β-芳氨基酮肟的Beckmann重排

β-氯代丙酰芳胺与仲胺,或β-二脂氨基丙酰氯与芳胺作用,得到的β-脂氨基丙酰芳胺具有高效麻醉作用。Scott 等人曾在五氯化磷-乙醚存在下,用β-二甲氨基苯丙酮肟进行Beckmann 重排,并在重排产物中,直接加入碘代甲烷,将它转换为碘代三甲铵基丙酰芳胺。二个芳基相同的β-芳氨基丙酰芳胺(3)可用丙烯酸与苯胺加热,芳胺与 H_2NCOCH_2-CH_2OSO_3H 的加合物在封闭管中加热,或用Pd(PPh_3)_4为催化剂,使氯乙烯、一氧化碳和     

Pd/C催化氢化芳香族硝基化合物合成芳胺

以5%Pd/C为催化剂,芳香族硝基化合物在温和条件(30℃,H2/0.1 MPa)下还原成芳胺。研究了芳环上的取代基对催化加氢反应的影响。结果表明:对位取代的芳硝基化合物的加氢反应速率为:HCH3CO2CH3CF3FOCH3;间位取代芳硝基化合物加氢反应速率为:HCH3CF3FCO2CH3OCH3CN;邻位取代芳硝基化合物加氢反应速率为:HCF3CH3OCH3FCO2CH3CN。     

三溴化三乙基苄铵对于苯偶姻的氧化反应

作者前曾报道,三溴化三乙基苄铵(PhCH_2Et_3NBr_3~-,TEBABr_3,1)和三碘化三乙基苄铵(TEBAL_3)能作为有效的溴代和碘代试剂而与芳胺反应,以高产率生成多溴代和多碘代芳胺。在进一步对TEBABr_3在有机合成     

一类新型水溶性膦配体及其钠盐的合成

在温和的反应条件下,以季Lin盐[Ph2P(CH2OH)2]^ Cl^-与含醚键和有机膦酸根的胺H2O3PCH2N CH2-CH2（OCH2CH2）nNH2(n=1,2,3)的曼尼希反应,高产率合成了含Ph2PCH2N=配位基团的水溶性膦配体,用NMR、MS、IR、UV和光电子能谱等对其结构进行了表征。     

水相中苯并噻唑类衍生物的微波辐射合成

在水相中建立了一种简单实用,廉价的2-碘芳胺与芳醛和硫氰酸钾反应生成苯并噻唑衍生物的微波辅助铜催化体系。该体系只需以碘化亚铜和1,10-菲罗啉为催化剂,以碳酸铯为碱的100 ℃水中反应30 min,就能得到大量苯并噻唑衍生物,最高产率达94%。     

含氮两亲膦配体N，N‘—双（二苯膦甲基）哌嗪及钯配合物的合成和催化羰化反应

在温和的条件下,以季Lin盐（Ph2P(CH2OH)2]^ Cl^-与胺的曼尼希反应,高产率合成了含Ph2PCH2N=配位基团的两亲膦配体N,N'-双（二苯膦甲基）哌嗪。在正丁醇中于氮气保护下制备了Ph2P/Pd摩尔比为2：1和1：1的钯配合物。该钯配合物对氯苄的常压羰基化反应有很高的催化活性,苯乙酸的产率可达91%。     

2-碘腺苷合成新方法

报道了核苷药物中间体2-碘腺苷的合成新方法.以2-氨基-6-氯-2′,3′,5′-三-O-乙酰基嘌呤核苷为原料,以CH3CN为溶剂,I2为碘源,5%的Cu I为催化剂,合成了到2-碘-6-氯-2′,3′,5′-三-O-乙酰基嘌呤核苷,继而在饱和的NH3/CH3OH溶液中氨解,以两步和78.2%的总收率得到2-碘腺苷.反应规模可以扩大到公斤级,收率没有降低.中间体及产物的分离、纯化不需要柱层析.该方法高效、简便、易于操作,显示出很好的应用前景.     

二(β-氨基乙基)胺型聚苯乙烯树脂的合成和性能研究

以二乙烯三胺和氯甲基化聚苯乙烯树脂微球为起始原料,通过伯胺保护、树脂胺化、脱保护等3个步骤,合成了以二(β-氨基乙基)胺为功能基的聚苯乙烯树脂,分析了该树脂的结构,研究了其对Cu2+的螯合性能。与二乙烯三胺型树脂相比,本文合成的树脂具有吸附速度快、吸附容量大,脱附完全,易于重复使用等优点,对Cu2+吸附量达2.42mmol/g,脱附率为99.8%,吸附-脱附3次后,活性仍达95.0%。     

空穴传输材料三芳胺衍生物的合成及性质研究

以二芳胺和芳碘体系为原料,经乌尔曼反应制备了一系列三芳胺衍生物,经NMR,IR,MS等表征了其结构,通过示差扫描量热法(DSC)测定了其玻璃化转变温度,并利用循环伏安法结合紫外可见光谱测定了其HOMO能级和LUMO能级.     

含吡咯基亚胺配体稀土铕配合物催化合成胍

以2-(2,4,6-Me3C6H2N=CH)C4H3NH为配体与铕配合物[(Me3Si)2N]3Eu(μ-Cl)Li(THF)3反应,合成了三价铕金属配合物[2-(2,4,6-Me3C6H2N=CH)C4H3N]3Eu(THF),以此配合物为催化剂催化芳胺与N,N’-二异丙基碳二亚胺反应,得到一系列胍产物,研究了反应时间、温度、催化剂用量和溶剂对催化反应的影响。结果表明:铕配合物具有良好的催化活性,以2%mol的催化剂用量、在THF中加热60℃反应8 h,得到高于80%产率的相应胍产物。     

聚苯乙烯基N-甲基-N-酰基磺酰胺树脂的制备及其作为酰基转移试剂在酰胺合成中的应用

聚苯乙烯基磺酰氯树脂(树脂1)与甲胺水溶液在吡啶的催化作用下反应，制备了N—甲基磺酰胺树脂(树脂2)．用酰氯在吡啶中与树脂2反应，得到N—酰基—N—甲基磺酰胺树脂(树脂3)．树脂3作为胺底物的酰基转移试剂，用来制备N—取代的酰胺，收率14～81％．树脂3可以有选择性地酰化乙醇胺中的氨基而不会使羟基酰化。     

SOLID PHASE SYNTHESIS OF ISOXAZOLINES

1. INTRODUCTION A solid phase organic synthesis (SPOS) has increasingly attracted chemist抯 attention over the past decades [1~3]. It was found that the compounds with biological activity are mostly derived from heterocycle structures. It is therefore no…     

SOLID PHASE SYNTHESIS OF ISOXAZOLINES

The solid-phase synthesis of isoxazolines on 2-polystyrylsulfonamidoethanol resin isreported. 2-Polystyrylsuifonamidoethanol resin 1 was reacted with acryloyl chloride to afford2-polystyrylsulfonylamidoethyl acrylate resin 2, which was further reacted with brominatedaldoximes by [3+2] cycioaddition to give isoxazoline resin 4. Resin 4 was treated with aqueous 6mol/L HCI solution to obtain isoxazolines in good yield and purity.     

Microwave Irradiated Reactions of N-Phenacylpyridinium Chloride with Aromatic Aldehydes and Ketones

Pyridinium cations show a great variety of synthetic applications,due to the aromatic character of the pyridine heterocycle, to its basicity, and the electron-attracting influence of the nitrogen atom1-3. N-phenacylpyridium bromide in the presence of base…     

Direct addition of Zr-C bonds of alkylzirconocenes to activated alkenes

Direct addition of alkylzirconocenes to activated alkenes was found, for the first time. Octyl- and decylzirconocene chloride reacted with benzylidenemalononitrile to give the corresponding addition products after hydrolysis in 86% and 79% yield, respectively. Zirconacyclopentanes showed a similar reactivity toward activated alkenes with a two-electron-withdrawing group. On the other hand, treatment of the reaction mixture of zirconacyclopentanes and ylidenemalononitriles with iodine afforded six-membered cyclic compounds in high yields. The diastereoselectivity of the cyclized compound was remarkably high and the high selectivity originated from the Zr-promoted cyclization. The structures of cyclic compounds 10b and the major diastereoisomer of 10d were determined by X-ray analysis. Zirconacyclopentenes reacted with ylidenemalononitrile with high chemoselectivity in which the sp(3)-carbon attached to zirconium reacted with ylidenemalononitrile.     

Solid-phase synthesis of N-acyl-N′-carbamoylguanidines

Amino acids immobilized on polystyrene-Wang or Rink amide resin were reacted with p-nitrophenyl chloroformate to give an activated urethane that was displaced by S-methylisothiourea. Following N-acylation with an acid chloride, the thiomethyl group was displaced by primary or secondary amines with the aid of mercury (II) chloride to yield the unsymmetrically substituted title compounds after resin cleavage.     

Alkylation of aromatic compounds with pummerer rearrangement intermediates. Application to the preparation of methyl-aryl compounds

Pummerer intermediates generated from dimethylsulfoxide reacted with aromatic compounds in the presence of tin (IV) chloride to give methyl-thiomethylaryl products which were in turn desulfurized to methylaryl compounds with Raney-Ni.     

Metal catalyst-free direct α-iodination of ketones with molecular iodine

Ketones are directly converted to the corresponding α-iodoketones in good yields with molecular iodine under metal catalyst-free conditions. A significant difference in the reactivities was observed for aliphatic and aromatic ketones; whereas aliphatic ketones reacted smoothly at room temperature giving a mixture of 1-iodo, 3-iodo and 1,3-diiodoketones with predominant formation of the 3-iodo product, the α-iodination of aromatic ketones proceeded conveniently under heating to give good yields of α-iodo products.     

Heterocyclic Synthesis with 4-Benzoyl-1-cyanoacetylthiosemicarbazide: Selective Synthesis of Some Thiazole, Triazole, Thiadiazine, Pyrrylthiazole, and Pyrazolo[1,5-a]triazine Derivatives

4-Benzoyl-1-cyanoacetylthiosemicarbazide undergoes coupling reaction with aromatic diazonium chloride to afford (arylhydrazono)thiosemicarbazide, which was reacted with phenacyl bromide regioselectivity to afford the thiazoline. The (arylhydrazono)thiosemicarbazide could be transformed into the pyrazolo[1,5-a]triazine. Heterocyclization of 4-benzoyl-1-cyanoacetylthiosemicarbazide with α-haloketones (bromoacetone and phenacyl bromide), ethyl iodide, and ethyl bromoacetate furnished the pyrrylthiazoles, 1,2,4- triazole, and 1,3,4-thiadiazine. The latter was coupled with aromatic diazonium chloride to give the bis(arylhydrazono)‐thiadiazine. The mechanism for the formation of the title compounds was suggested and discussed.     

An efficient chlorination of aromatic compounds using a catalytic amount of iodobenzene

An efficient method was developed for chlorination of aromatic compounds with electron-donating groups using iodobenzene as the catalyst and m-chloroperbenzoic acid as the terminal oxidant in the presence of 4-methylbenzenesulfonic acid in THF at room temperature for 24 h,and a series of the monochlorinated compounds was obtained in good yields.In this protocol,the catalyst iodobenzene was first oxidized into the hypervalent iodine intermediate,which then treated with lithium chloride and finally reacted with aromatic compounds to form the chlorinated compounds.