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51.
Yang L Mayr M Wurst K Buchmeiser MR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5761-5770
The synthesis of novel ruthenium-based metathesis catalysts containing the saturated 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene ligand, that is, [RuCl2(NHC)[=CH-2-(2-PrO)-5-NO(2)-C6H3]] (1) and [Ru(CF3COO)2(NHC)[=CH-2-(2-PrO)-5-NO2-C6H3]] (2) (NHC=1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) is described. Both catalysts are highly active in ring-closing metathesis (RCM) and ring-opening cross-metathesis (ROCM). Compound 1 shows moderate activity in enyne metathesis. Compound 2 is not applicable to enyne metathesis since it shows high activity in the cyclopolymerization of diethyl dipropargylmalonate (DEDPM). Poly(DEDPM) prepared by the action of 2 consists of 95% five-membered rings, that is, poly(cyclopent-1-enevinylene)s, and 5 % of six-membered rings, that is, poly(cyclohex-1-ene-3-methylidene)s. The polymerization proceeds in a nonliving manner and results in polyenes with broad polydispersities (1.9< or =PDI< or =2.3). Supported analogues of 2 were prepared by immobilization on hydroxymethyl-Merrifield resin and a monolithic support derived from ring-opening-metathesis polymerization (ROMP). Catalyst loadings of 1 and 2.5%, respectively, were obtained. Both supported versions of 2 showed excellent reactivity. With 0.24-2% of the supported catalysts, yields in RCM and ROCM were in the range of 76-100%. Leaching of ruthenium was low and resulted in Ru contaminations of the products of less than 0.000014% (0.14 ppm). 相似文献
52.
Synthesis of phthalide derivatives using nickel-catalyzed cyclization of o-haloesters with aldehydes
Rayabarapu DK Chang HT Cheng CH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):2991-2996
The reaction of o-bromobenzoate (1 b) with benzaldehyde (2 a) in the presence of [NiBr(2)(dppe)] (dppe=1,2-bis(diphenylphosphino)ethane) and zinc powder in THF (24 hours, reflux temperature), afforded 3-phenyl-3H-isobenzofuran-1-one (3 a) in an 86 % yield. Similarly, o-iodobenzoate reacts with 2 a to give 3 a, but in a lower yield (50 %). A series of substituted aromatic and aliphatic aldehydes (2 b, 4-MeC(6)H(4)CHO; 2 c, 4-MeOC(6)H(4)CHO; 2 d, 3-MeOC(6)H(4)CHO; 2 e, 2-MeOC(6)H(4)CHO; 2 f, 4-CNC(6)H(4)CHO; 2 g, 4-(Me)(3)CC(6)H(4)CHO; 2 h, 4-C(6)H(5)C(6)H(4)CHO; 2 i, 4-ClC(6)H(4)CHO; 2 j, 4-CF(3)C(6)H(4)CHO; 2 k, CH(3)(CH(2))(5)CHO; 2 l, CH(3)(CH(2))(2)CHO) also underwent cyclization with o-bromobenzoate (1 b) producing the corresponding phthalide derivatives in moderate to excellent yields and with high chemoselectivity. Like 1 b, methyl 2-bromo-4,5-dimethoxybenzoate (1 c) reacts with tolualdehyde (2 b) to give the corresponding substituted phthalide 3 m in a 71 % yield. The methodology can be further applied to the synthesis of six-membered lactones. The reaction of methyl 2-(2-bromophenyl)acetate (1 d) with benzaldehyde under similar reaction conditions afforded six-membered lactone 3 o in a 68 % yield. A possible catalytic mechanism for this cyclization is also proposed. 相似文献
53.
Dicyano-functionalized MCM-41-supported palladium complex was prepared from dicyano-functionalized MCM-41 and palladium chloride. This complex exhibited high catalytic activity in the allylation of aldehydes and ketones with allylic chlorides in the presence of SnCl2. This polymeric palladium complex can be recovered and reused without noticeable loss of activity. 相似文献
54.
纳米级金膜微电极的制作,表征及异相催化反应 总被引:1,自引:0,他引:1
报道了纳米级金膜微电极的制作方法,用XPS及SEM对电极表面进行了表征,考察了该电极的循环伏安及计时电流特性,在聚吡咯修饰微带金电极上成功地实现了葡萄糖氧化酶和电子传递媒体Fe(CN)6^3-的同时固定,并研究了GOD/Fe(CN)6^3-/PPy微酶电极对葡萄糖的响应,稳态响应电流与葡萄糖浓度之间存在Michealis-Menten动力学特征。 相似文献
55.
Simplistic modeling approach to heterogeneous dilute-acid hydrolysis of cellulose microcrystallites 总被引:9,自引:0,他引:9
Pär O. Pettersson Robert W. Torget Robert Eklund Qian Xiang Y. Y. Lee Guido Zacchi 《Applied biochemistry and biotechnology》2003,106(1-3):451-455
The classic kinetic model for cellulose hydrolysis is often referred to as pseudo-homogeneous, a term revealing the insight that the process is actually heterogeneous. During the past 10–15 yr, the shortcomings of this
model have been demonstrated in various studies and the interest in the heterogeneous aspects has increased. The present work
presents a simplistic model in which the intrinsic, heterogeneous hydrolysis and transport rates are coupled by the assumption
of a constant glucosidic surface concentration. The mechanisms affecting these two rates are largely unknown, but the model
serves as a guideline for further exploration of the process. 相似文献
56.
Subash C. Raghu Sheela Berchmans Dr. Kanala L. Phani Dr. Venkatraman Yegnaraman Dr. 《化学:亚洲杂志》2007,2(6):775-781
This paper describes the formation of catalytically active thin films of Pt, Pt/Au, and Pt/Ru on gold substrates stabilized by amine‐terminated polyamidoamine (PAMAM) dendrimers. A monolayer of dendrimer is initially self‐assembled on the gold substrate, which serves as a template for the growth of catalytically active thin films. As dendrimers contain tens to hundreds of functional groups at the periphery, the aggregate strength of the multidentate interactions with the gold substrate leads to the formation of robust films. The films were found to exhibit high catalytic activity for the oxidation of small hydrocarbons such as methanol. Such films offer versatility and scope for the design of effective electrocatalysts, especially in the context of microfuel cells and “dendrichips”; hence, they could find applications in the fields of sensors, fuel cells, and waste‐water treatment. 相似文献
57.
R. S. Mitchenko A. A. Shubin T. V. Krasnyakova 《Theoretical and Experimental Chemistry》2006,42(5):314-319
A heterogeneous catalyst for the hydrochlorination of acetylene by gaseous HCl is formed as a result of mechanical treatment
of the solid salt K2PtCl4 in an atmosphere of acetylene, ethylene, or propylene by the formation of π complexes of platinum(II) as active centers in
the surface layer under these conditions. The controlling stage of the catalytic reaction is chloroplatination of the π-coordinated
acetylene by the HCl molecule. The reaction takes place as a concerted process, in which an intermediate β-chlorovinyl derivative
of platinum(II), a complex of platinum with a coordination vacancy[PtCl
3
*
]−, and a new molecule of HCl are formed simultaneously with cleavage of the H—Cl and Pt—Cl bonds in the metal complex adjacent
to the π-acetylene complex. The catalytic cycle closes with rapid dissociation of the organoplatinum intermediate by the action
of HCl, giving the final product and the initial complex [PtCl4]2−.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 5, pp. 306–311, September–October, 2006. 相似文献
58.
Immobilized copper(Ⅱ) in organic-inorganic hybrid materials catalyzed Ar-N coupling of arylboronic acids with imidazoles has been developed. Arylboronic acids reacted with imidazoles smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper(Ⅱ) catalyst (10 mol%) in methanol without any additives and bases. The reactions generated the corresponding cross-coupling products in good yields. Furthermore, silica-supported copper can be recovered and recycled by a simple filtration procedure and used for five consecutive trials without decreases in activity. 相似文献
59.
Wang X Yu JC Yip HY Wu L Wong PK Lai SY 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(10):2997-3004
A novel metal/semiconductor nanocomposite with catalytic and photocatalytic functions has been prepared. The new material consists of highly dispersed platinum (Pt) nanoparticles embedded in a cubic mesoporous nanocrystalline anatase (meso-nc-TiO2) thin film. The porous thin film possesses a narrow pore-size distribution and a large surface area. The diameter of the Pt cluster can be controlled to below 5 nm, and the high dispersion of these clusters gives rise to catalytic activity for the oxidation of carbon monoxide, an important reaction for automobile exhaust treatment. This novel ordered mesoporous Pt/TiO2 nanoarchitecture is also a promising photochemical material, as demonstrated by the photo-driven killing of Micrococcus lylae cells on the film. 相似文献
60.
STUDY ON 1-HEXENE POLYMERIZATION BASED ON ZIEGLER-NATTA CATALYSTS WITH DOPED SUPPORT 总被引:1,自引:0,他引:1
XueJiang Zhi-qiangFan 《高分子科学》2004,(4):305-308
A series of Ti/Mg supported catalysts are prepared by using ball-milled mixtures of MgCl2-ethanol adducts and NaCl as supports, and 1-hexene polymerizations catalyzed by the novel catalysts are studied. It is found that the molecular weight distribution of poly(1-hexene) becomes apparently narrower when catalysts with doped supports are used, indicating that changing the structure of the support is an effective way to regulate the active center distribution of heterogeneous Ziegler-Natta catalyst. 相似文献