苯并单氮杂15-冠-5-与α, β-不饱和羰基化合物的 Michael加成

本文报道借Michael加成使苯并单氮杂15-冠-5与α,β-不饱和羰基化合物反应,合成了氮支套索冠醚(1,2)和酯型双冠醚(3,4)。并提供了合成酯型双冠醚的一种方法,该法条件温和,操作简便,收率高。产物均经IR,^1HNMR和MS鉴定。     

Two—dimensional Network Crown Ether Complex.Synthesis and Crystal Structure of 18—Crown—6 Complex：[K（18—C—6）]2[Cd—（nmt）2]

The novel complex [K(18-C-6)]2[Cd(mnt)2][18-C-6-18-crown-6,nmt=1,2-dicyanoethene-1,2-dithiolate,C2S2-(CN)2^2-] was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complex displays two-dimensional network structure of [K(18-C-6)] complex segments and [Cd(nmt)2] complex segment bridged by S-K-S,S-K-N and N-K-N interactions between adjacent[K(18-C-6)] and [Cd(mnt)2]units.     

Thermal decomposition products of copoly(arylene ether sulfone)s characterized by direct pyrolysis mass spectrometry

Pyrolysis products with mass of up to 850 Da were detected by direct pyrolysis mass spectrometric (DPMS) analysis of a series of copoly(arylene ether sulfone)s (PES-PPO) synthesized by nucleophilic condensation of either 4,4′-dichlorodiphenylsulfone (CDPS) or 4,4′-bis-(4-chlorophenyl sulfonyl) biphenyl (long chain dichloride, LCDC) with different molar ratios of hydroquinone (HQ) or dihydroxydiphenylsulfone (HDPS). Pyrolysis products retaining the repeating units of the initial copolymers were formed at temperatures ranging from 420 °C to 470 °C (near the initial decomposition temperature). At temperatures higher than 450 °C were observed products containing biphenyl units, formed by the elimination process of SO₂ from diphenyl sulfone bridges. Products having biphenyl and dibenzofuran moieties were detected in the mass spectra recorded at temperatures above 550 °C. These units were formed by loss of hydrogen atom from diphenyl ether bridges. Although the EI (18 eV) mass spectra of the pyrolysis products of the samples investigated were very similar, it was found that the relative intensity of some ions reflects the molar composition of the copolymers analysed. Cyclic and linear oligomers with very low molecular mass, present in the crude copolymers, were also detected by DPMS. Thermogravimetric analysis also showed their excellent thermal stability below 400 °C. It indicates that the copolymers yield a char residue of 40-45% at 800 °C, which increases with the PPO mole fraction in the samples.     

HPLC isolation and NMR structure elucidation of the most prominent octabromo isomer in technical octabromo diphenyl ether

The major octabromo isomer of technical octabromo diphenyl ether mixture (technical octaBDE) DE-79 was isolated by RP-HPLC. Three serially coupled columns (each 250 mm long) enabled a good separation of the target compound from other congeners using 100% ACN as eluent. Approximately 100 microg of the target compound was isolated with a purity of >90% and investigated by MS for confirmation of the degree of bromination. 1H-NMR and 2-D 1H-13C correlation NMR spectra unequivocally clarified that the octaBDE in question is 2,2',3,3',4,4',6,6'-octabromodiphenyl ether (BDE 197). Based on annual production rates of technical BDE products (1999/2001), approximately 380 tons of BDE 197 were annually produced which, on the long term, may enter the environment. Compared with other individual BDE congeners, BDE 197 has the seventh highest application rate. Reductive debromination of BDE 197 can lead to four hepta-, 15 hexa-, 23 penta-, and 28 tetra-BDE isomers, respectively. This variety includes all known major BDEs of environmental concern (BDE 47, 85, 99, 100, 153, 154, and 183). The identification of BDE 197 in technical octaBDE DE-79 strongly suggests that research on the environmental fate of BDEs should include this key-BDE congener.     

Reaction of early transition metal complexes with macrocycles. II. Synthesis and structure of TiCl3(H2O) · 18-crown-6, a compound with a unique bidentate bonding mode for the 18-crown-6 molecule

18-crown-6 reacts with TiCl₃ in CH₂Cl₂ to form a complex in which the crown ether functions as a tridentate ligand. Addition of moist hexane affords a molecular complex in which the crown ether functions as a bidentate ligand. A water molecule is bonded directly to the titanium atom and is further hydrogen bonded to three of the oxygen atoms of the crown. The deep blue crystals of the CH₂Cl₂ adduct belong to the monoclinic space groupP2₁/n witha=13.481(8),b=8.021(5),c=21.425(9) Å, =97.32(5)°, and _calc = 1.51 g cm^–3 forZ=4. Refinement led to a conventionalR value of 0.040 based on 873 observed reflections. The Ti–O bond distances for the crown oxygen atoms are 2.123(8) and 2.154(9) Å, while the oxygen atom of the water molecule is bonded at 2.072(8) Å. The octahedral coordination sphere of the titanium atom is completed by the three chlorine atoms at distances of 2.340(5), 2.352(4), and 2.373(4) Å. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82034 (10 pages).     

风毛菊化学成分研究（Ⅰ）

从风毛菊中分离得到16种化合物,经光谱方法鉴定为山奈素-3-O-(6＂-O-巴豆酰)-β-D-葡萄糖甙(1)、槲皮素-3-O-(6＂-O-巴豆酰)-β-D-葡萄糖甙(2)、丁香甙甲醚(3))、山奈素-3-O-β-D-葡萄糖甙、槲皮素-3-O-β-D-葡萄糖甙、丁香甙、α-香树脂醇棕榈酸酯、β-香树酯醇棕榈酸酯、羽扇豆醇棕榈酸酯、羽扇豆醇乙酸酯、羽扇豆醇、β-谷甾醇、棕榈酸、二十四烷酸、二十六烷酸、二十五烷烃,其中(1)、(2)和(3)为新化合物。     

Development of new solid-phase microextraction fibers by sol-gel technology for the determination of organophosphorus pesticide multiresidues in food

Allyloxy bisbenzo 16-crown-5 trimethoxysilane was first used as precursor to prepare the sol-gel-derived bisbenzo crown ether/hydroxyl-terminated silicone oil (OH-TSO) SPME coating. The coating procedure involving sol solution composition and conditioning process was presented. Compared with commercial SPME stationary phases, the new coatings showed higher extraction efficiency and therefore could provide higher sensitivity for organphosphorous pesticides (OPs). Limits of detection (LODs) were in the range of 0.003-1.0 ng/g for these OPs in food samples (honey, juice, orange and pakchoi). The optimal extraction conditions of the new coatings to OPs in these samples were investigated by adjusting extraction time, salt addition, extraction temperature, and dilution ratios of samples with distilled water by using SPME coupled with gas chromatography (GC)-flame photometric detection (FPD). The method was applied to determine the concentrations of OPs in real samples.     

A new isoprenyl phenyl ether compound from mangrove fungus

A new isoprenyl phenyl ether, 3-hydroxy-4-(3-methylbut-2-enyloxy)benzoic acid methyl ester (1), together with 4-hydroxybenzoic acid (2), 2-hydroxy-6-methylbenzoic acid (3), and 4-hydroxy-3-methoxybenzoic acid (4) were isolated from Mangrove fungus (No. B60) from the South China Sea. The structures of the compounds were established on the basis of NMR spectroscopic and mass spectrometric data. In the preliminary bioassay, compound 1 exhibited antibacterial and antifungal activities. Compound 1 also inhibited cytotoxicity to the hepG2 cell line with an IC₅₀ value of 10.0 μg/mL. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 313–314, July–August, 2007.     

聚醚醚酮微结构及反应特性的量子化学研究

利用AM1对聚醚醚酮重复单元进行条件优化,得出了此分子的最优构型,明确了聚醚醚酮分子链的微观构象,并在此构象基础上进行量子化学计算,给出了健序、净电荷、前线轨道等信息,从理论上研究了聚醚醚酮的磺化反应及热分解反应的一些特性.