The regioselectivity of the formation of 2-pyrazolylthiazoles and their precursors from the reaction of 2-hydrazinothiazoles with 4,4,4-trifluoro-1-hetaryl-1,3-butanediones

Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c.     

Lanthanum-based perovskites obtained in molten nitrates or nitrites

Lanthanum-based perovskites, LaMO₃ (where M = Mn, Fe, Co, Ni), have been synthesised from lanthanum precursors and corresponding 3d transition metal salts in molten alkali metal nitrates or nitrites. The reactivity of eight precursors in three molten salts of different basicity was analysed. Single phase orthorhombic LaMnO_3.11, and orthorhombic LaFeO₃ have been obtained in molten NaNO₂ at 723 K, for 2 h. LaCoO₃ is also formed in molten nitrite, but an increase of basicity, by adding Na₂O₂, was necessary to obtain LaNiO₃. The reaction systems were investigated by thermal analysis. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and specific surface area measurements (BET method) were used to characterise the synthesised nanopowders.     

K-Ce_(0.5)Zr_(0.5)O_2催化碳颗粒物燃烧性能

用等体积浸渍法制备了不同K负载量的xKNO3-Ce0.5Zr0.5O2系列催化剂,用程序升温氧化反应(TPO)考察催化剂对碳颗粒物(soot)燃烧的催化活性.并采用XRD、BET、FT-IR、XPS等技术对KNO3负载催化剂进行表征.结果表明KNO3负载量对催化剂的比表面、表面化学环境有显著的影响;KNO3能使催化剂对soot的催化燃烧活性有较大提高,且存在最佳负载量,当x=0.5时,催化剂的活性最好,碳颗粒物的起燃温度(T)i和峰顶温度(Tp)分别为290℃和360℃.在反应过程中,KNO3熔融状态的形成和K2CO3的生成,使催化活性明显提高.     

Reactions of 1-aryl-2-bromodiazene 1-oxides with acids and bases

The reactions of 1-aryl-2-bromodiazene 1-oxides with HCl in nonaqueous media give aryldiazonium chlorides, while 1,3,3-substituted triazenes-1 are formed in the reactions with secondary amines. Using 2-{¹⁵N} label, it was shown that the aryl group does not migrate in these reactions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 613–615, March, 1997.     

The role of complexing ligands in the formation of non-aggregated nanoparticles of zirconia

The hydrolysis and condensation of zirconium n-propoxide in n-propanol have been chemically controlled via the complexation of the zirconium precursor with acetylacetone. The size of the zirconium oxide-based particles is mainly controlled by the complexation ratio x=[acac]/[Zr]. the mean size increases from nanometric to submicronic range when x decreases from 1 to 0.1. Amorphous colloidal particles are obtained at room temperature. They result from a competitive growth/termination mechanism of zirconium-oxo species in the presence of acac surface capping agents. However non-aggregated nanocrystalline particles of tetragonal zirconia, about 2 nm in diameter are formed upon aging at 60°C when hydrolysis is performed in the presence of paratoluene sulfonic acid (PTSA).     

Enantioselective catalytic epoxidation of nonfunctionalized prochiral olefins by dissymmetric chiral Schiff base complexes of Mn(III) and Ru(III) metal ions II

A series of new dissymmetric chiral Schiff base complexes has been obtained by a systematic condensation of (1S,2S)(+)-diaminocyclohexane and 3-acetyl-4-hydroxy-6-methyl-2-pyrone with salicylaldehyde, 5-chloro-, 5-methoxy-and 5-nitrosalicylaldehyde and by subsequent metallation with manganese and ruthenium. The characterization of the complexes 1–8 was accomplished by physico chemical studies viz. microanalysis, IR-, UV/VIS-, and CD spectral studies, optical rotation, molar conductance measurements and cyclic voltammetry. Enantioselective epoxidation of non functionalised olefins, viz. cis-stilbene, trans-3-nonene and trans-4-octene with iodosyl benzene as oxidant was demonstrated in the presence of catalytic amounts of chiral Mn(III) and Ru(III) dissymmetric Schiff base complexes. Good optical yields of epoxides were obtained for the catalyst 4 with the substrates trans-3-nonene and cis-stilbene.     

镉化合物的~(113)Cd屏蔽张量2-氨基二甲基吡啶镉单晶的研究

2-氨基二甲基吡啶镉的单晶已被单晶定向的~(113)Cd核磁共振进行了研究。在CdCl_2+2-氨基二甲基吡啶中对于两个氯-四个氮的~(113)Cd的屏蔽张量元素分别是σ_(33)=368,σ_(22)=266,和σ_(11)=236×10~(-6)。     

活性炭负载磷钨酸催化合成季戊四醇缩酮(醛)

季戊四醇双缩酮(醛)可作为杀虫剂[1]、塑料的抗氧化剂及表面活性剂的消泡剂等[2,3];其单缩酮(醛)是有机合成的重要中间体。其合成反应常用无机酸催化剂(如H2SO4、HCl、H3PO4等)[4],副反应多、腐蚀性强和易污染。近年来,采用脱铝超稳Y沸石和对甲苯磺酸等作催化剂[5-7],效果良好。本文以活性炭负载磷钨酸作催化剂合成了12种季戊四醇缩酮(醛),催化剂用量少、反应速率快、产率高,催化剂可回收使用。其结构经元素分析、IR及1HNMR等表征。1　实验部分1 1　仪器与试剂Kofler熔点仪,温度计未经校正;美国NICO LETAVATAR 360FT光谱仪…     

Structure and Photosynthetic Mimicking of Bis(2,6-bis(benzimidazol-2-yl)pyridine)manganese(II)

Introduction　　Manganeseionsplayanimportantroleinthelight in ducedoxidationofwatertomolecularoxygeninphotosys temII (PSII)ofgreenplants.1 3Inrecentyears ,man ganesecomplexesofpolypyridineligands ,suchasbipyri dine ,1,10 phenanthrolineand 2 ,2′:6′,2″ terpyridine ,havehadconsiderableattentionasthecomplexesformedareusefulmodelsformanganese containingbimolecu lars .4 6 Therefore ,synthesisandcharacterizationofman ganeseinitsvariousoxidationstates ,withvariousligandtypesandnuclearities ,hav…