Carboalkoxylation

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In industrial chemistry, carboalkoxylation is a process for converting alkenes to esters. Also called hydroesterification, this reaction is a form of carbonylation. A closely related reaction is hydrocarboxylation, which employs water in place of alcohols

A commercial application is the carbomethoxylation of ethylene to give methyl propionate:[1][2]

C2H4 + CO + MeOH → MeO2CC2H5

The process is catalyzed by Pd[C6H4(CH2PBu-t)2]2. Under similar conditions, other Pd-diphosphines catalyze formation of polyethyleneketone.

Methyl propionate ester is a precursor to methyl methacrylate, which is used in plastics and adhesives.[3][4][5][6][7]

Carboalkoxylation has been incorporated into various telomerization schemes. For example carboalkoxylation has been coupled with the dimerization of 1,3-butadiene. This step produces a doubly unsaturated C9-ester:[8][9]

2 CH2=CH-CH=CH2 + CO + CH3OH → CH2=CH(CH2)3CH=CHCH2CO2CH3

References[]

  1. ^ Ahmad, Shahbaz; Bühl, Michael (2021-08-04). "Computational modelling of Pd-catalysed alkoxycarbonylation of alkenes and alkynes". Physical Chemistry Chemical Physics. 23 (30): 15869–15880. doi:10.1039/D1CP02426D. ISSN 1463-9084.
  2. ^ Ahmad, Shahbaz; Crawford, L. Ellis; Bühl, Michael (2020-11-04). "Palladium-catalysed methoxycarbonylation of ethene with bidentate diphosphine ligands: a density functional theory study". Physical Chemistry Chemical Physics. 22 (42): 24330–24336. doi:10.1039/D0CP04454G. ISSN 1463-9084.
  3. ^ Scott D. Barnicki "Synthetic Organic Chemicals" in Handbook of Industrial Chemistry and Biotechnology edited by James A. Kent, New York : Springer, 2012. 12th ed. ISBN 978-1-4614-4259-2.
  4. ^ Ahmad, Shahbaz; Lockett, Ashley; Shuttleworth, Timothy A.; Miles-Hobbs, Alexandra M.; Pringle, Paul G.; Bühl, Michael (2019-04-17). "Palladium-catalysed alkyne alkoxycarbonylation with P,N-chelating ligands revisited: a density functional theory study". Physical Chemistry Chemical Physics. 21 (16): 8543–8552. doi:10.1039/C9CP01471C. ISSN 1463-9084.
  5. ^ Ahmad, Shahbaz; Bühl, Michael (2021-08-04). "Computational modelling of Pd-catalysed alkoxycarbonylation of alkenes and alkynes". Physical Chemistry Chemical Physics. 23 (30): 15869–15880. doi:10.1039/D1CP02426D. ISSN 1463-9084.
  6. ^ Ahmad, Shahbaz; Bühl, Michael (2019). "Design of a Highly Active Pd Catalyst with P,N Hemilabile Ligands for Alkoxycarbonylation of Alkynes and Allenes: A Density Functional Theory Study". Chemistry – A European Journal. 25 (50): 11625–11629. doi:10.1002/chem.201902402. ISSN 1521-3765.
  7. ^ Ahmad, Shahbaz; Crawford, L. Ellis; Bühl, Michael (2020-11-04). "Palladium-catalysed methoxycarbonylation of ethene with bidentate diphosphine ligands: a density functional theory study". Physical Chemistry Chemical Physics. 22 (42): 24330–24336. doi:10.1039/D0CP04454G. ISSN 1463-9084.
  8. ^ J. Grub, E. Löser (2012). "Butadiene". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a04_431.pub2.CS1 maint: uses authors parameter (link)
  9. ^ Kiss, Gabor (2001). "Palladium-Catalyzed Reppe Carbonylation". Chemical Reviews. 101 (11): 3435–3456. doi:10.1021/cr010328q. PMID 11840990.
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