共查询到20条相似文献,搜索用时 15 毫秒
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采用原位法合成了不同类型的四羰基钴/咪唑离子液体催化剂, 并考察了其在氯乙酸甲酯羰基化反应中的催化性能. 研究了咪唑环上不同支链对催化活性的影响. 结果表明, 1-丁基-3-甲基咪唑羰基钴离子液体[Bmim][Co(Co)4]不仅催化活性高, 选择性好, 而且对空气和水有较好的稳定性能. 在pCO=2.0 MPa, 85 ℃, 反应3 h的条件下, [Bmim][Co(Co)4]催化剂循环使用4次, 氯乙酸甲酯的平均转化率为94.3%, 丙二酸二甲酯的平均选择性和平均产率分别为98.5%和92.9%. 与传统的Na[Co(Co)4]催化剂相比, [Bmim][Co(Co)4]催化剂在保证高活性的条件下可以实现羰基钴催化剂的直接循环使用. 相似文献
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4-N,N-Dimethylaminopyridine (DMAP) as catalyst in combination with benzyl bromide was developed for the selective oxidation of methyl aromatics. DMAP exhibited higher catalytic activity than other pyridine analogues, such as 4-carboxypyridine, 4-cyanopyridine and pyridine. The sp3 hybrid carbon-hydrogen (C-H) bonds of different methyl aromatics were successfully oxygenated with molecular oxygen. The real catalyst is due to the formation of a pyridine onium salt from the bromide and DMAP. The onium salt was well characterized by NMR and the reaction mechanism was discussed. 相似文献
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RuCl3 catalyst system has many advantages for the hydro‐esterification of methyl formate and ethylene to methyl propionate. However, the unsatisfied performance restricts the development of this route. In this work, high‐performance RuCl3 catalyst systems (RuCl3‐[PPN]Cl‐Et4NI and RuCl3‐NaI) are firstly reported for this reaction. In RuCl3‐[PPN]Cl‐Et4NI catalyst system, the conversion of methyl formate and the selectivity to methyl propionate are 93.9% and 90.9% at mild reaction conditions (165°C, 2.5 MPa), respectively. Noticeably, a simple inorganic RuCl3‐NaI catalyst system achieves 88.8% conversion of methyl formate and 97.6% selectivity to methyl propionate (86.7% yield) at same conditions. NaI, as a promoter, may inhibit the decomposition of methyl formate and be conducive to the formation of methyl propionate. The effects of solvents and promoters are investigated in detail. In addition, the reaction mechanism has been also analyzed. It is hoped to lay a certain foundation for further industrial application. 相似文献
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Jensen TR Yoon SC Dash AK Luo L Marks TJ 《Journal of the American Chemical Society》2003,125(47):14482-14494
This contribution describes coordinative/insertive stereoregular homopolymerizations and copolymerizations of styrene and methyl methacrylate (MMA) mediated by a highly active single-site organotitanium catalyst. The catalyst system used to effect these polymerizations of nonpolar and polar olefinic monomers is prepared by in situ Zn reduction of the precursor derived from the reaction (Me(5)Cp)TiMe(3) + Ph(3)C(+)B(C(6)F(5))(4)(-). The resulting catalyst produces polystyrene (>95% syndiotactic, 170 000 g/mol molecular weight; s-PS) by the established coordinative/insertive pathway. The same catalyst mediates polymerization of MMA to poly(methyl methacrylate) (>65% syndiotactic, >70 000 g/mol molecular weight; s-PMMA) by a group transfer protocol-like (GTP-like) pathway (1,4 insertion mechanism). Under optimal conditions, this catalyst also mediates the copolymerization of MMA + styrene (1:19 ratio) at 50 degrees C to yield random approximately 80% coisotactic poly[styrene-co-(methyl methacrylate)] (coiso-PSMMA) which contains approximately 4% MMA. Control experiments argue that a single-site Ti catalyst is the active species for the copolymerization. The catalyst formation process is quite general, and a variety of reducing agents can be substituted for Zn and still effect copolymerization. Control experiments also indicate that known noncoordination copolymerization mechanisms (i.e., ionic or radical) cannot explain this copolymerization. We suggest a new mechanism involving sequential conjugate addition steps to explain these copolymerization results. 相似文献
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Immobilization of Carbonylcobalt Catalyst by Poly(4‐vinylpyridine) (P4VP) through N→Co Coordination Bonds: The Promotional Effect of Pyridine and the Reusability of Polymer Catalyst 下载免费PDF全文
Yu‐Bing Liu Yi‐Ning Wang Dr. Hai‐Meng Lu Shuang Liang Dr. Bo‐Lian Xu Prof. Yi‐Ning Fan 《化学:亚洲杂志》2016,11(22):3159-3164
A carbonylcobalt catalyst, immobilized by poly(4‐vinylpyridine) (P4VP) through N→Co coordination bonds, has been prepared by solvothermal method. It has been revealed that the pyridine fragments in the polymer catalyst act not only as promoters to improve the catalytic performance of the carbonylcobalt catalyst for alkoxycarbonylation of ethylene oxide to methyl 3‐hydroxypropanoate but also as stabilizers to enhance the reusability of the polymer catalyst. Furthermore, the polymer catalyst could be easily separated by filtration and reused with only a slight loss of catalytic efficiency. 相似文献
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The vinylic polymerization of norbornene and its copolymerization with norbornene carboxylic acid methyl esters were investigated. Norbornene was polymerized by us using di-μ-chloro-bis-(6-methoxybicyclo[2.2.1]hept-2-ene-endo-5σ,2π)-palladium(II) as catalyst. The polymerization time can be decreased by a factor of 100000 by activation of the catalyst with methylaluminoxane (MAO). With this palladium catalyst activated by MAO, 140 t of norbornene can be polymerized per mol palladium per h. This catalyst system was much more active than [Pd(CH3CN)4](BF4)2 ( I ). The polymerization of norbornene by (6-methoxybicyclo[2.2.1]hept-2-ene-endo-5σ,2π)-palladium(II) tetrafluoroborate was also possible but it was not as fast as the polymerization by Pd catalysts activated with MAO. We were also able to obtain copolymers of norbornene and 5-norbornene-2-carboxylic acid methyl ester (exo/endo = 1/4 or 2/3) containing between 15 and 20 mol-% ester units. The copolymerization of norbornene and 2-methyl-5-norbornene-2-carboxylic acid methyl ester (exo/endo = 7/3) was faster than the copolymerization mentioned before. In contrast the homopolymerization of 2-methyl-5-norbornene-2-carboxylic acid methyl ester was 10 times slower than that of 5-norbornene-2-carboxylic acid methyl ester (exo/endo = 1/4). 相似文献
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Ashford DL Stewart DJ Glasson CR Binstead RA Harrison DP Norris MR Concepcion JJ Fang Z Templeton JL Meyer TJ 《Inorganic chemistry》2012,51(12):6428-6430
The synthesis and analysis of a new amide-linked, dinuclear [Ru(bpy)(2)(bpy-ph-NH-CO-trpy)Ru(bpy)(OH(2))](4+) (bpy = 2,2'-bipyridine; bpy-ph-NH-CO-trpy = 4-(2,2':6',2"-terpyridin-4'-yl)-N-[(4'-methyl-2,2'-bipyridin-4-yl)methyl]benzamide) assembly that incorporates both a light-harvesting chromophore and a water oxidation catalyst are described. With the saturated methylene linker present, the individual properties of both the chromophore and catalyst are retained including water oxidation catalysis and relatively slow energy transfer from the chromophore excited state to the catalyst. 相似文献
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以NiO担载量为0.08wt%~18.7wt%及焙烧温度为623 K~873 K的NiO/Al2O3催化剂进行乙炔与甲酸甲酯的加氢酯化反应,并结合TPR、XPS、XRD和BET技术对催化剂进行表征。催化剂在制备过程中,镍离子与载体氧化铝间的相互作用产生两种不同的镍物种,NiO晶相和NiAl2O4类物种,它们间的比例随担载量及焙烧温度而异,因而表现出其对乙炔与甲酸甲酯加氢酯化不同的反应性能。实验结果表明,在773 K焙烧的10Wt%NiO/Al_2O_3最适合乙炔与甲酸甲酯的加氢酯化反应。 相似文献
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Eini Puhakka Tuula T. Pakkanen Tapani A. Pakkanen 《Journal of molecular catalysis. A, Chemical》1997,120(1-3):143-147
Theoretical ab initio methods have been used to study the alkylation reaction of the MgCl2-supported TiCl4 catalyst. Investigation of the reaction path indicated that the Al(CH3)3 co-catalyst inserts into the coordination sphere of the titanium atom of the catalyst so that a methyl group of Al(CH3)3 interacts with the titanium. The methyl group migrates from Al(CH3)3 to the vacant coordination site of the catalyst. When the catalyst loses one of its chlorine atoms to the co-catalyst during this reaction, the catalyst maintains its vacant site, but the position of the vacant site changes. The presence of the external electron donor coordinated to the co-catalyst makes the alkylation reaction energetically more favourable. 相似文献
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A new method for the preparation of SBA-15-supported palladium catalyst for Heck reaction in supercritical carbon dioxide was presented.The newly formed SBA-15-supported palladium catalyst(Ph-SBA-15-PPh3-Pd) exhibited high catalytic activity for the Heck reaction of 4-nitrobromobenzene with methyl acrylate.The catalyst can be reused several times without a loss of activity. 相似文献
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The intermolecular N-H insertion reaction of methyl α-diazo α-arylacetate with acetamide has been investigated using transition-metal complexes as catalysts. The Cu(II) complex Cu(hfacac)2 (hfacac represents hexafluoroacetylacetonate) has proven to be the most active catalyst to yield methyl N-acetyl-2-phenylglycin in good isolated yield (73–80%) with 3 mmol% of catalyst loading in reflux toluene. The catalyst is also valuable to the substituted aryldiazoacetates at the 4-position on phenyl ring. 相似文献
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聚氯乙烯三氯化铁树脂催化合成肉桂酸甲酯 总被引:9,自引:0,他引:9
在聚氯乙烯三氯化铁催化下由肉桂酸和甲醇发生酯化合成了肉桂酸甲脂,当0.02mol.肉桂酸,0.10mol甲醇和1.5g催化剂一起回流加热7.0h时,产品收率达84.4%。 相似文献
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[reaction: see text] Cross metathesis of terminal alkenes with methyl (2Z,4E)-hexadienoate and related dienyl esters provides substituted (2Z,4E)-dienyl esters in good yields. Small-scale reactions are effectively promoted by the standard second-generation Grubbs-Hoveyda catalyst (GH-II), while a new fluorous GH-II catalyst is used for separation and recovery in gram-scale reactions. The transformation is featured in a rapid synthesis of the bottom fragments of the potent anticancer agents (-)-dictyostatin and 6-epi-dictyostatin. 相似文献
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新型5-溴嘧啶衍生物的选择性合成 总被引:1,自引:0,他引:1
对甲苯磺酰氯与三甘醇单甲酯完成酯化反应,再与对溴苯酚缩合制得对溴苯基三甘醇单甲醚(3);3与硼酸甲酯完成取代反应、酸解后在Pd(PPh3)4催化下与5-溴-2-碘嘧啶(5)在甲苯中通过Suzuki偶联反应选择性地合成了5-溴-2-对(甲基三甘醇基)苯基嘧啶(1a),收率73%。以1-十二烯和5为主要原料,通过Suzuki偶联反应,一锅法选择性地合成了5-溴-2-十二烷基嘧啶(1b),收率82%。1a和1b未见文献报道,其结构经1HNMR,13C NMR和MS表征。 相似文献
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研究了二苯并噻吩(DBT)、4-甲基二苯并噻吩(4-MDBT)和4,6-二甲基二苯并噻吩(4,6-DMDBT)在非负载型NiMoW催化剂上的加氢脱硫反应产物分布及反应机理,给出了它们在非负载型催化剂上加氢脱硫反应网络.研究发现,由于甲基的空间位阻效应,二苯并噻吩类化合物加氢脱硫转化率顺序为4,6-DMDBT≈4-MDBT<DBT,而非负载型NiMoW催化剂具有很高的芳环加氢活性,有利于烷基取代的芳环加氢,减弱空间位阻效应,使烷基取代的二苯并噻吩类化合物得到有效脱除.DBT的脱硫产物会被进一步加氢,其产物分布与联苯加氢产物相似.4-MDBT有两种预加氢脱硫反应路径,甲基取代的苯环由于甲基的供电子效应会被优先加氢.非负载型催化剂存在的L酸中心会使部分4-MDBT和4,6-DMDBT通过脱甲基反应生成DBT再进行脱硫反应. 相似文献
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A series of novel polylactide (PLA) polymers were synthesized initiated by 4‐dicyanomethylene‐2‐methyl‐6‐{4‐[(2‐hydroxyethyl)(methyl)amino]styryl}‐4H‐pyran (DCM) with Sn(Oct)2 as catalyst. The color and emission of the polymer can be tuned just with polymer molecular weight. 相似文献
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在(R)TTCA·K催化下由环己酮直接与丙烯酸甲酯进行Michael加成反应得到了(S)-3-(2′-氧环己基)-丙酸甲酯, [α]20D-4.14(41.5% e.e.). 相似文献
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Kei Matsuzaki Toshiyuki Uryu Akira Ishida Tatsumi Ohki Makoto Takeuchi 《Journal of polymer science. Part A, Polymer chemistry》1967,5(8):2167-2177
The stereoregularity of poly(methyl acrylate) and poly(methyl acrylate-αd) was determined from the NMR spectra. A method of quantitative determination of stereoregularity of poly(methyl acrylate) proposed in this paper is based on the fact that in the 100 Mc./sec. NMR spectrum the absorption peaks due to methylene protons in syndiotactic configurations overlap absorptions due to only one of two methylene protons in isotactic configurations. The stereostructure of poly(methy1 acrylates) polymerized with anionic catalysts such as Grignard reagents, n-butyllithium, and LiAlH4 is generally richer in isotactic diads than in syndiotactic diads. For example, poly(methyl acrylate) polymerized with phenylmagnesium bromide as catalyst at ?20°C. consists of 99% isotactic and 1% syndiotactic diads. In radical polymerization, the isotacticity of poly(methyl acrylate) is independent of polymerization temperature. Poly(methyl acrylates) polymerized with a Ziegler-Natta catalyst consisting of Al(C2H5)2Cl and VCl4 have configurations similar to those polymerized by radical initiators. The stereoregularity of poly(methyl acrylate-α-d) resembled that of poly(methyl acrylate) polymerized under the same conditions. 相似文献