Acylation of fluorine-containing spiro[cyclopropane-1-pyrazolines] and dehydrohalogenation of the resulting adducts

Acylation of 6-(1-fluorovinyl)-6-methyl- and 6-(2,2,3,3-tetrafluorocyclobutyl)-4,5-diazaspiro[2.4]hept-4-enes with acetyl chloride proceeds as electrophilic addition to the N(5) atom and is accompanied by opening of the cyclopropane ring to give 1-acetyl-3-(2-chloroethyl)-5-(1-fluorovinyl)-5-methyl- and 1-acetyl-3-(2-chloroethyl)-5-(2,2,3,3-tetrafluorocyclobutyl)-4,5-dihydropyrazoles, respectively. Under the same conditions, acylation of 6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-4-ene is not regioselective. The (2-chloroethyl) pyrazolines obtained undergo dehydrochlorination into vinylpyrazolines in the presence of an excess of MeONa in MeOH. The reaction of 4-acetyl-6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-5-ene with MeONa results in selective replacement of the F atom at the double bond by a methoxy group.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 419–422, February, 2005.     

5′-Noraristeromycin derivatives isomeric to aristeromycin and 2′-deoxyaristeromycin

A straightforward synthesis of (1S,2R,3R,4R)-4-(6-aminopurin-9-yl)-2-hydroxymethylcyclopentane-1,3-diol (2), an isomer of aristeromycin, and its 2′-deoxy derivative 3 from readily available disubstituted cyclopentenes is presented. An antiviral analysis of 2 showed it to have significant activity versus Epstein-Barr virus (IC₅₀ 0.62 μg/mL in the Elisa assay) and to be free of cytotoxicity effects against the host cells. In a much less comprehensive antiviral analysis, 3 also was active towards Epstein-Barr (IC₅₀ 7.58 μg/mL in the Elisa assay) but this was accompanied by cellular toxicity.     

Determination of the surface tension of surfactant solutions applying the method of Lecomte du Noüy (ring tensiometer)

Summary Starting from a comparative assessment of the outstanding works on the ring method (du Noüy) for the determination of the surface tension of liquids and its solutions it is shown that the application of this method to surfactant solutions can lead to substantial errors if one follows conventional conditions. These errors are mainly connected with so far unknown phenomena occurring during the raising of the ring and concerning the influence of the hydrophilic vessel wall above the solution level and the stretching of the solution surface. This is demonstrated quantitatively with surfactant solutions of different kind and concentration. These effects can be explained theoretically very simply by introducing certain assumptions on the behaviour of a surfactant adsorption layer on the inner vessel wall. Conditions leading to the elimination of these errors are given, thus enabling the application of the ring method to the determination of the surface tension of surfactant solutions.With 10 figures and 3 tables     

Absolute stereochemistries and total synthesis of (+)-arisugacins A and B, potent, orally bioactive and selective inhibitors of acetylcholinesterase

In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins.     

The alicyclic ring contraction of perfluoro-1-phenyltetralin in reaction with antimony pentafluoride

Perfluoro-1-phenyltetralin (1) heated with antimony pentafluoride at 130 °C, then treated with water, gave a mixture of perfluorinated 3-methyl-2-phenylindenone (3), 3-methyl-2-phenylindene (4), 3-hydroxy-1-methyl-3-phenylindan (5), 1-methyl-3-phenylindan (6), 9-methyl-1,2,3,4,5,6,7,8-octahydroanthracene (7), and 1,9-dimethyl-5,6,7,8-tetrahydro-β-naphthindan (8). When heated with SbF₅ in the presence of HF, then treated with water, compound 1 is transformed to a mixture of products 3-6. The reaction at 170 and 200 °C forms compounds 3-6 together with perfluoro-2-(cyclohexen-1-yl)-3-methylindene (10).     

烷基化螺吡喃吲哚的合成及光学性质研究

为了增加螺吡喃吲哚与透明聚合物（ＰＭＭＡ）的相溶性,在螺吡喃吲哚分子中引入长烷基链,合成了１′－「十八烷基」－３′,３′－二甲基－６－硝基－８－「二十二酰氧基」－螺「２Ｈ－１－苯并吡喃－２,２′－二氢吲哚」,并用ＮＭＲ确定各中间体和最终产物的结构,ＨＰＬＣ显示产物中烷基化螺吡喃吲哚含量在９７％以上。将烷基化螺吡喃吲哚与ＰＭＭＡ制成厚度为５００ｎｍ左右的膜,研究该膜对紫外光的响应,获得烷基化螺吡喃吲哚开环和紫外吸收的关系,以及Ｊ－耦合构型与陈化的关系。     

环氧烷化合物在有机合成中的应用

综述了近年来环氧烷化合物在有机合成中的应用。环氧烷化合物的开环反应可以用来合成其它方法难以合成的多官能团化合物，或通过开环和修饰合成其他环状化合物。另外，利用该反应还可以提供保护基以及立体、区域选择性地合成各种有机化合物。参考文献23篇。     

Synthesis of heliannuol D, an allelochemical from Helianthus annus

A synthesis of heliannuol D 1 is described involving regioselective oxidation of the benzoxabicyclo[3.2.1]octanone 20 followed by hydrogenolysis to generate the benzoxepane ring system of 1.     

On the Kernel of Restriction of Characters*

Let G be a finite group, H be a proper subgroup of G, and S be a unitary subring of C. The kernel of the restriction map S[Irr(G)] → S[Irr(H)] as a ring homomorphism is studied. As a corollary, the main result in [Isaacs, I. M. and Navarro, G., Injective restriction of characters, Arch. Math., 108, 2017, 437–439] is reproved.