4-甲基-3-硝基苯甲腈和2-甲基-5-硝基苯甲腈的合成与表征

4-甲基-3-硝基苯甲腈和2-甲基-5-硝基苯甲腈是重要的有机合成中间体[1,2],因其芳环上具有硝基和氰基两个第二类取代基,同时又有一个可参与反应的甲基而使得这两个化合物在有机合成领域有着广泛的应用前景.芳环上的甲基可以氧化为酸,也可进一步反应形成酰氯、酯等功能基;芳环上的氰基可水解成羧基,也可以与叠氮钠在Lewis酸催化下形成具有生物活性的四唑衍生物;芳环上的硝基经还原可形成氨基,如4-甲基-3-硝基苯甲腈通过化学反应可环合形成药物中间体6-氰基吲哚[2～4].     

含非交换氘的四唑-锌配合物

The solvothermal reaction (D₂O) of 2,6-dideuterium-4-cyanopyridine with ZnCl₂ in the presence of NaN₃ offers a novel complex Zn(OD)(C₆H₂D₂N₄) (1) in which Zn has a distorted tetrahedron composed of two N atoms from one tetrazoyl group and pyridyl group and two O atoms from two deuteratohydroxy OD groups. Crystal data for 1: Pbcn, a=1.456 8(5) nm, b=0.659 2(2) nm, c=1.645 3(5) nm, α=90°, β=90°, γ=90°, V=1.580 0(9) nm³, Z=8, M=231.54, D_c=2.236 Mg·m^-3, μ=3.070 mm^-1, R₁=0.043 4, wR₂=0.120 6, S=1.029. CCDC: 660629.     

一种铀(Ⅵ)配合物的水热合成、结构与性质

UO₂(EPC)₂ (EPC=5-ethyl-3-pyridinecarboxylate) was synthesized by the hydrothermal reaction of UO₂(NO₃)₂ ·6H₂O with imazethapyr [2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-5-ethyl-3-pyridine-carboxylic acid] at 120 ℃, which 2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl group was removed under this condition to result in the formation of 5-ethyl-3-pyridinecarboxylate ligand (EPC). The structure and fluorescent property of the synthesized complex is also reported. CCDC: 645641.     

The First Homochiral Diamond-Like Coordination Polymer Containing Cubane Cluster （Cu4I4） as Connecting Node and Cinchonine as Donor-Acceptor （or Push-Pull Electronic Effect） Building Block

The reaction of CuI with cinchonine （an organic donor-acceptor chromophore） afforded a homochiral 3D diamondoid network [Cu4I4（cinchonine）2]n （1） containing a cubane cluster （Cu4I4） as a connecting node. This is the first homochiral coordination polymer with diamondoid nets containing a cluster as a connecting note. Its thermal stability and solid state optical properties such as fluorescence, circular dichroism and second-harmonic generation response were also reported.     

5-甲氧基吲哚的合成

5-甲氧基吲哚是重要的有机合成中间体 ,可用于合成吲哚类衍生物 ,如 5-甲氧基色胺和松果腺素等[1,2 ] 。经典的 Reissert法[3] 以 2 -甲基 -4-甲氧基硝基苯与草酸二乙酯经缩合、还原、脱羧而得 ,该路线最后一步脱羧所需温度过高、易炭化导致收率低而难以工业化 ;Kita等[4 ] 以三甲硅基乙氧基甲酰 ( TEOC)将 2 -氨乙基 -4-甲氧基苯酚中的氨基保护后 ,在乙腈 -甲醇溶液中以高价碘试剂 PIFA( phenyliodinebistrifluoroacetate)催化氧化得醌式亚氨的缩醛化合物 ,分子内成环时去掉保护基团 TEOC,再以 1 0 %Pd/ C处理而得 5-甲氧基吲哚 ,该…     

单一手性烯烃铜(Ⅰ)配位聚合物

The solvothermal reaction of CuCl with R-(-)-1-allyl-3-methylpiperazine at 70 ℃ gives one-dimensional chain Cu-coordination polymer through olefin moiety binding to Cu atoms formulated as [Cu(C₈H₁₆N₂)Cl]. It is interesting to note that through Cu₂Cl₂ dimer unit 1 results in a supramolecular 3-dimensional coordination polymer. Powdered sample measurement of 1 reveals that 1 is second-harmonic generation (SHG) active compound. Crystal parameters for 1, space group P2₁2₁2₁, a=0.763 1(9) nm, b=0.891 0(10) nm, c=1.494 6(17) nm, α=90°, β=90°, γ=90°, V=1.016(2) nm³, Z=2, M=478.44, D_c=1.564 Mg·m^-3. CCDC: 650193.     

具有自旋涨落性质的单一手性三核镍(Ⅱ)配合物

[Ni₃O(TBPLA)(H₂O)](ClO₄)₄(H₂O)₆ [TBPLA=(S)-1,1′,1″-2,4,6-trimethylbenzene-1,3,5-triyl)-tris(methylene)-tris-(pyrrolidine-2-carboxylate)] was found to possibly display multiferroic property (the coexistence of ferroelectricity and ferromagnetism). The magnetic property of this compound was studied and no magnetic hysteresis loop was found probably due to an intrinsic fluctuation for the magnetic exchange energy.