STUDIES ON COMPLEXES OF RARE EARTHS WITH CROWN ETHERS(V)-SYNTHESIS AND CHARACTERIZATION OF THE COMPLEXES OF RARE EARTH NITRATES WITH 2,2''''-DINITRO-4,5,4'''',5''''-BIS-(15-CROWN-5)-DIBENZO DISULFIDE

Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15-crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L·6H_2O(RE=Ce, Pr, Nd) have been synthesized in acetonitrile. All the isolated complexes have beencharacterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetricanalysis, X-ray powder diffraction analysis, molar conductance and measurements of solubility insome general solvents.     

SYNTHESIS AND CHARACTERIZATION OF RARE EARTH METAL COMPLEXES WITH PIPERONAL ISONICOTINOYL HYDRAZONE

Complexes of La(Ⅲ),Nd(Ⅲ),Sm(Ⅲ),Eu(Ⅲ),Gd(Ⅲ),Dy(Ⅲ),Er(Ⅲ),Yb(Ⅲ)and Y(Ⅲ)with piperonal isonicotinoyl hydrazone(HPIN)have been synthesized in DMF and EtOH.The complexes have been characte-rized by elemental analysis,molar conductance,i.r.,UV and~1H n.m.r.spectra,magnetic measurements,X-ray powder diffraction and DTA.     

SYNTHESIS AND CHARACTERIZATION OF COMPLEXES OF LANTHANIDE NITRATES WITH 2,2''''-BIPYRIDYL

The interactions of 2,2'-bipyridyl with the lanthanide nitrates werestudied and complexes of the formula Ln(NO_8)_8(bipy)_8 were isolated from water-ethanol mixed solvent.The complexes were characterized by elemental analysis,conductivity measurments,IR spectra and DAT-TG analysis.     

STUDIES ON THE ELECTROANALYTICAL CHEMISTRY OF RARE EARTHS——THE ADSORPTIVE-COMPLEX WAVE OF THE COMPLEXES OF N, N'-DI-(2-HYDROXY-5-SULPHOPHENYL)-C-CYANFORMAZAN (DSPCF) AND LIGHT RARE EARTH ELEMENTS

The sensitive adsorptive-complex wave of the complexes formed by light rare earth elements and DSPCF is studied in this paper. The electroactivities of the complexes of light (La-Eu) and heavy rare earth elements (Gd-Lu), are quite different, so we can determine a certain light rare earth element or the total amounts of light rare earths without separating them from heavy rare earths. The mechanism of the adsorptive-complex wave and the reason why heavy rare earths could not form the electroactive complexes have been studied as well.     

PRELIMINARY STUDIES ON THE SYNTHESIS AND CHARACTERIZATION OF OXY-AND THIO-DIACETIC ACID HYDRAZITION AND THEIR FIRST-ROW TRANSITION METAL COMPLEXES

It has been made certain that thio-and oxy-diacetic acid hydrazidesare potential anticancer compounds.However,their ability to formcomplexes with transition metals and the properties of the complexes thusformed have not been studied.Employing a new potential anticancer ligand1,2-bis(thioacetic acid hydrazide)ethane prepared in our lab,along withligands oxydiacetic hydrazide and 1,2-bis(oxyacetic acid hydrazide)ethane,a series of 11 new first-row transition metal(M=Zn~(2+),Cu~(2+),Co~(2+),Ni~(2+))complexes with each of the above three ligands have been synthesizedand characterized by means of elemental analyses,IR,TG and X-raypowder diffraction.     

STUDIES ON HETERO-MACROCYCLIC POLYETHER(1).THE SYNTHESIS OF 10-SELENA BENZO-15-CROWN-5

The synthesis of a new type of hetero-macrocyclicpolyether 2,3-henzo-1,4,7,13-tetraoxa-10-selenacyclopentadeca-2-eneis deseribed.     

STUDIES ON THE TOTAL SYNTHESIS OF MAYTANSINOIDS (Ⅳ)——SYNTHESIS OF MAYTANSINE

This paper reports the total synthesis of optically pure maytansinol and maytansine. The physical constants and spectral data including R_f, m.p., specific rotation, HPLC, UV, CD, IR, NMR, and MS, of synthetic maytansinol and maytansine are identical with those of natural products in all respects. The preliminary biological test showed that synthetic maytansine possesses the same inhibitory activity in vitro against carcinoma cells as the natural product.     

NMR AND INFRARED SPECTROSCOPIC STUDY ON THE INTERACTION OF RARE EARTH WITH L-METHIONIHE

Five solid complexes of rare earth with L-methionine have been prepared. The interaction of rare earth with the ligand has been studied by NMR and IR spectroscopy.     

SYNTHESIS AND CHARACTERIZATION OF THE SOLID COMPLEXES OF Mn(Ⅱ), Co(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Ag(Ⅰ), Cd(Ⅱ) NITRATES WITH DISUBSTITUTED BENZO CROWN ETHERS

Nine new solid complexes of Mn(Ⅱ),Co(Ⅱ),Cu(Ⅱ),Zn(Ⅱ.),Ag(Ⅰ) nitrates with 4',5'-dibromobenzo-15—crown—5(L_A),Ag(Ⅰ),Cd(Ⅱ)nitrates with tetrabromodibenzo—18—crown—6(L_B)and Cu(Ⅱ), Ag(Ⅰ) nitrates with 4'—bromo—5'—nitrobenzo—15—crown-5(L_c),having the compositions of M(NO_2)_2·L·nH_2O(M=Mn,Co, Zn,L=L_A,n=2;M=Cu,L=L_A,n=1.5; M=Cd, L=L_B,n=0; M=Cu,L=Lc,n=2) and AgNO_·L·nCH_3CN(L=LA,n=0; L=L_B,n=1; L=Lc,n=1/2) have been synthesized in nonaqueous solvent. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X—ray powder diffraction analysis, molar conductance and measuremends of solubility in some general solvents.     

STRUCTURE-REACTIVITY STUDIES ON THE EXTRACTION OF RARE EARTHS BY DIALKYL ISOPROPYLPHOSPHONATES

Dialkyl isopropylphosphonates with various alkyl groups are synthesized for the structure-reactivity studies on the extraction of rare earths. Steric effect of ligands on the extrac-tion behaviour of rare earth is well demonstrated due to the lanthanide contraction. Thethermodynamic functions of the extraction reaction are estimated and the influence of chem-ical structure of extractants is discussed. By the method of continuous variation as well asthe elementary analysis, the composition of the extracted species is deduced as Ln(NO_3)_3·3L.The structure of the coordination compound is further elucidated by IR and NMR spectra.The magnetic property and the differential thermal analysis of the complexes are also studied.     

THE SYNTHESIS AND CHARACTERIZATION OF ANSYMMETRIC PENTAAZADENTATE PORPHYRIN-LIKE METAL COMPLEXES

This paper presents the synthesis and structural characterization of asymmetrictripyrrane-containing macrocycle.This macrocycle could be oxidized to the methinebridged,22 π-electron aromatic macrocyclic complexes containing cadmium(Ⅱ),samarium(Ⅲ),europium(Ⅲ)and gadolinium(Ⅲ)by treating with corresponding metal chloride inthe presence of air Their structures were characterized by spectral methods.     

SYNTHESIS AND CHARACTERIZATION OF THE COMPLEXES OF β－ALKOXYCARBONYLETHYLTIN TRICHLORIDES WITHDBSO AND HMPA

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STUDIES ON THE SYNTHESIS OF(±)-CEMBRENE-A

A precursor 2 of cembrene-A(a termite trail pheromone)was prepared fromgeraniol through 7 steps.     

SYNTHESIS AND CHARACTERISTICS OF HOMOBINUCLEAR MACROCYCLIC COMPLEXES OF RARE EARTH METAL ISOTHIOCYANATE AND PHENOLIC SCHIFF BASES

Eleven homobinuclear macrocyclic rare earth metal ions complexes are obtained as com-pounds of 2:2 Schiff base formed by condensing 2,6-diformyl-4-tert-Butylphenol and triethy-lenetetramine by a template procedure using rare earth metal isothiocyanates. These complexesare characterized by elemental analyses, FABMS, IR, conductivity and magnetic susceptibility.The variable-temperature magnetic susceptibility (4--300K) of complexes of Gd(Ⅲ) and Tb(Ⅲ) has been determined. A satisfactory fit to theoretical curve derived from spin Hamil-tonian operator was obtained by least squares method. The exchange interaction parameters areJ =-0.220 cm~(-1) for Gd, ,ZJ~?=-0.052 cm~(-1) for Tb. The results indicate a very weak anti-ferromagnetic interaction between Gd~(3+)-Gd~(3+), Tb~(3+)-Tb~(3+) ions.     

STUDIES ON HETERO-MACROCYCLIC POLYETHER (Ⅱ). THE SYNTHESIS OF PLATINUM COMPLEX OF 10-SELENABENZO-15-CROWN-5 AND ITS CATALYTIC BEHAVIOR IN HYDROSILYLATION

The title complex (PtL_2Cl_2) was synthesized by reacting 10-selenabenzo-15-crown-5 (L) with potassium chloroplatinite. Its catalytic activity for the hydrosilylation of olefins by triethoxysilane, was investi gated.     

COMPLEXES OF RARE EARTH NITRATE WITH SCHIFF BASE DERIVED FROM VANILLIN AND P-TOLUIDINE

In this paper,complexes of rare earth nitrate with Schiffbase derived from vanillin(3-methoxy-4-hydroxy-benzaldehyde)andp-toluidine[LnL_2(NO_3)_2]NO_3(Ln=La-Eu except Pm,L=Schiff base ligand)have been prepared and characterized.     

STUDIES ON SCHIFF BASE COMPLEXES——Ⅳ. SYNTHESIS AND CRYSTAL STRUCTURE OF Fe (SALDPT) SAL

制备了Fe(saldpt)sal单晶并作了晶体结构分析。晶体数据:单斜,空间群P2_1/C(#14),a=12.486(5),b=18.502(8),c=10.870(5)A,β=104.23(3)°,V=2434(2)A~3,Z=4,D_c=1.40g/cm~3     

SYNTHESES AND PROPERTIES OF ELEVEN-COORDINATED COMPLEXES FORMED FROM LANTHANIDE NITRATES AND 1,8-NAPHTHO-16-CROWN-5

Complexs formed from lanthanide nitrates Ln (NO_3)_3 (Ln=La, Ce, Pr, Nd) and 1, 8-naph-tho-161crown-5 with a 1:1 stoichiometry have been synthesized and characterized by elementalanalyses; IR spectra, X-ray powder diagrams as well as thermogravimetric and differentialthermal analyses. A single crystal X-ray structural analysis indicates that the coordination num-ber of these complexes is eleven.     

STUDIES ON THE SYNTHESIS OF THE SPIROKETAL FRAGMENT OF AZADIRACHTIN(Ⅰ)

The stereoselective synthesis of substituted [2,2,1]-bicyclo-heptan-2-one 12,a supposed intermediate to the spiroketal fragment of azadi-rachtin was described.When 12 was treated with mCPBA in CH_2Cl_2 in the pres-ence of excess amount of solid sodium bicarbonate,only 13 was obtained.Thespiroketal intermediate 20 was converted from 9 through 5 steps by an alterna-tive route.