Copper-catalyzed iminohalogenation of γ, δ-unsaturated oxime esters with halide salts: Synthesis of 2-halomethyl pyrrolines

A copper-catalyzed iminohalogenation of unactivated alkenes of γ, δ-unsaturated oxime esters is achieved by using readily available halide salts. Utilizing this protocol, a sequence of structurally diversiform 2-halomethyl pyrrolines are efficiently synthesized and a mechanism involving iminyl radical intermediates, which were initiated by Cu(I) species, was proposed.     

Cube‐like 12‐MC‐4 and Offset Stacked 10‐MC‐3 Metallacrowns: Synthesis,Structure, and Magnetic Properties

Two complexes [Mn^III₄(naphthsao)₄(naphthsaoH)₄] ( 1 ) and [Fe^III₆O₂(naphthsao)₄(O₂CPh)₆] ( 2 ) [naphthsao = 1‐(1‐hydroxy‐naphthalen‐2‐yl)ethanone oxime] were obtained through the reactions of naphthsao ligand and MnCl₂ · 4H₂O or FeCl₃ · 6H₂O in the presence of triethylamine (Et₃N). Their structures were determined by X‐ray single crystal diffraction, elemental analysis, and IR spectra. Complex 1 displays 12‐MC‐4 metallacrown structural type with cube‐like configuration and 2 shows an offset stacked 10‐MC‐3 structural type with the ring connectivity containing Fe–O–C–O–Fe–O–N–Fe–O–N. Magnetic susceptibility measurement reveals the ferromagnetic interactions and field‐induced slow relaxation of the magnetization for 1 , whereas out‐of‐phase signal is not observed for 2 .     

Crystal structure,spectroscopic characterization,DFT computations and molecular docking study of a synthesized Zn(II) complex

The Zn(II) complex, dichloro[N-hydroxy-1,1-di(2-pyridinyl)methanimine]zinc(II), was synthesized from the reaction between ZnCl₂ and di-2-pyridylketone oxime. The structural and spectral characterizations were performed by using single crystal X-ray diffraction, FT-IR, Laser-Raman, NMR and UV–Vis spectroscopic techniques. To support experimental evidences, computational results were obtained with the DFT/B3LYP method using the 6-311++G(d,p)+LanL2DZ mixed basis set. Theoretical analyses of some structural and spectroscopic results of effects of intermolecular Cl···H interactions in the crystal packing of the Zn(II) complex were investigated with the mentioned computational level. The non-bonding interactions in the experimental crystal packing of the complex were examined by Hirshfeld surface analysis. The HOMO and LUMO analyses were used for investigation of electronic transitions obtained with UV–Vis spectroscopy. NBO analyses were used to investigate the hyperconjugation interactions between donor and acceptor groups, coordination environment, electronic configuration and electron numbers of the Zn(II) metal ion and the natural atomic charges of the complex. The nucleophilic and electrophilic reactive sites of the complex were studied by MEP surface analysis. The static polarizabilities (α) and static hyperpolarizabilities (β) were analyzed theoretically to characterize NLO profile of the complex. The interaction with A-DNA (PDB ID: 1ZF6) of the Zn(II) complex was investigated with a molecular docking study.     

利用Wittig反应制备乙烷类液晶

以4-（反式4’-正烷基环己基）环己酮和氯甲醚三苯基磷盐为起始原料,经Wittig反应、水解、转型、Wittig反应和氢化反应合成了1-（3,4-二-氟苯基）-2-[反式4’-（反式4＂-正烷基环己基）环己基]乙烷类液晶,其结构经^1H NMR,^13C NMR及MS确证。纯化总收率约30％。     

铜(I)催化条件下酮肟衍生物与苄烯丙二腈的环化反应构建2-氨基吡啶

研究了铜催化条件下,酮肟的衍生物与苄烯丙二腈的环化反应,考察不同的催化剂、溶剂、添加剂等对反应的影响,成功的构建了一系列的2-氨基吡啶骨架化合物. 并对苯乙酮肟以及苄烯丙二腈芳环上不同位置具有不同性质取代基的底物进行了拓展,以31%～81%的收率分离得到相应的目标产物,反应具有较好的底物普适性.     

肟醚碳负离子对氮杂环丙烷的开环反应

苯乙酮肟醚α碳负离子在添加 HMPA 的条件下,顺利实现了对单取代和环状氮杂环丙烷的开环,取得中等到良好的收率。四氢萘酮肟醚 α 碳负离子在该条件下也可以对部分氮杂环丙烷开环。反应中 HMPA 起到对锂离子的络合作用,可以在一定程度上增加碳负离子的亲核性。     

回收灯用钨丝在H2O2催化氧化环己酮合成己二酸中的应用

以回收灯用钨丝为催化剂前驱物,30％H2O2为氧源,催化氧化环己酮合成了己二酸,反应体系中无须使用有机溶剂、酸性助剂和相转移剂。 IR和TG分析表明,钨丝与H2O2反应生成的新生态过氧钨酸是催化活性成分,合成己二酸后转化为钨酸。 钨丝为催化剂前驱物合成己二酸适宜反应条件为：100 mmol环己酮,50 mL 30%H2O2,钨丝的摩尔用量为环己酮摩尔数的1.5%,回流反应6 h,己二酸收率63.7%。 比相同反应条件下用钨酸和WO3为催化剂的收率高10%~18%。     

新型环己烯酮衍生物的合成

根据活性基团拼接原理,以烯草酮为先导化合物,通过修饰其肟醚位,引入具有除草活性的环苯草酮肟醚结构,设计并合成了一个新型的环己烯酮衍生物(7)。以对氯苯酚为原料,经取代、还原、卤代、肟醚化、水解等5步反应制得O-［2-(4-氯苯氧基)丙基］-羟胺盐酸盐(5); 5与5-［2-(乙硫基)丙基］-3-羟基-2-丙酰基-2-环己烯-1-酮反应合成了7,其结构经¹H NMR, ¹³C NMR, IR, ESI-MS和元素分析表征。     

一种可再生高选择性的硫化氢荧光探针

为了方便地检测环境样品中的硫化氢,利用香豆素酰肼肟配体构建了一个基于其铜配合物的可再生高选择性的硫化氢荧光探针(1-Cu²⁺)。 顺磁性Cu²⁺的荧光猝灭作用使探针的荧光很弱。 Na₂S溶液的加入可显著增强其荧光,其它常见阴离子(F^-,Cl^-,Br^-,I^-,CO32-,HPO42-,H₂PO4-,NO2-,NO3-,SO42-,CH₃COO^-,N3-,S₂O32-,CN^-)对配合物探针的荧光影响很小,共存时也不会干扰探针对硫化氢的增强响应。 Cu²⁺的加入能够再生探针(1-Cu²⁺),通过依次加入Cu²⁺和S^2- ,可重复地检测S^2-。 该探针响应时间快(~5 s),在0.5~5.0 μmol/L的范围内对H₂S响应呈线性,检测限低至37 nmol/L。     

一种同时测定环己酮肟水解反应中环己酮肟和硫酸羟胺含量的方法

在环己酮肟水解反应制备硫酸羟胺过程中,环己酮肟与产物硫酸羟胺在酸性条件下难以分离,硫酸羟胺的含量测定受到环己酮肟的干扰。 本文采用高效液相色谱法和氧化还原滴定法建立了一种简便、有效的新方法同时测定硫酸羟胺与环己酮肟的含量。 结果表明,在H⁺浓度大于2.4 mol/L,Fe³⁺/环己酮肟摩尔比大于5:1的条件下,环己酮肟和硫酸羟胺测定的标准滴定曲线的线性相关系数分别为0.99998和0.99996,相对标准偏差分别为0.39%和0.50%,水解反应样品的加标回收率为97.1%~100.6%。