Epoxide phenol reaction kinetics

Epoxidized novolacs, 411 Epoxy -phenol networks, 411-416 properties of, 413-416 Epoxy-phenolic reaction kinetics of, 413 mechanism of, 411-412 Epoxy structures, 414 e-Caprolactam, 174... 

In their initial studies, Shechter and Wynstra had demonstrated that these catalysts could achieve high selectivity of the epoxy-phenol reaction in a solution of excess phenol. They later reversed the situation and studied the reaction selectivity in a solution of excess glycidyl ether in which the phenol was used as the limiting reagent. The excess of epoxide over phenol was measured until phenol had practically disappeared, and the results in all cases indicated high selectivity towards the epoxy-phenol reaction. The tertiary amine, ben ldimethylamine, was somewhat more effective than potassium hydroxide benzyltrimethylammonium hydroxide was even more powerful. First-order kinetics were observed for all reactions. Since it was postulated that the phenoxide ion was common to all these reactions, the observed diffCTences in reaction rates were linked to the cation. In was not determined, however, whether the cation effect is one of different degrees of dissociation of the phenol salts or of some other phenonomenon. 

Detailed kinetic studies comparing the chemical reactivity ofK-region vs. non-K-region arene oxides have yielded important information. In aqueous solution, the non-K-region epoxides of phenanthrene (the 1,2-oxide and 3,4-oxides) yielded exclusively phenols (the 1-phenol and 4-phenol, respectively, as major products) in an acid-catalyzed reaction, as do epoxides of lower arenes (Fig. 10.1). In contrast, the K-region epoxide (i.e., phenanthrene 9,10-oxide 10.29) gave at pH < 7 the 9-phenol and the 9,10-dihydro-9,10-diol (predominantly trans) in a ratio of ca. 3 1. Under these conditions, the formation of this dihydrodiol was found to result from trapping of the carbonium ion by H20 (Fig. 10.11, Pathway a). At pH > 9, the product formed was nearly ex-... 

ARO reaction with phenols and alcohols as nucleophiles is a logical extension of HKR of epoxides to synthesize libraries of stereochemically defined ring-opened products in high optical purity. To this effect Annis and Jacobsen [69] used their polymer-supported Co(salen) complex 36 as catalyst for kinetic resolution of epoxides with phenols to give l-aiyloxy-2-alcohols in high yield, purity and ee (Scheme 17). Conducting the same reaction in the presence of tris(trifluoromethyl)methanol, a volatile, nonnucleophilic protic acid additive accelerates KR reaction with no compromise with enantioselectivity and yield. Presumably the additive helped in maintaining the Co(III) oxidation state of the catalyst. 

This article shows how successfully the cascade branching theory works for systems of practical interest. It is a main feature of the Flory-Stockmayer and the cascade theory that all mentioned properties of the branched system are exhaustively described by the probabilities which describe how many links of defined type have been formed on some repeating unit. These link probabilities are very directly related to the extent of reaction which can be obtained either by titration (e.g. of the phenolic OH and the epoxide groups in epoxide resins based on bisphenol A206,207)), or from kinetic quantities (e.g. the chain transfer constant and monomer conversion106,107,116)). The time dependence is fully included in these link probabilities and does not appear explicitly in the final equations for the measurable quantities. 

A number of studies of the kinetics and mechanism of the base catalysed reaction of epoxides with phenolic alcohols have served as background for the polymerization studies. These studies [14] showed that both the alcohol and the alkoxide participate in the rate determining step and subsequently a termolecular mechanism was proposed. 

The observations that the pH-independent reactions of deuterium-labeled 5-met-hoxyindene oxide and 6-methoxy-1,2,3,4-tetrahydronaphthalene-1,2-oxide show significant primary kinetic deuterium isotope effects for the ketone-forming reactions, whereas the pH-independent reactions of deuterium-labeled naphthalene oxide and benzene oxide do not, are quite puzzling. Clearly, more work needs to be done to fully understand why transition-state structures for rearrangement of arene oxides to phenols differ from those for rearrangement of benzylic epoxides to ketones. 

The HKR of epichlorhydrine (X = Cl, Scheme 141) and 4-hydroxy-l-butene oxide (X = OH, Scheme 141), the dynamic kinetic resolution of epibromhydrin and the enantioselective ring opening of epoxides by phenol were examined. In the first experiment, combination of the crude organic soluble products of the five recycle reactions and concentration led to the (5)-epichlorhydrine in 41% overall yield and > 99% ee and the (/ )-chlorodiol in 93% ee. In the second one, the sum of five experiments provided (iS)-triol in 36% overall yield and 94.4% ee while the enantioselectivity of the epoxide was only 59% ee. 

The ring opening of terminal epoxides by phenols usually requires forcing conditions and the reaction is unsuitable for sensitive substrates. It is, however, catalysed by certain (salen)Co(III) complexes and the reaction has now been applied to the asymmetric synthesis of a-aryloxy alcohols. The (salen)Co(ni)-catalysed ring opening of terminal epoxides is highly enantioselective, so that kinetic resolution of the... 

MS has been widely used to identify the products and their formation kinetics in the degradation of filled reaction layers, e.g., phenol-formaldehyde resins [53, 54], epoxide resins, polyesters and polyacrylates [55]. 

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