含1,2,4—三唑基硫代磷酰肟酯的合成及其生物活性

本文合成了１７种含１，２，４－三唑基硫代磷酰肟酯，其结构经ＩＲ、１ＨＮＭＲ、ＭＳ及元素分析确证．生物活性测定了它们的杀虫活性．     

钛硅分子筛在环己酮肟气相贝克曼重排反应中的失活

 对比了不同孔径的钛硅分子筛催化剂Ti－MCM－41（Si／Ti摩尔比＝27）和TS－1（Si／Ti摩尔比＝25）对环己酮肟气相贝克曼重排反应的催化性能，分析了它们在重排反应中的积碳量和孔体积的变化．结果表明，这些钛硅分子筛催化剂的失活主要是由积碳引起的，且积碳速率受催化剂孔径的制约．在重排反应过程中，TS－1催化剂微孔孔道内的积碳量随反应时间线性增加，微孔体积随反应时间线性下降；而二次孔内的积碳量随反应时间呈指数增加，孔体积随反应时间呈指数递减．     

Study of alkaloids from the flora of the Siberian and Altai regions. 6. Crystal and molecular structure of songorine Z-oxime

Oximation of songorine afforded a mixture of its Z- and E-oximes. The crystal and molecular structure of the Z-isomer was established by X-ray diffraction analysis. Its structure was also confirmed by the spectral data (2D ¹H—¹H and ¹³C—¹H NMR spectroscopy and mass spectrometry). The structure of isomeric E-oxime was established by comparing its NMR spectroscopic data (¹H and ¹³C) with the data for the Z-isomer.     

Cascade cyclization reactions of 3,4,5-triamino-1,2,4-triazole with aromatic aldehydes and cycloalkanones

A three-component condensation of 3,4,5-triamino-1,2,4-triazole (1) with aromatic aldehydes 2a–f and dimedone (3) or cyclohexanone (8) afforded partially hydrogenated 9-aryl-[1,2,4]triazolo[5,1-b]quinazolin-8-ones. The structure of 2-amino-6,6-dimethyl-3-(4-nitrobenzylidene)amino-9-(4-nitrophenyl)-5,6,7,9-tetrahydro[1,2,4]triazolo[5,1-b]quinazolin-8-one (4e) was confirmed by X-ray diffraction data. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1178–1182, July, 2006.     

Catalytic Hydrodehydration of Cyclohexanone,Hydrogenation of 2-Cyclohexen-1-one,and Dehydrogenation of Cyclohexene over a Mo Chloride Cluster with an Octahedral Metal Framework

A silica gel-supported molybdenum halide cluster, (H₃O)₂[(Mo₆Cl₈)Cl₆]·6H₂O (1), developed selective catalytic activity for the condensation of cyclohexanone to cyclohexylbenzene and cyclohex-1-enylbenzene, when it was allowed to react in a stream of helium at 300°C. Halide clusters of Nb, Ta, and W of the same metal framework supported on SiO₂ also catalyzed the condensation at 400°C. However, at 400°C, 1 catalyzed disproportionation, and selectivity increased with increasing temperature, yielding cyclohexene and its dehydrogenation products, 1,3-cyclohexadiene and benzene, and 2-cyclohexen-1-one and its dehydrogenation product, phenol. When the same reaction was performed in a stream of hydrogen above 400°C, hydrodehydration proceeded almost exclusively, producing cyclohexene and its dehydrogenation products. 2-Cyclohexen-1-one was hydrogenated to cyclohexanone under the same reaction conditions utilizing hydrogen molecules, whereas cyclohexene was dehydrogenated via 1,3-cyclohexadiene to benzene. The active site developed on 1 was assumed to be a molybdenum atom, which becomes isoelectronic with the platinum metals by accepting two or more electrons from the ligands.     

环己酮与查尔酮的无溶剂Michael加成反应

以环己酮和查尔酮为原料, 在 NaOH 存在下无溶剂室温研磨反应, 非常方便地得到Michael加成产物. 该方法具有反应条件温和、操作简单和产率较高等优点, 并通过IR, ¹H NMR和元素分析确证产物的结构.     

Heterocyclic synthesis using nitrile imines. 4. Synthesis of 3-substituted 1-aryl-1,2,4-triazaspiroalk-2-enes

Cycloalkanone oximes react with C-(2-furoyl)-, C-(2-thenoyl)- and C-(phenylaminocarbonyl)nitrile imines to give unexpected 3-substituted 1-aryl-1,2,4-triazaspiroalk-2-enes rather than the cycloaddition or the cyclocondensation products.For Part 3 see Ref. 1.Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1626–1631, November, 2004.     

Sodium dithionite initiated reactions of 1-bromo-1-chloro-2,2,2-trifluoroethane with enol ethers of cyclic ketones

Sodium dithionite initiated reactions of 1-bromo-1-chloro-2,2,2-trifluoroethane (1) with methyl and trimethylsilyl ethers of cyclopentanone and cyclohexanone enols (2a-d) in a MeCN/H₂O system were investigated. 2-(2,2,2-Trifluoroethylidene)cyclopentanone (4a) and 2-(2,2,2-trifluoroethylidene)-cyclohexanone (4b), respectively, were obtained as the main products and isolated in reasonable yields. The reaction with a 1:1 mixture of 5- and 3-methyl substituted 1-methoxycyclohexenes, 2e and 2f, revealed strong influence of steric hindrance on the reaction rate; a mixture of 2-(2,2,2-trifluoroethylidene)-5-methylcyclohexanone (6) and 2-(2,2,2-trifluoroethylidene)-3-methylcyclohexanone (7) in a 9:1 ratio was formed. Ketones 4a and 4b were reduced to the corresponding alcohols 8 and 9 and the reaction of 4b with hydrazine gave an indazole derivative 10.     

Vapor-phase Beckmann rearrangement of cyclohexanone oxime over B2O3 catalysts supported on TiO2-ZrO2 mixed oxide

A novel catalyst, boria supported on titania-zirconia mixed oxide, exhibits very high catalytic activity and selectivity in vapor-phase Beckmann rearrangement of cyclohexanone oxime to e-caprolactam. It gives 99.7% oxime conversion and 97.0% lactam selectivity at 300°C.     

2,2''-双〔2-(邻甲酰肟苯氧基)乙基〕醚与过渡金属配合物的合成及性质研究

含氮配位原子的希夫碱型化合物在分析化学、合成化学、药学等方面有广泛的应用。