- Real time imaging of supramolecular assembly formation via programmed nucleolipid recognition
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Supramolecular assembly formation resulting from molecular recognition between complementary nucleolipids has been visualized in real time at the micrometer scale. Copyright
- Moreau, Louis,Camplo, Michel,Wathier, Michel,Taib, Nada,Laguerre, Michel,Bestel, Isabelle,Grinstaff, Mark W.,Barthelemy, Philippe
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- Physico-chemical studies on calcium soaps
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Calcium soaps were prepared by the metathesis of the corresponding potassium soap with an aqueous solution of calcium acetate.The IR results showed that the fatty acids exist in a dimeric structure as a result of hydrogen bonding between the carbonyl groups of two acid molecules, whereas calcium palmitate has an ionic character.The X-ray analysis indicated that the zig-zag chains of the fatty acid radical constituent of the soap molecules extend straigthforward on both sides of each basal plane and that the molecular axes of the soaps are slightly inclined to the basal plane.The thermal decomposition of calcium palmitate was found to be kinetically of zero order and the energy of activation for the decomposition was in the region of 3 KJ/mole.
- Mehrotra, K. N.,Upadhyaya, S. K.
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- Process for the preparation of higher order alkanones, preferably 6 -undecanone and derivatives thereof
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The present invention relates to a method of producing higher alkanones, preferably 6 undecanone., from ethanol and/or acetate, the method comprising (a) contacting the ethanol and/or acetate with at least one microorganism capable of carrying out carbon chain elongation to produce hexanoic acid and/or an ester thereof from the ethanol and/or acetate; (b) extracting the hexanoic acid and/or ester thereof from (a) using at least one extractant in an aqueous medium, wherein the extractant comprises at least one alkyl-phosphine oxide and at least one alkane comprising at least 12 carbon atoms; or at least one trialkylamine and at least one alkane comprising at least 12 carbon atoms; and (c) contacting the extracted hexanoic acid and/or ester thereof from (b) with at least one ketonization catalyst and eventually a further alkanoic acid comprising 1 to 22 carbon atoms under suitable reaction conditions for chemical ketonization of hexanoic acid and eventually the further alkanoic acid to a higher alkanone, preferably 6-undecanone.
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Paragraph 0176-0181
(2021/08/05)
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- METHOD FOR PRODUCING HIGHER LINEAR FATTY ACIDS OR ESTERS
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The present invention relates to a method of producing linear fatty acids comprising 7 to 28 carbon atoms or esters thereof using a combined biotechnological and chemical method. In particular, the present invention relates to a method of producing dodecanoic acid (i.e. lauric acid), via higher alkanones, preferably 6-undecanone.
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Page/Page column 32-33
(2021/11/26)
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- Catalytic ketonization of palmitic acid over a series of transition metal oxides supported on zirconia oxide-based catalysts
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Modification of a ZrO2 based catalyst with selected transition metals dopants has shown promising improvement in the catalytic activity of palmitic acid ketonization. Small amounts of metal oxide deposition on the surface of the ZrO2 catalyst enhances the yield of palmitone (16-hentriacontanone) as the major product with pentadecane as the largest side product. This investigation explores the effects of addition of carefully chosen metal oxides (Fe2O3, NiO, MnO2, CeO2, CuO, CoO, Cr2O3, La2O3 and ZnO) as dopants on bulk ZrO2. The catalysts are prepared via a deposition-precipitation method followed by calcination at 550 °C and characterized by XRD, BET-surface area, TPD-CO2, TPD-NH3, FESEM, TEM and XPS. The screening of synthesized catalysts was carried out with 5% catalyst loading onto 15 g of pristine palmitic acid and the reaction carried out at 340 °C for 3 h. Preliminary studies show catalytic activity improvement with addition of dopants in the order of La2O3/ZrO2 CoO/ZrO2 MnO2/ZrO2 with the highest palmitic acid conversion of 92% and palmitone yield of 27.7% achieved using 5% MnO2/ZrO2 catalyst. Besides, NiO/ZrO2 exhibits high selectivity exclusively for pentadecane compared to other catalysts with maximum yield of 24.9% and conversion of 64.9% is observed. Therefore, the changes in physicochemical properties of the dopant added ZrO2 catalysts and their influence in palmitic acid ketonization reaction is discussed in detail. This journal is
- Aleem, S. A.,Asikin-Mijan, N.,Dolfi, A.,Hussain, A. S.,Sivasangar, S.,Taufiq-Yap, Y. H.,Voon, C. H.
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p. 31972 - 31982
(2021/12/01)
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- PROCESS FOR PRODUCING RENEWABLE PRODUCTS
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The present invention relates to a method for producing renewable ketones, paraffin waxes, base oil components and alkenes from a feedstock of biological origin, wherein the method includes ketonisation of esters of fatty acids and monohydric alcohols wherein the alcohols have carbon chain length of two or more.
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Page/Page column 22-23
(2020/07/21)
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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 21; 22
(2019/06/17)
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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 66-69
(2019/01/08)
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- Hydrodeoxygenation (HDO) of methyl palmitate over bifunctional Rh/ZrO2 catalyst: Insights into reaction mechanism via kinetic modeling
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Hydrodeoxygenation (HDO) of triglycerides into hydrocarbons is a novel catalytic process for the production of green biofuels. In this work, the HDO reaction mechanism over Rh/ZrO2 catalyst was studied by selecting methyl palmitate as a model compound. HDO of methyl palmitate proceeded initially via the hydrogenolysis into palmitic acid intermediate, followed by sequential hydrogenation-decarbonylation reaction into pentadecane via aldehyde intermediate. Bifunctional mechanism of the Rh/ZrO2 catalyst is advocated for the HDO process, in which both Rh sites and oxygen vacancy sites on ZrO2 synergistically contribute to the catalysis. The interface between Rh nanoparticle and support was proposed to host the most active sites. Based on our earlier work, a surface reaction mechanism was proposed and slightly modified to develop a set of mechanistic kinetic models. The mechanistic model consisting of two distinct types of adsorption sites for oxygenated components and H2, gave a good fitting to the kinetic data over a broad range of reaction conditions and conversion levels.
- Bie, Yuwei,Lehtonen, Juha,Kanervo, Jaana
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p. 183 - 190
(2016/09/13)
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- Surface and interlayer base-characters in lepidocrocite titanate: The adsorption and intercalation of fatty acid
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While layered double hydroxides (LDHs) with positively-charged sheets are well known as basic materials, layered metal oxides having negatively-charged sheets are not generally recognized so. In this article, the surface and interlayer base-characters of O2- sites in layered metal oxides have been demonstrated, taking lepidocrocite titanate K0.8Zn0.4Ti1.6O4 as an example. The low basicity (0.04 mmol CO2/g) and low desorption temperature (50-300 °C) shown by CO2- TPD suggests that O2- sites at the external surfaces is weakly basic, while those at the interlayer space are mostly inaccessible to CO2. The liquid-phase adsorption study, however, revealed the uptake as much as 37% by mass of the bulky palmitic acid (C16 acid). The accompanying expansion of the interlayer space by ~0.1 nm was detected by PXRD and TEM. In an opposite manner to the external surfaces, the interlayer O2- sites can deprotonate palmitic acid, forming the salt (i.e., potassium palmitate) occluded between the sheets. Two types of basic sites are proposed based on ultrafast 1H MAS NMR and FTIR results. The interlayer basic sites in lepidocrocite titanate leads to an application of this material as a selective and stable two-dimensional (2D) basic catalyst, as demonstrated by the ketonization of palmitic acid into palmitone (C31 ketone). Tuning of the catalytic activity by varying the type of metal (Zn, Mg, and Li) substituting at TiIV sites was also illustrated.
- Maluangnont, Tosapol,Arsa, Pornanan,Limsakul, Kanokporn,Juntarachairot, Songsit,Sangsan, Saithong,Gotoh, Kazuma,Sooknoi, Tawan
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p. 175 - 181
(2016/03/30)
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- Manipulating catalytic pathways: Deoxygenation of palmitic acid on multifunctional catalysts
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The mechanism of the catalytic reduction of palmitic acid to n-pentadecane at 260 °C in the presence of hydrogen over catalysts combining multiple functions has been explored. The reaction involves rate-determining reduction of the carboxylic group of palmitic acid to give hexadecanal, which is catalyzed either solely by Ni or synergistically by Ni and the ZrO2 support. The latter route involves adsorption of the carboxylic acid group at an oxygen vacancy of ZrO2 and abstraction of the α-H with elimination of O to produce the ketene, which is in turn hydrogenated to the aldehyde over Ni sites. The aldehyde is subsequently decarbonylated to n-pentadecane on Ni. The rate of deoxygenation of palmitic acid is higher on Ni/ZrO2 than that on Ni/SiO2 or Ni/Al2O3, but is slower than that on H-zeolite-supported Ni. As the partial pressure of H2 is decreased, the overall deoxygenation rate decreases. In the absence of H 2, ketonization catalyzed by ZrO2 is the dominant reaction. Pd/C favors direct decarboxylation (-CO2), while Pt/C and Raney Ni catalyze the direct decarbonylation pathway (-CO). The rate of deoxygenation of palmitic acid (in units of mmol moltotal metal -1 h-1) decreases in the sequence r (Pt black)≈r(Pd black)>r(Raney Ni) in the absence of H2. In situ IR spectroscopy unequivocally shows the presence of adsorbed ketene (Ci?￡34;Ci?￡34;O) on the surface of ZrO2 during the reaction with palmitic acid at 260 °C in the presence or absence of H2. Biomass to biofuels: The conversion of palmitic acid to n-pentadecane over ZrO2 mainly proceeds by hydrogenation of the carboxylic acid group to give hexadecanal (rate-determining step), which is catalyzed either solely by Ni sites or synergistically by Ni sites and sites on the ZrO2 support (see scheme). In the absence of H2, ketonization is the dominant reaction catalyzed by ZrO 2. Copyright
- Peng, Baoxiang,Zhao, Chen,Kasakov, Stanislav,Foraita, Sebastian,Lercher, Johannes A.
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p. 4732 - 4741
(2013/05/22)
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- DEOXYGENATION OF FATTY ACIDS FOR PREPARATION OF HYDROCARBONS
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Embodiments of methods for making renewable diesel by deoxygenating fatty acids to produce hydrocarbons are disclosed. Fatty acids are exposed to a catalyst selected from a) M1 /M2 /M3O2 where M1 is a transition metal, a transition metal oxide, or a combination thereof, wherein the transition metal is Fe, Mn, Mo, V, or W, M2 is Pt, PtO, PtO2, or a combination thereof, and M3 is Ti or Zr, or b) Pt/Ge or Pt/Sn on carbon, and the catalyst decarboxylates at least 10% of the fatty acids. Deoxygenation is performed without added hydrogen and at less than 100 psi. Disclosed embodiments of the catalysts deoxygenate at least 10% of fatty acids in a fatty acid feed, and remain capable of deoxygenating fatty acids for at least 200 minutes to more than 350 hours.
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Page/Page column 36; 40
(2012/02/15)
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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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- Infrared, X-ray diffraction studies and thermogravimetric behaviour of magnesium myristate and magnesium palmitate
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Magnesium soaps i.e., magnesium myristate and magnesium palmitate were prepared by the metathesis of potassium soaps with an aqueous solution of magnesium sulphate. The infrared results showed that the fatty acid exists in a dimeric structure as a result of hydrogen bonding between the carboxyl groups of two acid molecules, whereas magnesium soaps have an ionic character. The X-ray diffraction analysis indicates that the zig-zag chains of fatty acid radical constituent of the soap molecules extend straight forward on both sides of each basal plane. The thermal decomposition of these soaps was found kinetically of zero order and energy of activation for the decomposition process was in the range of 15-32 KJ mol-1.
- Singh, Chitra,Upadhyaya
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p. 3011 - 3013
(2012/02/02)
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- Formation of long-chain ketones in ancient pottery vessels by pyrolysis of acyl lipids
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Structural and isotopic (δ13C) evidence indicates the formation of series of long-chain ketones in archaeological pottery can occur by condensation of long-chain carboxylic acids. The formation of the ketones is confirmed by pyrolysis of free fatty acids or triacylglycerols in the presence of fired clay matrix.
- Evershed, Richard P.,Stott, Andrew W.,Raven, Anthony,Dudd, Stephanie N.,Charters, Stephanie,Leyden, Ann
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p. 8875 - 8878
(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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- The reaction of 3-oxo fatty acid esters with trehalose derivatives in an alkaline medium
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The primary 6′-hydroxyl function of the 6-0- [3-oxo-acyl] -α,α-trehalose participates in its base-catalyzed retro-Claisen decomposition.
- Aurelle,Prome
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p. 3277 - 3280
(2007/10/02)
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- 1,2-O-dialkylmethylidene-glycero-3-phosphatides
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Glycerol is reacted with a ketone having 19 to 35 carbon atoms to 1,2-O-dialkylmethylidene-glycerol which is phosphorylated by means of β-bromoethylphosphoric acid dichloride. The resulting intermediate is aminated with ammonia, methylamine, dimethylamine, or trimethylamine to a compound of the formula EQU1 wherein R1 and R2 are alkyl having 9 to 17 carbon atoms, and R3, R4, and R5 are hydrogen or methyl. The compounds and their non-toxic acid addition salts are surfactants which may be employed in detergent compositions or as emulsifiers in food.
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