Xiao-Bing Fan, N. Yan, Zhiyuan Tao
Oct 19, 2009
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0
Influential Citations
19
Citations
Journal
ChemSusChem
Abstract
The conversion of renewable resources, such as biomasses that are CO2-neutral but whose use does not have an adverse effect on food supplies, into useful organic compounds is a topic of intense current interest. Oxygenates, the use of which as fuel additives to improve the octane rating of gasoline or the cetane rating of diesel is well-established, 3] are one such class of useful products. It has been shown that acetals such as 1,3-dioxolane derivatives and 2-alkyl-dioxolanes are potentially effective replacements for both corn-based ethanol and the possibly hazardous methyl tert-butyl ether (MTBE), commonly used as oxygenates in gasoline, and dimethyl ether, used as an oxygenate in diesel. A comparison of the physical properties of some dioxolanes with those of commonly used fuels and fuel additives is shown in Table S1 in the Supporting Information. Accordingly, a way of producing 1,3-dioxolane derivatives from renewable resources would have significant potential environmental benefits. However, 1,3-dioxolanes are currently mainly manufactured by acid-catalyzed reaction of petrochemicalderived ethylene oxide or ethylene glycol (EG) and aldehydes/ ketones. 8] It has recently been shown that EG may be produced from cellulose using a non-precious-metal catalyst in an aqueous phase, demonstrating the possibility of a large-scale, cheap, and sustainable route for bioEG production. In this Communication we show how EG may be converted into dioxolanes by direct reaction with syngas (a 1:2 mixture of CO and H2) using a cheap iron nanoparticle catalyst under mild conditions. Because the syngas can be prepared by gasification of biomass, this represents the first viable synthesis of 1,3-dioxolanes from potentially renewable resources. In previous work, we have shown that soluble Ru nanoparticles exhibit a much higher low-temperature activity in the aqueous Fischer–Tropsch (F–T) synthesis than supported ones in traditional heterogeneous processes. To examine the possibility of coupling this novel F–T process with the conversion of EG, we simply changed the reaction medium from water to EG, resulting in the formation of a series of 2-alkyl-1,3-dioxolane derivatives (Scheme 1), as confirmed by GC–MS analysis with authentic samples (see Figure 1 and the Supporting Information for details). As shown in Table 1 when EG was used as