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1.
In the course of our continuing synthetic experiments on benzoquinolizidine2 and indoloquinolizidine alkaloids3, we have recently utilized palladium catalyzed amidation4 for the synthesis of the berbine alkaloids5. In this present paper we wish to report, what we believe is the first successful utilization of the palladium catalyzed amidation for the synthesis of the hexadehydroyohimbane skeleton. 相似文献
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Daniele Bianchi Rossella Bortolo Rino D'Aloisio Marco Ricci 《Angewandte Chemie (International ed. in English)》1999,38(5):706-708
Effective and stable Pd catalysts for the biphasic synthesis of hydrogen peroxide from carbon monoxide, oxygen, and water [Eq. (a)] can be obtained by the right choice of bidentate nitrogen ligand. The best turnover numbers (578) for this reaction have been achieved with palladium complexes with 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline ligands. 相似文献
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The reaction of phenols with carbon monoxide at atmospheric pressure and room temperature in the presence of palladium cholrode and tertiary amine produces diaryl carbonates and aryl salicylates. Only diaryl cabonates are produced when palladium carbonyl cholride is substituted for palladium chloride. Reaction pathways are proposed. 相似文献
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A review of the history and present state of the use of palladium complexes in the synthesis of alternating CO copolymers with different monomers (mainly ethylene, propylene, and styrene) is presented. The effect of mono- and bidentate phosphine ligands, the nature of reaction medium and acid on the rate of the CO copolymerization with ethylene, and the effect of different bidentate PP, PN, and NN ligands on the structure and properties of chiral CO–propylene and CO-styrene copolymers are considered. 相似文献
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Fausto Calderazzo 《Angewandte Chemie (International ed. in English)》1977,16(5):299-311
The synthetic potential and the mechanistic aspects of inorganic insertion reactions of carbon monoxide, especially into metal-carbon σ-bonds, are considered. Reactions of this type are encountered among most 3d, 4d, and 5d elements. In one case it has been demonstrated that the CO insertion proceeds by alkyl migration; this is likely to be a general feature of all such reactions. If an alkyl migration takes place, then insertion of CO into the M? C bond is governed kinetically by the cleavage of that bond. CO abstraction from RCO? M bonds most commonly proceeds by rate-determining vacation of a coordination position. Both CO insertion and abstraction are usually highly stereospecific. 相似文献
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无膦钯催化Heck反应合成新型芳维A酸类化合物 总被引:1,自引:0,他引:1
考察了以二环己基胺作配体的无膦钯催化Heck反应条件, 建立起一种新型的无膦钯催化Heck反应体系. 应用该体系可高收率(72%~84%)、高立体选择性(83%~95%)合成二取代和三取代二苯烯类化合物. 以2,4,5-三甲氧基苯乙烯、α-细辛脑为原料, 合成了4个尚未见文献报道的新型二苯烯类芳维A酸甲酯(3a, 3b, 4a, 4b), 并且在温和的水解体系[LiOH, V(THF)∶V(H2O)=5∶1]下顺利得到了它们的水解产物芳维A酸(5a, 5b, 6a, 6b), 产物通过1H NMR, 13C NMR, IR和MS进行了结构确认. 相似文献
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钯-稀土催化一氧化碳和苯乙烯交替共聚反应 总被引:1,自引:0,他引:1
利用稀土钇盐或钕盐和乙酸钯组成的催化体系催化一氧化碳和苯乙烯共聚,合成了聚(1-氧代-2-苯基丙撑). 用元素分析、红外光谱、示差扫描量热、热重分析及X射线光电子能谱(XPS)等方法对共聚产物进行了表征. 测试结果表明,共聚物为一氧化碳和苯乙烯的线性交替共聚产物,其玻璃化温度为235 ℃,熔点为250 ℃,分解温度为325 ℃,且用XPS未检测到聚合物中含有残留的金属. 同时考察了催化剂组分2,2′-联吡啶、对甲苯磺酸和对苯醌及溶剂甲醇等的用量对共聚反应的影响,并对聚合反应条件进行了优化. 在优化的反应条件下稀土与钯组成的复合催化剂对一氧化碳和苯乙烯交替共聚的催化活性可达1200 g/(g·h). 相似文献
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《Analytical letters》2012,45(14):2547-2559
Abstract The adsorption of carbon monoxide from basic solution (0.1 M LiOH) on a palladium electrode was investigated. It was found that adsorption of CO takes place below the potential -0.25 V (vs. SCE). Surface concentration of the adsorption products, their composition and structure depend on the adsorption potential. The CO adsorption products block hydrogen absorption in palladium but in contrary to acidic solutions don't block the hydrogen desorption process. 相似文献
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This article reviews recent discovery and progress of copolymerization of CO with cyclic monomers such as methylenecyclopropanes and propylene oxide promoted by transition metal complexes. 2-Aryl-1-methylenecyclopropanes react with CO in the presence of the Pd catalyst under mild conditions (1 atm, room temperature) to afford the polyketones. The reaction involves alternating insertion of the two monomers and opening of the three-membered ring of the cyclic monomers. Mechanistic study of the polymer growth revealed that 2-aryl-1-methylenecyclopropane undergoes 1,2-insertion into the Pd–acyl bond and subsequent -alkyl elimination of the cyclopropylmethylpalladium group. A bicyclic methylenecyclopropane, 7-methylenebicyclo[4.1.0]heptane, also reacts with CO in the presence of the Pd complexes with diimine ligands to afford the polyketone with six-membered rings in the repeating unit. The NMR spectra of the polyketone indicate the regulated tacticity of the monomer units. Co complexes and a mixture of Co and Ru complexes with carbonyl ligands promote the copolymerization of CO with propylene oxide in the presence of amine additives under CO pressure at 50 atm. Structures of the produced polyesters vary depending on the reaction conditions. 相似文献
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Benzoxazolinones are a known class of commercially available compounds that are widely used in agriculture and industry. Traditionally, these compounds are made by the intramolecular cyclization of phenyl N-(2-hydroxyphenyl)carbamate which is produced by the reaction of o-aminophenol with phenyl chloroformate[1], this route needs a large number of steps from commercially available starting materials; another method is the reaction of o-aminophenol with much more urea, a lot of NH3 is released during the process[2,3]; the last method is from salicylic acid by treatment with hydroxylamine and commercial polyphosphoric acid, the yield of the reaction is 33%[4]. 相似文献
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Xiaopeng Zhang 《合成通讯》2013,43(19):3291-3299
Catalyzed by selenium, oxidative carbonylation of aniline and thiols with carbon monoxide and oxygen affords the corresponding thiocarbamates mostly in moderate to good yields under solvent‐free conditions at ambient temperature. 相似文献
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Qing Bao SONG* Ru Xiang LIN Tian Hua SHEN College of Chemical Engineering Materials Science Zhejiang University of Technology Hangzhou 《中国化学快报》2005,16(1)
In the last two decades, molecular-based second-order nonlinear optical (NLO) chromo-phores1, have attracted much interest because of their potential applications in emerging 2opto-electronic technologies. These efforts have mainly focused on organic systems.More recently, organometallic molecules have been investigated as well. In comparisonto common organic molecules, they offer a large variety of novel structures3, . The 4possibility of high environmental stability, and divers… 相似文献
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The synthesis of N-acyl-α-aminoacids by catalytic carbonylation of aldehydes in the presence of amides was discovered by H. Wakamatsu1 and then investigated by P. Pino2 相似文献
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