Base-catalyst employed

A hydrosilylation/cyclization process forming a vinylsilane product need not begin with a diyne, and other unsaturation has been examined in a similar reaction. Alkynyl olefins and dienes have been employed,97 and since unlike diynes, enyne substrates generally produce a chiral center, these substrates have recently proved amenable to asymmetric synthesis (Scheme 27). The BINAP-based catalyst employed in the diyne work did not function in enyne systems, but the close relative 6,6 -dimethylbiphenyl-2,2 -diyl-bis(diphenylphosphine) (BIPHEMP) afforded modest yields of enantio-enriched methylene cyclopentane products.104 Other reported catalysts for silylative cyclization include cationic palladium complexes.105 10511 A report has also appeared employing cobalt-rhodium nanoparticles for a similar reaction to produce racemic product.46... 

Table 1 Non-noble metal-based catalysts employed in the steam reforming of ethanol (SRE) for hydrogen production... 

Ermakova and co-workers manipulated the Ni particle size to achieve large CF yields from methane decomposition. The Ni-based catalysts employed for the process were synthesized by impregnation of nickel oxide with a solution of the precursor of a textural promoter (silica, alumina, titanium dioxide, zirconium oxide and magnesia). The optimum particle size (10 0 nm) was obtained by varying the calcination temperature of NiO. The 90% Ni-10% silica catalyst was found to be the most effective catalyst with a total CF yield of 375 gcp/gcat- XRD studies by the same group on high loaded Ni-silica... 

Table 2.26. Non-Noble Metal-Based Catalysts Employed in the Steam Reforming of Ethanol (SRE) for Hydrogen Production... 

Catalytic enantioselective allylations of aldehydes already published can be classified into two methods carried out under the influence of chiral Lewis acid catalysts and chiral Lewis base catalysts. The process by chiral Lewis acid catalysts generally uses allyltrimethylsilane or allyltrialkylstannane as an allylating agent, both of which show low reactivity toward aldehydes without these catalysts. The process by chiral Lewis base catalysts employs allyltrichlorosilane or allylmetals possessing relatively higher reactivity. Both processes can be successfully applied to various substituted allylmetal compounds or allenylmetal compounds. 

A detailed systematic study of the reaction conditions revealed that the ratio of 1,3,4-oxa-diazine imidazole formed is dependent on the solvent, and on the acid or base catalyst employed <90JHC487>. Yields of 1,3,4-oxadiazine are optimal (60-70%) in boiling carbon tetrachloride or in -heptane, whereas in acetonitrile, 1,2-dimethoxyethane, or toluene only the isomeric imidazoles (200) and (201) are produced. Acid catalysis (p-TSA or acetic acid) in hot carbon tetrachloride favors the 1,3,4-oxadiazine (80%), but with silica in boiling carbon tetrachloride imidazoles are the sole products. 

Sun. N Klabiindc. KJ. High activiiy solid super base catalysts employing nanocrystuis of metal oxides isomerization and alkylation catalysis, including conversion of... 

In the final step, the conjugate base of the acid catalyst employed in the first step and the conjugate acid of the base catalyst employed in the first step catalyze ring closure. 

The current status of precious and non-precious metal-based catalysts employed at the PEMFC cathodes is discussed below. 

An interesting advantage to using alkaline electrolytes is that the oxidation of alcohol in this medium does not significanliy depend on the structure of the catalyst [81], which opens up the opportunity of using non-precious metals, such as Pd, Ag, Ni, and perovskite-type oxides [47,79,82-84]. The latter are significantly cheaper than Pt-based catalysts employed in acid fuel cells. However, when it comes to alkaline media, the use of non-precious metals becomes reality. 

Ruthenium-based catalyst employed in the racemization of amines. 

Manufacture. Furfuryl alcohol has been manufactured on an industrial scale by employing both Hquid-phase and vapor-phase hydrogenation of furfural (56,57). Copper-based catalysts are preferred because they are selective and do not promote hydrogenation of the ring. 

Tetrahydrofurfuryl alcohol reacts with ammonia to give a variety of nitrogen containing compounds depending on the conditions employed. Over a barium hydroxide-promoted skeletal nickel—aluminum catalyst, 2-tetrahydrofurfur5iarnine [4795-29-3] is produced (113—115). With paHadium on alumina catalyst in the vapor phase (250—300°C), pyridine [110-86-1] is the principal product (116—117) pyridine also is formed using Zn and Cr based catalysts (118,119). At low pressure and 200°C over a reduced nickel catalyst, piperidine is obtained in good yield (120,121). 

Catalysis. As of mid-1995, zeoHte-based catalysts are employed in catalytic cracking, hydrocracking, isomerization of paraffins and substituted aromatics, disproportionation and alkylation of aromatics, dewaxing of distillate fuels and lube basestocks, and in a process for converting methanol to hydrocarbons (54). 

Most catalysts for solution processes are either completely soluble or pseudo-homogeneous all their catalyst components are introduced into the reactor as Hquids but produce soHd catalysts when combined. The early Du Pont process employed a three-component catalyst consisting of titanium tetrachloride, vanadium oxytrichloride, and triisobutjlalurninum (80,81), whereas Dow used a mixture of titanium tetrachloride and triisobutylalurninum modified with ammonia (86,87). Because processes are intrinsically suitable for the use of soluble catalysts, they were the first to accommodate highly active metallocene catalysts. Other suitable catalyst systems include heterogeneous catalysts (such as chromium-based catalysts) as well as supported and unsupported Ziegler catalysts (88—90). 

Nonicosahedral carboranes can be prepared from the icosahedral species by similar degradation procedures or by reactions between boranes such as B H q and B H with acetylenes. The degradative reactions for intermediate C2B H 2 species (n = 6-9) have been described in detail (119). The small closo-Qr Yi 2 species (n = 3-5 are obtained by the direct thermal reaction (500—600°C) of B H using acetylene in a continuous-flow system. The combined yields approach 70% and the product distribution is around 5 5 1 of 2,4-C2B3H2 [20693-69-0] to l,6-C2B Hg [20693-67-8] to 1,5-C2B3H3 [20693-66-7] (120). A similar reaction (eq. 60) employing base catalysts, such as 2 6-dimethylpyridine at ambient temperature gives nido-2 >-(Z, ... 

The methanation reaction is currently used to remove the last traces (<1%) of carbon monoxide and carbon dioxide from hydrogen to prevent poisoning of catalysts employed for subsequent hydrogenation reactions. Processes for conversion of synthesis gas containing large quantities of carbon monoxide (up to 25%) into synthetic natural gas have been investigated to serve plants based on coal-suppHed synthesis gas. 

An interesting feature of the ring opening polymerization of siloxanes is their ability to proceed via either anionic or cationic mechanisms depending on the type of the catalyst employed. In the anionic polymerization alkali metal hydroxides, quaternary ammonium (I NOH) and phosphonium (R POH) bases and siloxanolates (Si—Oe M ) are the most widely used catalysts 1,2-4). They are usually employed at a level of 10 2 to KT4 weight percent depending on their activities and the reaction conditions. The activity of alkali metal hydroxides and siloxanolates decrease in the following order 76 79,126). 

Acid anhydrides have been employed with, and without the use of a base catalyst. For example, acetates, propionates, butyrates, and their mixed esters, DS of 1 to ca. 3, have been obtained by reaction of activated cellulose with the corresponding anhydride, or two anhydrides, starting with the one with the smaller volume. In all cases, the distribution of both ester groups was almost statistic. Activation has been carried out by partial solvent distillation, and later by heat activation, under reduced pressure, of the native cellulose (bagasse, sisal), or the mercerized one (cotton linters). No catalyst has been employed the anhydride/AGU ratio was stoichiometric for microcrystalhne cellulose. Alternatively, 50% excess of anhydride (relative to targeted DS) has been employed for fibrous celluloses. In all cases, polymer degradation was minimum, and functionalization occurs preferentially at Ce ( C NMR spectroscopic analysis [52,56,57]). 

With diphosphanes recently Stephan et al. reported an intriguing Al and P based macrocyclic structure [37]. A zirconium based catalyst precursor first was employed in the catalytic dehydrocoupling of the primary bidentate phosphane to give the tetraphosphane 6, (Scheme 4). The function of 6 as a molecular building block has been demonstrated by its reaction with MMe3(M = Al, Ga). Although, the gallium derivative 7 has not been... 

Telomerisation is an important, atom efficient reaction, which generates functionalised dienes from 1,3-diene feedstocks. The reaction, which typically employs a palladium based catalyst, comprises coupling two molecnles of a conjugated 1,3-diene... 

Propylene, ammonia, steam and air are fed to a vapour-phase catalytic reactor (item A). The feedstream composition (molar per cent) is propylene 7 ammonia 8 steam 20 air 65. A fixed-bed reactor is employed using a molybdenum-based catalyst at a temperature of 450°C, a pressure of 3 bar absolute, and a residence time of 4 seconds. Based upon a pure propylene feed, the carbon distribution by weight in the product from the reactor is ... 

---