the C–Hal bond occurs at the stage of pyranyl (flavanyl) radical.