生物素标记试剂的合成方法改进及其在DNA合成中的应用

以生物素,4,4’-二甲氧基三苯基氯甲烷,6-氨基-1-己醇,2-氰基乙氧基-双(N,N-二异丙基)亚磷酰胺等为原料,采用改进方法合成了生物素标记试剂——[1-N-(4,4’-二甲氧基三苯甲基)-生物素-6-氨基己基]-2-氰乙氧基-N,N-二异丙基亚磷酰胺(3),总收率51.0%,其结构经1H NMR,13C NMR,31P NMR和MS确证。通过固相亚磷酰胺三酯法,应用3合成了一段含有十个碱基的5’-端生物素标记的寡核苷酸链,其结构经MS确证。     

New Efficient Synthetic Pathways to Tetrakis{p‐[(diethylphosphono)methyl]}calix[4]arene

Various operating conditions have been applied on tetrakis[p‐(halogenomethyl)]‐ and tetrakis[p‐(aminomethyl)]calix[4]arene derivatives to improve the synthesis of the 5,11,17,23‐tetrakis[(diethylphosphono)methyl]‐25,26,27,28‐tetrahydroxycalix[4]arene. Two new, high yield, synthetic pathways have been selected, involving, for the first one, the 25,26,27,28‐tetrahydroxy‐5,11,17,23‐tetrakis[(trimethylamino)methyl]calix[4]arene, tetraiodide, DMF, and 10 equiv. of triethyl phosphite ((EtO)₃P), and, for the other one, the 5,11,17,23‐tetra(bromomethyl)‐25,26,27,28‐tetrahydroxycalix[4]arene, CH₂Cl₂, and only 4 equiv. of (EtO)₂P.     

亚磷酸三异丙酯的合成工艺研究

采用三氯化磷、异丙醇为原料,吡啶为有机碱合成亚磷酸三异丙酯.研究了溶剂、反应温度和不同的有机碱对酯产率的影响.在优化的反应条件下,亚磷酸三异丙酯的产率达到85%.对粗品进行减压精馏,产品含量达到95%.     

Crystal Structure And Magnetic Property of the Complex of Hydrogen-bonded Two-dimensional Layer Copper(Ⅱ) Acrylate with Trimethyl Phosphate

Coopper carboxylate complexes play an important role in catalysing the enzymatic activi-ties[1— 4] ,and the phosphate has an especial use in DNA recognition[5] .Indeed the reportabout copper carboxylate complexes with phosphate ligands is rare. A chain structuresupramolecule [Cu2 (CH2 CH— COO) 4 (H2 O) 2 ] n has been reported recently[6] ,in which aCu2 (CH2 CH—COO) 4 (H2 O) 2 unitislinked by four O(water)—H…O(carboxyl) hydrogenbonds with two adjacentunits(Fig.1 ) .In this work …     

Solution growth of new ferroelectric glycine phosphite unidirectional single crystals at room temperature

Glycine phosphite [NH₃CH₂COOH₃PO₃], abbreviated as GPI is the second hydrogen bonded ferroelectric crystal combination of phosphorous acid and amino acid following βnine phosphite crystals abbreviated as BPI. Sankaranarayanan and Ramasamy‐Technique was adopted to prepare the ferroelectric glycine phosphite unidirectional single crystal. The growth orientation was imposed by the pre‐grown 〈010〉 seed. As water was the solvent, transparent, colourless crystal with cylindrical shaped ingot of sized 20mm‐diameter was grown. Powder X‐ray diffraction, HRXRD, FTIR, dielectric and mechanical studies were carried out. The results are discussed in detail. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fluoride-mediated selective cross-coupling reactions of alkyl halides and trimethyl(perfluoroalkyl)silanes, Me3SiRf (Rf = CF3, C2F5) in the absence of any catalysts

A temperature range of −18 °C to room temperature was found to be effective for selective fluoride-mediated cross-coupling reactions of trimethyl(perfluoroalkyl)silanes, Me₃SiCF₃ and Me₃SiC₂F₅, and alkyl halides, RX (X = Br, I) in the absence of any catalyst.     

二丁胺甲基膦酸锆的苄基季胺化合物及其相转移催化作用

制得了二丁胺甲基膦酸－亚磷酸氢锆Ｚｒ（ＨＰＯ３）２－ｘ．（Ｏ３ＰＣＨ２ＮＢｕ２）．Ｈ２Ｏ（ｘ＝０．８，０．６，０．５，０．４，０．３５），用溴化苄季铵化，得部分季铵化产物，溴化苄基二丁铵甲基膦酸－二丁胺甲基膦酸－亚磷酸氢锆Ｚｒ（ＨＰＯ３）２－ｘ．（Ｏ３ＰＣＨ２ＮＢｕ２）ｘ－ｙ．（Ｏ３ＰＣＨ２Ｎ＾＋Ｂｕ２．ＣＨ２Ｐｈ．Ｂｒ＾－）．Ｈ２Ｏ（ｙ＜ｘ），用作相转移催化剂，对液／液或固／固／液相转移催化的取     

在H3PO4存在下2,3-二甲基-2-丁烯与乙酐的酰化反应

在H3PO4存在下进行了2，3－二甲基－2－丁烯与乙酐的酰化反应，结果表明，H3PO4是室温下催化2，3－二甲基－2－丁烯与乙酐酰化反应的有效催化剂，在H3PO4存在下，酰化产物的收率主要取决于：（a)H3PO4的用量，（b)乙酐的用量；（c)反应温度和（d)反应时间，在适宜反应条件下，所得3，3，4－三甲基－4－戊烯－2－酮（TMP）约为99％，另外还发现，反应体系中加入少量乙酸，不会明显减少酰化产物的收率，乙酐的纯度，反应物的加入顺序对该反应几乎没有任何影响，在有和没有溶剂CH2Cl2的条件下所得酰化产物的收率是可比的。     

New poly(amide-lmide)s syntheses. XV. Preparation and properties of poly(amide-imide)s derived from 9, 9-bis[4-(4-aminophenoxy) phenyl]fluorene and various bis(trimellitimide)s

Fifteen bis(phenoxy) fluorene-containing poly(amide-imide)s III were synthesized by the direct polycondensation of 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene (BAPPF) with var-ious aromatic bis(trimellitimide)s II in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly(amide-imide)s III having inherent vis-cosities up to 1.45 dL/g were obtained in quantitative yields. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 263–315°C and the 10% weight loss temperatures were above 510°C in nitrogen. Some properties of poly(amide-imide)s III were compared with those of the corresponding isomeric poly(amide-imide)s III ′ prepared from 9,9-[4-(4-trimellitimidophenoxy)phenyl]fluorene and various aromatic diamines. © 1995 John Wiley & Sons, Inc.     

Direct observation of a series of non-covalent complexes formed by phosphorylated flavonoid-protein interactions through electrospray ionization tandem mass spectroscopy

In the work described in this paper, 7-hydroxyflavone and chrysin were phosphoylated by a modified Atheron-Todd reaction. Three new phosphorylated flavonoids (PF) were obtained, and the structures of the target products were determined by X-ray and NMR data and electrospray ionization (ESI) tandem mass spectroscopy (MS). The mixed solutions of the phosphorylated flavonoids and different proteins such as insulin, lysozyme, and cytochrome c were injected in an ion trap mass spectrometer. The results show that all the phosphorylated flavonoids could form non-covalent complexes with the proteins mentioned above, while non-covalent complexes were not detected from the mixed solution of the chrysin or 7-hydroxyflavone with proteins. The research shows that the phosphorylated flavonoids could enhance the interaction with proteins. It may imply their important role in biological processes. The method described in this paper provides us additional information for studying such interactions for phosphorylated flavonoids in this important field.