从蓖麻油制取10-羟基癸酸的研究

本文报道了从蓖麻油制取10-羟基癸酸的研究,发现了从蓖麻油制取10-羟基癸酸的新的工艺路线和最佳的工艺条件,用氢氧化钠用量、2-辛醇量、反应时间和反应温度四因子三水平L_9(3~4)进行了正交试验,发现最佳工艺条件是:氢氧化钠(g)/蓖麻油(g):1.25:2-辛醇量(g)/蓖麻油(g):2:反应时间:6h;反应温度:180℃。在这一新的工艺路线和最佳工艺条件下,10-羟基癸酸产率可达75％。     

锡—邻菲咯啉络合物吸附极谱波的研究及应用

研究了锡－邻菲咯啉体系的极谱行为，在ｐＨ＝２．５０的０．１０ｍｏｌ／Ｌ氯乙酸－氯乙酸钠介质中，在单扫描极谱上，Ｓｎ－邻菲咯啉络合物于－０．４１Ｖ电位处产生一良好的吸附还原波。波高与Ｓｎ的浓度在２．０×１０＾－８－４．０×１０＾－６ｍｏｌ／Ｌ范围内呈线性关系；检出限为１．０×１０＾－８ｍｏｌ／Ｌ Ｓｎ，对合金标样中的锡进行测定，取得了满意的结果。     

苯乙烯基噻吩单体及对应的聚脲烷的合成 及其非线性光学性能

一种新型的反式-7-［4-N,N-二(β-羟基乙基胺基苯)］-3,5-二硝基乙烯基-噻吩（HBDT）单体分子及对应的预聚物和聚脲烷被合成和表征.由于噻吩环的电子去局域化能量低于苯环,在受授有机共轭化合物中噻吩环比苯环表现出更有效的共轭和更高的非线性,同时也能使目标分子保持好的光、热稳定性.该单体分子及其对应的聚脲烷在普通有机溶剂中具有良好的可溶性,聚脲烷膜具有好的热稳定性.制备了高质量的聚脲烷膜并进行了电晕极化.单体在甲醇中的紫外可见吸收峰（530nm）与对应未经电晕极化聚脲烷膜的吸收峰基本上没有改变.通过溶剂变色法及简并四波混频（DFWM）法测试了单体的二阶和三阶非线性极化率,其β     

镧系四元混合阴离子配合物[Ln(CCl3COO)2(CH3COO)(Phen)(H2O)]2的合成与晶体结构

在水乙醇溶液中合成了３ 种四元混合阴离子配合物, 用元素分析、ＩＲ、ＵＶ 及单晶Ｘ射线衍射进行了表征。［Ｌａ（ＣＣｌ３ＣＯＯ）２（ＣＨ３ＣＯＯ）（Ｐｈｅｎ）（Ｈ２Ｏ）］２·２ＤＭＦ 晶体属三斜晶系, Ｐ１ 空间群, 晶胞参数：ａ＝ １－２５１０（４） ｎｍ , ｂ＝ １－３４６０（５） ｎｍ , ｃ ＝ １－０３４３（３） ｎｍ , α＝ １０２－４７（３）°, β＝ １０２－３４（２）°, γ＝ １１３－８２（２）°, μ（ＭｏＫα） ＝ ２０．４７ ｃｍ －１ , Ｚ＝ １, Ｄｃ＝ １－８００ ｇ·ｃｍ － ３ , Ｆ（０００） ＝ ７８０－００。稀土配合物中醋酸根以桥联方式配位, 三氯醋酸根则有２ 种配位方式, 在二者共同参与配位的体系中呈现出丰富的配位模式。     

A new Far-Infrared Fourier Spectrometer

Summary This article describes a new commercial Far-Infrared Fourier Spectrometer system which has been developed for routine spectroscopy in the 10–1000 cm^–1 spectral region. The instrument incorporates real-time data processing and has been automated wherever possible for foolproof operation. A versatile sample chamber allows a wide range of spectroscopic studies to be performed, on solids, liquids and gases over a wide range of temperatures. A number of spectra are presented to illustrate the performance and typical applications of this Fourier spectrometer.

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Ein neues fourier-spektrometer für das ferne infrarot

Zusammenfassung Nach einer kurzen Einführung in die Methode der Fourier-Spektroskopie wird ein neues kommerzielles Fern-Infrarot-Fourier-Spektrometer mit real-time Datenverarbeitungsanlage beschrieben. Das Gerät ist für die Spektroskopie im Bereich 10–1000 cm^–1 konstruiert und weitgehend automatisiert. Eine vielseitig verwendbare Probenkammer ermöglicht umfangreiche spektroskopische Untersuchungen von Festkörpern, Flüssigkeiten und Gasen in einem sehr großen Temperaturbereich. Anhand einer Reihe von Spektren werden Leistung und typische Anwendungen dieses Fourier-Spektrometers erläutert.

Lecture presented at Euroanalysis I Conference, 28. 8.–1. 9. 1972 in Heidelberg, Germany.     

High speed liquid chromatography with small bore columns

Using a specially designed column system, we have systematically investigated the effect of mobile phase velocity on column efficiency. The performance of small bore columns operated at different linear velocities of mobile phase was examined for three different types of injection system. Using the value of H^∞/u or n^∞/t${}_{\text{r}}^{\text{º}}$ as a criterion of a high speed separation, we calculated values of n/t${}_{\text{r}}^{\text{º}}$ for different solutes according to the equation \documentclass{article}\pagestyle{empty}\begin{document}$ {{\rm n}\mathord{\left/ {\vphantom {{\rm n} {{\rm t}_{\rm r}^ \circ }}}\right. \kern-\nulldelimiterspace} {{\rm t}_{\rm r}^ \circ }} = {{{\rm n}^\infty } \mathord{\left/ {\vphantom {{{\rm n}^\infty } {{\rm t}_{\rm r}^ \circ }}} \right. \kern-\nulldelimiterspace} {{\rm t}_{\rm r}^ \circ }}\left({\frac{{1 + {\rm k'}}}{{{\rm k' + }\beta }}} \right)^2 $\end{document}; the results obtained are in agreement with the experimentally determined values. These systematic investigations culminated in the separation of seven compounds in less than 10 s; the respective chromatogram is shown.     

Stereochemistry of planarchiral compounds,part X

2,7-Dibromo-1,6-methano[10]anulene (3) and 2,9-Dibromo-syn-1,6:8,13-diimino[14]anulene (9) were quantitatively separated into their enantiomers by chromatography on triacetylcellulose (TAC) in ethanol. X-ray structure analysis (Bijvoet technique) established the chiralities (+)(R)-3 and (+)(S)-9 for the dextrorotatory enantiomers.Comparison of the CD spectra allowed the configurational assignment to further optically active [10] and [14] anulenes which were also accessible by chromatography onTAC. Conversion of (+)(R)-2-bromo-1,6-methano[10]anulene (2) into the corresponding methylester (–)-4 confirmed its previously proposed chirality (–)(R).2,7-Dibromo-1,6-oxido[10]anulene (7) and 2,9-dibromo-syn-diimino[14]anulene (9) are in contrast to the 2,9-dibromo-syn-dioxido[14]anulene (10) optically stable until 250°C. Consequently their inversion barriers are higher than 42 kcal (176 kJ) mol^–1.The CD spectra of mono and disubstituted anulenes (with C₁ and C₂ symmetry, resp.) are compared: For the [10]anulenes theCotton effect around 330 nm seems to be specific for their configuration with a positive effect indicating (S)-chirality and vice versa. Some regularities concerning the chromatographic resolutions are discussed.

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Stereochemie planar chialer Verbindungen, 10. Mitt.: Röntgenkristallstruktur und absolute Chiralität überbrückter [10]- und [14] Anulene

Zusammenfassung 2,7-Dibrom-1,6-methano[10]anulen (3) und 2,9-Dibrom-syn-1,6:8,13-diimino[14]anulen (9) wurden durch Chromatographie an Triacetylcellulose (TAC) in Ethanol quantitativ in ihre Enantiomeren getrennt. Röntgenstruktur-analyse (Bijvoet-Technik) bewies für die rechtsdrehenden Enantiomeren die Chiralität (+)(R)-3 bzw. (+)(S)-9.Ein Vergleich der CD-Spektren ermöglichte die Konfigurationszuordnung weiterer optisch aktiver [10]- und [14]Anulene, die gleichfalls durch Chromato-graphie anTAC erhalten worden waren. Umwandlung von (+)(R)-2-Brom-1,6-methano[10]anulen (2) in den entsprechenden Methylester (–)-4 bestätigte dessen schon früher vorgeschlagene Chiralität (–)(R).Dibrom-1,6-oxido[10]anulen (7) und Dibrom-diimino[14]anulen (9) sind im Gegensatz zum Dioxido[14]anulen (10) bis 250°C optisch stabil. Ihre Inver-sionsbarrieren liegen somit über 42 kcal (176kJ) mol^–1.Die CD-Spektren von mono- und disubstituierten Anulenen (mit C₁ bzw. C₂-Symmetrie) werden verglichen: Für die [10]Anulene scheint derCottoneffekt um 330 nm konfigurationsspezifisch zu sein, wobei ein positiver Effekt (S)-Chiralität anzeigt — und vice versa. Einige Regelmäßigkeiten bezüglich der chromatographischen Enantiomerentrennung werden diskutiert.

     

TLC of steroids VII. Comparative TLC properties of hydroxy-estrones,hydroxy-estradiols and their synthetic intermediates

Thin-layer Chromatographic behavior of 22 steroids were compared in five systems of different compositions and polarities. Some of the steroids studied are new: mainly aromatic steroid derivatives substituted with hydroxy on carbon-2 or carbon-4, or both carbon-2 and carbon-4 of the aromatic ring: from a biological point of view they are of importance as metabolic intermediates.     

大环二萜类化合物的研究(Ⅳ)——Isosarcophytol—A前体化合物的合成

Isosarcophytol-A(1)是1982年首次从澳大利亚软珊瑚(Nephthea brassica)中分离鉴定的西松烷型(Cembrane)大环二萜类化合物,其结构为6,10,14-三甲基-3-异丙基-3E,5E,9E,13E-环十四碳四烯-1-醇,是Sarcophytol—A(2)的异构体,但有关1的生物活性试验和全合成研究尚未见报道.我们在前文报道了以低价钛诱导的分子内二羰基偶联为环化方法,完成了天然大环二萜类化合物Cembrene—C的全合成和Sarcophytol—A(2)苄醚衍生物(3)的合成.本文报道以天然法呢醇4为起始原料,经区域选择性氧化、羟醛缩合等六步反应,合成了1的前体化合物11.合成路线如下:     

Syntheses,crystal structures and photophysical properties of d10 transition-metal (Ag+, Cu+, Cd2+ and Zn2+) coordination complexes based on a thiophene-containing heterocyclic thioamide

Four d¹⁰ transition-metal coordination complexes 1–4 (1: [Ag₂(TPT)₂(TPTH)₂]; 2: [Cu₆(TPT)₆]·2DMF; 3: [Cd(TPT)₂(TPTH)]·CH₃CH₂OH, 4: [Zn(TPT)₂]_n) have been constructed from a newly designed heterocyclic thioamide ligand, TPTH (TPTH = 4-(thiophen-2-yl)-pyrimidine-2-thiol). All complexes have been structurally elucidated by single crystal X-ray diffraction analyses. Except for 4, which shows a one-dimensional (1-D) chain structure, 1–3 are all discrete coordination complexes featuring dinuclear, hexanuclear and mononuclear entities, respectively. Their photophysical properties have been evaluated in the solid state at room temperature by UV–vis diffuse reflectance and luminescence spectra. Among them, 2 exhibits a strong red luminescence (λ_em = 699 nm) with a remarkable red-shift of the maximum emission compared to that of the TPTH ligand (λ_em = 536 nm). The red emission observed with 2 is ascribed to a LMCT (ligand-to-metal charge transfer) transition which agrees with the DFT calculations.