Formation of derivatives of chlorophenoxy acids and some other herbicides

Summary A fuming sulphuric acid-ethanol esterification method has been applied to chlorophenoxy acids and some other herbicides. This method is compared with esterification by iodoethane and diazomethane. The chlorophenoxy acids studied were: 2,4-D, dichlorprop, MCPA, MCPB, mecoprop and 2,4,5-T. Other herbicides studied were: benazolin, bentazone, bromophenoxime, bromoxynil, chlorthal, dicamba, 3,6-dichloropicolinic acid, dinoseb, ethephon, fluroxypyr, glyphosate, haloxyfop, ioxynil, picloram, 2,3,6-TBA and triclopyr. Fuming sulphuric acid-ethanol esterification can be successfully applied to chlorophenoxy acids, benazolin, 3,6-dichloropicolinic acid, dinoseb, fluroxypyr, haloxyfop, picloram and triclopyr. The reproductibility of the method is ±5%.     

STUDY OF CARBOXYL METHYL STARCH ON PAPER STRENGTH

INTRODUCTIONIn China, there is not abundant of wood resourceNon-wood fiber materials, especially like wheastraw and reed, would still be considerably used araw materials of papermaking in a long period ofuture. However, wheat straw pulp and reed pulwith the problem of short fiber and many mixed celllead to the paper in low strength. So in thmanufacture of papermaking, more and moradditives are added to make up the deficiency. Ipapermaking industry, different types of starch anstarch deri…     

Direct assignment of positional isomers by mass spectrometry: ortho,meta and para acyl and amidyl anilines and phenols and derivatives

A direct MS/MS method for the ortho, meta or para configuration assignment of any single molecule that forms reference ions upon ionization and dissociation is demonstrated. Gas-phase structure diagnostic ion–molecule reactions with acetonitrile are shown to distinguish the isomeric 2-, 3- and 4-hydroxybenzoyl cations and the 2- from the 3- and 4-aminobenzoyl cations. These reference ions, which display indistinguishable 15 eV collision-induced dissociation product ion mass spectra, react with acetonitrile to yield characteristic ratios of product ions, most particularly for the 2-isomers. The reactivity of the 2-benzoyl cations is the most characteristic since the ortho configuration allows for [4⁺ + 2] polar cycloaddition that yields relatively stable heterocycles in N-protonated forms. Distinction of the reference isomeric 2-, 3- and 4-hydroxy- and aminobenzoyl cations permits, therefore, partially or completely, direct ‘MS-only’ positional assignment of either ortho, meta or para configuration for any single molecule that forms such reference ions upon ionization and dissociation. This “class-universal” method for direct MS assignment of a single positional isomer should therefore be applicable to many members of the homologous series of isomeric ortho, meta and para acyl and amidyl anilines and phenols and derivatives. Such molecules dissociate, or are likely to dissociate, after or during ionization processes to form the reference and structurally diagnostic ortho, meta or para hydroxy- or aminobenzoyl cations. Copyright © 2004 John Wiley & Sons, Ltd.     

高电荷态同质异能态的寿命

分析了带电原子由于缺少内转换(同质异能态)或电子俘获跃迁(β衰变)引起的核寿命的变化.理论预言了随着电荷态的增加,内壳的电子在核表面的电子密度降低,内壳电子能级也降低,不稳定原子核的寿命由于前一原因而缓慢增加,但当内壳电子能级降到特殊能量时产生剧烈增加.比较了由于不同的跃迁能量和跃迁类型对内转换过程的半衰期的影响,并将计算的理论值与一些实验测量值进行了比对.并开发了进行这类计算的公共计算程序.     

Nonisothermal thermogravimetry of polymers

The model of weight loss taking place in each step of a scheme of consecutive reactions was applied to nonisothermal thermogravimetric records of bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide). The release of HBr was found to be faster in air than in nitrogen. A significant reduction in the apparent activation energy of dehydrobromination as compared with decomposition of the nonbrominated polymer was ascribed not only to a reduction in the activation energy of the initiation reaction, but also to an increase in the order of the termination reaction (from 1 for the nonbrominated polymer to 2 for the highly brominated polymer).     

Dephenylation of triphenylbismuth(v) and antimony(v) derivatives in a methyl acrylate—methanol system in the presence of copper and palladium salts

The influence of the central metal atom and acid residue in a molecule of organometallic compound Ph₃MX₂ (M = Bi, Sb; X = Cl, Br, OAc, O₂CEt) on the direction and yield of dephenylation products in a methyl acrylate— methanol system in the presence of Cu(OAc)₂ and Na₂PdCl₂(OAc)₂ was studied at 50 °C in acetonitrile. The main product of dephenylation of the antimony compounds is methyl cinnamate (yield 0.31–1.59 moles per mole of the starting Ph₃SbX₂), while anisole (0.55–0.97 mol) and halobenzene (0.67–1.04 mol) are those for compounds Ph₃Bi(O₂CR)₂ and Ph₃BiHal₂, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 655–658, April, 2006.     

Studies on the Chemical Constituents of Oxytropis Glabra DC (I)

Two new triterpenoid sapon.ins 1 and 2 were isolated from the crude saponin extract of Oxytropis glabra DC by Si gel chromato-grapny . Saponins 1 and 2 were determined to be 3-0-1 β-D-glucopyranosy 1 (1-2)- β -D-glucuronopyranosyl azukisapogenol methyl ester and 3-O-[β-D-glucopyranosyl(1 - 2 ) - β -D-glucuronopyranosyl] azukisapogenol amide, respectively by spectral analysis and chemical methods.     

三种C240异构体分子的AM1研究

采用RHF水平的AM1半经验量子化学方法,计算了线性4C60富勒烯聚合体、花生壳状4C60富勒烯聚合体,以及C240纳米碳管等三种C240异构体分子的几何构型、电子结构、分子能量,以及疏水常数LogP、极化率、偶极矩等物理化学特性,讨论了三种C240异构体分子的几何构型、前线分子轨道及能级、净电荷分布与静电势、分子能量等特性的差异.研究表明,三种C240分子的生成均为吸热,它们的稳定性依次排序为:C240纳米碳管>花生壳状4C60>线性4C60.     

Automated parallel investigations/optimizations of the reversible addition‐fragmentation chain transfer polymerization of methyl methacrylate

Poly(methyl methacrylate)s were successfully synthesized in a controlled fashion via reversible addition‐fragmentation chain transfer polymerizations utilizing an automated synthesizer. Sixteen polymers were synthesized in a parallel way utilizing the Chemspeed Accelerator? SLT100 to investigate the reproducibility and the control over the polymerizations. The obtained polymers were characterized by gel permeation chromatography (GPC) and automated MALDI TOFMS measurements, thereby proving the reproducibility and controllability of the investigated automated setup. Furthermore, temperature optimization reactions were performed utilizing an individually heatable reactor block. Moreover, to demonstrate the presence of active polymer chains in the reaction mixture, chain extension polymerizations were performed on the automated synthesizer. The results obtained from these chain extension experiments demonstrate the possibility to design well‐defined A‐b‐B block copolymers with different monomers as building units. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5775–5783, 2004     

Study on Soap-free P（MMA-EA-AA/MAA） Latex Particles With Narrow Size Distribution

In the past decades, more and more studies have been focused on the synthesis of monodisperse particles with different diameter by special polymerization technique. In 1980＇ s, Ugelstad, et al invented two-step swelling method to prepare monodisperse microsphere with large size more than 1μm. In the following decade, Okubo and his coworkers synthesized monodisperse crosslinked polymer particles above 3μm using one-step dynamic swelling method. New method has been developed to produce particles more than 50 gm in diameter with a standard deviation of less than 2 % . Up to now, most of the monodisperse particles were usually prepared by polymerization of St in the presence of surfactants. In this presentation, sub-micro sized P （MMA-EA-AA/MAA） particles with narrow size distribution were prepared by seeded emulsion polymerization in the absence of any surfactant materials.