新型YS类高分子铑配合物催化甲醇羰基化反应制备乙酸和乙酐

以含有两种不同配位原子的线型或交联大孔球型共聚物为配体的新型铑配合物,能在温和条件下催化甲醇羰基化为乙酸和乙酐.实验结果表明,这些新型共聚物铑配合物具有鳌合型顺-二羰基铑(Ⅰ)的结构特征,并有良好的热稳定性及高的催化活性和选择性.     

顺二羰基铑（Ⅰ）共聚物催化剂的合成,结构与催化甲醇羰基化反应性能的研究

我们曾报道一系列含有两种不同配位基团的高分子共聚物与四羰基二氯二铑形成的顺二羰基铑(Ⅰ)配合物。这些配合物在催化甲醇羰基化反应中显示出高催化活性和高稳定性。本文采用4-乙烯吡啶(Y)和丙烯酸甲酯(B)共聚物为配体,对其与四羰基二氯二铑形成的配合物(YBRh)进行了表征。对该系列配合物催化甲醇羰基化生成乙酸的性能进行了评价。     

丙二酸锂-铑配合物的结构及催化性能研究

本文采用丙二酸锂为配体，与四羰基二氯二铑形成双齿配位的顺二羰基铑配合物，研究表明，在催化甲醇羰基化制乙酸的反应中，该配合物显示出高的活性和选择性。     

吡啶甲酸锂-铑(Ⅰ)配合物催化甲醇羰基化反应

本文采用吡啶甲酸或吡啶二甲酸锂盐为配体,与铑形成顺二羰基配合物,用于催化甲醇羰基化制乙酸。研究表明,与通常的铑配合物相比,该类双金属配合物无论在催化活性或乙酸生成的选择性方面均有明显的提高。     

顺二羰基2－丁酸甲酯基吡啶铑配合物的合成与性能

顺二羰基２－丁酸甲酯基吡啶铑配合物的合成与性能潘平来，柳忠阳，黄茂开，袁国卿（中国科学院化学研究所，北京１０００８０）含有不同配位基团的共聚物配体与铑形成的配合物，在催化甲醇碳基化制备乙酸和乙酐的反应中具有很高的活性和选择性￣［１１］。本文采用含有Ｎ...     

螯合型高分子铑配合物催化甲醇羰基化反应的机理探讨

螯合型高分子铑配合物催化甲醇羰基化反应的机理探讨潘平来，柳忠阳，王晓筠，黄茂开，袁国卿（中国科学院化学研究所，北京１０００８０）１引言甲醇在铑催化剂的作用下，与一氧化碳反应羰基化为乙酸，是一个重要的基本有机合成，反应。在为数众多的催化剂中，锗的配合物...     

2-(5-碘-2-吡啶偶氮)-5-二甲氨基苯胺的合成及其与铑(Ⅲ)的高灵敏显色反应的研究

合成了新显色剂2-(5-碘-2-吡啶偶氮)-5-二甲氨基苯胺(5-I-PADMA),并研究了其与铑(Ⅲ)的显色反应。结果表明,在pH4.0~6.2的乙酸-乙酸钠缓冲介质中,铑(Ⅲ)与5-I-PADMA可形成稳定的1∶2配合物,该配合物呈现2个吸收峰,分别位于557、597 nm处。配合物形成后,以适量HClO4(0.24~5.57 mol.L-1)酸化,可转变为另一种具有较高吸收特性的质子化形体,其吸收峰分别红移至564、613 nm处。表观摩尔吸光系数达ε613=1.86×105L.mol-1.cm-1,铑的质量浓度在0~0.56 mg.L-1范围内符合比尔定律。该法是目前测定痕量铑的高灵敏显色体系之一,且具有良好的选择性。所建立的方法操作简单,应用于催化剂中微量铑的测定,结果满意。     

新型三甲基乙酸铑(Ⅱ)轴向配合物的合成、结构表征及催化性能

羧酸铑(II)配合物是一类结构独特的同核双金属化合物，通常表现出较高的催化活性和选择性，中心金属铑、配体类型和空间结构都影响其催化性能。本文以三甲基乙酸铑(II)为母体，吡啶-2-基(吡啶-3-基)甲酮(23ma)和二吡啶-2-基甲酮(22ma)为轴向配体，设计合成了2种新型的三甲基乙酸铑(II)轴向配合物。通过¹H NMR、¹³C NMR、 MS、 IR和X-单晶射线衍射对其结构进行表征，并测试了配合物对美罗培南类合成反应的催化性能。结果表明：与母体分子三甲基乙酸铑(II)相比，所合成的轴向配合物在美罗培南类合成体系中因存在溶解性较差等缺点，导致其催化性能均不佳。     

2-乙烯吡啶-丙烯酸甲酯共聚物与四羰基二氯二铑反应所得配合物的结构与催化甲醇羰基化性能的研究

聚(2-乙烯吡啶—丙烯酸甲酯)共聚物与四羰基二氯二铑形成的配合物是一种催化甲醇羰基化的新型催化剂.本文用X-射线衍射(XRD),光电子能谱(XPS)和红外光谱(IR)对其键合状态进行了表征,并探索了其分子骨架结构与催化甲醇羰基化活性之间的关系.     

[顺—二羰基（N—2—（2—吡啶）乙基芳胺）铑]的四苯硼酸盐的合成及其催化…

〔顺－二羰基（Ｎ－２－（２－吡啶）乙基对取代苯胺）铑〕的四苯硼酸盐作为催化剂，用于催化甲醇羰基化反应，在温和的条件下，可顺利催化甲醇羰基化反就得到乙酸和乙酸甲酯而无其它副产物。若以甲醇和乙本乡的混合液作反应物，则得到乙酸酐和乙酸甲酯，即使在大量水存在下，也仅有微量的水煤气转换反应发生。实验证明对位取代基团的电子效应对铑配合物的催化活性影响甚微在不同位置以不同链长相联的二吡啶配体对铑阳离子配合物性能     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。