Synthesis of Bio‐Based Methylcyclopentadiene from 2,5‐Hexanedione: A Sustainable Route to High Energy Density Jet Fuels

Abstract

The sustainable, bio-based, platform chemical, 2,5-hexanedione [HD (1)], was efficiently converted to methylcyclopentadiene [MCPD (4)] through a three-step process consisting of intramolecular aldol condensation, catalytic chemoselective hydrogenation, and dehydration. Base-catalyzed aldol condensation of 1 resulted in the formation of 3-methyl-2-cyclopenten-1-one [MCO (2)], which was then converted to 3-methyl-2-cyclopenten-1-ol [MCP (3)] by chemoselective reduction with a ternary Ru catalyst system [RuCl 2 (PPh 3) 3 /NH 2 (CH 2) 2 NH 2 /KOH]. The hydrogenation proceeded with 96 % chemoselectivity. 3 was then dehydrated over AlPO 4 /MgSO 4 at 70°C under reduced pressure to yield 4, which can undergo an ambient temperature [4 + 2]-Diels-Alder cyclization to generate dimethyldicyclopentadiene (DMDCPD), a commodity chemical useful for the preparation of high-performance fuels and polymers. Through this approach, advanced jet fuels and materials can be conveniently produced from sustainable cellulosic feedstocks.

Thermal cyclodimerization of isoprene for the production of high-performance sustainable aviation fuel

“…12 Multicyclic hydrocarbons like tetrahydrodicyclopentadiene (JP-10) have been synthesized from furfural 13 while dimethyltetrahydrodicyclopentadiene (RJ-4) has been synthesized from bio-based substrates including linalool, 14 and cellulose-derived platform chemicals. [15][16][17] Cyclic monoterpenes are an important class of bio-based cycloalkenes that can be derived from turpentine or produced via fermentation of biomass sugars. [18][19][20] Simple hydrogenation of these feedstocks can generate monocyclic and bicyclic hydrocarbons, 4 while chemoselective hydrogenation can afford bicyclic alkanes containing ring-strained cyclopropane groups.…”

Magnetic solid sulfonic acid-enabled direct catalytic production of biomass-derived N-substituted pyrroles

“…4,5 Under the action of suitable acid, alkali, and/or metal catalysts, biomass can be converted into oxygen-containing compounds (e.g., alcohols, organic acids, furan derivatives, and phenols) through a series of chemical or biological catalytic conversion pathways. 6 It is worth noting that nitrogen-containing biomass materials such as chitin, chitosan, and protein can be degraded in series and coupled with amination to synthesize nitrogencontaining compounds, such as acrylamide, 1,4-butanediamine, N-methylpyrrolidone, amino acids, and other nitrogen-containing high-value compounds. [7][8][9] Among many nitrogen-containing compounds, N-heterocyclic compounds often exhibit good biological activities.…”

Support Effect of Ru Catalysts for Efficient Conversion of Biomass-Derived 2,5-Hexanedione to Different Products

“…The gradual depletion of fossil resources (i.e., coal, oil, and natural gas) promotes us to seek alternative resources to produce fuels and value-added products. Owing to the renewable and abundantly available nature, biomass has been considered as one of the most promising alternatives for fossil resources, and various fuel products and valuable chemicals can be synthesized from biomass transformation. − In this context, further upgrading of biomass-derived compounds into bulk or fine chemicals is an important consideration for biomass transformation. − 2,5-Hexanedione (2,5-HD), which can be synthesized from cellulose, , can be utilized as an important building block to produce some valuable chemicals, − in which 2,5-dimethyltetrahydrofuran and N-substituted tetrahydropyrroles, two five-membered heterocyclic compounds, are significantly attractive.…”