硫脲化合物的合成及其生物活性

硫脲化合物的合成及其生物活性董燕红，司宗兴（北京农业大学应用化学系北京１０００９４）关键词噻二陛－甲酰基，硫脲，胺类，合成，生物活性酰基硫脲在抗真菌、抗结核、抗病毒、除草以及调节植物生长方面具有广泛应用［１，２］。１，２，３－噻二唑杂环作为有效前体正...     

A new flavanone glucoside from <Emphasis Type="Italic">Abrus precatorius</Emphasis>

A new flavanone glycoside, (2S)5,7,4′-trihydroxyflavanone-8-C-β-D-(6″-O-acetyl)glucopyranoside (1), together with six known flavonoids, isohemiphloin (2), vitexin (3), cirsimaritin (4), hispidulin (5), apigenin (6), and eupatorin (7), was isolated from the leaves and stems of Abrus precatorius. Their structures were elucidated on the basis of physical and spectral analysis. Rotamers exist for compounds 1, 2, and 3. Compounds 1–3, 6, and 7 were isolated from this plant for the first time.     

Chemical composition of essential oils of Litsea cubeba harvested from its distribution areas in China

Litsea cubeba (Lour.) Pers. is a promising industrial crop with fruits rich in essential oils. The chemical composition of essential oils of L. cubeba (EOLC) were determined for fruits harvested from eight regions in China. The overall essential oil content, obtained by hydrodistillation and analyzed by gas chromatography-mass spectrometry (GC-MS), ranged from 3.04% to 4.56%. In total, 59 compounds were identified, the dominant components being monoterpenes (94.4-98.4%), represented mainly by neral and geranial (78.7-87.4%). D-Limonene was unexpectedly a lesser constituent (0.7-5.3%) in fruits, which differed from previous reports (6.0-14.6%). Several components were only detected in certain regions and compounds such as o-cymene and eremophilene have never before been reported in EOLC. These results demonstrate significant regional variation in the chemical composition of EOLC. This investigation provides important information with regard to the bioactivity, breeding work and industrial applications of L. cubeba.     

Synthesis, structural characterization and catalytic activity of a multifunctional enzyme mimetic oxoperoxovanadium(V) complex

The synthesis and structural characterization of a novel oxoperoxovanadium(V) complex [VO(O(2))(PAH)(phen)] containing the ligands 2-phenylacetohydroxamic acid (PAHH) and 1,10-phenanthroline (phen) has been accomplished. The oxoperoxovanadium(V) complex was found to mimic both vanadate-dependent haloperoxidase (VHPO) activity as well as nuclease activity through effective interaction with DNA. The complex is the first example of a structurally characterized stable oxoperoxovanadium(V) complex with a coordinated bi-dentate hydroximate moiety (-CONHO(-)) from 2-phenylacetohydroximate (PAH). The oxoperoxovanadium(V) complex has been used as catalyst for the peroxidative bromination reaction of some unsaturated alcohols (e.g. 4-pentene-1-ol, 1-octene-3-ol and 9-decene-1-ol) in the presence of H(2)O(2) and KBr. The catalytic products have been characterized by GC-MS analysis and spectrophotometric methods. The DNA binding of this complex has been established with CT DNA whereas the DNA cleavage was demonstrated with plasmid DNA. The interactions of the complex with DNA have been monitored by electronic absorption and fluorescence emission spectroscopy. Viscometric measurements suggest that the compound is a DNA intercalator. The nuclease activity of this complex was confirmed by gel electrophoresis studies.     

A Novel Dinuclear Nickel(II) Complex with Three Bridges of Cl–, OAc– and (‐OCH2CH2O‐) Group of N,N, N′, N′‐Tetrakis(2‐benzimidazolyl methyl‐1, 4‐di‐ethylene amino) Glycol Ether

The novel dinuclear Ni²⁺ complex [Ni₂(μ‐Cl)(μ‐OAc) (EGTB)]·Cl·ClO₄·2CH₃OH, where EGTB is N, N, N′, N′‐tetrakis (2‐benzimidazolyl methyl‐1, 4‐di‐ethylene amino)glycol ether, crystallizes in the orthorhombic space group Pnma with a = 15.272(2), b = 14.768(2), c = 22.486(3) Å, V = 5071.4(12) ų, Z = 4, D_calc = 1.414 g cm^?3, and is bridged by triply bridging agents of a chloride ion, an acetate and an intra‐ligand (‐OCH₂CH₂O‐) group. The nickel coordination geometry is that of a slightly distorted octahedron with a NiN₃O₂Cl arrangement of the ligand donor atoms. The Ni–Cl distance is 2.361(2) Å, and two Ni–O distances are 1.996(5) and 2.279(6) Å. The three Ni–N distances are 2.033(7), 2.060(6), and 2.166(6) Å with the Ni–N bond trans to an ether oxygen the shortest, the Ni–N bond trans to an acetate oxygen the middle and the Ni–N bond trans to Cl the longest.     

Complete 1H and 13C NMR assignments of four new steroidal glycosides from a gorgonian coral Junceella juncea

Four new cholest-type steroidal glycosides, junceellosides A-D, isolated from the EtOH/CH(2)Cl(2) extracts of the South China Sea gorgonian coral Junceella juncea, were identified. Complete assignments of the (1)H and (13)C NMR chemical shifts for these compounds were achieved by means of one- and two-dimensional NMR techniques, including (1)H-(1)H COSY, HSQC, HMBC and NOESY spectra.     

2,3‐Di(2‐pyridyl)‐5‐phenylpyrazine: A NN‐CNN‐Type Bridging Ligand for Dinuclear Transition‐Metal Complexes

A new bridging ligand, 2,3‐di(2‐pyridyl)‐5‐phenylpyrazine (dpppzH), has been synthesized. This ligand was designed so that it could bind two metals through a NN‐CNN‐type coordination mode. The reaction of dpppzH with cis‐[(bpy)₂RuCl₂] (bpy=2,2′‐bipyridine) affords monoruthenium complex [(bpy)₂Ru(dpppzH)]²⁺ ( 12+ ) in 64 % yield, in which dpppzH behaves as a NN bidentate ligand. The asymmetric biruthenium complex [(bpy)₂Ru(dpppz)Ru(Mebip)]³⁺ ( 23+ ) was prepared from complex 12+ and [(Mebip)RuCl₃] (Mebip=bis(N‐methylbenzimidazolyl)pyridine), in which one hydrogen atom on the phenyl ring of dpppzH is lost and the bridging ligand binds to the second ruthenium atom in a CNN tridentate fashion. In addition, the RuPt heterobimetallic complex [(bpy)₂Ru(dpppz)Pt(C?CPh)]²⁺ ( 42+ ) has been prepared from complex 12+ , in which the bridging ligand binds to the platinum atom through a CNN binding mode. The electronic properties of these complexes have been probed by using electrochemical and spectroscopic techniques and studied by theoretical calculations. Complex 12+ is emissive at room temperature, with an emission λ_max=695 nm. No emission was detected for complex 23+ at room temperature in MeCN, whereas complex 42+ displayed an emission at about 750 nm. The emission properties of these complexes are compared to those of previously reported Ru and RuPt bimetallic complexes with a related ligand, 2,3‐di(2‐pyridyl)‐5,6‐diphenylpyrazine.     

Living Carbocationic Polymerization. XLIX. Two-Stage Living Polymerization of Isobutylene to Di-tert-chlorine Telechelic Polyisobutylene

Abstract

A two-stage process was developed for the living polymerization of isobutylene (IB) employing di-tert-alcohol initiators in conjunction with BCl₃ coinitiator in the first or initiation stage, followed by TiCl₄ coinitiator in the second or propagation stage; the process was shown to yield high molecular weight (up to M ⁿ 20,000), narrow molecular weight distribution (MWD) M ^w/M ⁿ = 1.1–1.2) di-tert-chlorine telechelic polyisobutylenes (^tCl-PIB-Cl^t). The initiation stage involves the homogeneous solution living polymerization of IB induced by the di-tert-alcohol/BCl₃ combination in the presence of an electron donor such as N,N-dimethylacetamide in CH₃Cl solvent at ?80°C and proceeds up to M ⁿ < 5000; this is followed by the propagation stage in which TiCl₄ and the bulk of IB plus a sufficient amount of n-C₆H₁₄ are added to the charge to bring the solvent composition to CH₃Cl/n-C₆H₁₄ 60/40 v/v and the living polymerization is continued until high M ⁿ product is obtained. This two-stage process was developed because 1) it employs very inexpensive chemicals; 2) di-tert-alcohol/BCl₃ combinations initiate living IB polymerization in CH₃Cl but the product after reaching M ⁿ ≤ 5000 precipitates out of the CH₃Cl solution, and di-tert-alcohol/BCl₄ combinations do not initiate IB polymerization; and 3) di-tert-alcohol/BCl₃ systems do not initiate (or only very slowly) the living polymerization of IB in CH₃Cl/n-C₆H₁₄ mixtures, whereas similar TiCl₄-based systems do. The polymerization remains living during both stages although the propagating species and solvent polarity are profoundly altered. The livingness of the system has been analyzed by kinetic experiments and the structure of the ^tCl-PIB-Cl^t product by routine spectroscopic means.