Ethylene epoxidation catalyst preparation

The first report of the copolymerization of an epoxide, namely, ethylene oxide and C02 is contained in a patent by Stevens [6]. However, this process, when carried out in the presence of polyhydric phenols, provided polymers which were viscous liquids or waxes possessing copious polyether linkages with only a few incorporated C02 units. The earliest metal-catalyzed copolymerization of epoxides and C02 was reported in 1969 by Inoue and coworkers, who employed a heterogeneous catalyst system derived from a 1 1 mixture of diethylzinc and H20 [7, 8], Subsequently, Kuran and coworkers investigated a group of related catalysts prepared from diethylzinc and di- and triprotic sources such as pyrogallol, with a slight improvement over Inoue s system for the production of polypropylene carbonate) from PO and C02 [9],... 

The search for a new epoxidation method that would be appropriate for organic synthesis should also, preferably, opt for a catalytic process. Industry has shown the way. It resorts to catalysis for epoxidations of olefins into key intermediates, such as ethylene oxide and propylene oxide. The former is prepared from ethylene and dioxygen with silver oxide supported on alumina as the catalyst, at 270°C (15-16). The latter is prepared from propylene and an alkyl hydroperoxide, with homogeneous catalysis by molybdenum comp e ts( 17) or better (with respect both to conversion and to selectivity) with an heterogeneous Ti(IV) catalyst (18), Mixtures of ethylene and propylene can be epoxidized too (19) by ten-butylhydroperoxide (20) (hereafter referred to as TBHP). 

Preparation of diols Acid-catalysed epoxides are easily cleaved by water. Water reacts as the nucleophile, and this is referred to as a hydrolysis. For example, hydrolysis of ethylene oxide in the presence of acid-catalyst produces 1,2-ethanediol (ethylene glycol). 

Epoxides (oxiranes) are three-membered cyclic ethers. The simplest and commercially most important example is ethylene oxide, manufactured from ethylene, air, and a silver catalyst. In the laboratory, epoxides are most commonly prepared from alkenes and organic peroxy acids. 

Silver-alumina type catalysts are by far the most widely used, especially since they are the main catalytic source in the epoxidation of ethylene. Therefore, they are readily available and already have undergone extensive studies. Many systems have sought to utilize the presence of NO (another harmful environmental species) in gas feeds. In this case, the NO species would be reduced to N2, causing oxidation of the hydrocarbon with the support of the catalyst. Studies have helped to elucidate the active species on the catalyst surface at varying temperatures and species leading to the desired products (31). Results from a recent study point to the active silver species being a [Ag O Al] bound intermediate that leads to N2 formation (32). If the silver is present in nanoparticle form, it is simply believed to be a spectator. Other work showed mixed results on the benefit of silver-based alumina systems for the oxidation of methane and higher hydrocarbons. The effect is dependent on the type of reactor system prepared (33,34). 

For the Au/Ce02 catalysts, the CO2 selectivity increased substantially with increasing reaction temperature, whereas the ethylene oxide selectivity decreased (see Table 9.2). The Au on Ce02 prepared by the sol-gel/impregnation method was found to favor the total oxidation reaction over the epoxidation reaction as compared to that prepared by the single-step sol-gel method. This is because the impregnation method provides more active Au reaction sites than single-step... 

Chiral Co(III)-salen complexes can also serve as efficient catalysts for HKR of terminal epoxides. Polymer-supported chiral salen complexes 156 were prepared from chiral Co complex 154 and ethylene glycol dimethacrylate 155, as shown in Scheme 3.45. The chemical reduction of 156, followed by treatment with acetic acid under aerobic conditions, produced the catalytically active polymer 157, which was used in the HKR of propylene oxide [87]. Some other examples of polymeric salen-Co complexes have also been reported for the same reaction [88, 89]. 

The TS-1 catalyst has also been found effective in the epoxidation of olefinic compounds. It is of particular interest in the preparation of propylene oxide by oxidation of propylene with hydrogen peroxide (Hoelderich, 1988). Ethylene has also been epoxidized to ethylene oxide with 30% H2O2 in aqueous /-butanol to obtain 96% selectivity at 97% H2O2 conversion (Sheldon, 1991). 

Ethoxylated amines are prepared by the reaction of epoxides with primary amines. This reaction is well known, and an example is shown in Figure 14.5. In a typical manufacturing process, two moles of ethylene oxide are reacted with primary amine to produce a dihydroxyethylamine. Addition of more than two moles of ethylene oxide usually requires the presence of a catalyst. Typical catalysts are sodium or potassium hydroxide. 

Ethylene oxide, one of the few epoxides manufactured on an industrial scale, is prepared by passing a mixture of ethylene and air (or oxygen) over a silver catalyst ... 

Now, let s draw out the forward scheme. This multi-step synthesis uses three equivalents of ethylene (labeled A, B, C in the scheme below) and one equivalent of acetic acid (labeled D). Ethylene (A) is converted to 1,2-dibromoethane upon treatment with bromine. Subsequent reaction with excess sodium amide produces an acetylide anion which is then treated with bromoethane [made tfom ethylene (B) and HBr] to produce 1-butyne. Deprotonation with sodium amide, followed by reaction with an epoxide [prepared by epoxidation of ethylene (C)] and water workup, produces a compound with an alkyne group and an alcohol group. Reduction of the alkyne to the cis alkene is accomplished with H2 and Lindlar s catalyst, after which the alcohol is converted to a tosylate with tosyl chloride. Reaction with the conjugate base of acetic acid [produced by treating acetic acid (D) with NaOH] allows for an Sn2 reaction, thus yielding the desired product, Z-hexenyl acetate. 

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