双环[2,2,1]庚-5-烯-2-甲氧,甲酰氧基二茂钛的合成和催化性能

二氯二茂钛可与醇、酚、酸等反应生成相应的烃氧基或酰氧基二茂钛。当钛一氧键中氧的未共用电子与π键发生共轭,或与氧相连的取代基上带有强吸电子基团时,这类化合物较稳定,所以近年来合成了一系列芳氧基和一些卤素取代的酰氧基二茂钛,二氯二茂钛及其衍生物,能引发某些烯类的聚合。     

直接合成三烷氧基硅烷铜系催化剂的研究现状

三烷氧基硅烷(HSi(OR)3)既含有可水解的Si-OR键,又具有活泼的Si-H键.其中,Si-OR键通过水解缩合可转化成聚硅氧烷,与格氏试剂反应可生成烷氧基硅烷;Si-H键在铂系催化剂作用下,可与一系列含不饱和基的化合物发生氢硅化加成反应,得到各种碳官能硅烷、硅氧烷及硅基改性有机聚合物[1     

邻苯二甲酸异丙酯酰氧基-丙烯酰氧基-乙酰乙酸乙酯络铝及其聚合物的合成与荧光性质

通过异丙氧基铝和邻苯二甲酸酐、乙酰乙酸乙酯及丙烯酸反应,合成了螯合物单体邻苯二甲酸异丙酯酰氧基-丙烯酰氧基-乙酰乙酸乙酯络铝,由自由基聚合法合成了聚合物,用元素分析仪、VPO、IR、¹HNMR和²⁷AlNMR证实了它们的结构,并研究了它们在DMF中的荧光性质。     

金属有机化合物的分析 Ⅲ、双(烷基环戊二烯基)二芳氧基钛、锆、铪的薄层色谱研究

双环戊二烯基钛、锆、铪化合物的研究工作,近年来取得了迅速的进展。我国科学工作者合成了一系列双环戊二烯基二芳氧基钛、锆、铪化合物。目前,这类化合物的催化特性和抗癌作用已引起有关方面的重视,因此,它们的分离分析工作亟需进行。关于双环戊二烯基钛、锆、铪衍生物的薄层色谱工作,仅Howarth 研究了(C_5H_5)_2TiCl_2及C_5H_5TiCl_3二化合物的分离;谢珍珍报导了双环戊二烯基二芳氧基钛、     

新型单茂钛催化剂乙烯均聚反应合成支化聚乙烯

单茂钛化合物Ｃｐ′ＴｉＬ3(Ｃｐ′为 η5 环戊二烯基或取代 η5 环戊二烯基 ;Ｌ为卤素、氢、烃基、烃氧基等 )和甲基铝氧烷 (ＭＡＯ)组成的催化剂催化苯乙烯聚合 ,表现出非常高的催化活性和间规立构选择性[1～ 3] .这类催化剂也可用于丙烯、丁烯等α 烯烃聚合 ,合成无规或立构嵌段聚合物[4～ 6] ;但用单茂钛 /ＭＡＯ催化剂进行乙烯均聚合研究[7] 较少 .本文报道用三甲基铝 (ＴＭＡ)含量不同的改性ＭＡＯ(ｍＭＡＯ)作助化催剂激活 1 ,2 ,3,4,5 五甲基茂基三苄氧基钛 [Ｃｐ Ｔｉ(ＯＢｚ) 3]催化乙烯均聚合 ,对聚合产物结构性能进行表征 ;发现…     

侧链对聚对苯撑乙炔溶解性和光谱性能的影响

利用钯催化反应合成了一类侧链含不同烷氧取代基(甲氧基，辛烷氧基，十二烷氧基)的聚时苯撑乙炔，讨论了侧链烷氧取代基对聚对苯撑乙炔的分子量和溶解性的影响，比较了聚合物的紫外吸收光谱和荧光光谱特征。     

不对称苯并菲盘状液晶的合成及取代基对介晶性的影响

合成了一系列新型含间位二硝基苯甲酸酯不对称苯并菲盘状液晶化合物2-(3,5-二硝基苯甲酰氧基)-3,6,7,10,11-五烷氧基苯并菲(3a～3f). 通过偏光显微镜(POM)和差示扫描量热计(DSC)对其介晶性进行了研究. 结果显示: 此类化合物有高的清亮点, 稳定的六方柱状相以及较宽的介晶相范围, 且随着软链碳原子数的增加, 化合物的熔点和清亮点均出现下降趋势, 但六方柱状相的有序性却没有发生很明显的变化. 同时通过与其它三类苯并菲盘状液晶2-苯甲酰氧基-3,6,7,10,11-五烷氧基苯并菲(4a～4f), 2-二茂铁甲酰氧基-3,6,7,10,11-五烷氧基苯并菲(5a～5f), 2,3,6,7,10,11-六烷氧基苯并菲(6a～6f)的对比研究, 探讨了酯基, 强吸电子基团, 以及取代官能团体积对介晶性的影响. 证实了苯并菲化合物中分子结构小的变化将引起介晶性大的改变.     

耐热聚合物

耐热聚合物取得日益增长的重要意义。本文综述了能耐约550℃的无机或“半”无机聚合物方面的新工作。具有氧架的化合物含铝化合物 W.C.吴茲(Woods)曾描述过具有氧架和适当的侧基的聚合物。聚铝氧烷可以认为是氧化铝的一种变型:     

双环戊二烯基二芳氧基钛的酸解反应

本文研究了双环戊二烯基二芳氧基钛于氢卤酸中的酸解反应。证明反应是分步进行的。因反应条件不同可得到二次酸解产物--双环戊二烯基二卤化钛或一次酸解产物--双环戊二烯基芳氧基卤化钛。对影响反应的诸因素进行了讨论。通过上述酸解反应合成了一系列新的双环戊二烯基芳氧基卤化钛,收率较高。由双环戊二烯基芳氧基卤化钛开始,又合成了几个新的Cp₂Ti(OAr)Ar＇及Cp₂Ti(OAr)(OAr＇)类型衍生物。     

双(取代苯酰氧基)二茂钛衍生物的质谱分析

二茂钛类衍生物具有催化抗肿瘤活性,因而引起人们的研究兴趣。我们曾探讨了一系列双(取代苯酰氧基)二茂钛衍生物、含茂钛聚合物的合成、光谱、质谱及其反应性。本文报道有关衍生物的质谱分析,并讨论其规律性。     

Chemical studies of marine invertebrates—XI : Sinulariolide,a new cembranolide diterpene from the soft coral Sinularia flexibilis (coelenterata,octocorallia, alcyonacea)

Sinulariolide, a novel diterpene lactone has been isolated from the alcyonarian Sinularia flexibilis. Its structure [1] has been determined by using spectroscopic and chemical methods. Its relative and absolute configuration was established by X-ray diffraction as depicted in 10.     

Synthesis and characterization of the Keggin-type ruthenium-nitrido derivative [PW11O39{RuN}]4- and evidence of its electrophilic reactivity

The ruthenium-nitrido POM derivative [PW11O39{RuVIN}]4- has been synthesized by reaction between [PW11O39]7- and [RuVINCl5]2- or [RuVINCl4]-. Its molecular structure has been confirmed from multinuclear 31P and 183W NMR spectroscopy together with an EXAFS study, while the oxidation state of the ruthenium bearing the nitrido ligand has been inferred both from 183W NMR and XANES analysis at the Ru-K edge. The potential of [PW11O39{RuVIN}]4- in N-atom transfer reactions has been demonstrated through reaction with triphenylphosphine, which ultimately leads to the release of the bis(triphenylphosphane)iminium cation [PPh3=N=PPh3]+ through several intermediates, among which the phosphoraniminato derivative [PW11O39{RuVNPh3}]3- has been structurally characterized. Its unusual oxidation state is in accordance with its EPR spectrum.     

Synthesis and Properties of A Novel Triphenylamine Derivative

A novel triphenylamine derivative of 4, 4‘-bis-[2-[4-[N,N-bis-(4-methoxyphenyl-amino)] phenyl-l-yl]-viny1-1-y1]-1, 1‘-biphenyl (DMPAVBI) was synthesized. The chemical structure was confirmed by IR, ^1H NMR spectroscopy and elemental analysis. Its properties were studied by UV-Vis spectroscopy, photoluminescence spectroscopy and cyclic voltammetry methods.     

Bimetallic cyanide-bridged complexes based on the photochromic nitroprusside anion and paramagnetic metal complexes. Syntheses, structures, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O, [Ni(en)2][Fe(CN)5NO]x3H2O, [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO], and [Mn(5-Brsalen)]2[Fe(CN)5NO

The synthesis, crystal structure, and physical characterization of the coordination compounds [Ni(en)2]4[Fe(CN)5NO]2[Fe(CN)6]x5H2O (1), [Ni(en)2][Fe(CN)5NO]x3H2O (2), [Mn(3-MeOsalen)(H2O)]2[Fe(CN)5NO] (3), and [Mn(5-Brsalen)]2[Fe(CN)5NO] (4) are presented. 1 crystallizes in the monoclinic space group P2(1)/n (a = 7.407(4) A, b = 28.963(6) A, c = 14.744(5) A, alpha = 90 degrees, beta = 103.26(4) degrees, gamma = 90 degrees, Z = 2). Its structure consists of branched linear chains formed by cis-[Ni(en)2]2+ cations and ferrocyanide and nitroprusside anions. The presence of two kinds of iron(II) sites has been demonstrated by M?ssbauer spectroscopy. 2 crystallizes in the monoclinic space group P2(1)/c (a = 11.076(3) A, b = 10.983(2) A, c = 17.018(5) A, alpha = 90 degrees, beta = 107.25(2) degrees, gamma = 90 degrees, Z = 4). Its structure consists of zigzag chains formed by an alternated array of cis-[Ni(en)2]2+ cations and nitroprusside anions. 3 crystallizes in the triclinic space group P1 (a = 8.896(5) A, b = 10.430(5) A, c = 12.699(5) A, alpha = 71.110(5) degrees, beta = 79.990(5) degrees, gamma = 89.470(5) degrees, Z = 1). Its structure comprises neutral trinuclear bimetallic complexes in which a central [Fe(CN)5NO]2- anion is linked to two [Mn(3-MeOsalen)]+ cations. 4 crystallizes in the tetragonal space group P4/ncc (a = 13.630(5) A, c = 21.420(8) A, Z = 4). Its structure shows an extended 2D neutral network formed by cyclic octameric [-Mn-NC-Fe-CN-]4 units. The magnetic properties of these compounds indicate the presence of quasi-isolated paramagnetic Ni2+ and Mn3+. Irradiated samples of the four compounds have been studied by differential scanning calorimetry to detect the existence of the long-lived metastable states of nitroprusside.     

Kinetics and Mechanism of Exothermic First-stage Decomposition Reaction for 2,6-Dinitro-4,8-bis(2,2,2-trinitroethyl)-2,4,6,8-tetra-azabicyclo[3.3.1] nonane-3,7-dionel

Introduction 2,6-Dinitro-4,8-bis(2,2,2-trinitroethyl)-2,4,6,8-tetraazabicyclo[3.3.1] nonane-3,7-dionel is a typical cyclourea nitramine. Its crystal density is 1.94 g/cm3. The detonation velocity corresponding to ρ=1.920 g/cm3 is about 8957 m/s. It has the potential application as high explosive due to the above-mentioned high performance. Its preparation[1], properties[1] and hydrolytic behavior[2] have been reported. In the present paper, we report its kinetic parameters and mechanism of the exothermic first-stage decomposition reaction studied with DSC, TG-DTG and IR.     

Cation-dependent binding of zinc diethoxycarbonylcalix[4]arenebis(porphyrinate) triethylenediamine

Zinc calix[4]arene-bis(porphyrinate) with two ethoxycarbonyl substituents at the lower rim of the calix[4]arene moiety was synthesized. Its complexation properties toward the sodium cation and triethylenediamine were studied. The influence of the binding of the sodium cation by the calix[4]arene moiety on the complexation properties of the interporphyrin cavity toward triethylenediamine was revealed.     

Cross-coupling of highly pyramidalized alkenes: A straightforward access to functionalized tetrasecododecahedradienes

The synthesis and chemical trapping of a highly pyramidalized pentacyclo[6.4.0.0(2,10).0(3,7).0(4,9)]dodec-8-ene containing ketal functions is reported. Its cross-coupling reaction with 3, 7-dimethyltricyclo[3.3.0.0(3,7)]oct-1(5)-ene followed by a [2 + 2] retrocycloaddition reaction gives a straightforward access to functionalized tetrasecododecahedradienes.     

Stereoselective Synthesis of Pillar[4]arene[1]cis‐diepoxy‐p‐dione and X‐Ray Crystal Structure of Host–Guest System

Herein, we successfully develop a novel route to give rise to polarity for the pillararenes by the introduction of oxygenated functionalities into pillar[5]arene to stereoselectively synthesize the pillar[4]arene[1]cis ‐diepoxy‐p ‐dione. Its host–guest properties with different dinitrile molecules were also investigated and characterized by NMR and X‐ray crystallography.     

Highly effective synthetic methods for substituted 2-arylbenzofurans using [3,3]-sigmatropic rearrangement: short syntheses of stemofuran a and eupomatenoid 6

A new and efficient synthesis of 2-arylbenzofurans has been achieved via a route involving acylation and subsequent [3,3]-sigmatropic rearrangement of oxime ethers. Its synthetic utility is demonstrated by a short synthesis of stemofuran A and eupomatenoid 6 in which no procedure for protection of the phenolic hydroxyl groups is needed. [reaction--see text]     

一种 Schiff碱类化合物的设计与合成及自组装膜模型的建立

采用巯其胺酰化法合成了自行设计的Schiff碱类巯基化合物4-[N-（2'-巯基乙基）]羧基酰胺-N-苯基苯甲亚胺，并对此化合物建立了自线装模型。