光促进温和条件下溴代烷烃与甲酸甲酯的羰基化反应

研究了光促进温和条件下,以甲酸甲酯为C1源,非贵金属钴盐、铜盐催化的溴代烷烃的羰基化反应.实验表明,在光促进下,钴盐、铜盐均可催化溴代烷烃与甲酸甲酯的羰基化反应,得到相应的羧酸甲酯.钴盐催化下,碱性添加物NaOAc对反应有很好的促进作用,直链溴代烷烃在反应中除了得到相应的正构酯外,还有少量异构酯生成;铜盐催化下,直链溴代烷烃在反应中主要生成相应的正构酯.机理研究表明,在光照下甲酸甲酯先分解为CO和CH3OH,再与溴代烷烃进行羰基化反应.     

On the Mechanism of Nickel Recovery from the Sulfide Component in the Ni-Cu-S System in Carbonylation

A mechanism of a solid-phase interaction between metallic copper released from the copper-nickel alloy in nickel recovery into the carbonyl gas phase with nickel sulfide in carbonylation of copper-nickel metallurgical half-products is suggested. Experimental data on carbonylation of the magnetic fraction of converter matte in a horizontal rotating reactor at a pressure of 70 gage atm and reaction zone temperature of 180°C are used to determine the coefficient of volume heterodiffusion of copper across a copper sulfide layer.     

Zerovalent metal polymer composites. III. Metallization of metal oxide surfaces with the aid of metallized functional polymer microdispersions

The adsorption of poly[N-(m- and p-vinylbenzyl)-N,N,N-trimethylammonium tetrachloropal-ladate] complex on inorganic oxide surfaces followed by reduction of the palladium salt to form a catalytically active zerovalent metal polymer composite dispersed on the oxide surface and further deposition of transition metals, e.g., nickel, cobalt, and copper, by “additive” or “subtractive” deposition from electroless plating solutions is described. γ-Ferric oxide was used as a template for such intermetallic replacement reactions, providing materials with controlled amounts of metal. Multimetallic catalysts based on aluminum oxide, zinc oxide, lanthanum oxide, magnesium oxide, and silica were prepared. Iron oxide modified by subtractive deposition of rhodium and iridium on nickel-clad iron oxide were evaluated in Fischer–Tropsch carbonylation reactions leading from synthesis gas to alkanols.     

常温常压下光促进烯烃与一氧化碳的羰基化反应

 报道了烯烃（环己烯和1－辛烯）与一氧化碳通过光促进实现常温常压非贵金属（钴配合物）催化的羰基化反应．研究发现，以Co（OAc）2为催化剂时，不需要加入光敏剂丙酮就能发生反应；CoSalen，吡啶－2－羧酸钴和大环配合物［Co（14）4，11－diene－N4］I2是较好的催化剂，其催化活性比Co（OAc）2高．其中，吡啶－2－羧酸钴与Co（OAc）2相同，反应中不需要光敏剂存在，其选择性很高．通过氘代丙酮和氘代甲醇同位素实验，进一步证实了反应中双键异构的存在和副产物的分析结果．     

Synthesis of heteroaromatic carboxylic acids by carbonylation of hetaryl halides with catalysts based on cobalt carbonyl modified with epoxides

A new method for the synthesis of heteroaromatic acids and their derivatives (esters and salts) by carbonylation of the corresponding halides was developed. Hetaryl halides were activated in alcoholic-alkali medium by highly active catalytic systems based on cobalt carbonyl modified with epoxides, developed previously for carbonylation of aryl halides.     

光促进下溴代烃在CH3OH/DMF体系中的羰基化反应

羰基化反应是有机合成中最重要的反应之一,其合成产品分别为醛、酮、酯、羧酸和酰胺等一系列化合物,可用作溶剂、增塑剂、润滑剂以及天然产物的替代品。卤代烷烃种类繁多,价格低廉,以其为底物进行羰基化反应,可以得到多种多样的羰基化合物。但常规羰基化反应往往需要高温(150-2     

环氧化合物羰基化反应研究新进展

通过催化的方法在有机化合物分子中引入羰基和其它基团而成为含氧化合物的羰基化反应,具有"原子经济性"反应的高选择性和对环境的友好性,可充分利用资源和保护环境,符合绿色化学发展趋势等优点,备受学术界及工业界青睐.综述了近年来羰基钴金属化合物催化的环氧化合物和一氧化碳羰基化反应研究的新进展,涉及的反应类型主要包括羰基化扩环、羰基化开环共聚以及羰基化开环,讨论了不同类型反应的相关机理,并展望了该领域的研究前景.     

Phase transfer catalysis using cobalt tricarbonyl nitrosyl

The first example of the use of a mononuclear cobalt complex in a phase- transfer catalyzed process is described. The carbonylation of halides catalyzed by cobalt tricarbonyl nitrosyl gives, depending on the organic substrate, appreciably different results as compared with dicobalt octacarbonyl.     

A new heterogeneous catalyst for the oxidative carbonylation of phenol to diphenyl carbonate

Using layered double hydroxides as a support, both the palladium catalyst and the cobalt co-catalyst are heterogenised and proven to form an acceptable catalytic system for the heterogeneous oxidative carbonylation of phenol to diphenyl carbonate (DPC).     

Carbonylation of polychlorinated biphenyls over cobalt carbonyl catalyst modified with propylene oxide

The positional and substrate selectivities in the carbonylation of polychlorinated biphenyls in the catalytic system cobalt carbonyl-1,2-epoxypropane-base were studied. No direct relation was found between the degree of chlorination of the initial compounds and the reaction rate. The rate and selectivity of carbonylation are determined by radical anion mechanism of the substrate activation stage and by the presence of halogen atoms in the ortho-positions of polychlorinated biphenyl molecules.     

Synthesis of Aromatic Carboxylic Acids by Carbonylation of Aryl Halides in the Presence of Epoxide-Modified Cobalt Carbonyls as Catalysts

A new procedure was developed for synthesis of aromatic and heteroaromatic acids and their derivatives (esters, salts) by carbonylation of the corresponding aryl halides. The acids are selectively formed in a high yield under very mild conditions. Highly active catalytic systems, base-containing alcoholic solutions of cobalt carbonyl modified with epoxides, were used to activate aryl halides.     

Copper‐Catalyzed Carbonylative Coupling of Cycloalkanes and Amides

Carbonylation reactions are a most powerful method for the synthesis of carbonyl‐containing compounds. However, most known carbonylation procedures still require noble‐metal catalysts and the use of activated compounds and good nucleophiles as substrates. Herein, we developed a copper‐catalyzed carbonylative transformation of cycloalkanes and amides. Imides were prepared in good yields by carbonylation of a C(sp³)?H bond of the cycloalkane with the amides acting as weak nucleophiles. Notably, this is the first report of copper‐catalyzed carbonylative C?H activation.     

Photopromoted Carbonylation of Alkyl Halides Under Ambient Conditions

Photopromoted carbonylation of alkyl halides with carbon monoxide can be carried out under ambient conditions with non-precious transition metal complexes(such as cobalt complexes) catalysts.Our preliminary work sowed that alkyl halides can be transformed into alkene and alkane directly under irradiation,but the esters can not be transformed.It is assumed that the carbonylation of alkyl halides may be proceeded in two ways.     

A versatile procedure for synthesis of organic acids by cobalt carbonyl catalyzed carbonylation of organic halides

A versatile procedure for synthesis of a broad range of fatty-aromatic and aromatic acids by carbonylation of the corresponding halides under very mild conditions in the presence of cobalt carbonyl as a catalyst was suggested. The main principles of a flexible process for production of practically significant acids and their derivatives were developed.     

Thermal and structural studies of the chloro complexes of cobalt,nickel and copper with 3-phenylpyridine

The chloro complexes of cobalt, nickel and copper with 3-phenylpyridine were prepared in ethanolic solution from which solid compounds were isolated. The cobalt and copper complexes have stoichiometry M₂LCl₄ while the nickel complex has stoichiometry NiLCl₂. The suggested structure for the cobalt and copper complexes is tetrahedral, while for the nickel complex it is octahedral. Thermal analysis studies show that the cobalt and copper complexes form intermediate complexes before their metal oxides are produced. The nickel complex also forms an intermediate complex and then nickel chloride before the nickel oxide is obtained.     

Syngas reactions XII. The selective preparation of acetaldehyde,alkanols, esters and acetic acid from synthesis gas

Several classes of commercially important oxygenates, including acetaldehyde, ethanol, methyl acetate, ethyl acetate and acetic acid as well as C₁–C₃ alcohol/acetate ester mixtures, may each be selectivelygenerated from synthesis gas through the application of novel classes of ruthenium-containing bimetallic catalysts particularly those of ruthenium and cobalt (Ru? Co). A particular feature of these versatile catalysts is that all precursors are iodidefree. Products are formed through a combination of carbon monoxide hydrogenation, methanol homologation, methyl acetate homologation and methanol carbonylation reaction sequences.     

A Novel Synthesis of Substituted Phenylpyruvic Acid by Double Carbonylation Using Cobalt Pyridine-2-Carboxylate Catalyst

Synthesis of a substituted phenylpyruvic acid was carried out at 60 °C and 3.0MPa using cobalt pyridine-2-carboxylate as a catalyst for the double carbonylation of benzyl chloride.     

Carbonylation of chlorobiphenyls catalyzed by modified cobalt carbonyl

Dichlorobiphenyls having both chlorine atoms in the same benzene ring undergo mild carbonylation in the presence of 1,2-epoxypropane-modified carbonyl cobalt complex to give biphenylcarboxylic acid esters. Monochlorobiphenyls fail to react under analogous conditions. The rate and selectivity of the reaction depend on the position of chlorine atoms. Carbonylation of dichlorobiphenyls having a chlorine atom in the meta position occurs preferentially at that position. 2,4-Dichlorobiphenyl gives rise mainly to the carbonylation product at the 2-position.     

Spectrophotometric simultaneous determination of cobalt, copper and nickel using nitroso-R-salt in alloys by partial least squares

Partial least squares modeling as a powerful multivariate statistical tool applied to spectrophotometric simultaneous determination of cobalt, copper, and nickel in aqueous solutions. The concentration range for cobalt, copper and nickel were 0.4-2.6, 0.6-3.4, 0.5-5.5 ppm, respectively. The experimental calibration set was composed with 36 sample solutions using a mixture design for three component mixtures. The absorption spectra were recorded from 470 to 600 nm. The effect of pH on the sensitivity and selectivity was studied according to net analyte signal (NAS). The values of root mean square difference (RMSD) for cobalt, copper and nickel using partial least squares (PLS) were 0.0192, 0.0263 and 0.0446 ppm, respectively. The effects of various cations and anions were investigated. The method was used to determination of cobalt, copper and nickel in two sample alloys based on copper, nickel and cobalt (known as cunico) and based on cobalt, nickel and iron (known as conife).     

Cobalt-catalyzed photopromoted carbonylation of chloroalkanes in the presence of KI

<正>The photopromoted carbonylation of chloroalkanes with carbon monoxide catalyzed by cobalt compounds[Co(OAc)_2,CoCl_2] in the presence of KI was carried out under ambient conditions.The results revealed that the catalytic activity of Co(OAc)_2 was higher than that of CoCl_2.A basic additive NaOAc was beneficial to the reaction.Interestingly,with NaOAc as an additive, Co(OAc)_2 and CoCl_2 exhibited similar catalytic activity.Preliminary work showed that the role of iodide ion was initially to form active iodoalkanes via substituting chloride ion in chloroalkanes in situ,and then,the carbonylation of iodoalkanes proceeded under irradiation.