Abstract
2,2,5,5-tetramethyloxolane (TMO) has recently been identified and demonstrated as a safer solvent to replace toluene, THF, and hydrocarbons in a handful of applications. Herein, several bio-based routes to TMO are presented and assessed for greenness, assisted by the CHEM21 Metrics Toolkit and BioLogicTool plots. Using glucose as a common starting point, two chemocatalytic routes and two biochemical routes to TMO were identified and the pathways compared using the aforementioned tools. In addition, bio-based TMO was synthesised via one of these routes; from methyl levulinate supplied by Avantium, a by-product of the sugar dehydration step during the production of 2,5-furandicarboxylic acid. First, methyl levulinate underwent triple methylation using methyl magnesium chloride (MeMgCl) to yield 2,5-dimethylhexane-2,5-diol (DHL) in high yields of 89.7%. Then DHL was converted to high purity TMO (>98.5%) by cyclodehydration using H-BEA zeolites based on the previously reported approach. Bio-based content of this TMO was confirmed by ASTM D6866-20 Method B and found to have 64% bio-based carbon, well above the threshold of 25% set by CEN/TC 411 standards and matching the anticipated content. This study represents the first demonstration of a bio-based synthesis of TMO and confirmation of bio-content by accepted standards.
Highlights
In 2017, the synthesis and testing of 2,2,5,5-tetramethyloxolane (TMO) from 2,5dimethylhexane-2,5-diol (DHL) was published, alongside rationale for its selection as a new non-polar solvent [1]
From DHL has previously been reported [1], so no further comments are made about that final step of the synthesis in this work
Lignocellulosic biomass would be the ideal source of glucose as it is a second-generation biomass source, an additional pre-treatment step to what is shown in Scheme 2 would be required [13]
Summary
In 2017, the synthesis and testing of 2,2,5,5-tetramethyloxolane (TMO) from 2,5dimethylhexane-2,5-diol (DHL) was published, alongside rationale for its selection as a new non-polar solvent [1]. TMO is a cyclic ether but has properties and performance remarkably similar to toluene in many applications. Unlike traditional ethers such as diethyl ether, cyclopentylmethylether (CPME) and tetrahydrofuran (THF), TMO does not form peroxides, even when exposed to bubbling air, UV light, and heat [1]. TMO been shown to behave more like toluene than other traditional ethers, 1,4-dioxane, THF and. Solute partitioning experiments showed a stronger affinity for lipophilic protic solutes (fatty acids, fatty alcohols, and phenols) compared to toluene [4,5].
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