苯基取代的环戊二烯基锆化合物的合成及催化乙烯聚合

一系列苯基取代的环戊二烯配体在甲苯中相继与丁基锂及ZrCl4作用，生成相 应的苯基取代的茂金属化合物，通过^1H NMR，MS和元素分析表征了化合物的分子 结构，并研究了在MAO（甲基铝氧烷的助催化下，化合物对乙烯聚合的催化性能， 结果发现单苯基取代茂金属化合物的催化活性和产物聚乙聚的分子量都随聚合温度 的升高而增大。     

1,1'-(四甲基二硅撑)双[环戊二烯基三羰基钼配合物]的合成及结构

1,2-二环戊二烯基四甲基二硅烷与正丁基锂作用生成(四甲基二硅撑)双[环戊二烯基负离子盐],后者随即与六羰基钼反应即形成1,1'-(四 甲基二硅撑)双[环戊二烯基三羰基钼负离子盐],分别与四种不同的卤化物反应,生成在钼原子上发生烃基化的产物与冰醋酸作用,随即分别与CCl~4及NBS反应,生成相应的钼氯化物和钼溴化物作用发生氧化偶联反应,生成Mo-Mo键断裂的钼碘化物,以元素分析、IR及^1HNMR表征了2-9的结构.并对5的单晶进行了X射线衍射分析.它的晶体属三斜晶系,PI空间群,晶体学数据:偏差因子R=0.043,R~W=0.055.     

1,1'-(四甲基二硅撑)双[环戊二烯基三羰基钼配合物]的合成及结构

1,2-二环戊二烯基四甲基二硅烷与正丁基锂作用生成(四甲基二硅撑)双[环戊二烯基负离子盐],后者随即与六羰基钼反应即形成1,1'-(四 甲基二硅撑)双[环戊二烯基三羰基钼负离子盐],分别与四种不同的卤化物反应,生成在钼原子上发生烃基化的产物与冰醋酸作用,随即分别与CCl~4及NBS反应,生成相应的钼氯化物和钼溴化物作用发生氧化偶联反应,生成Mo-Mo键断裂的钼碘化物,以元素分析、IR及^1HNMR表征了2-9的结构.并对5的单晶进行了X射线衍射分析.它的晶体属三斜晶系,PI空间群,晶体学数据:偏差因子R=0.043,R~W=0.055.     

大取代茂钼化合物的合成与结构分析

利用芳基锂与6,6-二烷基富烯发生加成反应,制得大取代环戊二烯基负离子.用六羰基钼配位,合成出13个钼-钼双核及5个钼-卤素单核羰基化合物.研究了其IR、^1HNMR、^95MoNMR.测定了[(CH~3)~2C(m-CH~3C~6H~4]Mo(CO)~3Br(1)的晶体结构.该晶体属于单余晶系,晶胞参数为a=1.175(3),b=1.4196(2),c=1.1894(4)nm,β=118.03(2)°,Ⅴ=1.75134nm^3.Z=4,D~0=1.733g/cm^3,F(000)=904,μ=30.0cm^-1,R=0.039,R~W=0.050,空间群为P2~1/α.     

多(三甲硅基)取代环戊二烯基二羰基钼环卡宾配合物的合成和结构

三(三甲基硅基)环戊二烯在一缩二乙二醇二甲醚或四氢呋喃中经n-BuLi处理后, 随之与Mo(CO)6加热, 生成相应的环戊二烯基羰基钼负离子锂盐[η^5-{(Me3Si)3C5H5-n}Mo^-(CO)3]Li^+(n=2, 3)(1), 同时观察到有脱硅基现象发生。1与X(CH2)3X在一缩二乙二醇二甲醚中反应, 无论X=I或Br, 均生成标题化合物[X=I: n=3(2), n=2(3); X=Br: n=3(4), n=2(5)]。1与X(CH2)3X的反应如在THF中进行, 则只有当X=I时才能生成环卡宾钼配合物。以元素分析, IR, 1H NMR和13C NMR表征了2-5的结构, 并用X射线衍射测定了4的晶体结构。晶体属单斜晶系,空间群为P21/n, 晶胞参数a=1.2611(3), b=1.2434(2),c=1.7095(6)nm, β=91.07(2)°, V=2.680(2)nm^3,Dc=1.563g.cm^-^3, Z=4, 最终偏差因子R=0.062, Rw=0.054.     

大取代环戊二烯基铪的合成与结构分析

芳基锂与6, 6-二烷基富烯发生加成反应, 生成含或不含手性碳的大位阻取代环戊二烯基负离子。用四氯化铪配合物, 合成了19个大取代茂铪化合物。讨论了其^1H NMR。化合物[(CH3)2C(C6H4-p-CH3)-C5H4]HfCl2经X射线衍射分析。晶体为单斜晶系, 空间群为I2/a, 晶胞参数a=2.2263(7), b=0.6674(2), c=2.5379(9)nm,β=135.13(3)°, R=0.058, Rw=0.069。结构研究表明, 取代基的引入, 使得茂环发生变型, 最大扭曲角为8.45°。     

取代苯甲醛-N-芳氧乙酰腙类化合物的合成与表征

利用取代苯甲醛与芳氧基乙酰肼反应,合成了8个新的芳氧基乙酰脘类化合物,其结构经IR,^1HNMR和元素分析证实。     

6-羟基富烯及环戊二烯并[d]哒嗪的合成

本文以6, 6-二烷基富烯与烯丙基格氏试剂反应所得的取代环戊二烯基负离子与芳酰氯反应, 合成了5个新的6-羟基富烯化合物(1-5)。用此化合物与肼反应, 合成了5个新的环戊二烯并[d]哒嗪化合物(6-10)。通过^1H NMR、IR及元素分析确定了它们的结构。     

1,1'-(四甲基二硅氧撑)双[环戊二烯基羰基钼配合物]的合成及结构

以1,3-二环戊烯基四甲基二硅氧烷相继与n-BuLi及Mo(CO)~6反应生成1,1'-(四甲基二硅氧撑)双[环戊二烯基羰基钼负离子盐](I),I分别与多种卤化物反应生成在钼原子上引入其它基团的衍生物,(Me~2SiOSiMe~2)[C~5H~4Mo(CO)~3R]~2.以元素分析、IR及^1HNMR谱表征了这些化合物的结构,并对其中之一的单晶(R=1)进行了X射线衍射分析.晶体属单斜晶系,P2~1/n空间群,晶体学数据,a=0.8707(2),b=1.0746(4),c=2.9719(8)nm,β=91.18(2)°,Ⅴ=2.7799nm^3,z=4,D~c=2.09g.cm^-3.最终偏差因子R为0.067.     

β-三芳基锗和β-三(α-噻吩基)锗取代丙酸的合成

本文用β-三氯锗基取代丙酸为中间体合成了六个β-三芳基锗取代丙酸化合物,八个β-三(α-噻吩基)锗取代丙酸化合物, 所有化合物均经元素分析、IR、^1HNMR 证实了它们的组成和结构。另外还合成了十个未见文献报道的β-(N-芳基酰胺基)丙基锗倍半氧化物, 用元素分析和IR证实了它们的组成和结构。     

Organolithium Displacement of Aryl Anions from Tertiary Phosphine Derivatives of Diphenyl Ether

Abstract

Methyllithium displaces a phenyl anion from 10-phenyl-10H-phenoxaphosphine to produce a 70:30 mixture of 10-methyl-10H-phenoxaphosphine and starting phosphine. Butyllithium gives 50% conversion to 10-butyl-10H-phenoxaphosphine. These reactions could take place either by a one-step nucleophilic displacement or by ring cleavage followed by recyclization. To show the feasibility of the two-step process, non-heterocyclic lithiated tertiary phosphines were generated and shown to cyclize to phenoxaphosphines. For example, reaction of 2-phenoxyphenyldiphenylphosphine with phenyllithium produced 10-phenyl-10H-phenoxaphosphine (by lithiation ortho to oxygen followed by cyclization) along with triphenylphosphine (by direct displacement of 2-lithiodiphenyl ether). Other compounds prepared in this work: 2,2′-bis(diphenylphosphino)-diphenyl ether, bis(2-phenoxyphenyl)phenylphosphine, tris(2-phenoxyphenyl)phosphine, 4-carboxy-10-phenyl-10H-phenoxaphosphine, and the oxides and sulfides of the phosphines.     

Aroylation of n-alkylmethanimines. A synthesis of novel substituted 2-aza-buta-1,3-dienes.

The aroylation of carbanions derived from N-benzyl-diphenylmethanimine and N-(diphenylmethyl )-arylmethanimines yields highly substituted 2-aza-buta- 1,3-dienes in which the imino group is conjugated with an enol ester. A similar reaction with N-(diphenylmethyl)-diphenylmethylmethanimine qives the expected iminoketone.     

Palladium‐Catalyzed Decarboxylative ortho‐C(sp2)−H Aroylation of N‐Sulfoximine Benzamides at Room Temperature

A palladium‐catalyzed method for the decarboxylative ortho C?H acylation of N‐sulfoximine benzamides is developed at room temperature. The catalytic method enables easy access to various functionalized 2‐aroylaromatic carboxylic acid derivatives in good isolated yields. Based on our mechanistic studies, a Pd(II)/Pd(IV) catalytic cycle that involves aroyl radical intermediate is proposed for the reaction.     

Direct regioselective phenylation of acridine derivatives by phenyllithium

Acridine and acridine derivatives have been converted directly to phenyl derivatives regioselectively using phenyllithium.     

Acylation and Aroylation of 3-Phenylsydnone

Various 4-acyl or 4-aroyl sydnones 2 can be prepared in good to excellent yield by reaction of 4-(3-phenylsydnonyl) copper with the appropriate acid chlorides, both with or without palladium(0) catalysis.     

取代邻苯二腈的合成

在室温条件下合成了一系列芳氧基邻苯二腈化合物,应用无素分析、1HNMR、IR确定了它们的结构,讨论了不同取代基对反应的影响.结果表明,酚的芳环上有推电子基时反应容易进行;酚的芳环上有拉电子基时反应慢或不反应.     

Cyclisation of bisphosphonate substituted enynes

A new synthetic route to the bisphosphonate enyne tetraethyl hept-1-yn-6-en-4,4-diylbisphosphonate has been developed and the enyne has been used successfully in a range of transition metal-catalysed cyclisations that give structurally varied products. The motifs generated via such reactions provide new scaffolds for constructing bisphosphonic acids, an important class of therapeutic agents. NMR experiments indicate that the introduction of phosphonate substitutents onto cyclisation substrates provides a promising new approach to studying metal-catalysed cyclisations.     

Studies towards the total synthesis of mumbaistatin: synthesis of highly substituted benzophenone and anthraquinone building blocks

Model compounds and building blocks for a planned total synthesis of the highly potent glucose-6-phosphate (G6P) translocase inhibitor mumbaistatin (1) and structural analogs were elaborated: compound 1 represents a lead structure in the development of potential new antidiabetic drugs. With the model substrate 20 it was demonstrated that highly functionalized, tetra-ortho-substituted benzophenones can be prepared by nucleophilic addition of an aryllithium-building block to a benzaldehyde followed by oxidation. For compound 37, a potential precursor of the anthraquinone part of mumbaistatin, various approaches via aryne/phthalide annulations were developed and evaluated. The required functionalized arenes were prepared exploiting, among others, regioselective bromination and ortho-lithiation reactions. Coupling reactions of the anthracene-carbaldehyde 44 derived from 37 with various metalated arenes proved to be unexpectedly difficult and failed so far.     

Gas transport properties of substituted PEEKs

Tert-butyl and di-tert-butyl were added as pendant groups to the ether-ether phenyl ring of poly(ether ether ketone), PEEK. tert-butyl PEEK, TBPEEK, was amorphous and di-tert-butyl PEEK, DBPEEK, was semicrystalline. However, a 2 : 1 random copolymer of TBPEEK and DBPEEK, TBDBPEEK, was amorphous. Gas transport of N₂, O₂, CH₄, and CO₂ through amorphous films of PEEK, TBPEEK, TBDBPEEK, and tetramethylbiphenyl PEEK were determined at 35°C and at pressures to about 15 atm. The results support previous observations that tert-butyl and tetramethylbiphenyl groups are very effective in disrupting chain packing in the polymer. For the present polymers, these substitutions led to a 5–18-fold increase in permeability, and, in some cases, at no loss in permselectivity. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2355–2362, 1997