设计非线性光学材料的新思路:质子转移增强光学非线性

从酸的电子给体HO-C₆H₄-CHCH-C₆H₄-NO₂(OSN)可以向碱的电子受体Me₂N-C₆H₄-CHCH-C₅H₄N(DAMS)发生质子转移,质子转移后形成的相应离子与其中性分子相比,光学非线性增强.采用ZINDO-SOS,FF/PM₃及CPHF/PM₃三种方法对其进行了系统的理论研究.三种方法研究结果均表明,质子转移后所产生的离子和相应的中性分子相比,其第一超极化率β和第二超极化率γ-都显著增强.     

硼化合物的研究(Ⅳ)——硼烷阴离子铵盐的合成与性质

通过硼烷阴离子网-B₃H₈^-和闭-B₁₀H₁₀^2-与一系列卤化铵反应合成出十五种新的硼烷阴离子铵盐。这些新化合物均经元素分析和红外光谱鉴定。它们的差热分析结果表明:B₁₀H₁₀^2-铵盐的热稳定性高于B₃H₈^-铵盐;在季铵离子中导入氨基以后,化合物的热稳定性降低,并且导入的氨基愈多,化合物愈不稳定。     

Etude des reactions de srn1—partie 10 : Action de sulfanions sur les halogenures d''aryle fonctionnalises. synthese directe de benzothiophenes et thienopyridines

Functionalized aromatic halides Ar₁XY (Ar₁ = C₆H₄, Y = OCH₃, CONH₂, CN, COCH₃, CHO, COC₆H₅) undergo S_RN1 reactions with sulphur anions ^-SR, either simple (R=C₂H₅, CH₂C₆H₅) or functionalized (R = (CH₂)₂OH, (CH₂)₂CO₂Et, CH₂CO₂Et). Products Ar₁YS^- formed from the fragmentation of the radical anion Ar₁YSR^- are related to the redox potential of the aryl moiety Ar₁Y and with the energy of the bond S-R. In the heterocyclic series (Ar₂ = pyridine, Ar₃ = quinoline) a similar relationship appears but a competitive S_N(Ar) reaction occurs for pyridine substrates bearing an electron withdrawing group. A direct synthesis of benzothiophen via S_RN1 reaction and an improved synthesis of thienopyridines based on the S_N(Ar) reaction are reported.     

Coupled Hartree-Fock calculations of the electric dipole polarizability and first hyperpolarizability of some “inorganic benzenes”

Extended basis sets of gaussian functions were used to calculate near Hartree-Fock estimates of the electric dipole polarizabilities, , and first hyperpolarizabilities, β, of the “inorganic benzenes” B₃N₃H₆, B₃O₃H₃, B₃P₃H₃ and Al₃N₃H₆. Assuming that electron delocalization is responsible for the enhanced polarizabilities of aromatic systems, an aromaticity scale can be set up according to the trend of theoretical polarizabilities obtained in this work, i.e. (B₃O₃H₃) < (B₃N₃H₆ ) < (C₆H₆ ), which is consistent with previous calculations of the degree of delocalization in these compounds.     

Studies on the synthesis and structural characterization of cyclomercurated ferrocenylimines containing heterocyclic ring

The cyclomercurated ferrocenylimines containing heterocyclic ring can be prepared by the cyclomercuration of acylferrocene, followed by the condensation of the resulting product with the appropriate heterocyclic amine. This procedure provides an efficient method for the synthesis of cyclomerucurated ferrocenylimines containing heterocyclic ring which is difficultly synthesized by the traditional method, i.e. imination and then cyclomercuration. A series of these compounds were synthesized by this new method and characterized. The X-ray crystal structure of [HgCl(η⁵-C₅H₃C(CH₃)=N-2-C₅H₃N-6-CH₃) Fe(η⁵-C₅H₅)] (3d) has been determined and the reaction mechanism was proposed.     

Systematische untersuchungen über das verhalten von organozinnverbindungen gegenüber flüssigem schwefeldioxid II. Reaktionen von arylstannanen mit flüssigem SO2

The behaviour of tetraarylstannanes, R₄Sn (R = C₆H₅CH₂, C₆H₅, o-, m-, p-CH₃C₆H₄), towards SO₂ under various conditions has now been studied in detail. Compared to aliphatic tetraorganostannanes, the variability of the reaction products is much less, so that in nearly all cases only disulfinates, R₂Sn(O₂SR)₂, are formed. The aromatic tin(IV) mono-, di- and tri-sulfinates are also obtained by metathetical reaction between the corresponding organotin halides and sodium sulfinates. A unique feature of triaryltin chlorides, R₃SnCl (R = C₆H₅, o-, m-, p-CH₃C₆H₄), is their disproportionation in liquid SO₂ leading to disulfinates, R₂Sn(O₂SR)₂, and dichlorides, R₂SnCl₂. (p-CH₃C₆H₄)₂SnCl₂, under more efficient conditions, also accepts SO₂ forming (p-CH₃C₆H₄SO₂)₂SnCl₂. The structural investigations of the newly prepared compounds are carried out on the basis of their IR and ¹H NMR spectra.     

Preparation and lithiation of tris(o-tolyldimethylsilyl)methane

The compound (o-MeC₆H₄Me₂Si)₃CH has been prepared and shown to be metallated slowly by MeLi in refluxing THF to give the lithium reagent (o-MeC₆H₄Me₂Si)₃CLi. This reacts with MeI to give (o-MeC₆H₄Me₂Si)₃CMe, but not with Me₂SiHCl nor with a range of other organosilicon halides.     

The Synthesis of Ferrocenyl Compounds with Nonlinear Optical Properties

There is currently considerable interest in the synthesis of new material with large second-order optical nonlinearities^[1-2]. Ferrocenyl derivatives that we synthesized should offer the nonlinear optical properties because they possess (-donor acceptor interactions and non-centrosymmetry. In these compounds, ferrocenyl moiety is strong donor and pyridinium moiety can provide low-lying (^* acceptor orbitals. Furthermore, these ferrocenyl compounds may also be used in preparation of self-assembled monolayers (SAMs)^[3] due to their long alkyl chain that can be anchored on metal oxide by carboxylic group. The synthesis of ferrocenyl derivatives is shown in Scheme 1.     

相转移催化下4-氯苯磺酰基乙酸异丙酯的烷基化反应

在有机合成中可用芳磺酰基作暂时性活化基团。芳磺酰基乙酸酯是具有活性亚甲基的弱酸性化合物。通常要在氢化钠、醇钠存在下才能起烷基化反应。Ono等曾报道4-甲苯磺酰基乙酸甲酯在DBu存在下进行烷基化反应,但反应时间长。近年来,相转移催化在有机反应中的应用受到重视,然而用固液相转移催化法使芳磺酰基乙酸酯起烷基化反应还未见报道。我们在K₂CO₃/DMF体系中,用TEBA作催化剂,研究了4-氯苯磺酰基乙酸异丙酯与不同类型卤代烃所起的烷基化反应。合成了尚未见报道的一或二烷基化产物。     

铜掺氧化锌多孔纳米棒的水热合成及其光催化性能

通过两步法合成铜掺杂的氧化锌纳米棒,通过X射线衍射（XRD）、扫描电子显微镜（FESEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）和紫外-可见（UV-Vis）分光光谱等技术对系列样品进行了表征,研究并探索了铜掺杂的氧化锌纳米棒光降解染料罗丹明B（RhB）和气体乙醛的催化活性。通过对多孔Cu掺杂ZnO纳米棒光催化分解乙醛进行了评价。多孔Cu掺杂ZnO纳米棒（CZ-5）光催化剂具有最高的催化分解乙醛的能力,比其它多孔Cu掺杂ZnO纳米棒具有很高的催化活性。多孔Cu掺杂ZnO纳米棒光催化剂在室温下在可见光（435 nm）下照射16 h,5.50×10^-4（φ,体积分数）的乙醛气体完全降解为二氧化碳（CO₂）。多孔铜掺杂的氧化锌纳米棒光催化剂的光催化性能的改善主要归因于铜和氧化锌纳米棒之间的协同作用。这种改进的光催化协同作用归因于Cu掺杂ZnO的可见光吸收的延伸和光生电子空穴对的抗重组。     

Ru3(CO)9(TPPTS)3催化的水/有机两相芳香硝基化合物CO选择性还原的研究

将水溶性膦/钌配合物Ru₃(CO)₉(TPPTS)₃(TPPTS:三苯基膦三-间磺酸钠)用于以CO为还原剂的水/有机两相芳香硝基化合物选择还原为芳胺的反应,发现相转移催化剂对反应有明显的促进作用,其中以添加十六烷基三甲基溴化铵(CTAB)的效果最好.以邻氯硝基苯为底物考察了相转移催化剂浓度、NaOH浓度、反应温度、压力等对反应转化率和选择性的影响.当反应条件为120℃,4MPa,3mol/LNaOH时,反应8h,邻氯硝基苯的转化率和邻氯苯胺的选择性均可达到99.9%.而且对含有羰基、氰基的芳香硝基化合物也有很高的活性和选择性.催化剂循环3次后,邻氯硝基苯的转化率和邻氯苯胺的收率仍可达到92%.     

Cyclooctatetraenide derivatives of divalent samarium

Owing to the lack of suitable precursor complexes and applicable synthetic methodology, few soluble divalent organosamarium compounds are known. Recently, a facile route to SmI₂(THF)₂ proceeding from the bulk metal powder and several organic halides has been described by Kagan & co-workers. We demonstrate herein that this material or the desolvated salt can be used directly in mathematical syntheses (as illustrated by the synthesis of insoluble Sm(C₈H₈) and the THF-soluble K₂Sm(C₈H₈)₂).     

Meerwein芳基化反应(Ⅰ)——N-乙烯基邻苯二甲酰亚胺的芳基化

Meerwein芳基化反应是在烯键上导入芳基的一种重要方法:ArN₂Cl+RCH=CHZ→ArCR=CHZ+ArCHRCHClZ化合物RCH=CHZ中Z为电子取代基时,反应容易进行,Z为OAc、OR时,也可以起芳基化反应,但烯胺(Z=NR₂)与芳基重氮盐作用,只得到偶联产物。烯胺与N,N-二烷基苯胺为插烯物(Vinglogs),由于氮原子上的未共电子对与π键共轭,使烯键或苯环碳原子上电子密度增加,容易起偶联反应。     

Synthesis of methyltrioxorhenium(VII) arylamine complexes and mono- and bis(ortho)-chelated arylaminorhenium(VII) trioxides

From the reaction of MeReO₃ with the neutral arylamine C₆H₅CH₂NMe₂ and the aryldiamine C₆H₄(CH₂NMe₂)₂−1,3, have been isolated in good yields the 1/1 adduct complex [MeReO₃ · C₆H₅CH₂NMe₂], 1, and the 2/1 adduct complex [(MeReO₃)₂ · C₆H₄(CH₂NMe₂)₂− 1,3], 2, respectively. The X-ray molecular structure of 2 shows that both rhenium centres have a trigonal bipyramidal geometry and in the axial positions of each rhenium centre are one of the NMe₂ units of the aryldiamine ligand and a methyl group. The mono(ortho)-chelated arylaminorhenium trioxide complex [ReO₃(C₆H₄CH₂NMe₂−2], 3, can be synthesized by a transmetallation reaction of ClReO₃ with [ZnC₆H₄CH₂NMe₂−2₂] in a 2:1 molar ratio. In a similar way the bis(ortho)-chelated arylaminorhenium trioxide complex [ReO₃C₆H₃(CH₂NMe₂)₂−2,6], 4, can be synthesized by addition of a mixture of [Li₂C₆H₃(CH₂NMe₂)₂−2,6₂] and ZnCl₂ to ClReO₃. Complexes 3 and 4 have been isolated as white solids in 66% and 81% yields respectively. The rhenium centre in complex 4 has a bicapped tetrahedral geometry in which the monoanionic C₆H₃(CH₂NMe₂)₂−2,6⁻ ligand is pseudo-facially bonded with a characteristic N1-Re-N2 angle of 107.7(3)°, a Re-C_ipso bond length of 2.112(11) Å and Re-N1 and Re-N2 bond lengths of 2.518(9) Å and 2.480(8) Å respectively.     

Synthesis and characterization of (C5H9C9H6)2Yb(THF)2(II) (1) and [(C5H9C5H4)2Yb(THF)]2O2 (2), and ring-opening polymerization of lactones with 1

Reaction of YbI₂ with two equivalents of cyclopentylindenyl lithium (C₅H₉C₉H₆Li) affords ytterbium(II) substituted indenyl complex (C₅H₉C₉H₆)₂Yb(THF)₂ (1) which shows high activity to ring-opening polymerization (ROP) of lactones. The reaction between YbI₂ and cyclopentylcyclopentadienyl sodium (C₅H₉C₅H₄Na) gives complex [(C₅H₉C₅H₄)₂Yb(THF)]₂O₂ (2) in the presence of a trace amount of O₂, the molecular structure of which comprises two (C₅H₉C₅H₄)₂Yb(THF) bridged by an asymmetric O₂ unit. The O₂ unit and ytterbium atoms define a plane that contains a C_i symmetry center.     

Fluorescent peptide sensor for the selective detection of Cu

A new fluorescent peptidyl chemosensor for Cu²⁺ ions with fluorescence resonance energy transfer (FRET) capabilities has been synthesized via Fmoc solid-phase peptide synthesis. The metal chelating unit, which is flanked by the fluorophores tryptophan (donor) and dansyl chloride (acceptor), consists of the amino acids glycine and aspartic acid (Gly-Gly-Asp-Gly-Gly-Asp-Gly-Gly-Asp-Gly-Gly-Asp-Gly-Gly). Coordination of the Cu²⁺ ions to the metal chelating unit results in fluorescent quenching of both the donor and acceptor fluorophores. Although it was determined that Cu²⁺ binding causes no change in FRET efficiency, emission and Cu²⁺-induced quenching of the acceptor dye can be used to monitor the concentration of the copper ions, with a detection limit of 32 μg L⁻¹. The sensor also demonstrated sensitivity, reversibility and selectivity towards Cu²⁺ in a transition metal matrix at pH 7.0.     

Spectres de rotation de la molécule de chlorobenzène : II. Variétés isotopiques multisubstituées et structure géométrique précise

In order to complete the r_s structure of chlorobenzene given in a preceding paper, a variety of isotopic species of this molecule were synthesized and their microwave spectra studied. This made twenty isotopic species available, enabling the determination of the geometrical parameters by a least squares method. Fitting only differences of moments of inertia either for monosubstituted species or to multiply substituted species gave the same result. They hardly differ from the r_o values and agree with the r_s values obtained by the Kraitchman equations. The resulting error limits were reduced, however.

The following structural parameters were obtained, C₁C₂ = 1.399 Å, C₂C₃ = 1.386 Å, C₃C₄ = 1.3976 Å, C₁Cl = 1.7248 Å, C₂H₂ = 1.080 Å, C₃H₃ = 1.081 Å, C₄H₄ = 1.081 Å, C₆C₁C₂ = 120° 16, C₁C₂C₃ = 119°78, C₂C₃C₄ = 120°24, C₃C₄C₅ = 119°80, C₁C₂H₂ = 119°45, C₂C₃H₃ = 119°76.

The structure of the ring differs significantly from C₆ symmetry. The deformation can be regarded as a compression of the position C₁ while the angle of C₂H₂ bond is also changed.     

Studies on Nucleosides(Ⅵ)-Stereoselective Synthesis of Triazoline-thione NuCleosides

A series of heterocyclic compounds of triazole thione substituted by tetrazole(I)were prepared using nicotinic acid as starting material through several steps.They reacted with 1-O-trifluoroacety1-2,3,5-O-tri-benxoyl-β-D-ribofuranose(Ⅱ) inanhydrous CH₂Cl₂ at room temperature in the presence of BF₃·Et₂O to give nine new nucleosides, named as 3-[5-(3-pyridyl)-tetrazol-2-yl-methylene]-4-aryl,2,4-triazole-5-(4H)-thione-2, 3, 5-O-tribenwyl-β-D-ribo-furanoside(Ⅲ)(Ar=C₆H₅,o-MeC₆H₄,m-MeC₆H₄,p-MeC₆H₄,o-MeC₆H₄,p-MeC₆H₄,p-EtOC₆H₃,3,4-Me₂C₆H₄,a-C₁₀H₇).The structures and compositions were characterized by means of elemental analysis and spectroscopic methods.     

A “vertex electron pair” scheme (VEPS) for describing the skeletal electron distribution in borane-type clusters

A predominantly localized electron pair scheme is outlined for describing the electron distribution and bonding in closo borane anions B_nH_n²⁻ and related electron deficient deltahedral clusters, in which a skeletal electron pair is assigned to each vertex, one pair being regarded as delocalized just inside the roughly spherical surface on which the skeletal atoms lie. The scheme gives a clearer picture of the electron distribution than is conveyed by resonating 2- and 3-centre bonds in the polyhedron edges and faces, and allows the bond orders of the polyhedron edge links to be calculated readily. The consequence of formal removal of BH²⁺ units from closo species B_nH_n²⁻ to generate nido species B_n−1H_n−1⁴⁻ and arachno species B_n−2H_n−2⁶⁻ is explored, and seen to allow rationalization of two features of such deltahedral-fragment clusters: (i) why a high-connectivity vertex is left vacant and (ii) why the frontier orbitals of such species concentrate electronic charge around their open faces. Moreover, in the case of D_4‘h B₄H₄⁶⁻ (cf. C₄H₄²⁻) and D_5h B₅H₅⁶⁻ (cf. C₅H₅⁻), the approach leads directly to the familiar picture for aromatic ring systems in which the highest filled, doubly degenerate π-bonding molecular orbital concentrates electronic charge in rings above and below the polygon on which the skeletal nuclei lie. It also leads to the expectation that arachno clusters with non-adjacent vacant vertices will be more stable than those with adjacent vacant vertices.     

SYNTHESIS OF AMPHIPATHIC PORPHYRINS AND THEIR PHOTOINDUCED ELECTRON TRANSFER REACTIONS AT THE LIPID BILAYER-WATER INTERFACE

A one flask synthesis of cis -substituted amphipathic porphyrins is reported. These porphyrins were used to study electrostatic effects on photoinduced electron transfer across the lipid bilayer-water interface. A neutral porphyrin undergoes only dynamic interfacial electron transfer reactions irrespective of charge of the acceptor, although ionic strength effects indicate a negative charge on the porphyrin donor species. A dianionic porphyrin forms an interfacial static complex with a dicationic electron acceptor, methyl viologen, at low ionic strength. The electron transfer rate within the complex is slow, 10⁵∼ 10⁶ s^-1, which is attributed to a near orthogonal orientation between the donor and the acceptor ∼ orbitals.