Shell Higher Olefin Process synthesis

This reaction was first used in petroleum reformation for the synthesis of higher olefins (Shell higher olefin process - SHOP), with nickel catalysts under high pressure and high temperatures. Nowadays, even polyenes with MW > 250,000 are produced industrially in this way. 

The reaction is applied in industrial processes (Phillips triolefin process. Shell higher olefin process) and has importance in ring opening-metathesis polymerization (ROMP) in polymer chemistry [1]. In the past, olefin metathesis was not commonly applied in organic synthesis [2] because of the reversibility of the reaction, leading to olefin mixtures. In contrast, industrial processes often handle product mixtures easily. In ROMP, highly strained cyclic olefins allow the equilibrium of the reaction to be shifted towards the product side. 

Two important industrial processes are based on biphasic systems the Shell higher olefin process (SHOP) [3] and the hydroformylation developed by Ruhrchemie/ Rhone Poulenc [4]. Prerequisite was the synthesis of water-soluble ligands, especially water-soluble phosphines. Scheme 1 shows a selection of optically active phosphines for asymmetric reactions under biphasic conditions. 

The liquid support may be water, supercritical fluids, ionic liquids, organic liquids or fluorous liquids [12]. The Shell higher olefin process (SHOP) and the Oxo synthesis (hydrofomylation) are examples of important industrial processes based on biphasic catalytic systems. 

Hydroformylations catalyzed by ECo(CO) are typically run at high temperature (120-170 °C) and high pressure of a 1 1 mixture of CO E, (200-300 atm "synthesis gas"). These reactions are typically conducted with alkenes, sudi as propene, 1-octene, or a mixture of internal and alkenes generated as part of the Shell higher olefin process (SHOP). 

The Shell higher olefin process (SHOP process) is an example for ethenolysis on an industrial scale. From the ethenolysis of an oleic double bond such as in tall oil fatty acid methyl ester using a Grubbs catalyst methyl-9-decenoate and 1-decene are formed (Figure 3B.15) key intermediates in the synthesis of flavors and fragrances, insect pheromones as environmentally friendly alternatives to pesticides, and prostaglandins on the one side and poly-a-olefins as lubricant base stock on the other. ... 

It is still unclear how the initiation step in alkene metathesis occurs and how the initial carbene forms. Commercial applications of metathesis include the triolefin process, in which propylene is converted to ethylene and butene, the neohexene process, in which the dimer of isobutylene, Me3CCH=CMe2, is metathesized with ethylene to give Me3CCH=CH2, an intermediate in the manufacture of synthetic musk, and a 1,5-hexadiene synthesis from 1,5-cy-clooctadiene and ethylene. Two other applications, SHOP and ROMP (Shell higher olefins process and ring-opening metathesis polymerization), are discussed in the next section. 

Oligomerization processes practized embrace monoenes and dienes. Here the synthesis of a-olefins from ethylene (Shell Higher Olefin Process), the oligomerization of propylene/butene (Dimersol Process), and... 

This reaction is widely used in large scale petrochemical processes (Phillips Triolefin Process and Shell Higher Olefin Process SHOP ) and in some specialty synthesis. 

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