Carboalkoxylation
In industrial chemistry, carboalkoxylation is a process for converting alkenes to esters. 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]
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:[5][6]
- 2 CH2=CH-CH=CH2 + CO + CH3OH → CH2=CH(CH2)3CH=CHCH2CO2CH3
Hydroesterification
Related to carboalkoxylation is hydroesterification, the insertion of alkenes and alkynes into the H-O bond of carboxylic acids. Vinyl acetate is produced industrially by the addition of acetic acid to acetylene in the presence of zinc acetate catalysts:[7] Presently, zinc acetate is used as the catalyst:
- CH3CO2H + C2H2 → CH3CO2CHCH2
References
- ^ 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. Bibcode:2021PCCP...2315869A. doi:10.1039/D1CP02426D. ISSN 1463-9084. PMID 34318843. S2CID 236472958.
- ^ 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. Bibcode:2020PCCP...2224330A. doi:10.1039/D0CP04454G. ISSN 1463-9084. PMID 33104152. S2CID 225072802.
- ^ 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.
- ^ 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. Bibcode:2019PCCP...21.8543A. doi:10.1039/C9CP01471C. hdl:10023/19712. ISSN 1463-9084. PMID 30957820. S2CID 102347387.
- ^ J. Grub, E. Löser (2012). "Butadiene". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a04_431.pub2.
{{cite encyclopedia}}: CS1 maint: uses authors parameter (link) - ^ Kiss, Gabor (2001). "Palladium-Catalyzed Reppe Carbonylation". Chemical Reviews. 101 (11): 3435–3456. doi:10.1021/cr010328q. PMID 11840990.
- ^ Bienewald, Frank; Leibold, Edgar; Tužina, Pavel; Roscher, Günter (2019). "Vinyl Esters". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. pp. 1–16. doi:10.1002/14356007.a27_419.pub2.