- A General Approach to Intermolecular Olefin Hydroacylation through Light-Induced HAT Initiation: An Efficient Synthesis of Long-Chain Aliphatic Ketones and Functionalized Fatty Acids
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Herein, an operationally simple, environmentally benign and effective method for intermolecular radical hydroacylation of unactivated substrates by employing photo-induced hydrogen atom transfer (HAT) initiation is described. The use of commercially available and inexpensive photoinitiators (Ph2CO and NHPI) makes the process attractive. The olefin hydroacylation protocol applies to a wide array of substrates bearing numerous functional groups and many complex structural units. The reaction proves to be scalable (up to 5 g). Different functionalized fatty acids, petrochemicals and naturally occurring alkanes can be synthesized with this protocol. A radical chain mechanism is implicated in the process.
- Guin, Joyram,Paul, Subhasis
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p. 4412 - 4419
(2021/02/05)
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- Efficient heterogeneous dual catalyst systems for alkane metathesis
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A fully heterogeneous and highly efficient dual catalyst system for alkane metathesis (AM) has been developed. The system is comprised of an alumina-supported iridium pincer catalyst for alkane dehydrogenation/olefin hydrogenation and a second heterogeneous olefin metathesis catalyst. The iridium catalysts bear basic functional groups on the aromatic backbone of the pincer ligand and are strongly adsorbed on Lewis acid sites on alumina. The heterogeneous systems exhibit higher lifetimes and productivities relative to the corresponding homogeneous systems as catalyst/catalyst interactions and bimolecular decomposition reactions are inhibited. Additionally, using a two-pot device, the supported Ir catalysts and metathesis catalysts can be physically separated and run at different temperatures. This system with isolated catalysts shows very high turnover numbers and is selective for the formation of high molecular weight alkanes.
- Huang, Zheng,Rolfe, Eleanor,Carson, Emily C.,Brookhart, Maurice,Goldman, Alan S,El-Khalafy, Sahar H.,Roy MacArthur, Amy H.
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experimental part
p. 125 - 135
(2010/06/20)
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- DEGRADATION OF POLYCYCLIC AROMATIC HYDROCARBONS TO RENDER THEM AVAILABLE FOR BIODEGRADATION
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A method for the degradation of polycyclic aromatic compounds is disclosed that involves dissolving ozone in a bipolar solvent comprising a non-polar solvent in which is of sufficiently non-polar character to solubilized the polycyclic aromatic compounds, and a polar-water-compatible solvent which is fully miscible with the non-polar solvent to form a single phase with the non-polar solvent. The bipolar solvent with dissolved ozone is contacted with the polycyclic aromatic compounds to solubilize the polycyclic aromatic compounds and react the dissolved polycyclic aromatic compounds with the ozone to degrade the dissolved polycyclic aromatic compounds to oxygenated intermediates. The bipolar solvent is then mixed with sufficient water to form separate non-polar and polar phases, the non-polar phase comprising the non-polar solvent and the polar phase comprising the non-polar solvent and the oxygenated intermediates. The polar phase is then diluted and incubated with bacteria to biodegrade the oxygenated intermediates.
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Page/Page column 5-8; 15-16
(2008/12/07)
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- Process for hydrogenation of carboxylic acids and derivatives to hydrocarbons
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A process for hydrogenating a carboxylic acid and/or derivative thereof having a carboxylate group represented by the general formula R1COO-, which process comprises feeding hydrogen and the carboxylic acid and/or derivative thereof to a reactor and maintaining conditions within the reactor such that hydrogen reacts with the carboxylic acid and/or derivative thereof to produce a product stream comprising carbon dioxide, carbon monoxide, methane and hydrocarbons represented by general formulae R1H and R1CH3, characterised in that the molar ratio of R1H : R1CH3 is above a pre-determined value and/or the mole ratio of the sum of carbon dioxide, carbon monoxide and methane to carboxylate groups is above a pre-determined value.
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Page/Page column 7-8
(2008/06/13)
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- Temperatures and enthalpies of solid-solid and melting transitions of the odd-numbered n-alkanes C21, C23, C25, C27, and C29
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Very high purity samples of normal pentacosane and heptacosane are made by synthesis: the procedures for the C25 and C27 synthesis and the original conditions of their purification, particularly using the extraction by supercritical carbon dioxide, are described. Measurements of temperatures and enthalpies of the solid-solid transitions and of the melting transition were carried out by differential scanning calorimetry on the C25 and C27 synthetic samples and the odd-numbered homologous n-alkanes (from C21 to C29). The results show the importance of the effect of the impurities, particularly for the δ and γ crystal-crystal transition temperatures of C25 and C27. Several current data of the literature are also shown concerning the temperatures and the enthalpies of solid-solid and melting transitions of these five n-alkanes.
- Chevallier, Virginie,Bouroukba, Mohammed,Petitjean, Dominique,Barth, Danielle,Dupuis, Paul,Dirand, Michel
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p. 1114 - 1122
(2007/10/03)
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- DISSOLVING METAL REDUCTION WITH CROWN ETHER----- REDUCTIVE DECYANATION
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Toluene radical anion generated from potassium metal/dicyclohexano-18-crown-6/toluene system has been proved to be highly effective for reductive decyanation reaction of primary, secondary and tertiary cyanides.
- Ohsawa, Tomihiko,Kobayashi, Takao,Mizuguchi, Yuko
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p. 6103 - 6106
(2007/10/02)
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