Synthesis of Novel Carbosilane Dendrimers Based on Pentaerythritol

Novel pentaerythritol-based carbosilane dendrimers centered at carbon have been synthesised. Starting from tetraallyl ether based upon pentaerythritol as the core molecule, a succession of alternate Pt-catalyzed hydrosilylation of allyl groups with HSiC13 and allylations of SiC1 groups thus introduced with CH2=CHCH2MgBr in THF provided a divergent synthesis of three generations of carbosilane dendrimers in which the Si atoms are linked by CH2CH2CH2 groups. The reaction conditions for hydrosilylation must be well controlled. After purification by chromatography on silica gel pure products for each generation were obtained. The IR, ^1H and ^13C NMR spectra and elemental analysis data are consistent with the proposed structures. The molecular weights of the resulting carbosilne dendrimers have been determined by vapor pressure osmometry.     

Syntheses of Some New Group 4 non-Cp Complexes Bearing Schiff-base, Thiophene Diamide Ligands Respectively and Their Catalytic Activities for a-Olefin Polymerization

Totally sixteen new titanium and zirconium non-Cp complexes supported by Schiff-base, or thiophene diamide ligands have been synthesized. The complexes are obtained by the reaction of M(OPr-i)4(M=Ti,Zr) with the corresponding Schiff-base ligand in 1:1 molar ratio in good yield. The thiophene diamide titanium complex has been prepared from trimethylsilyl amine [N,S,N] ligand and TiCl4 in toluene at 120℃. All complexes are well charac-terized by ^1H NMR, IR, MS and elemental analysis. When activated by excess methylaluminoxane (MAO), complexes show moderate catalytic activity for ethylene polymerization, and complex If (R^1=CH3,R^2=Br) exhibits the highest activity for ethylene and styrene polymerization. When the complexes were preactivated by triethylaluminum (TEA), both polymerization activities and syndiotacticity of the polymers were greatly improved.     

Synthesis, Characterization and Weak Intramolecular Interactions of Porphyrins Bearing Nucleobases

5,10, 15-Triphenyl-20-{2- [α- (adenine-9 ) acetylamino]} phenyl porphyrin ( 1 ), 5,10, 15-triphenyl-20-{2-[α-(cytosine-1)acetylamino]} phenyl porphyrin (2), 5, 10, 15-triphenyl-20-{4-[α-(cytosine-1)ethoxy]} phenyl porphyrin (3) and their zinc complexes Zn-1, Zn-2 and Zn-3 have been prepared and characterized by ^1H NMR spectra, elemental analyses, electronic absorption spectra and mass spectra (FAB). Intramolecular π-π interactions and intramolecular metal-~ interaction for 1, 2, Zn-1,and Zn-2 have been investigated by several methods. ^1H NMR studies demonstrate that the porphyrin π-system in 1 and 2 is parallel to the adenine and the cytosine aromatic ring, respectively. The electronic absorption spectral properties of free porphyrin derivatives and their zinc complexes have been compared with those of H2TPP and ZnTPP. The results show that the UV-vis spectra of 1 and 2 are the same as that of H2TPP,whereas the spectra of their zinc complexes show 7 nm red shifts of the Soret bands compared to that of ZnTPP. The emission spectra of Zn-1 and Zn-2 are independent of excitation wavelength. From combination of the evidence of absorption and emission spectra it is suggested the existence of intramolecular metal-π interaction in Zn-1 and Zn-2. The results of conformational analysis agreed quite nicely with that of experiments, thus it was further to validate the experimental conclusions.     

Palladium-Catalyzed Amination of Bromoanthancene

Triarylamines are an important class of compounds, because they have been used as the hole-transport layer in electroluminescent devices. [1] New palladium catalyzed methods to form arylamines have emerged recently from Hartwing and Bucchwald . [2,3] Our group have investigated unusual diboration of allenes catalyzed by palladium complex and organic iodides. [4] Here we will report that arylamines react with bromoanthrancene (or dibromoanthancene) to afford triarylamines in the presence of Ligand-palladium complex. The structures of products were de termined by 1H NMR, 13C NMR, 13C (DEPT), IR and MS (HREI and EI) spectra.     

Syntheses and Anti—inflammatory Actiobn of （η—C5H5）2Ti （Cin）2 and （η—C5H5）2Ti（Tzea）2

Two new Complexes(Cp)2Ti(Cin)2and (CP2)Ti(Tzea)2(CP=Cyclopentadienyl η^5-C5H5)have been synthesized in THF by the reaction of HCin(Cincofen,2-phenylquinoline-4-carboxylic acid)or HTzea(5-phenyltetrazolyl-2-ethanoic acid)with(Cp)2TiCl2,and characterized by elemental analyses,IR,1H NMR and 13C NMR,UV spectra,molar conductivity,TGDTA.In the complexes the carboxyl groups are coordinated to Ti(IV)in a monodentate manner,The inhibitory actions of the complexes on mice ear tumefaction caused by croton oil and the rat foot granulation growth produced by cotton wool are higher than those of the corresponding ligands HCin,HTzea and [(Cp)2TiCl2],while their toxicities are lower than those of the free ligands.ηη     

含硫有机膦多酸衍生物α–[RP(S)]2PW9O345-(R = –C6H5, –C6H11)的合成及结构表征

In the presence of Bu4NBr acting as phasetransfer reagent, organothiophosphoryl polyoxotungstate derivatives α-[RP(S)]2PW9O54^5- (R=C6Hs, C6H11) have been obtained by reaction of the trivacant β-[PW9O34]^9- anions with electrophilic C6H5P(S)Cl2 or C6H11P(S)Cl2 in acetonitrile. These new organic-inorganic hybrid anions have been characterized by elemental analysis, IR, ^31P and ^183W NMR spectroscopy. The collective application of the spectroscopy data of these new species indicates that the hybrid anion consists of an α-[PW9O34] framework on which are grafted two RP(S) groups through P-O-W bridges. The five-line ^183W spectra indicate that the hybrid anions possess Cs symmetry in acetonitrile.     

Synthesis,Crystal Structure of Cis—dioxo—catecholatotungsten（VI） Complex and Its NMR Studies on the Interaction with ATP

Cis-dioxo-catecholatotungsten(VI) complex anion[W^(VI)O2-(OC6H4O)2]^2- was obtained with discrete protonated ethylenediamine (NH2CH2CH2NH3)^ cations by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH3OH,CH3CN and ethylenediamine,and compared with its molybdenum anaogue [Mo^(V) O2(OC6H4O)2]^3- by crystal structure,UV,EPR,The results of the UV and EPR spectra show that tungsten is less redox active than molybdenum since the molybdenum is reduced from Mo(VI) to Mo(V) but tungsten stays in the original highest oxidized state Mo(VI) when they are crystallized from the solution above.It is worthy to note that [W^(VI)O2(OC6H4O)]^2- shows the same coordination structure as its molybdenum analogue in which the metal center exhibits distorted octahedral coordination geometry with two cis-dioxocatecholate ligands and might have the related coordination structure feature with the cofactor of flavoenzyme because [Mo^(V)O2(OC6H4O)2]^3- presented essentially the same EPR spectra as flavoenzyme.The NMR studies on the interaction of the title complex with ATP reveal that the reduction of W(VI) to W(V) occurs when the title complex is dissolved in D2O and the W(V) is oxidized again when ATP solution is mixed with original solution and the hydrolysis of the catecholato ligand take places at mean time being monitored by ^1H NMR and ^13C NMR spectra.     

SPONTANEOUS COPOLYMERIZATION OF 4-METHYLENE-1,3-DIOXOLANE DERIVATIVES WITH ACRYLONITRILE AND SUBSTITUENT EFFECT

The copolymerization of six 2-substituted 4-methylene-1, 3-dioxolane with aerylonitrile(AN) gives rise spontaneously to the alternating copolymers by the participation of charge-transfer(CT) complexes. The structures of copolymers was ascertained by their IR, ~1H and ~(13)C NMR spectra, etc.. The electron effect of suhstituents on 2-position of monomer 2 is the most important factor in predicting the reactivity of CT complexes. However the steric effect determines the ring-opening degree of monomer 2. The spontaneous copolymerization mechanism has been discussed.     

A Novel 5-Fluorouracil Salt of 12-Silicatungstic Acid： Synthesis, Structure Characterization and Antitumor Activity

A novel 5-fluorouracil salt of 12-silicatungstic acid was synthesized and characterized by means of elemental analysis, IR,^1H NMR and ^183W NMR spectra. The antitumor activity and toxicity of the complex have been evaluated both in vitro and in vivo.     

Dynamic Assembly Inclusion Complexes of Tweezer‐type Bis(zinc porphyrin) with 5,15‐Di(4‐pyridyl)porphyrin Derivatives

Dynamic assembly inclusion complexes of tweezer-type bis(zinc porphyrin) (1) with di(4-pyridyl)porphyrin derivatives have been designed and constructed. The complexes are induced by Zn-N coordination, and the weak binding allows the large-size di(4-pyridyl)porphyrin guests in random rotation. Dynamic characteristics of these assemblies, such as ligand exchange and dynamic fluorescence quenching, have been investigated by 1H NMR, UV-Vis and fluorescence spectra. The stability of such assembly has pronounced dependence on the size-matching effect and thermal effect.     

Synthesis of La(Ⅲ), Y(Ⅲ) complexes with polyglycol aldehyde-amino acid Schiff base and their high resolution solid state ~(13)C NMR spectra

La(Ⅲ), Y(Ⅲ) complexes with diglycol aldehyde bis-arginine (H_2DAAR) and tetraglycol aldehyde bislysine (H_2TALY) Schiff bases were synthesized. They were characterized and formulated as La(H_2DAAR) (NO_3)_3·6H_2O and Y (H_2TALY)(NO_3)_3·5H_2O separately by elemental analyses. The obtained complexes were investigated in detail by high resolution solid state (HRSS) ~(13)C NMR using cross polarization, magic angle spinning (CPMAS), and total suppression of sidebands (TOSS)techniques. The results are supported by the liquid state 2D-~1H-~(13)C COSY NMR spectra. Some new information about the splitting peaks of ~(13)C for—CH=N—group and alkene carbon bands, etc. in HRSS ~(13)C NMR spectra are given.     

NMR Studies on the Subacute Biochemical Effects of Aristolochic Acid on Rat Serum

The subacute effect of aristolochic acid （AA） on rat serum was studied by NMR method. The biochemical effects induced by AA were characterized by an increase in the amounts of creatinine, trimethylamine N-oxide, acetoacetate, acetate and 3-D-hydroxybutyrate and lactate in serum from ^1H NMR spectra. Principal component analysis was used for further comparing the similarities of ^1H NMR spectral profiles of serum from rats treated with AA and model toxins.     

Studies on synthesis and magnetic resonance of lanthanide complexes with novel Schiff base derived from noncyclic polyether and P-diketone

Nine Ln( Ⅲ ) complexes with a novel Schiff base derived from diglycolamine and benzoylacetone (BZDA) have been synthesized and characterized. They can be formulated as [Ln2(BZDA)3(NO3)3](NO3)3· nH2O(Ln=La, Pr, Nd, Sm, n = 4; Ln=Gd, Tb, Er, Yb, Y, n = l). Enamic form mechanism in this β-diketone Schiff base and its complexes were suggested and proved by IR, UV and NMR methods. The 13C spin-lattice relaxation time T1 and the ratios of r(ci-Ln)/r(cj-Ln) were measured by a 500 MHz NMR instrument for elucidating the formation of the stable sk-membered chelate ring structure in these complexes. The EPR spectrum of the Gd( Ⅲ ) complex exhibits the "U" spectral feature and "zero field effect". On the basis of them, the crystal field strength and the local symmetry around Gd3 in the complex have been discussed.     

Synthesis and Chemical Shifts Calculation of a-Acyloxycarboxamides Derived from Indane-l,2,3-trione by DFT and HF Methods

α-Acyloxycarboxamides are synthesized from three-component Passerini reaction between indane-1,2,3-trione, isocyanides, and thiophenecarboxylic acids in quantitative yields. The structures of the final products were confirmed by IR, 1H and 13C NMR spectroscopy, mass spectrometry, and elemental analysis. The B3LYP/HF calculations for computation of 1H and 13C NMR chemical shifts have been carried out for the title compounds at the 6-311+G** and 6-311++G** basis set levels within GIAO and CSGT approaches. Predicted 1H and 13C NMR che-mical shifts have been assigned and compared with experimental 1H and 13C NMR spectra and they are supported each other.     

NMR Parameters and Vibrational Investigation of 2-Dicyanovinyl-5-（4-ethoxyphenyl） thiophene by ab initio HF and DFT Calculations

Optimized geometry and harmonic vibrational frequency of 2-dicyanovinyl-5-(4- ethoxyphenyl)thiophene (C16H12N2OS) are calculated at the HF/6-31++G(d,p) and B3LYP/6- 311++G(d,p) levels. Mulliken charges in the ground state are also calculated. The research shows the presence of intermolecular interaction in the title compound. The scaled harmonic vibrational frequencies have been compared with experimental FT-IR spectra. A detailed interpretation of the infrared spectra of the title compound is reported. The theoretical spectrograms for IR spectra of the title compound have been constructed. The isotropic chemical shift computed by 13C and 1H NMR analyses also shows good agreement with the experimental observations.     

Syntheses,Structures and Herbicidal Activity of Bis(5-R-2-hydroxybenzylidene) Thiocarbohydrazide Monobutyltin Complexes [R: H(T1), Me(T2)]

The 1,5-disubstituted thiocarbohydrazide ligands were prepared by the condensation of thiocarbohydrazide with salicylaldehyde and 5-methylsalicylaldehyde, respectively. The butyltin complexes, [(5-R-2-hydroxy)ArCH=NNH]_2 CS(n-BuSnCl)_2, R = H(T1); R = Me(T2), based on the1,5-disubstituted thiocarbohydrazide were obtained by microwave-assisted solvothermal reaction of n-butyltintrichloride precursor with the ligands in methanol environments, which have been structurally characterized by elemental analysis, IR and(~1 H, ~(13) C) NMR spectra. The crystals belong to monoclinic system, space groups C2/c(T1) and Pc(T2), respectively. The Sn atom is six-coordinated with distorted octahedral geometry by O, N and S atoms from ligand, C atom of butyl and two Cl atoms. In the crystal, complex T1 forms three-dimensional supramolecular assembly mediated by noncovalent interactions such as C–H···Cl and π-stacking interactions.Similarly, T2 forms an interesting two-dimensional supramolecular structure by noncovalent interactions(e.g. C–H×××Cl and N–H×××Cl) of one-dimensional band-like chain. These ligands and its butyltin complexes have growth effect on the target plants, such as Portulaca oleracea L.,Amaranthus spinosus L., Cassia tora L., Brassica campestris L. ssp. chinensis var. utilis Tsen et Lee and Amaranthus tricolor L. The ligand L1 has a good inhibitory effect on the growth of Cassia tora L., and complex T2 has selective inhibition on the growth of Portulaca oleracea L. and Amaranthus tricolor L., which can be used as a candidate compound for Cassia tora L., Portulaca oleracea L.and Amaranthus tricolor L. herbicide.     

The Reaction of Molybdenum with 2,3-Dihydroxynaphthalene

[H2N（CH2）3NH312[MoO2（C10H6O2）2] （1） was synthesized by the 2,3-dihydroxynaphthalene in the mixed solvent of CH3OH, CH3CN reaction of （n-Bu4N）4[Mo8O26] with and 1,3-propanediarnine. （C5HllN2）2- [HeN（CH2）3NH2][MoO2（CloH6O2）2] （2） was obtained by the reaction of Na2MoO4.2H20 with 2,3-dihydroxynaphthalene in the same solvent above. Both of the complexes possess complex anion [Mo（VI）O2（OC10H6O）2]^2- which shows pseudo-octahedrally coordinated fashion, while the counterions are two protonated 1,3-propanediamine in complex 1 and （CsH11N2）^＋ in complex 2. （C5H11N2）＋ is the byproduct of reaction 2, which results from combination of acetonitrile with 1,3-propanediamine. Packing diagrams of the two complexes are also different. There is anti-parallel-aligned-double-meso-bilayer unit in complex 1. However there are four chiral anions arranged in anticlockwise orientation in complex 2.     

新型双核席夫碱配合物的合成及谱学性质

Eight novel binuclear tetradentate Schiff base complexes (M=Cu(Ⅱ),Ni(Ⅱ),Zn(Ⅱ)) are synthesized. The structure of complexes is two discrete Schiff base unit bridged. The complexes were condensed from series sub-stituent Ketones (5-chloro-2-hydroxybenzophenone, 5-methyl-2-hydroxy-benzophenone, 5-Bromo-2-hydroxybenzop- henone) and dialdehydes (5,5′-methylene-disalicylaldehyde) with the amino group of 1,2-diaminobenzene, and by Metal ion as template. The compounds were characterized by elemental analyses, FT-infrared spectra, Raman, ¹H NMR, UV-vis electronic spectra, EPR spectra. The FT-infrared spectra and Raman spectra of complexes were compared and discussed. The UV-vis election spectra, ¹H NMR and EPR spectra of complexes have also been attributed and minutely analyzed.     

Synthesis and Enantioselective Discrimination of Chiral Fluorescence Receptors Bearing Amino Acid Units

Two chiral fluorescence receptors （1, 2） were synthesized, and their structures were characterized by IR, ^1H NMR, ^13C NMR, mass spectra and elemental analysis. The chiral recognition of receptors was studied by ^1H NMR and fluorescence spectra. The results demonstrate that receptors and dibenzoyl tartrate anion formed a 1 ： 1 complex. The receptor 1 exhibited a good enantioselective recognition ability toward the enantiomers of dibenzoyl tartrate anion.     

Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2]

Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme.