On the Image Regularity Condition

In this paper, we continue the analysis of the image regularity condition (IRC) as introduced in a previous paper where we have proved that IRC implies the existence of generalized Lagrange-John multipliers with first component equal to 1. The term generalized is connected with the fact that the separation (in the image space) is not necessarily linear (when we have classic Lagrange-John multipliers), but it can be also nonlinear. Here, we prove that the IRC guarantees, also in the nondifferentiable case, the fact that 0 is a solution of the first-order homogeneized (linearized) problem obtained by means of the Dini-Hadamard derivatives.     

Symmetry specified enumeration of substituted derivatives: an easy solution to the complex problem

Several sophisticated methods to solution of symmetry specified enumeration problems are available in the modern literature. In this paper we propose a simple technique that allows one to manually compute the exact numbers of fixed-symmetry derivatives for a given structure either with inclusion or ignoring the substitution patterns. The basic idea of the method suggested consists in the derivation of Pólya-like cycle indices for the automorphism groups of specially constructed orbit partition graphs; the expansion of these indices and subsequent simple calculations result in the desired numbers of substituted derivatives with achiral substituents. Limitations of the new technique (and a method suggested earlier) depend on the relevance of the orbit partitions for particular subgroups of the point symmetry group. For illustration purposes, the results obtained for the prismane (D _3h ) and adamantane (T _d ) structures are discussed. In the former case the numbers of substituted derivatives can be found for all subgroups of the D _3h group, whereas in the latter case these numbers can be determined for eight out of eleven subgroups of the T _d point symmetry group. This work is based on the text of the lecture presented by the authors at the 5th All-Russia Conference on Molecular Modeling (Moscow, April 2007). The paper deals with the methodology and detailed treatment of applied aspects related to solution of enumeration problems for substituted derivatives with prescribed symmetry groups. Unlike the known methods of symmetry specified enumeration, the technique suggested is simple enough and may be regarded as generalization of the Pólya methodology, which is widely used by chemists. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 227–245, February, 2008.     

Sugar conjugates of fulvestrant (ICI 182,780): efficient general procedures for glycosylation of the fulvestrant core

We have prepared glucose and cellobiose conjugates at the phenolic 3- and hydroxylic 17-positions of the pure anti-estrogenic compound fulvestrant (ICI 182,780), which has recently been approved in the USA for the treatment of advanced postmenopausal breast cancer. Glycosylation at the 17-position was achieved most effectively using pivaloyl protection of the sugar imidates employed, which we found suppressed the competing transacylation reaction and led to improved yields of the product glycosides.     

Crystallographic report: Crystal structure of 1‐bromo‐1′‐[(2S)‐N‐(1‐hydroxy‐3‐methylbutane‐2‐yl)]‐ferroceneamide

For the unsymmetrical title compound, 1‐bromo‐1′‐[(2S)‐N‐(1‐hydroxy‐3‐methylbutane‐2‐yl)]‐ferroceneamide, two independent molecules were found in the asymmetric unit. Copyright © 2003 John Wiley & Sons, Ltd.     

三嗪类光学探针与标记分析

评述了以三聚氰氯作桥联剂或骨架而合成的三嗪类衍生物、特别是其光学标记探针的研究进展及分析应用。     

Conversion of acids to benzimidazoles with transition metal/zeolites

Transition metal/Y zeolites were prepared using microwave solid state and aqueous solution ion exchange methods. The activity of these zeolites was investigated in a conversion of acids to benzimidazoles reaction between 4-methyl-1, 2-phenylenediamine and 3-nitrobenzoic acid. The yield of these reactions increased in order of CuY < Fe²⁺Y < NiY < CoY < NaY < CrY < MnY < ZnY for both methods. The solid state ion-exchanged zeolites showed higher activity in comparison to the aqueous solution exchange. Yields of products in the presence of the ZnY zeolite were of the order of 69–83%. It seems that the Lewis sites are better sites compared to the Bronsted sites for this reaction.     

The synthesis and reaction of N-sulfenyl heterocycles: development of effective sulfenylating reagents

Various N-sulfenyl heterocycles were synthesized by transamination of sulfenamides using a chlorine gas-free method. The N-sulfenyl heterocycles behaved as sulfenylating reagents of anilines; N-sulfenylbenzimidazoles were the most effective.     

Air‐stable and recoverable catalyst for copper‐catalyzed controlled/living radical polymerization of styrene; In situ generation of Cu(I) species via electron transfer reaction

Copper‐catalyzed controlled/living radical polymerization (LRP) of styrene (St) was conducted using the silica gel‐supported CuCl₂/N,N,N′,N′,N″‐pentamethyldiethylenetriamine (SG‐CuCl₂/PMDETA) complex as catalyst at 110 °C in the presence of a definite amount of air. This novel approach is based on in situ generation and regeneration of Cu(I) via electron transfer reaction between phenols and Cu(II). Sodium phenoxide or p‐methoxyphenol was used as a reducing agent of Cu(II) complexes in LRP. The number–average molecular weight, M_n,GPC, increases linearly with monomer conversion and agrees well with the theoretical values up to 85% conversion The molecular weight distribution, M_w/M_n, decreases as the conversion increases and reaches values below 1.2. The catalyst was recovered in aerobic condition and reused in copper‐catalyzed LRP of St. For the second run, the number–average molecular weights increased with monomer conversion and the polydispersities decreased as the polymerization proceeded and reached to the value <1.3 at 81% conversion. The recycled catalyst retained 90% of its original activity in the subsequent polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 77–87, 2006     

血卟啉衍生物的色谱分离

本文拟定的纸色谱法是以苯-乙酸乙酯-甲醇-乙酸(9:2:1:1)作展开剂,将血卟啉衍生物(HPD)分离为五部份,分别测定各部份浸取液的荧光发射光谱,作为一种对血卟啉衍生物组份作对比鉴定的参考方法。采用Ward的高效液相色谱程序对比研究结果表明,国产与美国产HPD的组份近似,均以血卟啉为主要组份,而前者血卟啉的含量较高;二者还均含有羟乙基乙烯基衍生物和羟基乙酸酯,初步研究了血卟啉衍生物在甲醇-水溶剂系统中的高效液相色谱行为,进一步将血卟啉衍生物分离为九部份,有利于单一组份研究。     

Lewis acid promoted reactions of γ,γ-dialkoxyallylic zirconium species with various carbonyl compounds

The reactions of γ,γ-dialkoxyallylic zirconium species with carbonyl compounds in the presence of Lewis acid are reported. The reactivity of γ,γ-dialkoxyallylic zirconium species and reaction pathway were strongly dependent on the structure and electrostatic nature of the carbonyl compounds.