Ethenolysis is a form of
methylenation, i.e., the installation of
methylene (−CH2−) groups.
Applications
Using ethenolysis, higher molecular weight internal alkenes can be converted to more valuable terminal alkenes. The
Shell higher olefin process (SHOP process) uses ethenolysis on an industrial scale. The SHOP α-olefin mixtures are separated by distillation, the higher molecular weight fractions are isomerized by alkaline alumina catalysts in the liquid phase. The resulting internal olefins are reacted with ethylene to regenerate α-olefins. The large excess of ethylene moves the reaction equilibrium to the terminal α-olefins. Catalysts are often prepared from
Rhenium(VII) oxide (Re2O7)
supported on
alumina.[1]
In one application,
neohexene, a precursor to perfumes, is prepared by ethenolysis of diisobutene:[2]
α,ω-Dienes, i.e., diolefins of the formula (CH2)n(CH=CH2)2, are prepared industrially by ethenolysis of cyclic alkenes. For example,
1,5-hexadiene, a useful crosslinking agent and synthetic intermediate, is produced from
1,5-cyclooctadiene:
In an application directed at using renewable feedstocks,[3]methyl oleate, derived from natural seed oils, can be converted to
1-decene and methyl 9-
decenoate:[4][5]
References
^K. Weissermel, H. J. Arpe: Industrial Organic Chemistry: Important Raw Materials and Intermediates. Wiley-VCH Verlag 2003,
ISBN3-527-30578-5
^Metzger, J. O.; Bornscheuer, U. (2006). "Lipids as renewable resources: current state of chemical and biotechnological conversion and diversification". Applied Microbiology and Biotechnology. 71 (1): 13–22.
doi:
10.1007/s00253-006-0335-4.
PMID16604360.
S2CID28601501.
^Marinescu, Smaranda C.; Schrock, Richard R.; Müller, Peter; Hoveyda, Amir H. (2009). "Ethenolysis Reactions Catalyzed by Imido Alkylidene Monoaryloxide Monopyrrolide (MAP) Complexes of Molybdenum". J. Am. Chem. Soc. 131 (31): 10840–10841.
doi:
10.1021/ja904786y.
PMID19618951.
^Schrodi, Yann; Ung, Thay; Vargas, Angel; Mkrtumyan, Garik; Lee, Choon Woo; Champagne, Timothy M.; Pederson, Richard L.; Hong, Soon Hyeok (2008). "Ruthenium Olefin Metathesis Catalysts for the Ethenolysis of Renewable Feedstocks". CLEAN - Soil, Air, Water. 36 (8): 669–673.
Bibcode:
2008CSAW...36..669S.
doi:
10.1002/clen.200800088.