钌配合物高效催化酮和烯烃的氢转移反应

RuHCl（PPh3）3为主催化剂的不同催化体系能分别有效地催化1－己烯双键移动异构化和酮的氢转移还原成醇的反应．考察了反应条件（温度,时间和催化剂量）对1一己烯转化率的影响;优化结果为,在RuHCl（PPh3）3浓度为1．1×10^-2mol／L（甲苯为溶剂,底物与溶剂比为4）,反应温度为120℃时,在18min建立了催化平衡,得到了1-己烯的转化率为97．6％,其中2．己烯占19．3％,3-己烯占78．3％．在筛选了酮还原有效催化体系RuHCl（PPh3）3-KOH—NH2（CH2）3OH—Me2CHOH的基础上,在反应底物：RuHCl（PPh3）3：KOH：NH2（CH2）3OH为5000：1：1：1（摩尔比）下,催化不同酮底物还原为醇的产率为60％-99％;并通过IR和NMR对催化反应机理进行了初步研究．     

钯催化合成2-(2,4-二氟苯基)吡啶

以Pd(OAc)2为主催化剂,PPh3为配体,2-溴(氯)吡啶和2,4-二氟苯硼酸通过Suzuki偶联反应合成了2-(2,4-二氟苯基)吡啶,产率＞90%,其结构经1H NMR,19F NMR和IR确证.     

RuCl3/PPh3催化顺酐加氢为琥珀酸酐的反应机理研究

利用原位^31P NMR,IR技术跟踪了RuCl3/PPh3催化顺酐加氢过程，并考察了酸碱的添加对反应的影响。根据实验结果，提出了在RuCl3/PPh3催化剂体系作用下，顺酐均相加氢生成琥珀酐的反应历程：RuCl3/PPh3在反应体系中生成活性物种RuHCl(PPh3)，顺酐以C＝C双键与Ru-H活性物种配位生成配合物，此配合物分子内氢转移，形成金属烷基化物，该化合物再与氢进行氧化加成，还原脱出产物琥珀酸酐和Ru-H活性物种，完成整个催化循环。     

5-甲基-3-硝甲基己酸乙酯的合成

以异戊醛和膦酰乙酸三乙酯为原料,1,8-二氮杂二环［5,4,0］十一碳-7-烯(DBU)为催化剂,碘化钠为磷酸酯碳负离子稳定助剂,经Horner-Wadsworth Emmons反应合成了5-甲基-2-己烯酸乙酯(3),收率90%;仍以DBU为催化剂,3与硝基甲烷经Michael加成反应合成5-甲基-3-硝甲基己酸乙酯,收率98%,两步总收率88.2%,其结构经¹H NMR和IR确证。     

新型2-芳氨基嘧啶衍生物的合成

通过间羟基苯硼酸与2,4-二氯嘧啶的Suzuki反应及其后酚羟基的烷基化得到4-芳基-2-氯嘧啶衍生物. 然后, 采用Pd(PPh3)4/dppf催化剂, 在温和的条件下实现了4-芳基-2-氯嘧啶类化合物和芳香胺的偶联. 合成了3个结构新颖的2-芳氨基嘧啶类化合物. 中间体及产物的结构均经由IR, 1H NMR, 13C NMR, MS和元素分析表征而予以证实.     

Cu(Ⅰ)与乙酰乙酸乙酯、氰基乙酸乙酯、丙二腈及中性膦配合物的电化学合成

用牺牲金属阳极的电化学方法在非水溶剂中合成了一价铜配合物 Cu( ) [CH( CN) 2 ]( PPh3) 2 ,Cu( )( Me COCHCO2 Et) ( PPh3) 2 及 Cu( ) ( CNCHCO2 Et) ( PPh3) 3· Me CN,对配合物进行了元素分析 ,IR,1 H NMR和 1 3C NMR测试及表征 ,并讨论了反应机理。     

离子液体中Yb(OTf)_3催化下喹唑啉酮衍生物的绿色合成

以邻氨基苯甲酰胺和芳醛为原料,离子液体[BMIm]Br为溶剂,Yb(OTf)3为催化剂室温下合成了一系列的2-芳基-2,3-二氢化喹唑啉-4-(1H)-酮衍生物.和其他方法相比,该方法具有反应条件温和、产率高(85%～96%)、环境友好等优点.产物的结构通过熔点,IR,1H NMR和高分辨质谱分析确证.     

新型3-(1,3,4-噻二唑基)-1,3-苯并噁嗪类化合物的合成和杀菌活性

以2-[(1,3,4-噻二唑基-2-氨基)甲基]苯酚和CH2Cl2为原料,首次采用相转移催化法合成了一系列新型3-(1,3,4-噻二唑基)-1,3-苯并噁嗪类化合物,产率为47%～62%.研究了相转移催化剂的用量、反应物用量、反应温度等对反应产率的影响.产物结构用IR,1H NMR,13C NMR和元素分析进行了表征.初步研究了目标化合物的杀菌活性,大部分化合物具有一定的杀菌活性.     

串联合成新型色烯-茚二酮类化合物

报道了一种合成新型色烯-茚二酮类化合物3的方法.该反应以简单易得的2-羟基查尔酮(1)和1,3-茚二酮(2)为原料,以甲苯为溶剂在无催化剂条件下进行反应.所有化合物的结构都通过了1H NMR,13C NMR,IR和HRMS的表征.该反应的可能机理为分子间迈克尔加成/分子内环化/氧化的串联过程.目标产物3a~3h的紫外最大吸收波长在464~482 nm之间.     

5-取代-3,4-二卤-2(5H)-呋喃酮的Sonogashira偶联反应

以5-取代-3,4-二卤-2(5H)-呋喃酮为底物进行Sonogashira偶联反应, 考察了反应温度、反应时间、钯催化剂种类与用量、碱种类与用量、溶剂、底物结构等对偶联反应的影响, 合成了28种新的2(5H)-呋喃酮衍生物, 其结构用IR, ¹H NMR, ¹³C NMR, MS和元素分析等方法进行了表征. 在优化的反应条件下, 即反应溶剂为甲苯、催化剂为3 mol% Pd(PPh₃)₄和10 mol% CuI、碱为6 equiv. KF、反应时间72 h、反应温度30 ℃时, 反应产率42%～84%. 利用该Sonogashira偶联反应合成新型的多官能团烯二炔结构化合物, 不仅合成途径简捷、反应条件温和, 绝大部分反应产率中等以上, 而且无需额外加入配体, 适用于芳香的和脂肪的末端炔烃.     

Die Kristallstruktur des W3CoB3 und der dazu isotypen Phasen Mo3CoB3, Mo3NiB3 und W3NiB3

Zusammenfassung Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃ und W₃NiB₃ kristallisieren in einem eigenen Typ (W₃CoB₃-Struktur). Das trigonal prismatische Bauelement [T ₆B]^* ist zu Ketten vereinigt, wobei B₃-Gruppen entstehen. Die Phasen sind vermutlich Bor-reicher als obiger Formel entspricht.

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The crystal structure of W₃CoB₃ and the isotypic phases Mo₃CoB₃, Mo₃NiB₃, and W₃NiB₃

Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃, and W₃NiB₃ were found to possess a new type of crystal structure (W₃CoB₃-structure type). Trigonal prismatic groups [T ₆B]^* are linked together forming chains in such a way that B₃-groups occur. These borides do probably exist with a larger amount of boron as to compared with the formula.

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γ-Nitro-γ-butyrolacton

γ-Nitro-γ-butyrolactone By oxidation of 3-(1-nitro-2-oxocyclohexyl)propanal ( 1 ) with KMnO₄, besides 3-(1′-nitro-2′-oxocyclohexyl)pripionic acid ( 2 ), the complete hydrolysis product 4-oxononanedioic acid ( 4 ) and the oxidized semi-hydrolysis product 5-(2-nitro-5-oxotetrahydro-2-furyl)pentanoic acid ( 3 ) were formed. The crystalline 3 decomposes at r.t. forming 4 and nitrous gases; its structure was established by X-ray determination.     

Synthesis of γγγ-trifluorocarbonyl compounds

γγγ-Trifluorocarbonyl compounds are easily obtained in a good yield by introduction of the 1,1,1-trifluoroethyl moiety (CF₃-CH₂-) on the -methylene group of a ketone.     

3x-pyrrolizin-3-ones

Condensation of pyrrole-2-dithiocarboxylates with CH acids containing ester groups, in the KOH-DMSO system, was used to prepare previously unknown 1-alkylthio-3H pyrrolizin-3-ones. The latter, treated with secondary amines, are readily converted to the corresponding 1-amino derivatives.     

3-H-pyrrolizin-3-ones

Previously unknown 1-alkylthio-3H-pyrrolizin-3-ones have been obtained by the condensation of pyrrole-2-dithiocarboxylates with CH acids containing ester groupings in the KOH-DMSO system. On treating the products with secondary amines they are readily converted into the corresponding 1-amino derivatives.Irkutsk Branch of the Russian Academy of Sciences, Irkutsk 664033. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–924, July, 1996. Original article submitted May 2, 1996.     

K3BiSe3, Rb3BiSe3 und Cs3BiSe3 – Substitutionsvarianten des Th3P4-Typs

K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ – Derivatives of the Th₃P₄ Structure Type The compounds K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ were synthesized by heating mixtures of Bi₂O₃ and the respective alkalicarbonate in a stream of hydrogen saturated by selenium at 850°C. Thin crystals of the compounds appear red in transmitted light. They crystallize isostructural with Na₃AsS₃, space group P2₁3, lattice constants a = 9.771(5) Å, a = 10.161(3) Å, and a = 10.587(5) Å for K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃, respectively. The Na₃AsS₃ structure type is a derivative of the Th₃P₄ structure type.     

Die Akzeptoreigenschaften von AsCl3, AsBr3, asJ3, SbCl3, SbBr3 und SbJ3

Zusammenfassung Es wurden die Enthalpien der Reaktionen von AsCl₃, AsBr₃, AsJ₃, SbCl₃, SbBr₃ und SbJ₃ mit Tributylphosphat, N,N-Dimethylacetamid und Hexamethylphosphorsäuretriamid bestimmt. Das Verhalten der Addukte bei Gegenwart eines Überschusses der Donoren wird beschrieben.

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Acceptor properties of AsCl₃, AsBr₃, AsI₃, SbCl₃, SbBr₃, and SbI₃

The enthalpies of the reactions of AsCl₃, AsBr₃, AsI₃, SbCl₃, SbBr₃ and SbI₃ with tributylphosphate, N,N-dimethylacetamide and hexamethylphosphoric acid triamide were measured. The behavior of the adducts in the presence of excess donor molecules is described.

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Freezing the polarization of CH3NH3PbI3 and CH3NH3PbI3-xClx perovskite films

Thin films of methylammonium lead halides, CH₃NH₃PbI₃ and CH₃NH₃PbI_3-xCl_x, were deposited onto symmetrical microstructured electrode arrays of gold or platinum on Si/SiO₂ wafers. Polarization studies were carried out on perovskite films under vacuum in the dark. For poling, a constant voltage was applied to the samples while the temperature was cycled between 295 K and 4 K. The measured current densities depending on the temperature showed distinct characteristics relating strongly to the crystal phase and the dielectric properties of the perovskite films. Voltage sweeps were carried out at different scan rates at specific temperature intervals after poling. The polarization of the films due to the migration of iodide vacancies in direction of the blocking perovskite/metal interface was frozen almost up to room temperature. Charge carriers were only able to cross the blocking barrier and contribute to the current where the ions have accumulated during poling. All J-V curves showed hysteresis: inverted and regular hysteresis at room temperature and below, respectively. Inverted hysteresis originates from the slow accumulation of ions at the blocking barrier, while regular hysteresis arises from a distortion in the adjacent crystals which will be discussed.