铽与4—酰代吡唑啉酮—5的三元配合物的合成与荧光性质

合成并表征了一系列铽与含不同４－酰代的１－苯基－３－甲基－吡唑啉酮－５的三元配合物Ｔｂ９Ｌ）３．２Ｈ２Ｏ和Ｔｂ（Ｌ）３．Ｄｉｐｙ「Ｌ＝１－苯基－３－甲基－４－乙酰基吡啥林酮－５（ＰＭＡＰ），１－苯基－３－甲基－４－丙酰基吡唑啉酮－５（ＰＭＰＰ），１－苯基－３－甲基－４－异丁酰基吡唑啉酮－５（ＰＭＩＢＰ），１－苯基－３－甲基－４－特戊酰基吡唑啉酮－５（ＰＭＰＶＰ），１－苯基－３－甲基－４－苯甲酰基吡     

卟啉试剂与贵金属高灵敏显色反应的研究 Ⅴ.Ru(Ⅲ)-T(4-AOP)P-TritonX-100体系

本文研究了在Ｃｄ（Ⅱ）和ＴｒｉｔｏｎＸ－１００存在下，ｍｅｓｏ－四（４－乙酰氧基苯）卟啉［Ｔ（４－ＡＯＰ）Ｐ］与钌（Ⅲ）的显色反应。结果表明，在ｐＨ９．７～１０．３介质中，Ｒｕ（Ⅲ）与Ｔ（４－ＡＯＰ）Ｐ形成了灵敏度很高的稳定络合物，其表观摩尔吸光系数为７．０４×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。钌浓度在０～１．２μｇ／１０ｍＬ范围内服从比尔定律。络合物的摩尔比为Ｒｕ（Ⅲ）∶Ｔ（４－ＡＯＰ）Ｐ＝１∶１。在掩蔽剂存在下，方法有一定的选择性，应用于合成试样中钌的测定，结果满意。     

4个新型有机磷缩合试剂的合成及其在生物活性肽合成中…

报道了４个新型有机磷化合物：Ｎ－二乙氧基磷酰并恶唑酮（ＤＥＰＢＯ０，Ｎ－（２－氧－１，３，２－二氧杂磷环己烷基）－苯并恶唑酮（ＤＯＰＢＯ），３－（２′－氧－１′，３′，２′－二氧杂磷杂环己烷基）－氧－１，２，３－苯并三嗪－４（３Ｈ）－酮（）ＤＯＰＢＴ）和３－（二乙氧基磷酰基）－氧－１，２，３－苯并三嗪－４（３Ｈ）－酮（ＤＥＰＢＴ）的合成，并研究了它们作为缩合试剂的多肽合成中的应用，研究结果表明，它     

四（4—甲氧基—3—磺酸苯基）卟啉分光光度法测定微量铅

研究了水溶性卟啉５，１０，１５，２０－四（４－甲氧基－３－磺酸苯基）卟啉（Ｔ（４－ＭＯＰ）ＰＳ４）与铅的显色反应，在ｐＨ１１和酒石酸钾存在下铅与Ｔ（４－ＭＯＰ）ＰＳ４在室温时间形成１：１的配合物，其最大吸收波长在位于４６４．４ｎｍ，摩尔吸光系数为２．３×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，铅量在０～２０μｇ／２５ｍＬ，范围为符合比尔定律，工作工线回归方程Ａ＝０．０２６２＋０．０４３５ｃ相关系数ｒ     

meso－四（4－甲基－3－磺基苯）卟啉分光光度法测定痕量钯的研究

本文研究了Ｐｄ（Ⅱ）与ｍｅｓｏ－四（４－甲基－３－磺基苯）卟啉（Ｔ（４Ｍ３ＳＰ）Ｐ）的显色反应在表面活性剂十二烷基磺酸钠（ＳＤＳ）和抗坏血酸存在下，ｐＨ４８的ＨＡｃ－ＮａＡｃ介质中，沸水浴加热，Ｐｄ（Ⅱ）与Ｔ（４Ｍ３ＳＰ）Ｐ形成１∶１（Ｍ∶Ｌ）配合物配合物最大吸收波长４１４ｎｍ，表观摩尔吸光系数ε＝２０×１０５Ｌ·ｍｏｌ－１·ｃｍ－１钯量在０－２．２５μｇ／１０μＬ范围内符合比耳定律本法应用于催化剂中痕量钯的测定，结果满意     

三环己基锡O，O＇－二（4－氯苯基）二硫代磷酸酯和二丁基锡双［O，O＇－二（4－甲基苯基）二硫代磷酸酯］的分子和晶体结构

三环己基锡Ｏ，Ｏ＇－二（４－氯苯基）二硫代磷酸酯（Ⅰ），Ｃ＿（３０）Ｈ＿（４１）Ｃｌ＿２Ｏ＿２ＰＳ＿２Ｓｎ，Ｍ＿ｒ＝７１８．３６，单斜晶系，Ｐ２＿１／ｎ，ａ＝１６．１５１（２），ｂ＝９．４１５（１），ｃ＝２２．９８７（３），β＝１０５．６９（１）°，Ｚ＝４，Ｄｃ＝１．４１８ｇ·ｃｍ￣（－３），Ｒ＝０．０６３；二丁基锡双［Ｏ，Ｏ＇－二（４－甲基苯基）二硫代磷酸酯］（Ⅱ），Ｃ＿（３６）Ｈ＿（４６）Ｏ＿４Ｐ＿２Ｓ＿４Ｓｎ，Ｍ＿ｒ＝８５１．６６，单斜晶系，Ｐ２＿１／ｃ，ａ＝１２．２８４（４），ｂ＝９．８０７（１），ｃ＝３４．４７１（８），β＝９９．０２（２）°，Ｚ＝４，Ｄ＿ｃ＝１．３７９ｇ·ｃｍ（－３），Ｒ＝０．０４２。化合物Ⅰ具有单分子的四配位变形四面体结构。其Ｓｎ－Ｓ（１）键长为２．５０１（２）；而Ｓｎ与Ｓ（２）的原子间距则为３．５９７；化合物Ⅱ具有单分子的六配位变形八面体结构，其Ｓｎ－Ｓ（１），Ｓｎ－Ｓ（２），Ｓｎ－Ｓ（３）和Ｓｎ－Ｓ（４）的键长分别为２．４９５（３），２．４９３（２），３．２４４（４）和３．２２８（３）。     

二价铕中性芳烃配合物［Eu（C_6Me_6）（AlCl_4）_2_4·Me_4

首次合成了二价铕中性芳烃配合物［Ｅｕ（Ｃ６Ｍｅ６（ＡｌＣｌ４）２］·Ｍｅ４Ｃ６Ｈ２，并经红外光谱，激发光谱和荧光光谱表征，测定了晶体结构。配合物属单斜晶系，Ｐ２／ｃ空间群，晶胞参数ａ＝１．７６５２（４）ｎｍ，ｂ＝１．５９１８（４）ｎｍ，ｃ＝１．８７５２（５）ｎｍ；β＝９７．６１（５）°，Ｚ＝２，Ｒ＝０．０４９６，Ｒｗ＝０．０４６２。     

磷酸锡盐的水热合成及其表征

用水热合成出系列化合物ＭＳｎ２（ＰＯ４）３（Ｍ＝Ｎａ，Ｋ，ＮＨ４），该化合物具有ＮＡＳＩＣＯＮ型三维骨架结构，测得其晶胞参数为：（１）ＮａＳｎ２（ＰＯ４）３，ａ＝０．８５２６９２）ｎｍ，ｃ＝２．２４７（４）ｎｍ；（２）ＫＳｎ２（ＰＯ４）３，ａ＝０．８３６６（１）ｎｍ，ｃ＝２．３５６（４）ｎｍ；（３）ＮＨ４Ｓｎ２（ＰＯ４）３，ａ＝０＼８３３０（１）ｎｍ，ｃ＝２＼３９０（５）ｎｍ．热分析结果表明，在较     

NH4ZnPO4的非水合成与晶体结构

从非水体系中制得ＮＨ４ＺｎＰＯ４单晶，并用Ｘ线测定了晶体结构；晶体属六方晶系，Ｐ６３空间群，晶胞参数；ａ＝１．０６８８（２）ｎｍ，ｃ＝８７０６（２）ｎｍ，Ｚ＝８，Ｄｃ＝２．７５１ｇ．ｃｍ＾－３，结构中的锌和磷均为四面体本位，且严格交替排列，无Ｚｎ－Ｏ－Ｚｎ和Ｐ－Ｏ－Ｐ联结方式。     

三环己基锡O,O‘—二（4—氯苯基）—二硫代磷酯酯和二丁基锡双（O,O’—二…

三环己基锡Ｏ，Ｏ’－二（４－氯苯基）二硫代磷酸酯（Ｉ），Ｃ３０Ｈ４１Ｃｌ２（Ｏ２ＰＳ２Ｓｎ，Ｍｒ＝７１８．３６，单斜晶系，Ｐ２１／ｎ，ａ＝１６．１５１（２），ｂ＝９．４１５９（１），ｃ＝２２．９８７（３），Ａ，β＝１０５．６９（１）°，Ｚ＝４，Ｄｃ＝１．４１８ｇ．ｃｍ＾－３，Ｒ＝０．０６３；二丁基锡双（Ｏ，Ｏ’－二（４－甲基苯基）二硫代磷酯酯（Ⅱ），Ｃ３６Ｈ４６Ｏ４Ｐ２Ｓ４Ｓｎ，Ｍｒ＝８５１．６６     

Effects of Base for the Efficient Synthesis of 4-Formylcoumarins and 4-Formylcarbostyrils

The first efficient transformation of 4-bromomethylcoumarins and 4-bromomethylcarbostyrils to 4-formylcoumarins and 4-formylcarbostyril under aqueous conditions has been achieved by modifying the Kornblum method, resulting in excellent yield. The experimental method is very simple and economical; no further purification is required and the experimental conditions have been optimized. All the isolated compounds were characterized by infrared, NMR, and mass spectroscopy, and some of the compounds have been analyzed by single-crystal x-ray analysis.     

合成2-芳基-3-烷基-7-硝基-1,4-氧硫杂萘-4,4-二氧化物的新方法

在K₂CO₃－TEBA－DNIF体系中,2－(2-氧-4-硝基苯磺酰基)－1-芳基乙酮与各种烷基化试剂发生烷基化-环化反应,得到一系列3-位取代的1,4-氧硫杂萘4,4-二氧化物,并讨论了反应机理和反应条件.     

溶胶-凝胶法合成Li_4SiO_4

Li4SiO4具有有利于离子传导的结构,为锂离子导体理想的基质材料[1].在硅酸盐体系中,硅的聚合态很复杂,难以得到纯相,鉴于固相法操作简单,在已有的文献中,合成方法多为固相法,但固相法不易保证成份的准确性、均匀性且合成温度较高.溶胶-凝胶法是近几年来发展起来的湿化学合成方法,用此法合成离子导体具有纯度高、均匀性好、颗粒小、反应过程易于控制等优点[2],而通常的溶胶-凝胶法是用金属醇盐与有机盐为前驱物,这样成本较高,且易造成污染.本文用金属醇盐及无机盐为前驱物,用溶胶-凝胶法合成了Li4SiO4纯相,并同一般固相法相比较,对合成的…     

Experimental and statistical validation of HPLC analysis of hydroquinone and its 4-methoxyphenol, 4-ethoxyphenol and 4-benzyloxyphenol ethers in cosmetic products

Summary The isocratic HPLC analysis of hydroquinone and its derived ethers in cosmetic preparations, as described in the sixth Directive 95/32/EC of the European Commission, was investigated with a view to determining the fundamental validation parameters of the technique. The calibration lines are highly linear with coefficients of determination >0.9996; the slopes of the calibration equations as well as the slopes normalised to the standard deviations indicate increased sensitivities for all compounds. The method is very reproducible; both the repeatability and the intermediate precision confirm a system performance of <2% variation; the limits of repeatability and intermediate precision are consistently <6% for every compound studied. The detection limits correspond to concentrations of 0.03 and 0.02% (m:m) for hydroquinone and the derived ethers, respectively. Application of the response factor calculation gives reliable results and signifies a practical and economic advantage when compared to laborious calibration with several replicate standard injections. Comparison of the response factor and calibration techniques did not reveal significant differences. The obviously insufficiently efficient extraction preceding chromatographic analysis might constitute the only drawback of the method, especially when the concentrations applied border the allowable.     

NH4VO3在NH4H2PO4-H2O和(NH4)3PO4-H2O体系中的溶解度

采用等温溶解法测定了偏钒酸铵(NH₄VO₃)在NH₄H₂PO₄-H₂O和(NH₄)₃PO₄-H₂O体系中T = 298.15-328.15 K时的溶解度以及溶液的密度和pH值。结果表明, NH₄VO₃的溶解度随着(NH₄)₃PO₄或NH₄H₂PO₄溶液浓度的增大,先降低后升高,这是由于同离子效应、化学反应平衡及离子活度的共同作用。比较T = 298.15K时, NH₄VO₃分别在NH₄H₂PO₄-H₂O、(NH₄)₂HPO₄-H₂O和(NH₄)₃PO₄-H₂O体系中溶解度,发现在相同的磷酸盐浓度下, NH₄VO₃的溶解度在NH₄H₂PO₄-H₂O体系中最大,在(NH₄)₃PO₄-H₂O体系中居中,在(NH₄)₂HPO₄-H₂O体系中最小。进一步地,在T = 298.15 K和磷酸盐浓度C = 0.5 mol·kg^-1时,结合pH值和反应溶度积常数K_SP等计算三个体系中的平均离子活度系数(γ_±),发现γ_±值在(NH₄)₂HPO₄-H₂O体系中最大,在(NH₄)₃PO₄-H₂O体系中居中,在NH₄H₂PO₄-H₂O体系中最小,与溶解度规律一致。     

Stabilization Studies on Divalent Five‐Membered Rings C4H4C,C4H4Si,C4H4Ge,C4H4Sn,and C4H4Pb

Energy differences, ΔX_S‐t (X = E, H and G) (ΔX_S‐t = X_(singlet)‐X_(triplet)) between singlet (s) and triplet (t) states are calculated at B3LYP/6‐311++G (3df,2p). The DFT calculations show that the triplet state of C₄H₄C is a ground state with planar conformer respect to its corresponding nonplanar singlet state. Both singlet and triplet states of C₄H₄M (M = Si, Ge, Sn and Pb) have a planar conformer with the singlet ground state. Four isodesmic reactions are presented for determining the stability energies, SE. NICS calculations are carried out for C₄H₄M to determine the aromatic character.     

Facile Synthesis of 4-Oxo-4H-quinolizine-2-carboxamide Derivatives

A facile synthetic method for the construction of 2-substituted-4-oxo-4H-quinolizine-based core structure has been successfully developed. The synthesis made use of a one-pot Stobbe condensation followed by cyclization starting from the commercially available 2-pyridinecarbaldehyde. The structure of the formed 4-oxo-4H-quinolizine-2-carboxylate was fully confirmed by mass spectra, ¹H NMR and ¹³C NMR, correlation spectrography, heteronuclear multiple bond correlation, and heteronuclear single quantum coherence (HSQC) spectra. The ethyl carboxylate moiety was then further functionalized via direct aminolysis by a range of amines to afford the corresponding 4-oxo-4H-quinolizine-2-carboxamides 4a–i in moderate to good yields.     

Synthesis of 1,3,5-trisubstituted 1,2,4-triazolio-4-nitroimides

A method for the synthesis of 1,3,5-trisubstituted 1,2,4-triazolio-4-nitroimides was developed. The method is based on the alkylation of the corresponding salts of 3,5-disubstituted 4-nitramino-1,2,4-triazoles.     

NH4BF4改性Y沸石的结构和性质

用NH₄BF₄溶液处理普通的Y沸石后,得到了一系列不含B的脱铝Y沸石。本文运用多种实验手段对它们进行了表征,并与其它改性方法得到的脱铝Y沸石进行比较,发现这类Y沸石脱铝羟基空穴较少,晶格热稳定性较高,且具有特殊的表面酸性分布,因而NH₄BF₄处理亦是一种有特色的Y沸石改性方法。     

Esterification and Chemoselective Synthesis of R-Tetrahydrothiazo-2- thione-4-carboxylic Esters Catalyzed by TiCl4

A series of esters of R-tetrahydrothiazo-2-thione-4-carboxylic acid[R-TTCA] was synthesized by direct esterification of R-TTCA with alcohols(CH3OH,C2H5OH,n-C3H7OH,i-C3H7OH,n-C4H9OH,sec-C4H9OH)in the presence of TiCl4 as the catalyst at room temperature without using any other solvent or dehydrant in high yields,91.6%-99.1% for primary alcohols and 55%- 80% for secondary alcohols.The catalyst has a strong chemoselective activity for the esterification of primary alcohols with R-TTCA in the presence of secondary alcohols.Owing to high yield,high chemoselectivity,and mild conditions used,this is an efficient method for the esterification of primary alcohols with R-TTCA.