(178q) Renewable Chemical Herder from Direct Coupling of Furans with Allylic Alcohols over Aluminosilicate

Oil spills from petroleum production and transportation in aquatic environments are a major threat to the ecosystems, and the enduring socio-economic impacts on the communities that depend on aquatic resources have been prevalent for decades. Chemical herder-assisted in situ burning (ISB) has been proven to be a successful approach for oil spill remediation in marine and freshwater environments. Chemical herders, once applied at the periphery of the oil spill, reduce the air-water surface tension retracting the oil sheen to a thick slick with ignitable thickness (> 3 mm) for efficient and rapid removal by ISB. However, the U.S. EPA-approved commercial herders for ISB operations pose environmental risks due to their toxicity and non-biodegradability. To address this concern, we developed novel, bio-based, and eco-friendly chemical herders to minimize the environmental footprint of chemical herder operations in oil spill remediation.

In this presentation, we will show our newly developed amphiphiles by coupling algae-extracted phytol to furan and furan derivatives with a new synthesis route. The as-formed alkyl furan molecules serve as bio-derived surfactants with evaluated herding performance. These alkyl furans have also demonstrated potential in a vast array of areas, including food additives/flavorings, cosmetic additives, and insecticides. A variety of methods exist for their synthesis, with the most common being through ortho-lithiation; Friedel-Crafts alkylation, or transition metal-catalyzed C-H functionalization. While these methods can certainly be effective there are various issues, particularly when considering their use on large scales. The direct reaction of furans with alcohols to affect a dehydrative substitution represents an attractive approach to generating alkyl furans. Not only does this approach remove an entire step in any synthetic route, that of the pre-functionalization of the alcohol and the accompanying waste generated, but itself would produce water as the only byproduct. Allylic alcohols represent an alternative reactive motif that is readily available in biomass-derived chemicals such as the terpenoids prenol and geraniol, as well as phytol, which can be obtained from chlorophyll. Combining these aspects, we therefore developed a method for the direct reaction of furans with allylic alcohols. Zeolites were targeted as the mediator for this reaction, as they are readily available and environmentally benign but also capable of generating and stabilizing carbocations, including from propargylic alcohols.