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与芳香胺相比,芳香硝基化合物具有廉价易得、官能团兼容性好等优点,作为氮源在下游含氮化学品合成中具有广泛的应用.目前烯烃羰化酰胺化反应绝大多数以胺类化合物为氮源,其中直链和支链酰胺产物的选择性主要是通过具有特定电子和位阻特性的配体调控实现.已报道的芳香硝基化合物的还原酰胺化反应研究中,需要外加还原剂或者利用金属羰基化合物Mo(CO)6释放的CO为羰基源和还原剂.本文发展了一种毋须外加还原剂的钯催化芳香硝基化合物与烯烃的还原羰化酰胺化反应新方法.研究发现,钯金属催化剂(特别是离子型)的抗衡阴离子是还原羰化酰胺化反应中化学选择性和羰化区域选择性的关键因素.抗衡阴离子为氯离子、硼酸为助剂时,最优钯前驱物K2PdCl4的产物主要为支链酰胺,此时不同的膦配体并不能调控其区域选择性,这与胺的烯烃酰胺化反应可以通过配体调控羰化的区域选择性表现出明显的不同.含氮中间体原位捕捉、硝基化合物还原下游可能中间体对照实验等研究表明,芳香硝基化合物在以一氧化碳为还原剂的催化还原体系下被完全脱氧还原为氮烯(Ar-N:),再经过烯酰胺中间体进一步烯键还原得到相应的支链酰胺;当离子型钯前驱物的抗衡阴离子配位性较弱时,最优钯前驱物为Pd(CH3CN)4(OTf)2时,以直链酰胺为主要产物,此时不同的膦配体可以调控酰胺化的区域选择性.同样的机理研究表明,在该催化剂体系下芳香硝基化合物首先被还原为芳基胺,然后再发生与现有报道类似的胺类化合物的烯烃羰化酰胺化反应.这两个催化反应体系都表现出了较好的底物适用性,并且可以高效地应用于除草剂(敌稗)的一步合成.本文为以硝基化合物为起始氮源,通过催化控制生成特定含氮中间体,从而可控合成不同的含氮化学品提供了一条新思路. 相似文献
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配体参与的有机金属化合物对亚胺的不对称加成反应* 总被引:1,自引:0,他引:1
手性胺类化合物是一类重要的有机化合物,在生物化学及药物合成中有广泛应用.有机金属化合物对亚胺的不对称加成反应是合成手性胺类化合物的重要方法之一.本文对近年来外加配体参与的有机金属化合物对亚胺的不对称加成反应,特别是催化合成手性胺类化合物的研究进展作一概述. 相似文献
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论述了动态动力学拆分的原理,介绍了化学酶法拆分消旋体胺类化合物的反应和近年来的研究进展;指出手性胺是构成许多中间体的基础化合物,化学酶法动态动力学拆分是制备单一手性胺类化合物的重要方法. 相似文献
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微波萃取高效液相色谱法测定口红中芳香胺类化合物 总被引:6,自引:0,他引:6
利用微波萃取高效液相色谱法测定了口红中芳香胺类化合物.先将口红涂于玻璃片上,然后用微波萃取和高效液相色谱法测定萃取液中的芳香胺类化合物.研究了3种市售口红并得到了芳香胺类化合物的定量测定结果.考察了微波萃取的条件,并将薄层色谱等萃取分离方法和微波萃取法进行了比较,证明微波萃取法在萃取膏状物和蜡状物中的组分时,具有比其它方法更加方便、快速等优点. 相似文献
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I. Ya. Postovskii Yu. A. Azev G. A. Mokrushina 《Chemistry of Heterocyclic Compounds》1976,12(8):942-945
2-Amino-3-hydrazinopyridine reacts with carbon disulfide to give 1,2,3,4-tetrahydropyrido[2,3-e]-asym-triazine-3-thione. The methylthio derivative obtained from it is oxidized to the sulfone, which undergoes exchange of the methylsulfonyl group for an amine residue in the cold. The methylthio derivative undergoes this sort of reaction only on heating, whereas in the cold it reacts with amines to give adducts that are unstable in solution and on heating. 相似文献
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Butadiene reacts with nitroalkanes in the presence of triphenylphosphine complexes of palladium, α-Hydrogens of nitroalkanes are displaced with 2,7-octadienyl groups to give nitroolefins. The nitroolefins thus obtained are reduced to give novel long chain amines, which have a primary amino group at the middle of the carbon chain. 相似文献
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Adenier A Chehimi MM Gallardo I Pinson J Vilà N 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):8243-8253
The electrochemical oxidation of aliphatic amines (primary, secondary, and tertiary) has been investigated by cyclic voltammetry and preparative electrolysis. The oxidation mechanisms have been established, and the lifetimes of the radical cations have been measured for secondary and tertiary amines. These results have been put in parallel with the attachment of amines to glassy carbon, Au, and Pt electrodes by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and infrared reflection-absorption spectroscopy (IRRAS). It is then possible to show that it is not the radical cation but the radical obtained after the deprotonation which reacts with the electrode surface. XPS results also point to the existence of a covalent bond between Au or Pt and the organic moiety. 相似文献
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A selection of 2-lithiopyrrolidines with different N-alkyl-substituents were prepared and tested for their dynamic resolution in the presence of the chiral ligand (−)-sparteine. Good yields of the electrophile-quenched products were obtained with enantiomer ratios up to 85:15 using branched N-alkyl derivatives. The major product was shown to have the opposite absolute configuration compared with that obtained in the asymmetric deprotonation of N-Boc-pyrrolidine with (−)-sparteine. The enantioselectivity arises from a dynamic thermodynamic resolution in which the minor diastereomeric complex reacts faster with the electrophile. 相似文献
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Carbon dioxide reacts with amines in the presence of phosphorus compounds and tertiary amines to give the corresponding ureas in high yield, and carbon disulfide gave thioureas. The presence of tertiary amines such as pyridine or imidazole facilitated the reactions. Aryl esters of phosphorous, phosphonous, phosphinous and phosphonic acids were effective, whereas their corresponding alkyl esters were ineffective. Various molar ratios of phosphite:tartiary amine:amine (aniline), produced variations in yield showing that the reaction proceeds via a carbamoyloxy and a thiocarbamoylthioxy N-phosphonium salt of the tertiary amine. 相似文献
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Tetramethylethylenediamine (TMED) reacts with ethylene (propene) under the influence of catalytic amounts of alkyllithium to give dimethylvinylamine and dimethylethylamine (dimethylisopropylamine). In competitive reactions alkyl-lithium and the amides formed by this with primary or secondary amines in presence of tetramethylethylenediamine enhance the addition of primary or secondary amines to ethylene more strongly than in the absence of the diamine. The pressures are to of those needed when sodium catalysts are used and the temperatures required are 50–100° lower. Dimethylamine but not diethylamine, which however reacts with cycloolefins containing strained double bonds, adds to propene. 相似文献
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Chan Sik Cho Li Hong Jiang Dong Yub Lee Sang Chul Shim Hyung Soo Lee Sung-Dong Cho 《Journal of heterocyclic chemistry》1997,34(4):1371-1374
2-Bromobenzaldehyde reacts with an excess of primary amines under a carbon monoxide in the presence of a catalytic amount of bis(triphenylphosphine)palladium(II) chloride together with triethylamine to give the corresponding 3-(alkylamino)isoindolin-1-ones in good yields. 相似文献
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Montmorillonite K 10 efficiently catalyses the opening of epoxide rings by amines in high yields with excellent regio- and diastereo-selectivities under solvent-free conditions at room temperature affording an improved process for synthesis of 2-amino alcohols. Reaction of cyclohexene oxide with aryl/alkyl amines leads to the formation of trans-2-aryl/alkylaminocyclohexanols. For unsymmetrical epoxides, the regioselectivity is controlled by the electronic and steric factors associated with the epoxide and the amine. Selective nucleophilic attack at the benzylic carbon of styrene oxide takes place with aromatic amines, whereas, aliphatic amines exhibit preferential nucleophilic attack at the terminal carbon. Aniline reacts selectively at the less hindered carbon of other unsymmetrical epoxides. The difference in the internal strain energy of the epoxide ring in cycloalkene oxides and alkene oxides led to selective nucleophilic opening of cyclohexene oxide by aniline in the presence of styrene oxide. Due to the chelation effect, selective activation of the epoxide ring in 3-phenoxy propylene oxide takes place in the presence of styrene oxide leading to preferential cleavage of the epoxide ring in 3-phenoxy propylene oxide by aniline. 相似文献
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Dufrasne F Gelbcke M Galanski M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,65(3-4):869-873
The applicability of (-)-myrtenal as a chiral derivatizing agent in combination with (13)C NMR spectroscopy was investigated. (13)C NMR was found to be a valuable tool for the identification and enantiomer differentiation of primary amines including beta-amino alcohols and vicinal diamines. The enantiomeric excess could be determined via automated deconvolution and integration, and was found to be in good accordance with the expected values even in the cases, when enantiomer differentiation was not possible in (1)H NMR spectra. 相似文献