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.     

Synthesis,spectroscopic, biological,and theoretical studies of new complexes from (E)-3-(2-(5, 6- diphenyl-1,2,4- triazin-3- yl)hydrazono)butan-2- one oxime

New mononuclear Fe (III), Cu (II), Ag (I), ZrO ( IV) and UO₂(VI) complexes were synthesized by the reaction of metal ions with (E)-3-(2-(5, 6- diphenyl-1,2,4- triazin-3- yl)hydrazono)butan-2- one oxime. The structures of the metal complexes were characterized using analytical, spectral (infrared, electronic, ¹H NMR, electron spin resonance (ESR), and mass), magnetic moment, molar conductance, thermal gravimetric analysis, and powder X-ray diffraction (XRD) measurements. All complexes have octahedral geometries except the Cu (II) complex, which has square planar geometry, and the UO₂(VI) complex, in which the coordination number is seven. The ligand acts as a (neutral, monoanionic or dianionic) tridentate with N₂O coordinating sites: N-azomethine, N-triazine, and O-oxime. Fluorescence spectral studies were carried out in solid state and in dimethylformamide (DMF). The kinetic parameters of the thermal decomposition stages were calculated using Coats–Redfern equations. The morphological structures of the ligand and some complexes were determined using XRD. The molecular orbital calculations were carried out for the ligand and metal complexes using the Hyperchem 7.52 program on the basis of the PM3 level. The antimicrobial activities of the ligand and its complexes were investigated towards the microorganisms S. aureus and B. subtilis as Gram-positive bacteria, S. typhimurium and E. coli as Gram-negative bacteria, C. albicans, and A. fumigatus. The ligand and its complexes showed antitumor activity against Hep G-2 cell lines, where Cu (II) and Ag (I) complexes seem to be promising as they showed IC₅₀ values that are lower than and comparable to that of the antitumor drug doxorubicin.     

4－氯苯基环丙基酮肟－O－(3－苯氧基苄基)醚的新合成途径

采用农药厂副产物三乙基-3-苯氧基苄基氯化铵与4-氯苯基环丙基酮肟在碱性的条件下反应合成4-氯苯基环丙基酮厉-O-(3-苯氧基苄基)醚,产率80%。     

钛硅分子筛催化环己酮液相氨肟化固定床工艺

采用固定床模式,研究了钛硅分子筛催化环己酮制环己酮肟液相氨肟化反应.结果表明,该工艺模式具有可行性与普适性.优化的反应条件为:温度333K,体系氨浓度>2%,酮/H₂O₂摩尔比=5,H₂O₂空速0.083h^-1.此时环己酮转化率、环己酮肟选择性、H₂O₂转化率及其有效利用率分别达18.7%,99.5%,94.7%和98.7%.进一步研究了H₂O₂在该过程中的反应行为,发现固定床工艺模式能有效提高H₂O₂的有效利用率,其主要原因是该模式有利于羟胺的生成及其进一步与酮反应生成肟.适当的空速与氨和酮的浓度是实现H₂O₂高效利用的关键因素.     

Liquid Crystal and Rheological Behavior of 2,6-Bis(benzylidene)cyclohexanone

The liquid crystalline compound, 2,6-bis(benzylidene)cyclohexanone was synthesized using benzaldehyde and cyclohexanone as raw material, and tetrabutyl ammonium bromide as phase-transfer catalyst in the solution of sodium hydroxide. The effect of several factors, such as reaction time, reaction temperature, and concentration of sodium hydroxide, has been investigated. The product was characterized by infrared spectra, ¹H NMR and elemental analysis. The physicochemical behavior of the crystalline compound was studied by differential scanning calorimetry, polarizing microscope, and rheometer. The experimental results show that the synthesized compound exhibits typical semectic thermot liquid crystal. Meanwhile, the crystal of the compound was determined by x-ray single crystal diffraction analysis. The crystal of the compound belongs to monoclinic system with space group P2(1)/c, a = 9.586(1) Å, b = 18.391(2) Å, c = 9.433(1)Å, α = 90°, β = 115.816(2)°, γ = 90°, Dc = 1.217 g · cm^?3, V = 1496.9(3) Å^?3, and Z = 4.     

1-取代哌啶-4-酮肟醚的合成与杀菌活性测定

以取代苄胺或苯乙胺为起始原料, 依次经Michael 加成, Dieckmann缩合, 水解脱羧, 肟化和醚化等多步反应合成了11个未见文献报道的1-取代哌啶-4-酮肟醚5a～5k. 目标化合物的结构经元素分析, IR, 1H NMR和MS测定确证. 初步杀菌活性测试表明, 部分化合物有较好的杀菌活性.     

wo3催化h2o2氧化环己酮合成己二酸

以WO3为催化剂,在无有机溶剂和相转移催化剂的情况下,用H2O2氧化环己酮合成己二酸。探讨了催化剂用量、H2O2用量、反应温度和时间等条件对反应的影响。在优化条件下:n(环己酮)∶n(H2O2)∶n(WO3)=100∶500∶2,反应温度为120℃,反应6 h,己二酸分离收率可达80.3%,纯度为99.8%;催化剂重复使用5次后己二酸收率仍可达70.2%。     

磺化聚苯乙烯大孔树脂催化醛、酮与乙二醇缩合

合成了交换量不同的磺化聚苯乙烯大孔树脂,并将其运用于催化环已酮与乙二醇、苯甲醛与乙二醇的缩合反应。实验表明,磺化聚苯乙烯大孔树脂对醛、酮与乙二醇的缩合反应的催化效果良好,在0.2mol酮(或醛)中加入0.1g树脂,催化环己酮与乙二醇缩合反应的产率最高可达98.2%,催化苯甲醛与乙二醇缩合反应的产率可达73.3%。同时还发现磺化聚苯乙烯大孔树脂的交换量与催化合成缩酮、缩醛的产率有关,交换量为1.00mmol/g时其产率最高,催化性能较稳定。交换量小和交换量太大的树脂催化产率低。该树脂可以重复使用。催化反应完成后,树脂与反应液的分离十分方便,且催化剂对环境没有污染。     

Novel and Efficient Synthesis of 4-Indazolyl-1,3,4-trisubstituted Pyrazole Derivatives

In the present study, 1-(4,5-dihydro-3,6-dimethyl-4-(1,3-diphenyl-1H-pyrazol-4-yl)-3aH-indazol-5-yl)methanone derivatives (9–12) and isoxazoleyl (13–16) have been synthesized by the condensation of 1,3-diphenyl-1H-pyrazole-4-carbaldehyde (1–4) with acetyl acetone via Knoevenagel/Michael/aldol reactions in a sequential manner to yield intermediate cyclohexanone (5–8). The intermediates (5–8) treated with NH₂NH₂ · H₂O/NH₂OH · HCl afforded 4-indazolyl-1,3,4-trisubstituted pyrazole and isoxazoleyl derivatives. All of these compounds are reported for the first time, and the structures of these compounds were confirmed by means of infrared, ¹H NMR, ¹³C NMR, and mass spectroscopy.     

基于2,6-二(4-羧基苯亚甲基)环己酮的金属-有机框架化合物的合成与表征

以2,6-二(4-羧基苯亚甲基)环己酮(H2L)为配体得到一例锰金属-有机框架化合物[MnL]n,并运用红外、热重、循环伏安、固体紫外、X射线光电子能谱和X射线单晶衍射对其进行表征.单晶衍射分析表明该配合物属于三斜晶系,空间群P(1),不对称单元由Mn(Ⅱ)离子和一个L2-配体组成.配体两端的羧基均为单齿配位,配体中间...