US NAVY, NAWCWD, Research Department, Chemistry Division, China Lake, California, 93555, USA.
ChemSusChem. 2021 Jan 7;14(1):339-343. doi: 10.1002/cssc.202002209. Epub 2020 Nov 17.
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 (PPh ) /NH (CH ) NH /KOH]. The hydrogenation proceeded with 96 % chemoselectivity. 3 was then dehydrated over AlPO /MgSO 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.
可持续的、基于生物的平台化学品 2,5-己二酮 [HD（1）] 通过三步法高效转化为甲基环戊二烯 [MCPD（4）]，该三步法包括分子内羟醛缩合、催化选择性氢化和脱水。1 的碱催化羟醛缩合生成 3-甲基-2-环戊烯-1-酮 [MCO（2）]，然后通过用三元 Ru 催化剂体系[RuCl（PPh）/NH（CH）NH/KOH]进行选择性还原转化为 3-甲基-2-环戊烯-1-醇 [MCP（3）]。氢化反应具有 96%的化学选择性。然后在减压下于 70°C 用 AlPO/MgSO 脱水得到 4，4 可以在环境温度下发生[4+2]-Diels-Alder 环化反应生成二甲基二环戊二烯（DMDCPD），这是一种商品化学品，可用于制备高性能燃料和聚合物。通过这种方法，可以方便地从可持续的纤维素原料生产先进的喷气燃料和材料。
