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.     

钇与2-(4′-氯-2′-膦酰基一苯偶氮)-7-(2′,6′-二溴-4′-氯-一苯偶氮)-1,8-二羟基-3,6-萘二磺酸配位反应动力学研究和机理探讨

用停流分光光度法获得反应的经验速率方程为R=k[y(H_2O~n)~(3+)]·[H_6R]·[H~+]~(-1)。参考Eigen-Tamm机理和测得的动力学参数,拟出了反应的可能机理。     

Structural and photocatalytic properties of the new solid photocatalyst In2BiTaO7

In₂BiTaO₇ was synthesized using the solid-state reaction method and its photocatalytic properties were investigated. The results of powder X-ray diffraction (XRD) indicated that the compound crystallizes in the pyrochlore-type structure, cubic system with space group Fd-3m. The lattice parameter is 10.6972(1) ?. In addition, the compound shows strong optical absorption in the visible region (λ > 420 nm) and the band gap of In₂BiTaO₇ was estimated to be about 2.47 eV. For the photocatalytic reaction, H₂ or O₂ evolution was observed from CH₃OH/H₂O or AgNO₃ solution respectively with In₂BiTaO₇ as the photocatalyst under visible light irradiation, indicating that In₂BiTaO₇ is responsive to visible light for splitting water. Furthermore, the catalyst remained photoactive in the wavelength range up to 510 nm. Photocatalytic degradation of methylene blue (MB) dye over the compound was further investigated under visible light irradiation. The results showed that complete removal of aqueous MB could be achieved after irradiation for 135 min over In₂BiTaO₇. Furthermore, under visible light irradiation In₂BiTaO₇ showed markedly higher catalytic activity compared to P-25 for MB photocatalytic degradation.     

光学纯7,7′-二取代联二萘酚催化乙基锌对醛的对映选择性加成

合成了一类光学纯的7,7′-二取代联二萘酚, 并将其用在乙基锌对醛的对映选择性加成, 以54%～88%的产率和最高88%的对映选择性得到了光学活性的1-苯基-1-丙醇.     

7-Substituted prostaglandin analogues. A new synthetic approach

Starting from methyl 7-oxo-7-(1-cyclopentene)-heptanoate, a simple synthesis of the methyl esters of 7-oxo- and 7-hydroxy-9,11-dideoxy-PGF ₁ as a model for 7-substituted prostaglandin analogues is described.

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7-Substituierte Prostaglandin-Analoge — ein neuer Syntheseweg

Zusammenfassung Ausgehend von Methyl-7-oxo-7-(1-cyclopenten)-heptanoat wird eine einfache Synthese der Methylester von 7-Oxo- und 7-Hydroxy-9,11-dideoxy-PGF ₁ als Modellverbindungen für 7-substituierte Prostaglandinanaloge beschrieben.

     

Cr_2O_7~(2-)对B-Z振荡反应的影响及其分析应用

研究了Cr2O72-对B-Z化学振荡反应的影响.结果表明,Cr2O27-的加入明显改变该振荡反应的诱导期,且诱导期的改变值Δtin与所加入Cr2O72-的浓度有良好的线性关系,线性范围3.45×10-6~6.20×10-4mol·L-1,相关系数为0.9992,对Cr2O72-扰动B-Z振荡反应的机理进行了探讨.     

微波溶样肉桂基荧光酮和表面活性剂连续荧光测定葡萄酒中铁和钴

观察到肉桂基荧光酮(略作CF)在pH≈8与Fc(Ⅲ)配位后荧光增强,CPB的加入使荧光更强,络合物与试剂荧光强度之比F_(FeR)/F_R随0～0.01μg/ml Fe(Ⅲ)线性变化,λ_(ex)=410nm,λ_(ex)=480nm;而CF在pH≈10与Co(Ⅲ)配位后荧光却减弱,乳化剂OP存在时使试剂荧光增强,若以荧光熄灭Co(Ⅲ)灵敏度便提高,试剂与络合物荧光强度之比F_R/F_(CoR)对0～0.016 μg/ml Co(Ⅲ)呈直线关系,λ_(ex)=300nm,L_(em)=352nm。控制化学条件和激发、发射波长,可不经分离测定葡萄酒(微波溶样)中铁和钴。     

Synthesis,molecular structures,and thermal decomposition of heterometallic (π-cyclooctadiene)platinum-bis(tricarbonyliron-μ3-chalcogenides)[Fe—Fe], (π-C8H12)Pt(μ3-X)2Fe2(CO)6, where X = S,Se, or Te

Transmetallation of the Fe₃(₃-X)₂(CO)₉ clusters (X = S, Se, or Te) under the action of (-C₈H₁₂)PtCl₂ afforded new heterometallic clusters (-C₈H₁₂)Pt(₃-X)₂Fe₂(CO)₆ (2—4, respectively), which were characterized by X-ray diffraction analysis. The (-C₈H₁₂)Pt fragment in these clusters is bound to two ₃-bridging chalcogen atoms X. The iron atoms are linked to each other. The coordination environment about the Pt atom is planar-square; the Pt...Fe distance is larger than 3.2 . In the synthesis of cluster 4, a new Pt complex was also obtained for which the structure (CO)₂Pt(-Te)₂Pt(CO)₂ (5) was proposed. According to the results of differential scanning calorimetry, thermal decomposition of complex 5 gave rise only to PtTe, whereas complexes 1—4 gave products with the empirical formula Fe₂PtX₂C₂O₂. The influence of the steric effects on the geometry of the clusters is discussed.     

Investigation on relation between TL and OSL of Li2B4O7:Cu, In

Polycrystal Li₂B₄O₇ (LBO) doped with Cu and In was prepared and then sintered at different temperatures. X-ray diffraction (XRD) was applied to get the parameters of the LBO structure, thermoluminescence (TL) and optically stimulated luminescence (OSL) were measured, and a second-order exponential decay model was fitted to the OSL decay curves. The results indicate that the original number of OSL traps that have captured electroncs is linearly related with the sum of TL decay during the OSL process. Mean decay constant of OSL is related to the sintered temperature. The possible reason is that the sintered temperature affects the crystal sizes of the polycrystal, and consequently affects the stimulating lights’s intensity and the photoionization cross-section of the electrons, which have been captured by the traps. __________ Translated from Acta Scientiarum Naturalium Universitatis Sunyatseni, 2005, 44(4) (in Chinese)     

An Investigation of Inclusion Complexes of Cyclodextrins with Phenylurea Herbicides by Photochemically-Induced Fluorescence. Analytical Applications

The effect of -cyclodextrin (-CD) and hydroxypropyl--cyclodextrin (HP--CD) upon the photochemically-induced fluorescence (PIF) properties of four phenylurea herbicides, including linuron, diuron, isoproturon and neburon has been studied. Photochemical conversion of these nonfluorescent herbicides into strongly fluorescent photoproducts was shown to occur in -CD and HP--CD aqueous media. The influence of pH, UV irradiation time and photoproduct stability on the fluorescence intensity was also investigated. In addition, the stoichiometry and formation constants of the complexes formed between herbicides and -cyclodextrin (-CD) or 2-hydroxypropyl--cyclodextrin (HP--CD) were determined. The formation constant values, ranging from 184 ± 40 to 1498 ± 245 M^-1, were calculated by applying the iterative nonlinear regression (NLR) approach to the PIF data. Linear calibrations graphs were established in the interval 1–12 g/mL, for diuron, linuron and neburon. The IUPAC limits of detection ranged between 580 and 700 ng/mL, according to the compound. Application to the analysis of phenylurea herbicides in spiked river water was also described.