A review of fatty epoxide ring opening reactions: Chemistry, recent advances, and applications

Abstract

Fatty epoxides are produced from the corresponding alkenes by oxidation in the presence of peracids or other oxidants. The classic method is the Prilezhaev epoxidation in which peracids are generated by in situ oxidation of formic or acetic acids with hydrogen peroxide. Epoxidized vegetable oils and esters are used directly as biobased plasticizers and stabilizers for poly(vinyl chloride) or as important platform chemicals for the oleochemical industry. Nucleophilic attack at the oxirane moiety affords a variety of ring opened monomeric or polymeric products, which in many cases undergo further synthetic modification to yield finished products. The most common nucleophiles include water, alcohols, carboxylic acids, acid anhydrides, and amines, although numerous others can also lead to valuable functionalized fatty derivatives. This review summarizes the chemistry of fatty epoxide ring opening reactions as well as applications of the resultant products. Literature from the last 20 years will be emphasized, although older publications of particular significance will be included. Important applications include biobased lubricants as well as polyols for subsequent production of polyurethanes. In addition, ring-opening reactions hitherto unreported on fatty oxiranes will be suggested to facilitate further advancements in the chemistry and utility of fatty epoxides. Finally, interest in fatty epoxides and their consequent products will continue to grow due to the simplicity, efficiency, and versatility of oxirane formation and ring opening as well as the continued societal transition away from petroleum to a sustainable, circular, low-carbon, and biobased economy.

Acrylated soybean oil: a key intermediate for more sustainable elastomeric materials from silicones

“…13 When good nucleophiles like amines are used, as with epoxy-based resins, accelerators are common; co-catalysts are also frequently exploited under acidic conditions, including with fatty acid-derived epoxides. 14 A systematic examination of the reaction of 1 with acrylic acid demonstrated that, by controlling both concentrations of reagents and temperature, catalysts were not required (Fig. 1A).…”

Synthesis, Characterization, and Physicochemical Performance of Nonionic Surfactants via PEG Modification of Epoxides of Alkyl Oleate Esters

“…Many of the previous studies involving ring opening of methyl oleate and fatty acid epoxides utilized the boron trifluoride catalyst. ,,, However, boron trifluoride’s acceptance as an effective catalyst for this reaction continues to wane not only because it is a homogeneous catalyst but also because of its high toxicity. Some heterogeneous catalysts such as saponite clays and Nafion-silica have been reported as being effective for epoxide ring opening of epoxy methyl oleate. , However, their effectiveness with longer-chain fatty esters is unknown.…”

“…The resulting surfactants gave promising results that could further be exploited in personal and home care products. A comprehensive list of the nucleophiles most commonly used to functionalize fatty derivatives, as well as the chemistry of fatty epoxide ring-opening reactions leading to valuable chemicals was recently reported by Moser and co-workers …”

“…A comprehensive list of the nucleophiles most commonly used to functionalize fatty derivatives, as well as the chemistry of fatty epoxide ring-opening reactions leading to valuable chemicals was recently reported by Moser and co-workers. 18 The properties of surfactants resulting from epoxy ring opening of methyl oleate epoxide such as earlier reported can be tailored to have a more hydrophilic influence and to give a broader application by introducing polyethylene glycol (PEG) of varying chain lengths. PEGs are short-chain polyethers soluble in water and a number of organic solvents, including toluene, acetone, ethanol, and dichloromethane, depending on their molecular weight.…”

Comparison of aliphatic polyesters prepared by acyclic diene metathesis and thiol‐ene polymerization of α,ω‐polyenes arising from oleic acid‐based 9‐decen‐1‐ol

“…9DO is naturally occurring and can be obtained synthetically by selective reduction of 9DA (Bouzidi et al, 2013). Aliphatic polyesters were of interest due to their applications as components in fibers, coatings, adhesives, and resins (Moser et al, 2022; Rybak & Meier, 2008). Lastly, aliphatic polyesters find use in biomedical fields such as surgery and pharmacology because of their biodegradable and nontoxic nature (Turunc & Meier, 2011).…”