- Manufacture of C13 higher fatty acids from their esters by carbonylation of dodecene-1 in ionic liquid medium
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The effect of catalyst nature, temperature, acidity, promoters, and feedstock composition on dodecene-1 carbonylation in the presence of Pd compounds in an ionic liquid medium yielding higher fatty acid and their esters was studied. Palladium salts without phosphine ligands show high activity in tetrabutylammonium bromide. In systems of this kind, the catalyst is suspended in the reaction mass in the form of Pd particles with a size of 4-10 nm. It was shown that the catalytic system can be repeatedly used without loss of activity. It is acceptable to use synthesis gas instead of bare carbon monoxide with the selectivity for tride-canoic acid increasing.
- Lapidus,Eliseev,Bondarenko,Chau
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experimental part
p. 442 - 449
(2011/10/03)
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- PRODUCTION OF DETERGENT RANGE ALCOHOLS
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This invention relates to a process for the production of a mixture of detergent-range alcohols having an average of between 8 and 20 carbon atoms per molecule. The process includes the steps of providing a hydrocarbon stream containing olefins and paraffins in which more than 5% by volume of olefin molecules in the hydrocarbon stream have a total number of carbon atoms which is different from the total number of carbon atoms of the most abundant two carbon numbers of olefins in the hydrocarbon stream; reacting the hydrocarbon stream with CO and an alcohol in the presence of a catalyst in a hydroesterification reaction to form a hydrocarbon stream containing esters and paraffins; separating esters from the hydrocarbon stream containing esters and paraffins; and subjecting the esters to a hydrogenation reaction to provide the mixed alcohol product.
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Page/Page column 3
(2009/01/24)
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- Palladium-catalyzed oxidative carbonylation of alkyl and aryl indium reagents with CO under mild conditions
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CO now can react with organoindium reagents. A novel palladium-catalyzed oxidative carbonylation reaction of organoindium reagents by CO gas with desyl chloride as oxidant was developed in supplementation with the classical methods for preparation of carboxylic acid derivatives. Primary, secondary alkyl indium reagents with β-hydrogens and aryl indium reagents were suitable substrates, and the reaction could be carried out at 60°C under 50 psi CO. Carbonylation of alkyl indium reagents can occur smoothly without additional base. Although the indium reagents were prepared from corresponding Grignard reagents (at low temperature), they displayed full compatibility with various functional groups under the protic reaction conditions. Preliminary mechanistic studies including stoichiometric and catalytic reaction examination provided evidence to support the operation of the mechanism consisted of oxidative addition of deslyl chloride to Pd(0) and quick tautomerization to give a palladium enolate species II (ROPdCl), displacement of the enolate group in II by R2OH, followed by CO insertion to give alkoxycarbonyl palladium complex V, which undergoes transmetalation with R13ln and reductive elimination to afford the product and a Pd(0) species. In this mechanism, the alkoxycarbonyl group was transferred to the palladium center prior to the alkyl group, different from traditional ways initiated from oxidative addition of alkyl halides to a Pd(0) species.
- Zhao, Yingsheng,Jin, Liqun,Li, Peng,Lei, Aiwen
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supporting information; body text
p. 9429 - 9433
(2009/02/03)
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- PALLADIUM(0) AND RHODIUM(I) CATALYSIS OF THE CARBONYLATION OF UNACTIVATED BROMIDES
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Alkyl, vinyl, and aromatic bromides react with organoborates and carbon monoxide, in the presence of catalytic quantities of 1,5-hexadienerhodium(I) chloride dimer and tetrakis(triphenylphosphine)palladium(0), to give carboxylic esters in good yields.
- Hashem, Khaled E.,Woell, James B.,Alper, Howard
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p. 4879 - 4880
(2007/10/02)
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