Greenness Assessment and Synthesis for the Bio-Based Production of the Solvent 2,2,5,5-Tetramethyloxolane (TMO)

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 BioLo...

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Bibliographic Details
Published inSustainable chemistry Vol. 2; no. 3; pp. 392 - 406
Main Authors Byrne, Fergal P., Clark, James H., Angelici, Carlo, de Jong, Ed, Farmer, Thomas J.
Format Journal Article
LanguageEnglish
Published Basel MDPI AG 01.09.2021
Subjects
bio-based solvents
Biomass
Carbon
Dehydration
Glucose
green metrics
Hydrochloric acid
Lignocellulose
Magnesium
Magnesium chloride
Methylation
platform molecules
Rubber
safer solvent
solvent substitution
Solvents
Spectrum analysis
Synthesis
Toluene
Zeolites
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Summary: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.
ISSN:2673-4079
2673-4079
DOI:10.3390/suschem2030023