TY - JOUR
T1 - [4 + 4]-cycloaddition of isoprene for the production of high-performance bio-based jet fuel
AU - Rosenkoetter, Kyle E.
AU - Kennedy, C. Rose
AU - Chirik, Paul J.
AU - Harvey, Benjamin G.
N1 - Funding Information:
B. G. H. and K. E. R. thank the Naval Air Warfare Center, Weapons Division PL-219 program for financial support of this work. We also thank Dr Josanne Woodroffe for conducting viscosity studies of DMCO/HEFA blends, Ms Alicia Hughes for conducting flash point studies, Dr Patrick Fedick for GC-MS analysis of DMCOD and DMCO, and Dr Tim Edwards (AFRL) for supplying HEFA-Jet. C. R. K. thanks the NIH for a Ruth L. Kirschstein National Research Service Award (F32 GM126640).
Publisher Copyright:
© 2019 The Royal Society of Chemistry.
PY - 2019
Y1 - 2019
N2 - Isoprene was efficiently converted to 1,6-dimethyl-1,5-cyclooctadiene (DMCOD) by selective [4 + 4]-cycloaddition with a catalyst formed by in situ reduction of [(MePI)FeCl(μ-Cl)]2 (MePI = [2-(2,6-(CH3)2-C6H3-NC(CH3))-C4H5N]). DMCOD was isolated in 92% yield, at the preparative scale, with a catalyst loading of 0.025 mol%, and a TON of 3680. Catalytic hydrogenation of DMCOD yielded 1,4-dimethylcyclooctane (DMCO). The cyclic structure and ring strain of DMCO afforded gravimetric and volumetric net heats of combustion 2.4 and 9.2% higher, respectively, than conventional jet fuel. In addition, the presence of methyl branches at two sites resulted in a-20 °C kinematic viscosity of 4.17 mm2 s-1, 48% lower than the maximum allowed value for conventional jet fuel. The ability to derive isoprene and related alcohols readily from abundant biomass sources, coupled with the highly efficient [Fe]-catalyzed [4 + 4]-cycloaddition described herein, suggests that this process holds great promise for the economical production of high-performance, bio-based jet fuel blendstocks.
AB - Isoprene was efficiently converted to 1,6-dimethyl-1,5-cyclooctadiene (DMCOD) by selective [4 + 4]-cycloaddition with a catalyst formed by in situ reduction of [(MePI)FeCl(μ-Cl)]2 (MePI = [2-(2,6-(CH3)2-C6H3-NC(CH3))-C4H5N]). DMCOD was isolated in 92% yield, at the preparative scale, with a catalyst loading of 0.025 mol%, and a TON of 3680. Catalytic hydrogenation of DMCOD yielded 1,4-dimethylcyclooctane (DMCO). The cyclic structure and ring strain of DMCO afforded gravimetric and volumetric net heats of combustion 2.4 and 9.2% higher, respectively, than conventional jet fuel. In addition, the presence of methyl branches at two sites resulted in a-20 °C kinematic viscosity of 4.17 mm2 s-1, 48% lower than the maximum allowed value for conventional jet fuel. The ability to derive isoprene and related alcohols readily from abundant biomass sources, coupled with the highly efficient [Fe]-catalyzed [4 + 4]-cycloaddition described herein, suggests that this process holds great promise for the economical production of high-performance, bio-based jet fuel blendstocks.
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U2 - 10.1039/c9gc02404b
DO - 10.1039/c9gc02404b
M3 - Article
C2 - 33790688
AN - SCOPUS:85073616069
VL - 21
SP - 5616
EP - 5623
JO - Green Chemistry
JF - Green Chemistry
SN - 1463-9262
IS - 20
ER -