Magnesium oxide , epoxidation with

Reactant for /-butyl phenolic resins. Magnesium oxide reacts in solution with /-butyl phenolic resin to produce an infusible resinate (Fig. 36) which provides improved heat resistance. The resinate has no melting point and decomposes above 200°C. Although oxides of calcium, lead and lithium can also be used, they are not as efficient as magnesium oxide and also tend to separate from solution. Where clear adhesive solutions are required epoxide resins, zinc-calcium resinates or zinc carbonate can be used. 

Various magnesium oxide crystals [commercial MgO, CM-MgO (SSA 30 m /g), conventionally prepared MgO, NA-MgO (SSA 250 m /g), aerogel prepared MgO, NAP-MgO (SSA 590m /g)] were initially evaluated in the CSC and AE reactions separately in order to understand the relationship between structure and reactivity. All these MgO samples catalyzed both CSC of benzaldehyde with acetophenone to form chalcone quantitatively and selectively, and subsequent AE using (- -)-diethyl tartrate (DET) as a chiral auxiliary to obtain a chiral epoxy ketone in good yield and impressive ee. The nanocrystalline MgO (NAP-MgO) was found to be more active than the NA-MgO and CM-MgO in the condensation and epoxidation reactions (Figure 5.6). 

In the proposed mechanism for the epoxidation of olefins such as styrene, the Mn(III) on nano magnesium oxide is complexed with a chiral ligand and subsequently oxidized by f-BuOOH to form a metal-oxo [Mn(IV) = O] (B) (Scheme 5.9), as indicated by XPS analysis.Mn(IV) is indeed found as an active species in Jacobsen-Katsuki catalytic epoxidations. Interaction of the olefin and (B),... 

The reaction of alkenyl epoxides with organometallic species (lithium, magnesium, copper, and boron) affords allylic alcohols, following an Sn and/or Sn mechanism. These processes can accommodate only little organic functionality and exhibit low regio- and/or stereoselectivity. Under smooth conditions, C—C bond formation proceeds by nucleophilic alkylation of vinyl epoxides in the presence of catalytic amounts of zerovalent palladium. Regio- and stereoselectivity can be achieved via the formation of a Tr-allylpal-ladium complex. Trost and Molander and Tsuji and co-workers simultaneously reported the first studies in 1981. Since then, numerous papers have dealt with this subject. Essentially, after chelation and oxidative addition of the palladium onto the vinyl epoxide, the zwitterionic 7r-allylpalladium complex deprotonates the nucleophile, which can in principle attack either carbon 2 (proximal attack) or 4 (distal attack) (Scheme 1). 

Scheme 4.5 illustrates a route for the synthesis of spiro-8-lactones from the magnesium complex of l,2-bis(methylene)cyclohexane 1 [126]. Initially, treatment of the l,2-bis(methylene)cyclohexane-magnesium reagent 2 with an excess of ethylene oxide at -78°C resulted in the formation of the 1,2-adduct of 3 by the incorporation of one equivalent of epoxides with the diene complex. Significantly, the bis-organomagnesium reagent 2 reacted with only one mole... 

Magnesium-aluminum mixed oxides are also excellent catalysts for the reaction of several epoxides with carbon dioxide to give the cyclic carbonates 80. 

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). 

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