过氧化物模拟酶生物传感器—二茂铁衍生物为介体

本文用三种二茂铁衍生物－双羟基乙基二茂铁、单羟基乙基二茂铁和羧基二茂铁为介体，在过氧化物模拟酶－ｍｅｓｏ－四（４－磺基苯）卟啉锰存在下，检测过氧化氢，以双羟基，单羟基乙基二茂铁为介体时，获得了良好的结果。     

聚乙二醇(PEG)桥连的新型双N-杂环卡宾-膦的合成及其在水相Suzuki反应中的应用

通过乙酸1-(2-二苯膦基二茂铁基)乙基酯与PEG-400衍生的双咪唑化合物反应,制得新型PEG桥连的双咪唑盐-膦配体,其结构经1HNMR,<31>PNMR和MS鉴定.初步催化研究表明,该PEG桥连的双咪唑盐一膦可作为支持配体在有机和水相中高产率地实现Pd催化的溴代芳烃和苯硼酸的Suzuki偶联反应.     

新型非对称1,1＇-双取代咪唑二茂铁的合成

以二茂铁为原料,通过Friedel-Crafts烷基化反应、Vilsmeier-Haack反应等合成了12个新型1-取代咪唑二茂铁与非对称1,1’-双取代咪唑二茂铁,其结构经1H NMR,IR和ESI-MS表征。     

新型1,1-双二茂铁基丁烷衍生物的合成

1,1-双二茂铁基丁烷和乙酸酐经Friedel-Crafts酰基化反应得6-乙酰基-1,1-双二茂铁基丁烷(2);2经LiAlH4还原得6-α-羟乙基-1,1-双二茂铁基丁烷(3);3经消除反应合成了6-乙烯基-1,1-双二茂铁基丁烷(4)。2~4为新化合物,其结构经1H NMR,IR,MS和元素分析表征。     

含二茂铁核的硅有机衍生物的合成

合成了一系列含二茂铁核的硅有机衍生物.试图从环戊二烯基三甲基硅烷与FeCl₂在二乙胺存在下制取1,1'-双(三甲基硅烷基)二茂铁,由于Si-C键的断裂,未获预期产物而得二茂铁. 为了合成双有机硅基二茂铁,采用了两种方法.方法之一是从1,1'-二茂铁二钠与相应的三烷基氯硅烷反应制得1,1'-双(三甲基硅烷基)二茂铁、1,1'-双(三丁基硅烷基)二茂铁和1,1'-双(二甲基苯基硅烷基)二茂铁.为了取得单取代硅烷基二茂铁,采用二茂铁锂,但一般得单和双取代衍生物的混合物,它们很难分离;如减少有机氯硅烷用量,则可得纯的单取代乙烯基二乙基硅烷基二茂铁.另一方法是将三甲基-γ-氯丙基硅烷的格氏试剂与二乙酰基二茂铁反应制得含二茂铁核的双叔醇.     

螯合物(FcCOCHCOCH3)2Cu与(FcCOCHCOCH3)3Fe的合成及其燃烧催化活性

含有铁、铬、铜等过渡元素的一些化合物,如铁的氧化物、铜的亚铬酸盐、二茂铁及其衍生物等都可作为复合固体推进剂的燃速催化剂.在二茂铁衍生物中主要是烷基衍生物,如叔丁基二茂铁、正辛基二茂铁、γ-二茂铁丁酸丁酯以及1,7-二(二茂铁基)庚烷、2,2-双(乙基二茂铁基)丙烷等.上述催化剂的变化趋势是由单二茂铁基向双二茂铁基发展,     

新型1,1′-双(4,5-二烷基)咪唑二茂铁的合成及其晶体结构

1,1′-二茂铁二甲醛与烷基二酮反应合成了3种新型的1,1′-双(4,5-二烷基咪唑)二茂铁,其结构经1HNMR,13C NMR,IR,ESI-MS及元素分析表征。1,1′-双(4,5-二苯基咪唑)二茂铁醋酸盐(1a′)的晶体结构经X-射线单晶衍射表征。1a′的晶体结构显示二茂铁的两个取代咪唑通过与醋酸的氢键作用形成顺式构型,探讨了顺式构型与反式构型的转化条件。1a′属单钭晶系,C2/c空间群,晶胞参数:a=15.832(4),b=19.255(4),c=14.781(4),β=121.837(3)°,V=3828.0(15)3,Z=4,F(000)=1 687,Dc=1.395 g.cm-3,Mr=804.07。     

乙基二茂铁与乙酰丙酸甲酯的缩合反应

以多聚磷酸-浓硫酸-甲醇为催化剂和环已烷为溶剂,由乙基二茂铁与乙酰丙酸甲酯缩合合成4,4-双（乙基二茂铁基）成酸甲酯,转化率73%,产率84%。正交实验法获得的适宜反应条件：乙基二茂铁55mmol,乙酰丙酸甲酯75mmol,浓硫酸3.0mL,环已烷20mL,甲醇11mL。通过元素分析、IR、^1H NMR和^13C NMR确证了缩合产物的结构。     

N-烷基双二茂铁甲胺类化合物的合成研究

双二茂铁甲醇、2，1′二乙基双二藏铁甲醇和3，1′－二乙基双二茂铁甲醇与BF3在CH2C12中作用，形成相应的双二茂铁甲基碳正离子。无需从反应混合物中分离出来，该离子与乙胺、丙胺以及丁胺分别反应得到了9种标题化合物。研究了化合物的物性与其结构的关系；研究了反应物质的量比对反应的影响。通过元素分析、IR和^1HNMR确证了化合物的结构。     

三苯基氧膦和三氟磺酸酐参与的二茂铁咪唑啉合成

二茂铁咪唑啉可以有效地从二茂铁羧酸出发合成．二茂铁羧酸和乙二胺衍生物反应制得的二茂铁酰胺，在三苯基氧膦和三氟磺酸酐所形成的锛盐作用下有效地脱水得到二茂铁咪唑啉化合物．该反应条件温和、反应快、产率高，为二茂铁咪唑啉化合物提供了一个有效的合成方法．     

Helic[6]arene-Based Chiral Pseudo[1]rotaxanes and [1]Rotaxanes

Chiral pseudo[1]rotaxanes and [1]rotaxanes constructed from macrocyclic arenes still remain a big challenge mainly owing to the lack of such chiral macrocycles. In this work, a new system of chiral pseudo[1]rotaxanes formed by self-inclusion of helic[6]arene containing amide linked with the terminal tertiary amines was first discovered. Based on an atom-economic stopping strategy, a pair of chiral [1]rotaxanes were conveniently obtained in almost quantitative yields by blocking the pseudo[1]rotaxanes with monobenzyl bromide of tetraphenylethene. The structures of pseudo[1]rotaxanes and [1]rotaxanes were characterized by 2D NMR spectra in solution, combined with DFT calculations. The photophysical properties further revealed the efficient chirality transfer of helic[6]arene to the tetraphenylethene moiety, compared to their unthreaded chiral isomers. The discovery of the chiral pseudo[1]rotaxanes allows for a wide and available synthesis of chiral [1]rotaxanes, and also opening a new avenue to the design of chiral supramolecular materials.     

The synthesis of [1]benzothieno[2,3-c]quinolines, [1]benzothieno[2,3-c][1,2,4]triazolo[4,3-a]quinoline,and [1]benzothieno[2,3-c]tetrazolo[1,5-a]quinoline

Photocyclization of 3-chloro-N-phenylbenzo[b]thiophene-2-carboxamide 10 afforded [1]benzothieno[2,3-c]-quinolin-6(5H)-one 11 which was chlorinated to 6-chloro[1]benzothieno[2,3-c]quinoline 12 followed by dechlorination to give [1]benzothieno[2,3-c]quinoline 5 . A series of 6-substituted alkoxy and thioalkoxy[1]benzothieno[2,3-c]quinoline derivatives were prepared along with the N-methyl quaternary salt 13 of 5 . 6-Chloro[1]-benzothieno[2,3-c]quinoline 12 was converted into 6-hydrazino[1]benzothieno[2,3-c]quinoline 23 which upon treatment with formic acid yielded [1]benzothieno[2,3-c][1,2,4]triazolo[4,3-a]quinoline 6 . Treatment of 23 with nitrous acid resulted in [1]benzothieno[2,3-c]tetrazolo[1,5-a]quinoline 7 . Compounds 6 and 7 are novel heterocyclic ring systems.     

Selenium heterocycles. XXXII . Synthesis of [1]benzoxepino[3,4-d]-thiazole, [1]benzothiepino[3,4-d]thiazole, [1]benzoxepino[3,4-d]selenazole,and [1]benzothiepino[3,4-d]selenazole. four novel heterocycles

Starting from the readily available ethyl 2-phenyl-4-methyl-thiazole-5-carboxylate (III), 2-phenyl-4-chloromethyl-thiazole (VIII) and 2-aryl-4-chloromethylselenazole (XIV), 2-phenyl-4,10-dihydro-10-oxo-[1]benzoxepino[3,4-d]thiazole (Ia), 2-phenyl-4,10-dihydro-10-oxo[1]benzothiepino[3,4-d]thiazole (Ib), 2-aryl-4,10-dihydro-10-oxo[1]benzoxepino[3,4-d]selenazoles (IIa-IIe) and 2-aryl-4,10-dihydro-10-oxo[1]benzothiepino[3,4-d]selenazoles (IIf-IIj) were prepared.     

Synthesis of 1-azacycl[3.2.2]azine and 1-azabenzo[h]cycl[3.2.2]azine

1-Azacycl[3.2.2]azines were synthesized from 2-methylthioimidazo[1,2-a]pyridines, 2a and 2b , by using [2 + 8] cycloaddition reaction with dimethyl acetylenedicarboxylate as the key step. Synthesis of 1-azabenzo-[h]cycl[3.2.2]azine was also described.     

Synthesis and total 1H-NMR assignment of [1]benzothieno-[2,3-c] [1,10]phenanthroline

The synthesis of [1]benzothieno[2,3-c][1,10]phenanthroline ( 5 ) is described. It was obtained in four steps from known starting materials. The basic skeleton of the molecule and of the phenanthroline ring were formed via photocyclization. The total assignment of ¹H-nmr spectra was accomplished with the aid of two-dimensional nmr methods.     

Chemistry of 1,2,3-thiadiazole. IV. Synthesis of [1]benzoxepino-[3,4-d][1,2,3]thiadiazole, [1]benzothiepino-[3,4-d][1,2,3]thiadiazole, [1]benzoxepino[4,3-d][1,2,3]thiadiazole, [1]benzoxepino[4,3-d]oxazole and [1]benzoxepino[4,3-d]oxazole. Four novel heterocycles

Starting from the readily available 4-bromomethy-5-carbethoxy 1,2,3-thiadiazole (V), 5-bromomethy-4-carbethoxy-1,2,3-thiadiazole (IX) and ethyl 2-aryl-5-bromomethyloxazole-4-carboxylate (XIV), 4,10-dihydro-10-oxo[1]benzoxepino[3,4-d][1,2,3]thiadiazole (Ia), 4,10-dihydro-10-oxo[1]benzothiepino[3,4-d][1,2,3]thiadiazole (Ib), 4,10-dihydro-4-oxo[1]benzothiepino[4,3-d] [1,2,3]thiazole (II), 2-aryl-4,10-dihydro-4-oxo[1]benzoxepino[4,3-d]oxazoles (XIXa-XIXc) and 2-aryl-4,10-dihydro-4-oxo[1]benzothiepino[4,3-d]oxazoles (XIXd-XIXf) were prepared.     

A comparative study on the synthesis of the 1H[1]benzothieno[2,3-d]-imidazole and 1H[1]benzothieno[2,3-d]-v-triazole

Alternate routes for the synthesis of the new title compounds are described. The experimental procedure for the isolation of the unstable 2,3-diaminobenzo[b]thiophene as the dichloride salt is presented.     

Mass spectrometric investigation of some [1]benzopyrano[3,4-c]pyrazole and [1]benzopyrano[4,3-d]isoxazole derivatives

The fragmentation behaviour of some [1]benzopyrano[3,4-c]pyrazole and [1]benzopyrano[4,3-d]isoxazole derivatives under electron impact is described.