Studies on Epitaxial Polymerization of 1,3-Bis （3-quinolyl）- 1,4-butadiyne

During investigating what causes the low yield of the polymerization product of 1,4-bis (quinolyl)-1, 3-butadiyne (DQ), we found that the DQ crystals formed on the surface of PDQ cauld be polymerized to give blue crystals, in which DQ could be sublimated and crystallized on the surface of PDQ film. According to the experimental results, the reason why the DQ crystals can be polymerized is that the sublimation of DQ changes the molecular orientation of DQ in the crystal. The crystals formed in epitaxial growth on the surface of DQ or PDQ during sublimation of DQ are suitable for 1,4-addition polymerization.     

The synthesis and electrochemical behavior of 1,4-di-(2,5-dimethylazaferrocenyl)-1,3-butadiyne

Rigid-rod ferrocene capped alkynes have attracted a lot of attention recently. In this note we report an efficient synthesis of the 1,4-di-(2,5-dimethylazaferrocenyl)-1,3-butadiyne which is the first known azaferrocene capped diacetylene derivative. The cyclic voltammetry measurements at different scan rates and temperatures indicate good electronic communication between two iron centers. Better shaped reduction peaks at higher scan rates in 22 °C and −40 °C can point to increased stability of the monocation.     

Synthesis of an axially chiral Ir–NHC complex derived from BINAM

The Ir–NHC complex 6 was successfully synthesized from the reaction of axially chiral binaphthyl dibenzimidazolium salt 5 with [Ir(COD)Cl]₂ (COD = 1,5‐cyclooctadiene) in tetrahydrofuran in the presence of KO^tBu base under reflux. Its unique crystal structure is unambiguously disclosed by X‐ray diffraction. Complex 6 is orthorhombic, with space group P2₁2₁2₁, unit cell dimensions a = 12.1406(16) Å, b = 19.110(3) Å, c = 20.312(3) Å, α = β = γ = 90° and volume 4712.6(11) ų, Z = 4, D_calc = 1.930 Mg m^?3. Copyright © 2004 John Wiley & Sons, Ltd.     

基于二芳炔硫醚的2,6-二芳基-1,4-二噻烯的合成

描述了一种基于二芳炔硫醚(Ar—C≡C—S—C≡C—Ar)底物合成2,6-二芳基-1,4-二噻烯的方法.将二芳炔硫醚和Na2S·9H2O在C2H5OH/C2H5ONa体系中回流反应,以80%~96%的产率合成了一系列2,6-二芳基-1,4-二噻烯化合物.该方法反应条件温和、产率高并且表现出很好的选择性.反应机理涉及硫负离子对底物分子的两个C≡C键的选择性亲核加成,即硫负离子(包括S2-和中间体B硫负离子)总是选择性地加到芳基一侧的炔碳上形成1,4-二噻烯.对化合物1a进行了X线晶体结构解析.分子中的六元杂环呈"船式"构型.C(1)—C(2)和C(1A)—C(2A)具有典型的双键性质,S(1)—C(2)和S(2)—C(1)的键长数则比一般C—S单键稍短,显示硫原子上的孤对电子与C(1)=C(2)双键上的π电子存在一定程度的共轭作用.1a的晶体学参数:属正交晶系,Pnma空间群,a=10.1330(11),b=27.318(3),c=5.5402(6),α=90.00°,β=90.00°,γ=90.00°,V=1533.6(3)3,Z=4,ρcalcd=1.422 g/cm3.最终偏离因子R=0.038,Rw=0.102。     

Synthesis of chiral aza-bis(oxazolines) derived from (+)-camphor

Two novel chiral structurally azabis(oxazoline) ligands were synthesized using (+)-camphor as the starting material. Each of the ligands was prepared through the corresponding aminoalcohols. The structures of some crystalline derivatives were unambiguously established by X-ray analysis.     

(1S,3S)-1,3-二苯基-1,3-丙二胺的合成

以二氯甲烷作溶剂,N-Boc保护的二氢吡唑在六甲基磷酰胺存在下与苯基格氏试剂反应,比较大量地制备了对应的四氢吡唑(4);再由4合成消旋的1,3-二苯基-1,3-丙二胺(1,总收率35%);1经L-二苯甲酰酒石酸盐拆分制得光学纯的(1S,3S)-1,3-二苯基-1,3-丙二胺,其结构经1HNMR确证。     

N,N‘—1,4—亚丁基双[螺吲哚啉萘并恶嗪]的合成

在无水乙醇中，１－亚硝基－２萘酚同Ｎ，Ｎ＇－１，４－亚丁基双［２，３，３－三甲基－３Ｈ－吲哚］溴化物反应制得Ｎ，Ｎ＇－亚丁基双［螺吲哚啉萘并恶嗪］，经ＩＲ，ＵＶ，＾１ＨＮＭＲ和元素分析确认了结构，并对其光致变色性能进行了初步的考察。     

N，N＇－1，4－亚丁基双〔螺吲哚啉萘并噁嗪〕的合成

在无水乙醇中，１－亚硝基－２萘酚同Ｎ，Ｎ＇－１，４－亚丁基双［２，３，３－三甲基－３Ｈ－吲哚］溴化物反应制得Ｎ，Ｎ＇－亚丁基双［螺吲哚啉萘并嗪］，经ＩＲ，ＵＶ，￣１ＨＮＭＲ和元素分析确认了结构，并对其光致变色性能进行了初步的考察。     

“一锅法”简便合成1,4—双（2,4—二羟基苯基）—丁二酮—1,4

１，４－双（２，４－二羟基苯基）丁二酮－１，４－是Ｐｒａｋａｓｈ等从买麻藤属龈（ＧｅｎｅｈｕｍＵＬａ）中分离得到的一种微量组分。文中报道了以丁二腈和间苯二酚为原料，“一锅法”简便合成了此化合物。     

Synthesis of new electron-donor compounds: Bis(2-thia-1,3-propylenedithio)teterathiafulvalene and bis(2-oxo-1,3-propylenedithio)tetrathiafulvalene

1,3-Dithiole-2-thione derivatives, which are starting compounds for the synthesis of new electron donors of the tetrathiafulvalene class, viz., bis(2-thia-1,3-propylendithio)tetrathiafulvalene and bis(2-oxo-1,3-propylendithio)tetrathiafulvalene, were obtained by the reaction of bis(tetraalkylamonium) bis(1,3-dithiole-2-thione-4,5-dithiolato)zincates with 1,3-dichlorodimethyl sulfide and 1,3- dibromoacetone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 471–474, April, 1990.     

Synthesis and ferroelectric properties of new chiral liquid crystals derived from (S)-lactic acid with alkoxyethanols

A homologous series of chiral materials derived from (S)-lactic acid with alkoxyethanols has been synthesized and their mesomorphic properties investigated. The mesophases and their corresponding transition temperatures were identified by differential scanning calorimetry and polarizing optical microscopy. The spontaneous polarization and electro-optical response of ferroelectric SmC* phase are measured and reported.     

Impact on the mesophase transition temperatures of 1,4-bis(naphthyl)-1,3-butadiyne of the attachment of terminal alkoxy chains

The synthesis of 1,4-bis(2-naphthyl)-1,3-butadiynes, containing terminal alkoxy chains, is reported. The mesomorphism of these compounds has been characterized by differential scanning calorimetry and polarizing optical microscopy. The introduction of terminal alkoxy chains, significantly lowers the melting temperature of the analogous core without terminal chains. The induction of a smectic phase occurred when two decyloxy chains were attached. The solid state structures and packing arrangements of the butyloxy derivative and the chainless core were determined by single crystal X-ray diffraction, and revealed greater layer interpenetration for the substituted material.     

Synthesis of novel axially chiral Rh-NHC complexes derived from BINAM and application in the enantioselective hydrosilylation of methyl ketones

Novel axially chiral Rh N-heterocyclic carbene complexes were prepared from axially dissymmetric 1,1'-binaphthalenyl-2,2'-diamine and applied in the Rh-catalyzed enantioselective hydrosilylation of methyl ketones. The corresponding sec-alcohols can be obtained in high yields with good to excellent ee.     

A chiral, heterometallic metal-organic framework derived from a tris(chelate) coordination complex

A novel tris(chelate) metalloligand has been used to synthesize a chiral, heterometallic metal-organic framework that is robust to solvent removal and shows selective uptake of nitroaromatic compounds.