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71.
3,4-Dihydro-5(1H)-pyrromethenones are easier attacked at themeso-position by electrophiles than 5(1H)-pyrromethenones. This is demonstrated both by aMannich-type-substitution or deuterium-exchange-experiments and by the addition of O-, S-, and N-Nucleophiles to the exocyclic double bond of the model-dihydropyrromethenone (Z)-1 under very mild reaction conditions. Applying these results to the chemistry of 2,3-dihydro-bilatrienes-abc, their chemical characteristics—especially their tautomeric behavior and their dominant C-5-selectivity towards electrophiles—become better understandable. 相似文献
72.
The new layered ternary compound Nb3GexTe6 (x ? 0.90) was prepared by direct combination of the elements taken in the stoichiometric proportions 3 : 1 : 6, heated at 1 000 °C for 10 days in silica tubes and quenched to room temperature. The phase crystallizes in the orthorhombic symmetry, space group Pnma (#62), with the following single crystal refined parameters: a = 643.18(5) pm, b = 1391.98(11)pm and c = 1 154.07(5) pm, with Z = 4. The structure was refined to an R of 3.4% (Rw = 4.6%), with 1969 independent reflexions and 49 parameters. The structure is based on the close stacking of trigonal prismatic (TP) slabs in the AA/BB mode. The slabs can be seen as built up from face sharing biprisms, which are filled either by one or by two niobium cations situated in the middle of the trigonal prisms. The germanium is located in the middle of the common face of two prisms, leading to a rather unusual anionic square coordination. The refinements showed that this latter cation does not fill completely its square site. No cation was found in the van der Waals gap between the slabs. The mean dGe? Te distance (276.5 pm) is in agreement with GeII cations, while some Te …? Te distances (from 333.84 to 361.65pm) are too short for anions in a simple contact. These bonding distances, already mentionned in some MTe2 compounds, are to be ascribed to charge transfer in the structure, with a partial oxidation state for the tellurium anions. Short Nb? Nb and Nb? Ge distances (292.0 and 281.3 pm, respectively) imply intercationic bonding within the slabs. 相似文献
73.
E. V. Tulyakova O. A. Fedorova Yu. V. Fedorov G. Jonusauskas A. V. Anisimov 《Russian Chemical Bulletin》2007,56(11):2166-2174
Using 1H NMR spectroscopy and steady-state and time-resolved electronic spectroscopy, the optical properties of mono-and bis(styryl)pyridinium
perchlorates and their complexes with Mg2+, Ba2+ cations were studied. The stability constants of the complexes were determined using spectrophotometric titration. The formation
of inclusion complexes for Mg2+ and sandwich type complexes for Ba2+ results in fluorescence enhancement and increases the lifetimes of the excited states of the initial bis-styryl ligands.
The variation of position of the styryl fragment in the pyridinium aromatic ring gives rise to photochromic crown ethers with
different optical and photophysical characteristics and is also an easy route to bis(crown-ethers) of symmetrical and unsymmetrical
structure.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2092–2100, November, 2007. 相似文献
74.
Electronic structure of optimized Ge5, Ge17, Ge5–O and Ge5 embedded in SiO2 nanoparticles have been studied by density functional theory to find out the effect of cluster size and Ge–O bond(s) on the optical energy gap between LUMO and HOMO. It was found that the optical energy gap depends on both cluster size and the number of Ge–O bonds nonlinearly. The optical energy gap was found to be in visible light range when the Ge5 nanoparticle has been embedded in SiO2 matrix. 相似文献
75.
Vyacheslav Ya. Sosnovskikh Boris I. Usachev Mikhail I. Kodess 《Tetrahedron letters》2004,45(39):7351-7354
Reactions of chromones with dilithiooximes proceed via nucleophilic 1,2-addition to give, on acidification, 4H-chromene-4-spiro-5′-isoxazoline derivatives in high yields. On treatment with concentrated H2SO4 the isoxazoline ring of this novel spiroannulated heterocyclic system opens to give α,β-unsaturated oximes, which undergo nitrosation, bromination, and the Beckmann rearrangement to the corresponding spiroisoxazolines and α,β-unsaturated amides, respectively. The latter can be obtained directly by the Beckmann rearrangement of 4H-chromene-4-spiro-5′-isoxazolines. 相似文献
76.
Wanxing Wei Yuanjiang Pan Yaozu Chen Cuiwu Lin Tengyou Wei Shukai Zhao 《Chemistry of Natural Compounds》2005,41(1):17-21
Five compounds, terephthalic acid mono-[2-(4-carboxy-phenoxycarbonyl)-vinyl] ester (1), (E)-3-(5′-hydroperoxy-2,2′-dihydroxy[1,1′-biphenyl]-4-yl)-2-propenoic acid (2), 3,4,5-trihydroxybenzoic acid (3), succinic acid (or butanedioic acid) (4), and 2,3,4,5,6-pentahydroxybenzoic acid (5), were isolated from Phyllanthus urinaria. The structures of these compounds were elucidated by means of spectral techniques including IR, MS, and 1D/2D NMR. 1 and 2 are new compounds.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 14–17, January–February, 2005. 相似文献
77.
为建立一种快速、简便、灵敏测定葡萄糖酸锌含量的方法,在非离子型表面活性剂聚氧乙烯异辛基苯基醚(TritonX-100)存在下,用2-(3,5-二溴-2-吡啶偶氮)-5-二甲氨基酚(3,5-diBr-DM-PAP)作显色剂,直接光度法测定了葡萄糖酸锌。结果表明,该法显色络合物最大吸收波长为560 nm,线性范围为0~1.5μg.mL-1,表观摩尔吸光系数为1.10×105L.mol-1.cm-1,回收率为98.7%~102.2%,具有操作快速、简便,结果灵敏可靠等优点,应用该法直接测定补锌口服液葡萄糖酸锌含量,结果满意。 相似文献
78.
(Z)-3-丁烯基苯酞和它的衍生物广泛地存在于微形科植物,如当归、川芎等,这些植物有些是重要的中药材。(Z)-3-丁烯基-4,5-二羟基苯酞是(Z)-3-丁烯基苯酞的类似物;它对前列腺素F2α具有抑制作用。本文以3,4-二甲氧基苯甲醇(2)或价廉易得的胡椒醇(6)为起始原料,分别经四步反应顺利地合成了(Z)-3-丁烯基-4,5羟基苯酞(1)。和一步是本方法的关键,即利用杂原子诱导的区域选择性的芳环 相似文献
79.
Emmanuel Burgos 《Tetrahedron letters》2004,45(17):3465-3469
4-deoxy-4-Phosphonomethyl-d-erythronate, an isosteric and hydrolytically stable analogue of the known ribose-5-phosphate isomerase inhibitor 4-deoxy-4-phospho-d-erythronate, was obtained by a 14-step synthesis from d-arabinose through an highly improved synthesis of the precursor 5-deoxy-5-phosphonomethyl-d-arabinose. The title compound appears as the first stable and potent competitive inhibitor of the enzyme catalyzed isomerization of ribose-5-phosphate to d-ribulose-5-phosphate (Ki=74 μM, Km/Ki=100), exhibiting only a 3-fold weaker inhibitory activity than its phosphate analogue. 相似文献
80.
甲烷在Mo/HZSM-5催化剂上的脱氢聚合反应 总被引:1,自引:0,他引:1
对不同Mo含量的Mo/HZSM-5催化剂的结构进行了表征,并对这些催化剂的甲烷非氧气氛下的转化反应进行了考察.催化剂的BET比表面积及酸性随Mo含量的增加而降低,当Mo含量大于5%时,Mo对ZSM-5分子筛的晶型有影响,并出现MoO3物相.甲烷在700℃时可高选择性地生成苯和乙烯,最佳Mo含量大约为2%.纯的MoO3或HZSM-5上该反应几乎不进行,因此,可能是分散的钼氧离子和分子筛的酸中心是甲烷转化的活性中心,只有二者的协同作用才能促进甲烷的转化.反应后催化剂中的钼物种被还原了.催化剂上的积炭可能是催化剂失活的主要原因之一,烧炭后催化剂活性基本恢复. 相似文献