Epoxide side groups

Binding enzymes to solid supports can be achieved via covalent bonds, ionic interactions, or physical adsorption, although the last two options are prone to leaching. Enzymes are easily bound to several types of synthetic polymers, such as acrylic resins, as well as biopolymers, e.g., starch, cellulose [52], or chitosan [53,54]. Degussa s Eupergit resins, for example, are used as enzyme carriers in the production of semisynthetic antibiotics and chiral pharmaceuticals [55], Typically, these copolymers contain an acrylamide/methacrylate backbone, with epoxide side groups... 

Polymers carrying epoxide side groups (Chart 5.12) can be transformed into intermolecularly crosslinked networks by acid-catalyzed polymerization of the epoxide groups. Formulations comprised of commercially available epoxide resins and an acid generator have been employed in lithography [150]. 

The reaction actually involves the sodium salt of bisphenol A since polymerization is carried out in the presence of an equivalent of sodium hydroxide. Reaction temperatures are in the range 50-95°C. Side reactions (hydrolysis of epichlorohydrin, reaction of epichlorohydrin with hydroxyl groups of polymer or impurities) as well as the stoichiometric ratio need to be controlled to produce a prepolymer with two epoxide end groups. Either liquid or solid prepolymers are produced by control of molecular weight typical values of n are less than 1 for liquid prepolymers and in the range 2-30 for solid prepolymers. 

The trichothecenes may also have side groups as hydroxyl, esterified hydroxyl, keto, or epoxide groups in various combinations. Type-A trichothecenes have a functional group other than a carbonyl group at C-8 and are differentiated by various combinations of hydroxyl or acyloxyl (OAc) groups at C-3, 4, 7, 8, and 15, similarly to the type-B trichothecenes, which have a typical carbonyl bond (keto group) at C-8 as well (Table 1). ... 

In most articles relative to the study of the base-catalyzed reaction, a general mechanism is put forward unfortunately the contribution of the side reactions is very often disregarded. If the contribution of some of them (esterification or etherification of the hydroxy side groups, hydrolysis, etc.) can be avoided or at least reduced to a low extent, that of some others (especially those resulting from the amine/epoxide interaction) is more difficult to eliminate. Some studies provided information on the kinetic contribution of these side reaction. 

The epoxidation of diene-based polymers is advantageous because it provides active sites along the polymer chains for further modification. Furthermore, introducing an epoxide functional group to unsaturated polymers can help improve abrasion resistance, adhesive strength, and heat stability. Epox-idized polymers can be prepared by polymerizing epoxidized monomers however, this method typically results in many side reactions. Numerous reports have focused on the epoxidation of diene-based polymers with... 

Next in what amounts to an intramolecular Williamson ether synthesis the alkoxide oxygen attacks the carbon that bears the halide leaving group giving an epoxide As m other nucleophilic substitutions the nucleophile approaches carbon from the side oppo site the bond to the leaving group... 

The epoxidation is generally conducted in two steps (/) the polyol is added to epichlorohydrin in the presence of a Lewis acid catalyst (stannic chloride, boron triduoride) to produce the chlorohydrin intermediate, and (2) the intermediate is dehydrohalogenated with sodium hydroxide to yield the aliphatic glycidyl ether. A prominent side-reaction is the conversion of aliphatic hydroxyl groups (formed by the initial reaction) into chloromethyl groups by epichlorohydrin. The aliphatic glycidyl ether resins are used as flexibilizers for aromatic resins and as reactive diluents to reduce viscosities in resin systems. 

Steroids possessing an epoxide grouping in the side chain have likewise been converted to fluorohydrins. Thus, 20-cyano-17,20-epoxides of structure (19) furnish the 17a-fluoro-20-ketones (20) after treatment of the intermediate cyanohydrins with boiling collidine. The epimeric 5a,6a 20,21-oxides (21) afford the expected bis-fluorohydrins (22). The reaction of the allylic... 

In general, epoxidation of steroids with trans-anti-trans ring fusions leads to exclusive formation of the a-oxirane. Steroid Reactions lists examples of exclusive a-epoxide formation from 2-, 4-, 6-, 7-, 8(9)-, 14-, 16- and 17(20)-unsaturated steroids. Further examples of a-epoxidation of steroid 1-enes, 3-enes, 8-enes, 9(ll)-enes, 8(14)-enes and 16-enes have been reported. The preferred attack by the reagent on the a-side of the steroid nucleus can be attributed to shielding of the -side of the molecules by the two angular methyl groups. 

Hydroxyl groups are stable to peracids, but oxidation of an allylic alcohol during an attempted epoxidation reaction has been reported." The di-hydroxyacetone side chain is usually protected during the peracid reaction, either by acetylation or by formation of a bismethylenedioxy derivative. To obtain high yields of epoxides it is essential to avoid high reaction temperatures and a strongly acidic medium. The products of epoxidation of enol acetates are especially sensitive to heat or acid and can easily rearrange to keto acetates. 

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