Dipotassium Hydrogen Phosphate Powder Catalyzed Stereoselective O-Vinylation of 1-(2-Hydroxy-1-naphthyl)-1-ethanone

Protonation of the highly reactive 1:1 intermediates, produced in the reaction between triphenylphosphine and dialkyl acetylenedicarboxylates, by 1-(2-hydroxy-1-naphtyl)-1-ethanone leads to vinyltriphenylphosphonium salts, which undergo a Michael addition reaction with a conjugate base to produce corresponding stabilized phosphorus ylides. Dipotassium hydrogen phosphate powder was found to catalyze the conversion of stabilized phosphorus ylides to dialkyl (E, Z)-2-(1-acetyl-2-naphthyl)-2-butenedioates under thermal and microwave conditions in a solventless system.     

Role of chloroolefins in the formation of copper complexes catalytically active in isomerization of dichlorobutenes

Tetranuclear copper(I) complexes with organic donor ligands were found to be the best precursors of a catalyst for dichlorobutene isomerization. The products of interaction between allyl chloride and a tetranuclear triphenylphosphine complex of copper bromide were investigated by diffraction and spectral analysis. This reaction yields [Cu(PPh₃)Br _n Cl_1−n ]₄ and complexes containing the products of transformation of both triphenylphosphine and allyl chloride. Presented at the First Moscow Workshop on Highly Organized Catalytic Systems. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1830–1834, October, 1997.     

Triphenylphosphine-Catalyzed,Novel, One-Pot,Multicomponent Synthesis of Functionalized β-Acetamido Carbonyls

An efficient triphenylphosphine-catalyzed synthesis of β-acetamido carbonyls via multicomponent reaction of aromatic aldehydes, enolizable ketones or β-keto esters, acid chlorides and acetonitrile at room temperature is described. The process is remarkably simple, environmentally benign, and uses Lewis base for the first time in such type of reaction.     

PPh3⋅HBr‐DMSO Mediated Expedient Synthesis of γ‐Substituted β,γ‐Unsaturated α‐Ketomethylthioesters and α‐Bromo Enals: Application to the Synthesis of 2‐Methylsulfanyl‐3(2 H)‐furanones

An efficient chemoselective general procedure for the synthesis of γ‐substituted β,γ‐unsaturated α‐ketomethylthioesters from α,β‐unsaturated ketones has been achieved through an unprecedented PPh₃?HBr‐DMSO mediated oxidative bromination and Kornblum oxidation sequence. The newly developed reagent system serves admirably for the synthesis of α‐bromoenals from enals. Furthermore, AuCl₃‐catalyzed efficient access to 3(2H)‐furanones from the above intermediates under extremely mild conditions are described.     

Synthesis,reactions, and biological study of some new thienopyrimidine derivatives as antimicrobial and anti‐inflammatory agents

Pyrimidine and thienopyrimidine derivatives play a very important role in organic chemistry because of their wide applications as bioactive compounds with multiple biological activities. However, a literature survey revealed that the merger of different groups in the thieno[2,3‐d]pyrimidine heterocyclic ring enhances its antibacterial, antifungal and anti‐inflammatory activities. This encouraged us to prepare a new series of thieno[2,3‐d]pyrimidine heterocyclic compounds and to test them as antimicrobial and anti‐inflammatory agents. These compounds have shown remarkable activity toward fungi, bacteria, and inflammation. Thus, these compounds have been prepared by the chloroacylation of 5‐amino‐4‐phenyl‐2‐(p‐tolylamino)thieno[2,3‐d] pyrimidine‐6‐carboxamide ( 4 ) using chloroacetyl chloride under neat condition to afford the target compound ( 6 ), which was used as precursor for the synthesis of a number of bioactive compounds. Thus reaction of the chloromethylpyrimidine derivative ( 6 ) with triphenylphosphine in dry benzene gave the corresponding ((4‐oxo‐9‐phenyl‐7‐(p‐tolylamino)‐3,4‐dihydropyrimido[4′,5′:4,5]thieno[2,3‐d]pyrimidin‐2‐yl)methyl) triphenylphosphonium chloride ( 7 ). Compounds 8a – 8c and 9a – 9c were obtained by the reaction of 7 with some selected aromatic aldehydes and ketones in methanol and sodium methoxide under Wittig reaction condition. The structures of the all new synthesized compounds were established on the basis of their analytical and spectral data (IR, ¹H NMR, ¹³C NMR, and MS).     

Self-propagating high-temperature synthesis in the solid-phase triphenylphosphine-chloramine system

The macrokinetics and products of self-propagating high-temperture synthesis (SHS) in the solid-phase triphenylphosphine—chloramine system were studied by TGA-DTA, XRD, and³¹P NMR techniques. The temperature of SHS ignition (59°C), the velocity of reaction waves (1.6–5.0 mm s⁻¹), and the maximum temperature (155–239°C) in the SHS wave were measured. The chemical composition of the product obtained was established: phosphine oxide, triphenyl-N-(phenylsulfoyl)-phosphinimine, benzenesulfonamide, NaCl, and water. The scheme of chemical reactions occurring during SHS was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 301–305, February, 1999.     

三苯基膦铜（I）配合物的合成与结构

概述了三苯基膦铜(I)配合物的研究进展，包括三苯基膦铜(I)配合物的四种合成方法：置换法、还原法、电化学法和直接加成法，以及单核、双核、多核和异核铜(I)配合物的结构特征。参考文献36篇。     

伯胺N1923、三苯基氧化膦的界面吸附特性

在25±1℃下考察了N_(1923)(或TPHPO)-CHCl_3/HCl(或HCl-AuCl_4)和N_(1923)-TPhPO-CHCl_3/HCl(或HCl-AuCl_4~-)等6个体系的界面吸附特性,得到了各体系C_(min)、Γ_∞、A_1等界面吸附特性参数。结果表明,N_(1923)的界面活性明显强于TPhPO.当N_(1923)-TPhPO共存时的Γ_∞值较之N_(1923)或TPhPO单独存在时均有增加,可用于解释萃取动力学行为。     

三苯基麟氧化物萃取金及其机理

本文研究三苯基膦氧化物从盐酸介质中萃取金,考察了多种因素对萃取的影响,借等温曲线法、斜率法、紫外吸收光谱和反萃等方法确定了被萃络合物的组成.红外光谱指出,系由试剂中P=O基团发生配合作用,由三个试剂分子与水分子发生氢键缔合而成萃合物H_3O~ ·3TPPO…AuCl_4~-.     

两种基于硫醇配体的银(Ⅰ)配合物的合成、表征和晶体结构

通过AgCl、PPh₃和MBT以1:2:1的物质的量之比反应得到2种不同的配合物[AgCl(PPh₃)₂(BTZT)]·CH₃OH (1)和[AgCl(PPh₃)₂ (BTZT)]₂ (2)(PPh₃=三苯基膦;MBT=2-巯基苯并噻唑;BTZT=苯并噻唑-2-硫酮)(其中2已报道)。配合物[AgBr(PPh₃)₂(BTZT)]·CH₃OH (3)和[AgBr(PPh₃)₂(BTZT)]₂ (4)改用AgBr以相似的反应获得(其中4已报道)。通过红外光谱、元素分析、核磁共振氢谱、X射线单晶衍射、荧光光谱对配合物1和3进行了分析和表征。我们发现在不同的化学环境中,MBT配体可以转化为BTZT配体,原因是其具有化学活性基团。荧光光谱表明1和3的发射峰均源于配体中的π-π^*跃迁。