Application of cobalt phthalocyanine as a nanostructured catalyst in the synthesis of biological henna‐based compounds

The present investigation describes synthesis of a good range of henna‐based compounds in the presence of novel nano cobalt phthalocyanine like molten salt (tetra‐2,3‐pyridiniumporphyrazinato cobalt tribromomethanide) [Co (TPPABr)]CBr₃ as an efficient, recyclable and thermally stable heterogeneous catalyst.     

Catalytic olefin hydrogenation with the application of a new water soluble rhodium catalyst

The catalyst precursor preparedin situ from rhodium dimer [Rh(cod)Cl]₂ and a new water-soluble phosphine Ph₂PCH₂CH₂CONHC(CH₃)₂CH₂SO₃H (in Li⁺ salt form) has been found to act as an effective olefin hydrogenation catalyst. Catalytic hydrogenation reactions have been tested in either two phase: aqueous catalyst/insoluble olefin or methanolic catalyst/olefin systems. The observed reaction rates were higher for terminal than for internal olefins. 1-Hexene in methanolic solution has been hydrogenated with a turnover frequency of about 8000 h^–1. This system has also been applied in the form of a supported aqueous phase catalyst.     

Catalytic synthesis of fluoroaromatic urethanes in the presence of selenium-containing compounds

Conclusions Urethanes of a fluoroaromatic series were synthesized by carbonylation of the corresponding fluoro-nitro compounds in alcohol, using selenourea as the catalyst with the addition of organic bases.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1350–1352, June, 1983.     

Galvinoxyl相转移催化合成芳基双偶氮酮类化合物

以二芳基卡巴肼为原料,以Galvinoxyl(自由基)为相转移催化剂,高产率地制得了芳基双偶氮酮类化合物。讨论了反应的可能机理。     

苯并噻唑 盐催化合成1,4-二羰基化合物

在苯并噻唑 盐和三乙胺存在下, 醛可以作为酰基负离子的合成等价物对α,β-不饱和酮进行Michael加成, 生成相应的1,4-二羰基化合物. 文中对 盐的制备, 催化反应条件及催化反应的机理进行了研究和讨论.     

负载型钾盐催化剂用于合成苯甲醚的研究

采用固定床连续进料的反应器代替传统间歇反应釜作为评价反应器,以环境友好的碳酸二甲酯为甲基化试剂,由苯酚合成苯甲醚的反应新工艺。采用SiO2负载的钾盐类催化剂,考察了反应温度、进料空速、原料配比、活性组分负载量以及催化剂用量等对反应性能的影响。研究表明,在该负载型钾盐催化剂上苯酚的转化率均较高,且生成苯甲醚的选择性较好。尤其是在KF/SiO2催化剂上,在DMC/苯酚摩尔比为2∶1,进料空速为2 h-1,反应温度为250℃时,苯甲醚收率和选择性分别高达93.93%和98.19%。而且该负载型催化剂活性比较稳定,未发现活性组分流失,反应运行16 h催化剂未见失活。     

Catalytic synthesis of sulfur and phosphorus compounds via atom-economic reactions

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Catalytic reactions in emulsions in the presence of a polymeric catalyst

The theory of reactions between a surface-active substrate and a polymeric catalyst in emulsions has been developed. The conditions under which the rate of reaction in such systems substantially surpasses the rate of reaction in homogeneous systems have been determined and the regimes that make it possible to reduce the total time of the process have been established.     

Catalytic synthesis of 1,4-hexadiene by a nickel-based catalyst. Factors controlling activity and selectivity

The nature of the phosphine ligand and the aluminum cocatalyst strongly affect activity and stereoselectivity in the Al/Ni/P type (e.g. R_nAlX_3−n + NiX₂ · 2 PR₃ or Ni⁰[L] + R₃P) catalyst system to synthesize trans- and cis-1,4-hexadiene from ethylene and butadiene.     

Catalytic thia-Sommelet-Hauser rearrangement: application to the synthesis of oxindoles

A series of 3-arylthio-1,3-disubstituted-oxindoles were prepared in good yields by the reaction of α-diazocarbonyl compounds and sulfenamides. The reaction involves a Rh-catalyzed thia-Sommelet-Hauser-type rearrangement.     

Catalytic cyclometalation reaction of unsaturated compounds in synthesis of magnesa- and aluminacarbocycles

The investigation results on design and application of the new catalytic cyclometalation reaction of olefins, dienes, acetylenes and allenes with Al, Mg and halogen alkyls mediated by Ti or Zr based metallocene catalysts to produce novel classes of cyclic organometallics namely aluminacyclopropanes, aluminacyclopropenes, aluminacyclopentanes, aluminacyclopentenes, aluminacyclopenta-2,4-dienes, magnesacyclopentanes, magnesacyclopentenes, magnesacyclopenta-2,4-dienes as well as metallamacrocycles are summarized and systematized. Selected literature data on thermal synthesis of cyclic organoaluminum and organomagnesium compounds for comparison the efficiencies of catalytic and classic synthetic methods are given. Mechanistic aspects of catalytic cyclometalation of unsaturated compounds and chemical transformations of Al and Mg metallacycles are discussed.     

Catalytic destruction of brominated aromatic compounds studied in a catalyst microbed coupled to gas chromatography/mass spectrometry

The capability of solid porous catalysts has been studied for the destruction or modification of halogenated aromatic compounds contaminating the pyrolysis oil of recycled plastics from electronic waste. A fast and simple experimental procedure is carried out using a micropyrolyser coupled to GC-MS in such a way that catalyst microbed was placed in the sample tube of the pyrolyser. The pyrolysis products of polycarbonate blended with a frequently applied flame retardant tetrabromobisphenol A (TBBPA) and epoxy resin containing TBBPA monomer units have been analysed, and the brominated components were compared with the thermal decomposition products of TBBPA and its diallyl ether. When TBBPA vapour passes through molecular sieve 4A a slight debromination and a partial cleavage of bisphenol A into phenols occur. Over molecular sieves of larger pore size (13X and NaY zeolite) an important decrease of TBBPA amount is observed indicating effective trapping ability of these catalysts of basic character for brominated aromatic compounds. A total chemical modification of the vapour was achieved by Al-MCM-41 catalyst that split TBBPA into bromophenols. Analogous results were obtained by carrying out similar experiments on diallyl ether of TBBPA. Moreover, it was revealed that brominated bisphenol A compounds are modified essentially the same way, either evaporated or evolved from a polycarbonate blend or produced by pyrolysis from an epoxy resin.     

One-pot three-component reaction for the synthesis of pyran annulated heterocyclic compounds using DMAP as a catalyst

The one-pot three-component reaction for the synthesis of pyran annulated heterocycles is reported by condensing aromatic aldehydes, ethyl cyanoacetate, or malononitrile and C-H activated acidic compounds in the presence of catalytic amount of 4-(dimethylamino)pyridine (DMAP) in ethanol under reflux conditions. The significant features of the present protocol are simple, environmentally benign, high yields, non-aqueous work-up procedure, no chromatographic separation and recyclability of the catalyst.     

Novel application of a Fe-Zn double-metal cyanide catalyst in the synthesis of biodegradable, hyperbranched polymers

The use of Fe-Zn double-metal cyanide as a solid catalyst for synthesizing biodegradable, hyperbranched polymers from diacids and glycerol has been reported, for the first time, wherein acidity, micro-mesoporosity and hydrophobicity of the catalyst played an important role in controlling gelation.     

有机高价碘化合物在合成中的应用

本文综述了有机高价碘化合物在合成中应用的进展, 介绍了有机高价碘化合物的制备, 阐述了有机高价碘化合物作为芳基, 烷基, 烯基, 炔基, 转移剂及芳基碘盐应用于复杂化合物的合成。     

Catalytic enantioselective Reissert-type reaction: development and application to the synthesis of a potent NMDA receptor antagonist (-)-L-689,560 using a solid-supported catalyst.

Full details of the first catalytic enantioselective Reissert-type reaction are described. Utilizing the Lewis acid-Lewis base bifunctional catalyst 5 or 6 (9 mol %), the Reissert products were obtained in 57 to 99% yield with 54 to 96% ee. Electron-rich quinolines produced better yields and enantioselectivities than electron-deficient substrates. Kinetic studies indicated that the reaction should proceed via the rate-determining acyl quinolinium formation, followed by the attack of a cyanide. The catalyst does not facilitate the first rate-determining step; however, it strongly facilitates the second cyanation step. The reaction was successfully applied to an efficient catalytic asymmetric synthesis of a potent NMDA receptor antagonist (-)-L-689,560. A key step is the one-pot process using the Reissert-type reaction from quinoline 1f, followed by stereoselective reduction of the resulting enamine 2f. This step gave the key intermediate 20 in 91% yield with 93% ee, using 1 mol % of 6. The enantiomerically pure target compound was obtained through 10 operations (including recrystallization) in total yield of 47%. Furthermore, 6 was immobilized to JandaJEL, and the resulting solid-supported catalyst 11 afforded 20 in a comparable yield to the homogeneous 6, but with slightly lower enantioselectivity.     

Catalytic partial oxidation of methane to synthesis gas over a ruthenium catalyst: the role of the oxidation state

The catalytic partial oxidation of methane to synthesis gas over ruthenium catalysts was investigated by thermogravimetry coupled with infrared spectroscopy (TGA-FTIR) and in situ X-ray absorption spectroscopy (XAS). It was found that the oxidation state of the catalyst influences the product formation. On oxidized ruthenium sites, carbon dioxide was formed. The reduced catalyst yielded carbon monoxide as a product. The influence of the temperature was also investigated. At temperatures below the ignition point of the reaction, the catalyst was in an oxidized state. At temperatures above the ignition point, the catalyst was reduced. This was also confirmed by the in situ XAS spectroscopy. The results indicate that both a direct reaction mechanism as well as a combustion-reforming mechanism can occur. The importance of knowing the oxidation state of the surface is discussed and a method to determine it under reaction conditions is presented.     

Catalytic recycling of polyesters via a binuclear catalyst

<正>Plastics play a crucial role in modern society life. While the increasing use of plastics and rapid accumulation of plastic waste in nature environment have caused severe environmental crisis and the waste of carbon resources. Catalytic upcycling is a promising approach to transform plastic waste into high value-added chemicals to achieve a sustainable circular economy.