Optical Rotatory Feature of （R or S）—1,1’—Binaphthalene—2,2’—diol（BINOL）in various Solvents

The changes of the specific rotation and sign of optically active BINOL have been studied in polar/non-polar solvents and at the different pH values of solvent.It is considered that these changes are determined by the equilibriurn studies between cisoid and transoid conformations of BINOL with the same configuration(R or S) which related to the change of the dihedral angle between two naphthalene ring planes of BINOL.     

Copper(Ⅱ)and 1,1 '-Trimethylene-2,2'-biimidazole-promoted Arylation of Acetylacetone with Aryl Iodides

A new and efficient way was developed to carry out the reaction of acetylacetone with aryl iodides under the assistance of Cu(II) and 1,1′‐trimethylene‐2,2′‐biimidazole at 100°C. 3‐Aryl‐2,4‐pentanediones were obtained in excellent yields.     

Synthesis of Dinaphtho-dioxaphosphepin-4-oxides, Epoxides and Bisphosphonates

A few new seven-membered phosphorus heterocyclic compounds and bis-phosphonates (5a—5g, 5f’, 5g’, 9 and 10) were prepared by the reaction of 4-bromo dioxaphosphepin (2) with various Grignard reagents followed by their oxidation with H2O2. All the compounds were thoroughly characterized by elemental analysis, IR, 1H, 13C, 31P NMR and mass spectral data. Their antimicrobial activity was evaluated and some of them possess significant activity.     

双功能手性联萘酚配体在炔基锌对醛的不对称加成反应选择性能研究

单体2-溴吡啶, 2-溴-5-甲基吡啶, 2-氯-4-氟吡啶, 2-氯-3-三氟甲基吡啶分别与( R )-3,3′-二硼酸-2,2′-二甲氧基-1,1′-联萘 [( R )-2]在钯催化下, 通过Suzuki交叉耦合反应合成得到四个类似手性化合物( R )-3a-d。将它们应用到炔基锌对醛的不对称催化加成反应中,结果表明( R )-3a和( R )-3b的催化效果不好, 而( R )-3d只对脂肪醛有很好的催化效果,( R )-3c则对这类不对称催化反应均有很好的催化效果, 能给出高达95%的收率和99%的选择性结果。结果还表明所产生相应炔丙醇异构体构型为S,这与手性催化剂构型相反。     

Novel Chiral Aminophosphine Ligand:Synthesis and Application in Saymmetric Catalytic Hydrogenation Reaction

A new chiral aminophosphine ligand 6,6′-dimethoxy-2,2′-bis(diphenylphosphinoamino)biphenyl(DMBDPPABP) was prepared and its rhodium complex was found to be an effective catalyst for the asymmetric hydrogenation of amidoacrylic acid and its dervatives.The effects of solvent and reaction temperature on enantioselectivity were also studied.     

Chiral separation of 1,1'-bi-2-naphthol and its analogue on molecular imprinting monolithic columns by HPLC

Two molecular imprinting polymer (MIP) monolithic columns with (S)-(-)-1,1'-bi-2-naphthol and (R)-(+)-5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol as the templating molecules, respectively, have been prepared by in situ polymerization using 4-vinylpyridine and ethylene dimethacrylate as functional monomer and cross-linker, respectively. The columns with good flow-through properties were obtained by changing the molar ratio of the functional monomer and the template molecule. The effects of mobile-phase composition on separation of enantiomers were systematically investigated. The results indicate that hydrophobic interaction in aqueous solution and hydrogen-bonding interaction in ACN between the enantiomers and polymers could play important roles in the retention and resolution. The effects of chromatographic conditions, such as flow rate, column temperature, sample loading, on the enantioseparation were also studied. Further, these two MIP columns show a cross-reactivity.     

二价铜离子和联咪唑催化的酚与碘代芳烃的乌尔曼反应研究

Ullmann-type diaryl ether synthesis can be performed at 100 ℃ in good to excellent yields by aryl iodides as the substrates under the assistance of copper（Ⅱ） and 2,2＇-biimidazolyl.     

A Novel Cu(Ⅱ） Complex with 2,2′-Bipyridyl and L-Methioninate -synthesis,Characterization,Molecular Structure and Stability

The ternary Cu(II) complex with 2,2′‐bipyridyl (bipy) and L‐methioninate (L‐Met) has been synthesized and characterized by elemental analysis, molar conductivity, UV‐Vis spectra, IR spectra and pH‐potentiometric titration methods. The structure of the complex [Cu(L‐Met) (bipy) (H₂O)]ClO₄ · 3/8H₂O was characterized by the X‐ray diffraction analysis. It crystallizes in the triclinic system, space group P1 with four molecules in a unit cell of dimensions, a = 0.7656(2) nm, b = 1.3142(3) nm, c = 2.0596(4) nm, α = 97.70(3)°, β = 97.96(3)°, γ = 94.33(3)°, V= 2.0244(8) nm³, R₁, = 0.0441 and wR₂ = 0.0678. The crystal contains four crystllographically independent [Cu(L‐Met) (bipy) (H₂O)]⁺ complexes (Cu1—Cu4), having a distorted square‐pyramidal geometry with the same coordinated atoms around each copper center. The base plane is occupied by two nitrogen atoms of one bipy, the amino nitrogen atom and one carboxylate oxygen atom from each independent L‐Met moiety, and one water oxygen at an axial position. Cu1 and Cu3 are essentially enantiomers of Cu2 and Cu4. The four molecules are packed with each other by intermolecular hydrogen‐bonding and aromatic‐ring stacking interactions.     

Structures of 3,3′-dicarbometoxy-2,2′-bipyridine complexes with silver(I) and copper(II) cations

The structures of 3,3′-dicarbometoxy-2,2′-bipyridine (dcmbpy) complexes with copper(II) and silver(I) cations have been determined using single crystal X-ray-diffraction. The crystals of Cu(dcmbpy)Cl₂ are monoclinic, C2/c, a = 16.966(3), b = 18.373(3), c = 13.154(2) Å, β = 126.543(3)°. The crystals of Ag(dcmbpy)NO₃ · H₂O are also monoclinic, C2/c, a = 16.7547(13), b = 11.0922(9), c = 18.7789(18) Å, β = 100.228(7)°. The results have been compared with the literature data on the complexes of dcmbpy and its precursors: 2,2′-bipyridine (bpy) and 3,3′-dicarboxy-2,2′-bipyridine (dcbpy). Two types of complexes of 3,3′-carboxy derivatives of bpy are distinguished: (1) with metal atom bonded to two N atoms of the same molecule and (2) with metal atom bonded to two N atoms of two different molecules. The Cu(dcmbpy)Cl₂ complex belongs to the first type, whereas Ag(dcmbpy)NO₃ · H₂O belongs to the second type.     

A Novel Coordination Polymer, [Ag4^1 （bpdc）（H2bpdc）（Hbpdc）2]n （bpdc = 2,2＇-bipyridyl-3,3＇-dicarboxylate）： Coordination Models of bpdc Ligands

A novel coordination polymer, [Ag₄ppdc)(H₂bpdc)(Hbpdc)₂] (bpdc = 2,2′‐bipyridyl‐3,3′‐dicarboxylate), was hydrothermally synthesized at 403 K and structurally characterized by single crystal X‐ray diffraction analysis. The compound crystalizes in the monoclinic space group C2/c with a=1.9516(4) nm, b=1.9503(4) nm. c=1.2566(3) nm, and β=112.48(3)°. In the two‐dimensional crystal structure, Ag^I center is coordinated, in a scarce coordination environment, double‐capped tetrahedron, by one bpdc ligand to form N‐Ag‐N chelate bond via two pyridyl N atoms, and other two bpdc ligands to form two O‐Ag‐O chelate bonds, respectively, via two carboxyl O atoms. The bpdc ligands are present in one non‐protonated form, bpdc, and two protonated forms, Hbpdc and H2bpdc, which all act as μ3‐ligand in a hexadentate fashion (N, N′; O, O′; O, O′) to coordinate with three Ag centers, respectively, through the three chelate bonds. This coordinated fashion of bpdc ligand is first found in the title compound. W‐Us‐NIR reflectance spectroscopy study revealed insulator nature for the crystal with an optical energy gap of 3.1 eV.     

两个新颖的联环十二烷衍生物的合成及结构表征

2-（2＇-Oxo-3＇-oximidocyclododecyl） cyclododecanone （1） and 2-（1＇-hydroxylcyclododecyl） cyclododecanone （2） were synthesized and characterized. The conformation analysis was carried out based on the NMR, molecular mechanics calculation and X-ray diffraction. The conformation of two cyclododecyl moieties of both 1 and 2 was found to be the [3333]-2-one or [3333] square conformation both in the crystal state and the solution. The dihedral angle between carbonyl and the oxime double bond of the ring B is 180°in the crystal of 1. The protons or hydroxyl group of carbon atoms to link the two cyclododecyl moieties of 1 and 2 constitute dihedral angles of 174°in the crystal, and 175°in the solution, and the C-C 6 bond between two cyclododecyl moieties can not freely rotate in the solid state and the solution. In addition, compound 2 was the first example of a-comer-anti-monosubstituted cyclododecanone. synthesis     

Study of the Ion Channel Behavior of Didodecyldimethylammonium Bromide Formed Bilayer Lipid Membrane Stimulated by PF6

Bilayer lipid membranes(BLM) formed from didodecyldimethylammonium bromide were made on the freshly exposed surface of a galssy carbon(GC) and were demonstrated by the acimpedance spectroscopy.The ion channels of membrane properties induced by PF6^- were studied by the cyclic voltammetric methods.Experimental results indicated that the ion channel of BLM was open in the presence of the PF6^- due to the interaction of PF6^- with the BLM,while it was switched off in the absence of PF6^-.Because the ion channel behavior was affected by the concentration of PF6^-,a sersor for PF6^- can be developed.     

1H, 13C, 15N NMR coordination shifts in Fe(II), Ru(II) and Os(II) cationic complexes with 2,2':6',2″-terpyridine

(1)H, (13)C and (15)N NMR studies of iron(II), ruthenium(II) and osmium(II) bis-chelated cationic complexes with 2,2':6',2″-terpyridine ([M(terpy)(2) ](2+) ; M = Fe, Ru, Os) were performed. Significant shielding of nitrogen-adjacent H(6) and deshielding of H(3'), H(4') protons were observed, both effects being mostly expressed for Fe(II) compounds. The metal-bonded nitrogens were shielded, this effect being much larger for the outer N(1), N(1″) than the inner N(1') atoms, and enhanced in the Fe(II) → Ru(II) → Os(II) series.     

New Chiral Ligand N—Toluenesulfony1—2,2‘—dimethoxy—6,6’—di—aminobiphenyl for Catalytic Asymmetric Transfer Hydrogenation of Ketones

A new chiral ligand N‐p‐toluenesulfonyl‐2,2′‐dimethoxy‐6,6′‐diaminobiphenyl (Ts‐DMBDPPA) was prepared from 2,2′‐dimethoxy‐6,6′‐diaminobiphenyl via N‐tosylation. Its Ru(II) complex was effective catalysts for catalytic asymmetric transfer hydrogenation of aromatic ketones (with ee's up to 69.3%).     

Preparation and properties of aromatic polyamides from 2,2′-bis(p-carboxyphenoxy) biphenyl or 2,2′-bis(p-carboxyphenoxy)-1,1′-binaphthyl and aromatic diamines

New aromatic dicarboxylic acids having kink and crank structures, 2,2′-bis(p-carboxyphenoxy) biphenyl and 2,2′-bis(p-carboxyphenoxy)-1,1′-binaphthyl, were synthesized by the reaction of p-fluorobenzonitrile with biphenyl-2,2′-diol and 2,2′-dihydroxy-1,1′-binaphthyl, respectively, followed by hydrolysis. Biphenyl-2,2′-diyl-and 1,1′-binaphthyl-2,2′-diyl-containing aromatic polyamides having inherent viscosities of 0.58–1.46 dL/g and 0.63–1.30 dL/g, respectively, were obtained by the low-temperature solution polycondensation of the corresponding diacid chlorides with aromatic diamines. These polymers were readily soluble in a variety of organic solvents including N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, m-cresol, and pyridine. Transparent, pale yellow, and flexible films of these polymers could be cast from the DMAc or NMP solutions. These aromatic polyamides containing biphenyl and binaphthyl units had glass transition temperatures in the range of 210–272 and 260–315°C, respectively. They began to lose weight around 380°C, with 10% weight loss being recorded at about 450°C in air. © 1993 John Wiley & Sons, Inc.     

Preparation and properties of aromatic polyamides from 2,2′-bis(p-aminophenoxy) biphenyl or 2,2′-bis(p-aminophenoxy)-1,1′-binaphthyl and aromatic dicarboxylic acids

New aromatic diamines having kink and crank structures, 2,2′-bis(p-aminophenoxy)biphenyl and 2,2′-bis(p-aminophenoxy)-1,1′-binaphthyl, were synthesized by the reaction of p-fluoronitrobenzene with biphenyl-2,2′-diol and 2,2′-dihydroxy-1,1′-binaphthyl, respectively, followed by catalytic reduction. Biphenyl-2,2′-diyl- and 1,1′-binaphthyl-2,2′-diyl-containing aromatic polyamides having inherent viscosities of 0.44–1.18 and 0.26–0.88 dL/g, respectively, were obtained either by the direct polycondensation or low-temperature solution polycondensation of the diamines with aromatic dicarboxylic acids (or diacid chlorides). These polymers were readily soluble in a variety of organic solvents including N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, m-cresol, and pyridine. Transparent, pale yellow, and flexible films of these polymers could be cast from the DMAc or NMP solutions. These aromatic polyamides containing biphenyl and binaphthyl units had glass transition temperatures in the range of 215–255 and 266–303°C, respectively. They began to lose weight at ca. 380°C, with 10% weight loss being recorded at about 470°C in air. © 1993 John Wiley & Sons, Inc.