- Production of renewable oleo-furan surfactants by cross-ketonization of biomass-derived furoic acid and fatty acids
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Synthesis of 2-dodecanoyl furan is a crucial step in the formulation of oleo-furan sulfonates as bio-surfactants from biomass-derived furans and vegetable-oil-derived molecules. Herein, cross-ketonization of 2-furoic acid and lauric acid is proposed to produce the bio-surfactant precursor. Among the commonly reported metal oxide ketonization catalysts, the inexpensive and abundant iron oxides are demonstrated as effective and recyclable catalysts, enabling up to 77% selectivity to 2-dodecanoyl furan at 56% lauric acid conversion. Catalyst characterization by X-ray diffraction, H2temperature-programmed reduction, and X-ray photoelectron spectroscopy indicates that Fe3O4is the catalytically active and stable phase.13C isotopic tracing experiments suggest that cross-ketonization on Fe3O4proceedsviaa β-keto acid intermediate.
- Fu, Jiayi,Moglia, David,Nguyen, Hannah,Orazov, Marat,Vlachos, Dionisios G.,Wang, Yunzhu,Zheng, Weiqing
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p. 2762 - 2769
(2021/05/10)
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- Heterogeneous ketonic decarboxylation of dodecanoic acid: Studying reaction parameters
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Ketonic decarboxylation has gained significant attention in recent years as a pathway to reduce the oxygen content within biomass-derived oils, and to produce sustainable ketones. The reaction is base catalysed, with MgO an economic, accessible and highly basic heterogeneous catalyst. Here we use MgO to catalyse the ketonic decarboxylation of dodecanoic acid to form 12-tricosanone at moderate temperatures (250 °C, 280 °C and 300 °C) with low catalyst loads of 1% (w/w), 3% (w/w) and 5% (w/w) with respect to the dodecanoic acid, with a reaction time of 1 hour under batch conditions. Three different particle sizes for the MgO were tested (50 nm, 100 nm and 44 μm). Ketone yield was found to increase with increasing reaction temperature, reaching approximately 75% yield for all the samples tested. Temperature was found to be the main control on reaction yield, rather than surface area or particle size.
- Greenwell, Hugh Christopher,Perera-Solis, Diego D.,Whiting, Andrew,Zholobenko, Vladimir L.
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p. 35575 - 35584
(2021/11/30)
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- Highly productive α-alkylation of ketones with alcohols mediated by an Ir-oxalamidato/solid base catalyst system
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An Ir-oxalamidato complex in combination with a solid base (e.g., magnesium aluminometasilicate/Ca(OH)2) significantly improved the catalyst productivity in α-alkylation of methyl ketones with primary alcohols. Optimization through systematic variation of the oxalamidato ligand led to a practical turnover number (TON) of 10 000.40 000.
- Maeda, Hironori,Nara, Hideki,Shimizu, Hideo
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supporting information
p. 2772 - 2779
(2020/12/29)
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- PROCESS FOR THE PREPARATION OF ALKOXYLATES COMPOSITIONS
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A mixture of two alkoxylates surfactants, one being an aryl aliphatic carbinol alkoxylate, the other one being a dialiphatic carbinol alkoxylate, said mixture being useful for stabilizing emulsions and dispersions used in agricultural or pharmaceutical formulations. The alkoxylates surfactants may serve as substitutes for nonylphenol ethoxylates (NPE) and tristyrylphenol ethoxylates (TSE).
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Page/Page column 23
(2019/06/17)
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- A Redox Strategy for Light-Driven, Out-of-Equilibrium Isomerizations and Application to Catalytic C-C Bond Cleavage Reactions
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We report a general protocol for the light-driven isomerization of cyclic aliphatic alcohols to linear carbonyl compounds. These reactions proceed via proton-coupled electron-transfer activation of alcohol O-H bonds followed by subsequent C-C β-scission of the resulting alkoxy radical intermediates. In many cases, these redox-neutral isomerizations proceed in opposition to a significant energetic gradient, yielding products that are less thermodynamically stable than the starting materials. A mechanism is presented to rationalize this out-of-equilibrium behavior that may serve as a model for the design of other contrathermodynamic transformations driven by excited-state redox events.
- Ota, Eisuke,Wang, Huaiju,Frye, Nils Lennart,Knowles, Robert R.
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supporting information
p. 1457 - 1462
(2019/01/25)
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- ZWITTERIONIC SURFACTANTS SUITABLE FOR ENHANCED OIL RECOVERY
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The instant invention relates to surfactants having the following formula (I) wherein: each of Ra and Rb is a a linear or branched, saturated or unsaturated, hydrocarbon chain, each of Rc and Rd is a alkyl chain having 1 to 10 carbon atoms, each of (E1) and (E2) is a divalent hydrocarbon radical, A is: a group a carboxylate group —COO? (optionally in all or part in the form —COOH); or a sulfonate group —SO3? (optionally in all or part in the form —SO3H). The invention also relate to the preparation of these surfactants and their use in oil extraction, especially in EOR applications.
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Paragraph 0107; 0108; 0109; 0110; 0111; 0112; 0113; 0114
(2019/06/07)
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- PROCESS FOR THE CATALYTIC DECARBOXYLATIVE CROSS-KETONIZATION OF ARYL AND ALIPHATIC CARBOXYLIC ACID
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The present invention pertains to a process for the cross-ketonization (Piria reaction) between an aryl carboxylic acid and an aliphatic carboxylic acid using a metal-based compound and a slight or a moderate excess of aryl carboxylic acid. A good selectivity, up to 99 mol %, can be achieved. The aryl aliphatic ketone can be used for the preparation of surfactants and other downstream products.
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Page/Page column 66; 67; 71
(2019/01/08)
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- PROCESS FOR THE DECARBOXYLATIVE KETONIZATION OF FATTY ACIDS OR FATTY ACID DERIVATIVES
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The present invention is directed to a process for synthesizing an internal ketone K1 by decarboxylative ketonization reaction of a fatty acid, a fatty acid derivative or a mixture thereof in a liquid phase with a metal compound as catalyst in a reaction medium, said process being characterized in that a ketone K2 at liquid state, which is identical or similar to the ketone K1, is introduced into the reaction medium. The so-synthesized internal ketone K1 can be used for the preparation of a variety of end compounds, including surfactants having a twin-tail structure or a Gemini structure.
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Paragraph 00523-00525
(2018/03/09)
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- Ether lubricants from fatty acids
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Long chain ether compositions may comprise at least one long chain ether of general Formula I: wherein R1′ and R2′ are independently selected from C5-C21 linear or branched alkyl and C5-C21 linear or branched alkenyl, and R1′ and R2′ are the same or different, and R is selected from linear or branched alkyl having up to 52 carbon atoms and linear or branched alkenyl having up to 52 carbon atoms. In an embodiment, long chain ether compositions of matter such as those disclosed herein may find applications as lubricants.
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Page/Page column 15
(2018/02/27)
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- DIAMINES SURFACTANTS SUITABLE AS EMULSIFIER
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The instant invention relates to diamines having the formula (I) wherein: ? each of Ra and Rb is a hydrocarbon chain, ? each of Rc and Rd is a alkyl chain with 1-10 carbon atoms, ? (E1) is a divalent hydrocarbon chain. The invention also relate to the preparation of these diamine and to their use as surfactant, especially in bitumen emulsions.
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Page/Page column 12
(2017/11/08)
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- Farnesane alkylation
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An alkylate base oil of biological origin and a process to make an alkylate base oil comprising: a) hydrogenating a farnesene to make a farnesane comprising from zero to less than 5 wt % unsaturated molecules; and b) alkylating the farnesane with one or more C6 to C43 olefins in the presence of an acidic alkylation catalyst to make the alkylate base oil having a kinematic viscosity at 100° C. from 3 mm2/s to 20 mm2/s.
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Page/Page column 13; 14
(2017/12/27)
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- PROCESS FOR THE DECARBOXYLATIVE KETONIZATION OF FATTY ACIDS OR FATTY ACID DERIVATIVES
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A process for the decarboxylative ketonizationof fatty acids, fatty acid derivatives or mixtures thereof in the liquid phase with metal compounds as catalyst wherein the fatty acids, fatty acid derivatives or mixtures thereof are added sequentially.
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Paragraph 00129-00138
(2016/11/21)
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- KETONIZATION PROCESS USING OXIDATIVE CATALYST REGENERATION
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Processes for fatty acid ketonization and alcohol dehydration, wherein an alumina catalyst disposed in, or removed from, a reaction zone may be regenerated by contacting the catalyst with steam during or after a coke oxidizing step. In an embodiment, such processes may provide C2 - C43 alkenes. In another embodiment, such processes may provide C11 - C43 ketones, which can be deoxygenated to give saturated hydrocarbons, unsaturated hydrocarbons, and mixtures thereof. Base oils and transportation fuels may be produced via such processes.
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Page/Page column 14
(2016/06/06)
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- FORMULATIONS FOR ENHANCED OIL RECOVERY COMPRISING SULFONATES
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Compositions suitable for enhanced oil recovery comprising a) a mixture of a-sulfocarbonyl compounds of formulae (1 ) and (2) in a mixture ratio (1) to (2) of from 1:99 to 99:1 wherein R1, R3 and R5, which may be the same or different at each occurrence, are hydrogen or a linear or branched alkyl chain having 1 to 20 carbon atoms, R2 and R4, which may be the same or different at each occurrence, may be a linear or branched alkyl group having 4 to 24 carbon atoms and in which the alkyi chain may comprise one or more cycloaliphatic groups, and X is H or a metal forming a salt with the sulfonate group, and b) a salt containing aqueous solution.
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Paragraph 0072-0080
(2016/11/21)
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- Long chain secondary alcohols from fatty acids and fatty oils
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Processes for producing long chain secondary alcohols from fatty acids and fatty oils, wherein at least one fatty acid or a fatty acid mixture is contacted with a ketonization catalyst in a ketonization catalyst under ketonization conditions to provide a long chain ketone, and the long chain ketone is contacted with a selective ketone hydrogenation catalyst that lacks catalytic activity for alcohol dehydration to selectively hydrogenate the long chain ketone to provide the corresponding long chain secondary alcohol.
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Page/Page column 11; 12
(2015/12/04)
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- Ether lubricants from fatty acids
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Processes for producing long chain ethers from long chain secondary alcohols using fatty acid containing feedstocks. In an embodiment, a long chain secondary alcohol may be reacted with a primary alcohol, a secondary alcohol, or an olefin to form a long chain ether. In another embodiment, a long chain secondary alcohol or the corresponding alkoxide may be reacted with an alkyl halide to form a long chain ether. In yet a further embodiment, a long chain secondary alcohol may be converted to a halide, and the halide may be reacted with a second alcohol or the corresponding alkoxide to form a long chain ether. Long chain ether compositions of matter are also disclosed.
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Page/Page column 17
(2015/12/04)
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- Purification and characterization of OleA from Xanthomonas campestris and demonstration of a non-decarboxylative claisen condensation reaction
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OleA catalyzes the condensation of fatty acyl groups in the first step of bacterial long-chain olefin biosynthesis, but the mechanism of the condensation reaction is controversial. In this study, OleA from Xanthomonas campestris was expressed in Escherichia coli and purified to homogeneity. The purified protein was shown to be active with fatty acyl-CoA substrates that ranged from C 8 to C16 in length. With limiting myristoyl-CoA (C 14), 1 mol of the free coenzyme A was released/mol of myristoyl-CoA consumed. Using [14C]myristoyl-CoA, the other products were identified as myristic acid, 2-myristoylmyristic acid, and 14-heptacosanone. 2-Myristoylmyristic acid was indicated to be the physiologically relevant product of OleA in several ways. First, 2-myristoylmyristic acid was the major condensed product in short incubations, but over time, it decreased with the concomitant increase of 14-heptacosanone. Second, synthetic 2-myristoylmyristic acid showed similar decarboxylation kinetics in the absence of OleA. Third, 2-myristoylmyristic acid was shown to be reactive with purified OleC and OleD to generate the olefin 14-heptacosene, a product seen in previous in vivo studies. The decarboxylation product, 14-heptacosanone, did not react with OleC and OleD to produce any demonstrable product. Substantial hydrolysis of fatty acyl-CoA substrates to the corresponding fatty acids was observed, but it is currently unclear if this occurs in vivo. In total, these data are consistent with OleA catalyzing a non-decarboxylative Claisen condensation reactionin the first step of the olefin biosynthetic pathway previously found to be presentin at least 70 different bacterial strains.
- Frias, Janice A.,Richman, Jack E.,Erickson, Jasmine S.,Wackett, Lawrence P.
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experimental part
p. 10930 - 10938
(2012/03/26)
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- Catalytic conversion of C12-C14 primary alcohols mixture into long-chain ketones
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A charge of raw primary alcohols of high molecular weight from commercial plant was transformed into long-chain ketones fraction of potential commercial use. In this continuous flow method LaMnO3/La-Al2O 3 catalyst was used. At 420 °C and a normal pressure mixture of 74.2 wt.% C12 and 25.8 wt.% C14 primary alcohols and toluene (weight ratio alcohols:toluene = 1:1) was converted into ketones with 73.4% yield in relation to the theoretical value. Ketones were analyzed by TLC, NMR and GC-MSD.
- Klimkiewicz, Roman,Morawski, Ireneusz,Trawczyński, Janusz
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experimental part
p. 1143 - 1147
(2010/11/16)
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- Copper-Mediated, Palladium-Catalyzed Coupling of Thiol Esters with Aliphatic Organoboron Reagents
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Thiol esters and B-alkyl-9-BBN derivatives couple in the presence of a copper(I) carboxylate mediator and a palladium catalyst. In contrast to copper-mediated, palladium-catalyzed cross-couplings of thioorganics with boronic acids, the current coupling reaction of 9-BBN derivatives is facilitated by the addition of a base such as Cs2CO3. Under optimized conditions, a variety of thiol esters react with different B-alkyl-9-BBN derivatives giving ketones in moderate to excellent yields.
- Yu, Ying,Liebeskind, Lanny S.
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p. 3554 - 3557
(2007/10/03)
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- Double-chain type sulfated compounds having acid degradability and process for producing the same
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Described herein are sulfated compounds represented by the formula (I): STR1 wherein X respectively represent --OSO3 M or a hydroxyl group and at least one of X represents --OSO3 M, a process for producing the sulfated compounds and a process for decomposing the sulfated compounds in an aqueous acid solution.
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- ELECTRON TRANSFER REACTIONS OF ALIPHATIC ESTERS TO THE CORRESPONDING ALIPHATIC KETONES BY LITHIUM 4,4'-DI-T-BUTYLBIPHENYL RADICAL ANION
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Sonication of some representative aliphatic esters with lithium in the presence of catalytic amounts of 4,4'-di-t-butylbiphenyl (DBB) in dry THF under N2 afforded the corresponding aliphatic ketones in good yields.Monitoring studies by GC/MS and 1H-NMR spectroscopy after quenching indicate the intermediacy of the corresponding β-ketoesters.
- Karaman, Rafik,Fry, James L.
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p. 4935 - 4938
(2007/10/02)
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- PREPARATION OF KETONES BY A NOVEL DECARBALKOXYLATION OF β-KETO ESTERS: STEREOELECTRONIC ASSISTANCE TO C-C BOND FISSION
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Reaction of β-keto esters with the sodium derivative of propane-1,2-diol in an excess of anhydrous propane-1,2-diol causes facile decarboxylation to ketones in excellent yields.
- Aneja, R.,Hollis, W. M.,Davies A. P.,Eaton, G.
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p. 4641 - 4644
(2007/10/02)
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- PREPARATION D'ESTERS PAR DESHYDROGENATION D'ALCOOLS PRIMAIRES EN PHASE LIQUIDE CATALYSEE PAR L'OXYDE DE CUIVRE - OBSERVATIONS PRELIMINAIRES
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Linear primary alcohols with at least 7 carbon atoms are quite quantitatively transformed in esters, by CuO, at temperatures > 17O deg C, without air in liquid phase. Preponderant influence of carbon in position 2 is evidenced.In the same conditions lactones are obtained from diols, and benzylic alcohols undergoes, by hydride transfer, a disproportionation into toluene, benzaldehyde and water.
- Berthon, Bruno,Forestiere, Alain,Leleu, Gerard,Sillion, Bernard
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p. 4073 - 4076
(2007/10/02)
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