Preparation of sulfonyl aromatic polyamides and copolyamides by means of di- or triphenyl phosphite

High molecular-weight aromatic polyamides were obtained by the direct polycondensation reaction of 4,4′-sulfonyldibenzoic acid (SDA) with various aromatic diamines, by means of di- (DPP) or triphenyl phosphite (TPP) in N-methyl-2-pyrrolidone (NMP)-pyridine solution containing metal salts such as LiCl and CaCl₂. The factors affecting the phosphorylation reaction were investigated, in particular for the reaction of SDA and 4,4′-oxydianiline (ODA). For the polymerization by means of TPP, the optimum conditions are: molar ratio of TPP to diacid, higher than 2.3; concentration of metal salts, 8 wt % LiCl or 6 wt % CaCl₂; reaction temperature, 100°C; and monomer concentration, 0.4 mol/L. For the polymerization by means of DPP, the optimum conditions are: molar ratio of DPP to diacid, higher than 3.8; concentration of metal salts of 8 wt % LiCl or 10 wt % CaCl₂; reaction temperature, 110°C; and monomer concentration, 0.4 mol/L. Copolyamides were also prepared from the reaction of ODA with the mixed diacids of SDA and other dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid by using TPP and DPP as the condensing agents.     

Total synthesis of didmolamides A and B

The first total synthesis of didmolamides A (1) and B (2) has been accomplished by the solid phase assembly of thiazole-containing amino acids and commercially available Fmoc-protected amino acids. The synthesis of didmolamide B was also achieved in high yield using solution phase peptide synthesis. The thiazole-containing amino acid composing 1 and 2 was synthesized by a MnO₂ oxidation of a thiazoline, prepared from an Ala-Cys dipeptide using bis(triphenyl)oxodiphosphonium trifluoromethanesulfonate. The final macrolactamization was accomplished efficiently by PyBOP and DMAP in solution.     

New poly(amide-imide) syntheses. V. Preparation and properties of poly(amide-imide)s based on the diimide—diacid condensed from 2,2-bis[4-(4-aminophenoxy)phenyl]propane and trimellitic anhydride

A dicarboxylic acid ( 1 ) bearing two pre-formed imide rings, was prepared from the condensation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and trimellitic anhydride. A new family of poly(amide-imide)s having inherent viscosities of 0.53–1.68 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide—diacid I with various aromatic diamines in a medium consisting of N-methyl-2-pyrolidone (NMP), pyridine, and calcium chloride. 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 poly(amide-imide)s were in the range of 237–293°C and the 10% weight loss temperatures were above 508°C in nitrogen. © 1993 John Wiley & Sons, Inc.     

常温下合成磷酸三苯酯的研究

研究了常温下由苯酚钠悬胶体与三氯氧磷反应合成磷酸三苯酯的工艺条件, 找到了一条比较好的合成方法. 此方法具有操作方便、条件温和、反应时间短、能耗低、腐蚀小、污染少、产物纯、产率高等优点.     

Benzyl(triphenyl)phosphonium Dichloroiodate: A New Reagent for Coiodination of Alkenes

A mild, efficient, and regio‐ and stereoselective method for iodoalkoxylation and iodohydroxylation of olefins has been developed using benzyl(triphenyl)phosphonium dichloroiodate as iodine source. This procedure led to the corresponding iodoalkoxylated and iodohydroxylated products in moderate to excellent yields.     

格氏反应制备醇实验的改进

对有机化学必修实验“格氏反应制备醇”进行了研究。采用四氢呋喃(THF) 替代无水乙醚做反应溶剂,对教材中实验的试剂无水处理、反应的引发、试剂的用量、反应的后处理、产品的重结晶及用薄层色谱(TLC)检测产品纯度等进行了探讨和改进。结果表明,在THF中进行格氏反应制备三苯甲醇,实验现象明显,产率较高,降低了实验成本,全面提高了学生综合实验能力。     

三苯基膦氧基团在合成高性能有机电致发光材料中的应用

有机电致发光技术在通讯、信息、显示和照明等领域显现出巨大的商业应用前景, 十几年来一直是光电信息领域的研究热点之一。相对于无机电致发光材料,有机电致发光材料具有许多优点。近年来,三苯基膦氧基团在合成高性能有机电致发光材料方面的研究吸引了大批研究者的关注。由于磷原子自身性质,可以形成5个共价键,所以膦氧基团极易和其他基团连接形成以其为核的衍生物。由于氧原子具有很强的电负性,这就使膦氧结构高度极化并具有强的吸电子性。吸电子的膦氧基团连接苯环形成的三苯基膦氧单元也具有较强的吸电子性,其对所形成的化合物的能级结构也会产生明显影响。本文从材料合成的角度综述了三苯基膦氧基团在合成高性能有机电致发光材料中的应用方面所取得的最新研究进展,重点介绍了三苯基膦氧基团在合成高性能磷光二极管主体材料、电子传输材料和单分子电致发光材料等方面的应用。最后讨论了三苯基膦氧基团在上述领域应用过程中所存在的问题和功能拓展方向,并对下一步需要研究的热点问题作了展望。     

液相色谱/质谱/质谱联用法测定润滑油中磷酸三苯酯含量

探讨了用ＬＣ／ＭＳ／ＭＳ联用仪测定液压油中的微量添加剂磷酸三苯酯的方法。应用ＭＲＭ方式记录了ＨＰＬＣ的流出峰,结果表明被分析样品浓度在１～７ｍｇ／Ｌ范围内,色谱峰面积与浓度有良好的线性关系。讨论了ＬＣ／ＭＳ／ＭＳ技术实验条件的选择方法。     

Synthesis and properties of novel aromatic polyamides based on “multi-ring” flexible dicarboxylic acids

The five benzene rings-containing (hereafter referred to as “five-ring”) dicarboxylic acids α,α′-bis[4-(4-carboxyphenoxy)phenyl]-1,4-diisopropylbenzene (p- III ) and α,α′-bis[4-(4-carboxyphenoxy)phenyl]-1,3-diisopropylbenzene (m- III ) were prepared by the fluoro-displacement of α,α′-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene and α,α′-bis(4-hydroxyphenyl)-1,3-diisopropylbenzene with p-fluorobenzonitrile, and subsequent alkaline hydrolysis of the intermediate dinitriles. A number of high-molecular-weight polyamides based on these two “five-ring” dicarboxylic acids (p- III and m- III ) and various aromatic diamines were directly synthesized in N-methyl-2-pyrrolidone (NMP) containing lithium chloride (LiCl) or calcium chloride (CaCl₂) using triphenyl phosphite and pyridine as condensing agents. These polyamides were obtained with inherent viscosities above 0.51 and up to 0.91 dL/g. The weight-average molecular weight were in the range of 51,000–211,000. Most of these polyamides were amorphous and readily soluble in polar solvents such as NMP, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO), and afforded tough, flexible, and transparent films by solution-casting. The films had tensile strength of 50–83 MPa, elongation to break of 4–8%, and tensile modulus of 1.3–2.0 GPa. Most polyamides showed distinct glass transitions on the differential scanning calorimetry (DSC) curves ranging from 147 to 177°C. In nitrogen or air, all the polymers showed no significant weight loss up to 490°C, as indicated by thermogravimetric analysis (TG). © 1996 John Wiley & Sons, Inc.     

Lead(II) Siloxides

Although Pb^II-siloxides have been known until now to decompose to oxoclusters, here [{RO^F}PbOSi(SiMe₃)₃] (RO^F=fluoroalkoxide) and, most importantly, [Pb₂{OSi(SiMe₃)₃}{μ₂-OSi(SiMe₃)₃}₃], are presented. The unusual bonding pattern in the latter thermally stable dinuclear complex was investigated by crystallographic and computational methods. Its stability is much higher than that of the simple, yet elusive “[Pb(OSiPh₃)₂]”, for which decomposition pathways towards [Pb₄(μ₄-O)(μ₂-OSiPh₃)₆] have been clearly established.