Epoxidation reactions and catalysts

TABLE 1.1 Epoxy resins Epoxidation reactions and catalysts... 

Reetz and coworkers tested catalysts for different reactions such as enantiose-lective acylation of a chiral secondary alcohol by lipases, the enantioselective ring opening of epoxides to non-racemic diols, and metathesis reactions [11, 12]. The two first examples are exothermic reactions and catalyst activity is revealed by hot spots in the IR image. The catalytic performance found by use of time-resolved IR-thermography correlated well with already known activity of the tested catalysts [11]. The metathesis reaction is particularly interesting, because it is the first example of the monitoring of endothermic reactions by means of an IR camera [12]. 

Among the most active transition metals are Mo and V, and both are effective in their highest oxidation state during reaction. Linden and Farona have foimd that Mo(V) is inactive for the epoxidation reaction and that V(IV) is converted to V (V) when contacted with a hydroperoxide [467]. The metals are added as compounds soluble in the reaction mixture, for example, Mo(CO)6, MoO2(acac), and VO(acac)2 (acac = monoanion of acetylacetone). Sheldon and Van Doom [266] have found that irrespective of the starting material, all molybdenum catalysts give rise to a common compound, a 1,2-diol complex (Fig. 1.11b). This is formed... 

A major challenge that remains is the hydrogen efficiency of the catalyst. Since the propene epoxidation is performed in the presence of hydrogen, it is desirable that the hydrogen is used only in the epoxidation reaction and is not converted directly into water. At this time none of the catalysts have a sufficiently high hydrogen efficiency to be able to run a process profitable and, therefore, this remains one of the key challenges to be solved for this catalyst system for propene epoxidation. 

The subjects presented span a wide range of oxidation reactions and catalysts. These include the currently important area of lower alkane oxidation to the corresponding olefins, unsaturated aldehydes, acids and nitriles. In this manner, the abundant and less expensive alkanes replace the less abundant and more expensive olefins as starting materials for industrially important intermediates and chemicals. In the oxidative activation of methane the emphasis is shifting towards the use of extremely short contact times and newer more rugged catalysts. In the area of olefin oxidations, of particular note are the high efficiency epoxidation of propylene, and new detailed mechanistic insights into the... 

From this scheme, and accepting some assumptions, Fiala and Lidarik established a complex reaction giving orders 1,0.5, and 0.5 in epoxide, add, and catalyst, respectively. Unfortunately, this relation involves the concentration of intermediary spedes which were not experimentally measured. 

After epoxidation a distillation is performed to remove the propylene, propylene oxide, and a portion of the TBHP and TBA overhead. The bottoms of the distillation contains TBA, TBHP, some impurities such as formic and acetic acid, and the catalyst residue. Concentration of this catalyst residue for recycle or disposal is accompHshed by evaporation of the majority of the TBA and other organics (141,143,144), addition of various compounds to yield a metal precipitate that is filtered from the organics (145—148), or Hquid extraction with water (149). Low (<500 ppm) levels of soluble catalyst can be removed by adsorption on soHd magnesium siUcate (150). The recovered catalyst can be treated for recycle to the epoxidation reaction (151). 

One of the most significant developmental advances in the Jacobsen-Katsuki epoxidation reaction was the discovery that certain additives can have a profound and often beneficial effect on the reaction. Katsuki first discovered that iV-oxides were particularly beneficial additives. Since then it has become clear that the addition of iV-oxides such as 4-phenylpyridine-iV-oxide (4-PPNO) often increases catalyst turnovers, improves enantioselectivity, diastereoselectivity, and epoxides yields. Other additives that have been found to be especially beneficial under certain conditions are imidazole and cinchona alkaloid derived salts vide infra). 

The oxidation of alkenes and allylic alcohols with the urea-EL202 adduct (UELP) as oxidant and methyltrioxorhenium (MTO) dissolved in [EMIM][BF4] as catalyst was described by Abu-Omar et al. [61]. Both MTO and UHP dissolved completely in the ionic liquid. Conversions were found to depend on the reactivity of the olefin and the solubility of the olefinic substrate in the reactive layer. In general, the reaction rates of the epoxidation reaction were found to be comparable to those obtained in classical solvents. 

In light of the previous discussions, it would be instructive to compare the behavior of enantiomerically pure allylic alcohol 12 in epoxidation reactions without and with the asymmetric titanium-tartrate catalyst (see Scheme 2). When 12 is exposed to the combined action of titanium tetraisopropoxide and tert-butyl hydroperoxide in the absence of the enantiomerically pure tartrate ligand, a 2.3 1 mixture of a- and /(-epoxy alcohol diastereoisomers is produced in favor of a-13. This ratio reflects the inherent diasteieo-facial preference of 12 (substrate-control) for a-attack. In a different experiment, it was found that SAE of achiral allylic alcohol 15 with the (+)-diethyl tartrate [(+)-DET] ligand produces a 99 1 mixture of /(- and a-epoxy alcohol enantiomers in favor of / -16 (98% ee). 

The observation that addition of imidazoles and carboxylic acids significantly improved the epoxidation reaction resulted in the development of Mn-porphyrin complexes containing these groups covalently linked to the porphyrin platform as attached pendant arms (11) [63]. When these catalysts were employed in the epoxidation of simple olefins with hydrogen peroxide, enhanced oxidation rates were obtained in combination with perfect product selectivity (Table 6.6, Entry 3). In contrast with epoxidations catalyzed by other metals, the Mn-porphyrin system yields products with scrambled stereochemistry the epoxidation of cis-stilbene with Mn(TPP)Cl (TPP = tetraphenylporphyrin) and iodosylbenzene, for example, generated cis- and trans-stilbene oxide in a ratio of 35 65. The low stereospecificity was improved by use of heterocyclic additives such as pyridines or imidazoles. The epoxidation system, with hydrogen peroxide as terminal oxidant, was reported to be stereospecific for ris-olefins, whereas trans-olefins are poor substrates with these catalysts. 

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