Olefin industrial applications

If cobalt carbonylpyridine catalyst systems are used, the formation of unbranched carboxylic acids is strongly favored not only by reaction of a-olefins but also by reaction of olefins with internal double bonds ( contrathermo-dynamic double-bond isomerization) [59]. The cobalt carbonylpyridine catalyst of the hydrocarboxylation reaction resembles the cobalt carbonyl-terf-phos-phine catalysts of the hydroformylation reaction. The reactivity of the cobalt-pyridine system in the hydrocarboxylation reaction is remarkable higher than the cobalt-phosphine system in the hydroformylation reaction, especially in the case of olefins with internal double bonds. This reaction had not found an industrial application until now. 

Copper olefin complexes are usually generated by the direct reaction of a Cu(l) source, the ligand, and the corresponding olefin. Copper ethylene complexes are of interest in view of their biochemical importance,98,98a-98e their applications in organic chemistry,99,99a,99b and industrial applications.100 100 Because of this, many copper alkene complexes have been reported, with different nuclearity, in compounds with one, two, or even three C=C units coordinated to a given copper center. 

Pentachlorophenol is readily soluble in most organic solvents, oils, and highly aromatic and olefinic petroleum hydrocarbons — a property that makes it compatible for inclusion in many pesticide formulations (Table 23.1 Figure 23.1). Purified PCP, however, is practically insoluble in water therefore, the readily water-soluble sodium pentachlorophen-ate salt is substituted in many industrial applications (Table 23.1) (Bevenue and Beckman 1967 USPHS 1994). 

Further important industrial applications of olefin metathesis include the synthesis of 3,3-dimethyl-l-butene ( neohexene , intermediate for the production of musk perfume) from ethene and 2,4,4-trimethyl-2-pentene, the manufacture of a,co-dienes from ethene and cycloalkenes (reversed RCM), and the ROMP of cyclooctene and norbomene to Vestenamer and Norsorex , respectively. 

The treatment of equivalent amounts of two different alkenes with a metathesis catalyst generally leads to the formation of complex product mixtures [925,926]. There are, however, several ways in which cross metathesis can be rendered synthetically useful. One example of an industrial application of cross metathesis is the ethenolysis of internal alkenes. In this process cyclic or linear olefins are treated with ethylene at 50 bar/20 80 °C in the presence of a heterogeneous metathesis catalyst. The reverse reaction of ADMET/RCM occurs, and terminal alkenes are obtained. 

There are a number of industrial applications for paraffins, olefins and mixtures in the C9-C16 range that are produced in the FT process. Among such uses is as a precursor to linear alkylbenzene (LAB), which is used to produce linear... 

Peroxidases have been used very frequently during the last ten years as biocatalysts in asymmetric synthesis. The transformation of a broad spectrum of substrates by these enzymes leads to valuable compounds for the asymmetric synthesis of natural products and biologically active molecules. Peroxidases catalyze regioselective hydroxylation of phenols and halogenation of olefins. Furthermore, they catalyze the epoxidation of olefins and the sulfoxidation of alkyl aryl sulfides in high enantioselectivities, as well as the asymmetric reduction of racemic hydroperoxides. The less selective oxidative coupHng of various phenols and aromatic amines by peroxidases provides a convenient access to dimeric, oligomeric and polymeric products for industrial applications. 

Aliphatic polyketones are made from the reaction of olefin monomers and carbon monoxide using a variety of catalysts. Shell commercialized a terpolymer of carbon monoxide, ethylene, and a small amount of propylene in 1996 under the trade name Carilon (structure 4.79). They have a useful range between the Tg (15°C) and (200°C) that corresponds to the general useful range of temperatures for most industrial applications. The presence of polar groups causes the materials to be tough, with the starting materials readily available. 

Olefin metathesis chemistry has had a profound impact in several areas of chemical research, including organome-tallics, polymer chemistry, and small molecule synthesis,many of which have industrial applications. For example, CM is currently utilized in the commercial preparation of several agrochemicals, polymer and fuel additives, and pharmacophores. Unlike RCM reactions, which are typically conducted under dilute... 

Metal-catalysed hydrocarboxylation of olefins (Equation 3) is the poor relative of the more famous hydroformylation. It generally requires forcing reaction conditions and suffers from mediocre activities and selectivities (n/i ratio). Moreover, the same products can be made via hydroformylation and oxidation of the aldehyde product.431 Consequently, there are few industrial applications of hydrocarboxylation e.g. Ni(CO)4-catalysed production of propionic acid by hydrocarboxylation of ethylene.432,433... 

For industrial applications for the polymerization of norbomenes into COCs, zirconium based metallocene catalysts are most popular. However, other metal based catalysts have been described too. Catalysts for olefin polymerization have been reviewed in the literature (10,23,24). 

Arylation, olefins, 187, 190 Arylketimines, iridium hydrogenation, 83 Arylpropanoic acid, Grignard coupling, 190 Aspartame, 8, 27 Asymmetric catalysis characteristics, 11 chiral metal complexes, 122 covalently bound intermediates, 323 electrochemistry, 342 hydrogen-bonded associates, 328 industrial applications, 8, 357 optically active compounds, 2 phase-transfer reactions, 333 photochemistry, 341 polymerization, 174, 332 purely organic compounds, 323 see also specific complexes Asymmetric induction, 71, 155 Attractive interaction, 196, 216 Autoinduction, 330 Axial chirality, 18 Aza-Diels-Alder reaction, 220 Azetidinone, 44, 80 Aziridination, olefins, 207... 

Olefin isomerization (Continued) industrial applications, 9, 95 ligand synthesis, 96 rhodium-catalyzed, 98 Olefins ... 

Curtin-Hammett principle, 23 industrial applications, 8, 26 mechanism, 21 phosphine ligands, 7, 18 reaction conditions, 18 scope and limitations, 27 Wilkinson complex, 17 Rhodium-catalyzed olefin isomerization ab initio calculations, 110... 

The most common oxidation state of palladium is H-2 which corresponds toa electronic configuration. Compounds have square planar geometry. Other important oxidation states and electronic configurations include 0 ( °), which can have coordination numbers ranging from two to four and is important in catalytic chemistry, and +4 (eft), which is octahedral and much more strongly oxidizing than platinum (IV). The chemistry of palladium is similar to that of platinum, but palladium is between 103 to 5 x 10s more labile (192). A primary industrial application is palladium-catalyzed oxidation of ethylene (see Olefin polymers) to acetaldehyde (qv). Palladium-catalyzed carbon—carbon bond formation is an important organic reaction. 

Olefin fibers are used for a variety of purposes from home furnishings to industrial applications. These include carpets, upholstery, drapery, rope, geotextiles, and both disposable and nondisposable nonwovens. Fiber mechanical properties, relative chemical inertness, low moisture absorption, and low density contribute to desirable product properties. 

Since the mid-fifties sulfonated resins based on styrene/divinylbenzene copolymers, initially developed as ion exchangers mainly for water treatment, nave also been used as strongly acidic solid catalysts. Witn few exceptions, industrial application in continuous processes is limited to the manufacture of bulk chemicals, sucn as Disphenol A, (meth)acrylates, metnyl ethers of branched olefins (MTBE, TAME) and secondary alcohols (IPA, SBA). 

The focus of this chapter is to acquaint the reader with details of catalytic asymmetric dihydroxylation with osmium tetroxide and the scope of results that one can expect to achieve with current optimum conditions. The literature through mid-1992 has been reviewed in compiling this chapter. Osmium tetroxide catalyzed hydroxy]ations of olefins and acetylenes are the subject of an extensive review by Schroder published in 1980 [2a]. A comprehensive review of research and industrial applications of asymmetric dihydroxylations is in preparation [2b]. 

Hydroformylation (the oxo process) involves the addition of H2 and CO to an olefin to form aldehydes (eq. 2.8), which have a number of important industrial applications. Extensive mechanistic studies have shown that this reaction involves migratory insertion of a bound alkyl group (formed by insertion of an olefin into a metal hydride) into a bound CO, followed by reductive elimination of the aldehyde. The rate-limiting step for the hydroformylation in liquids is either the reaction of olefin and HCo(CO)4 or the reaction of the acyl complex with H2 to liberate the product aldehyde. The high miscibility of CO in sc C02 is therefore not necessarily a major factor in determining the rate of the hydroformylation. Typically, for a-olefins, linear aldehydes are preferred to branched products, and considerable effort has gone into controlling the selectivity of this reaction. 

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