- Nickel-butadiene catalytic system for the cross-coupling of bromoalkanoic acids with alkyl grignard reagents: A practical and versatile method for preparing fatty acids
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The knights who say Ni: A practical and convenient synthetic route to fatty acids involves the Ni-catalyzed alkyl-alkyl cross-coupling of bromoalkanoic acids and alkyl Grignard reagents in the presence of 1,3-butadiene as an additive (see scheme). Copyright
- Iwasaki, Takanori,Higashikawa, Kiyokazu,Reddy, Vutukuri P.,Ho, Willbe W. S.,Fujimoto, Yukari,Fukase, Koichi,Terao, Jun,Kuniyasu, Hitoshi,Kambe, Nobuaki
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- Optimizing reaction conditions for the isomerization of fatty acids and fatty acid methyl esters to their branch chain products
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In order to improve the oxidative stability and cold flow properties of oleic acid or methyl oleate, branch chain isomerization was conducted using a beta zeolite catalyst. Reaction conditions of temperature (200-300 °C), pressure (0.1-3.0 MPa), and co-catalyst (0-2 wt%) were optimized based on branch chain conversion and the cloud point of the ester following the isomerization reaction of oleic acid or methyl oleate. Fourier transform infrared spectroscopy (FTIR) and Gas Chromatograph equipped with Mass Spectrometry (GC/MS) analyses were used to analyze and quantify the isomerization product samples, while the cloud point of each sample was tested. The lowest and therefore, best cloud point measured was -15.2 °C at conditions of 200 °C, 3 MPa, and 2% co-catalyst using methyl oleate as a starting material. The highest branch chain conversion achieved was 50% under conditions of 300 °C, 1.5 MPa and 0% co-catalyst using oleic acid as a starting material. The use of oleic acid and methyl oleate is based on whether it is optimal to carry out the skeletal isomerization before or after the esterification reaction. Performing the isomerization reaction on the ester was preferred over the fatty acid based on the trans isomerization and cloud point results. Reducing the unbranched trans isomers was desirable in obtaining a low cloud point. AOCS 2010.
- Reaume, Stephen J.,Ellis, Naoko
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- Homogeneous catalytic hydrogenation of lipids in aqueous dispersions and bacterial cell membranes with an efficient water-soluble Pd(II)-sulfosalan catalyst, Na2[Pd(HSS)]
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The recently synthesized water-soluble Na2[Pd(HSS)] (Na2HSS = hydrogenated sulfonated salen) was shown to be a non-toxic, active catalyst for modification of model and biomembranes by homogeneous catalytic hydrogenation. Hydrogenation of the unsaturated fatty acyl residues in soy-bean lecithin liposomes and in biomembranes of intact Pseudomonas putida F1 cells was accompanied by substantial cis-trans isomerization around the C[dbnd]C double bonds. The hydrogenations could be run in aqueous media under mild conditions (25 °C, 1 bar H2). Partial saturation (up to 10% conversion) of the membrane lipids of P. putida F1 did not damage the cells.
- Bunda, Szilvia,Gombos, Réka,Joó, Ferenc,Nagyházi, Brigitta
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- Hydrogenation of Oleic Acid to 9-Octadecen-1-ol with Rhenium-Tin Catalyst
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A new supported bimetallic catalyst, rhenium-tin, is able to reduce oleic acid to 9-octadecen-1-ol (cis and trans isomers) with appreciable yield under mild hydrogenation conditions.This paper reports investigations on the effects of catalyst preparation methods, types of support, catalyst raw materials, mole ratio of the metals, activation and reaction conditions on the activity and selectivity of the catalyst.Catalyst derived from the combination of ammonium perrhenate and stannic chloride on alumina gave the best performance, and the presence of tin in the catalyst is essential for the preservation of the olefinic bond of the oleic acid during hydrogenation.KEY WORDS: Hydrogenation, 9-octadecen-1-ol, oleic acid, rhenium-tin catalyst.
- Tang, Thin-Sue,Cheah, Kien-Yoo,Mizukami, Fujio,Niwa, Shu-ichi,Toba, Makoto,Choo, Yuen-May
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- Catalytic hydrogenation of linoleic acid on nickel, copper, and palladium
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The catalytic activity and selectivity for hydrogenation of linoleic acid were studied on Ni, Cu, and Pd catalysts. A detailed analysis of the reaction product was performed by a gas-liquid chromatograph, equipped with a capillary column, and Fourier transform-infrared spectroscopy. Geometrical and positional isomerization of linoleic acid occurred during hydrogenation, and many kinds of linoleic acid isomers (trans-9,trans-12; trans-8,cis-12 or cis-9,trans-13; cis-9,trans-12; trans-9,cis-12 and cis-9,cis-12 18:2) were contained in the reaction products. The monoenoic acids in the partial hydrogenation products contained eight kinds of isomers and showed different isomer distributions on Ni, Cu, and Pd catalysts, respectively. The positional isomers of monoenoic acid were produced by double- bond migration during hydrogenation. On Ni and Pd catalysts, the yield of cis-12 and trans-12 monoenoic acids was larger than that of cis-9 and trans-9 monoenoic acids. On the contrary, the yield of cis-9 and trans-9 monoenoic acids was larger than that of cis-12 and trans-12 monoenoic acids on Cu catalyst. From these results, it is concluded that the double bond closer to the methyl group (Δ12) and that to the carboxyl group (Δ9) show different reactivity for hydrogenation on Ni, Cu, and Pd catalysts. Monoenoic acid formation was more selective on Cu catalyst than on Ni and Pd catalysts.
- Kitayama, Yoshie,Muraoka, Masahiro,Takahashi, Megumi,Kodama, Tatsuya,Itoh, Hirofumi,Takahashi, Eriko,Okamura, Mutsuo
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- Electrochemical Proton Reduction over Nickel Foam for Z-Stereoselective Semihydrogenation/deuteration of Functionalized Alkynes
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Selective reduction strategies based on abundant-metal catalysts are very important in the production of chemicals. In this paper, a method for the electrochemical semihydrogenation and semideuteration of alkynes to form Z-alkenes was developed, using a simple nickel foam as catalyst and H3O+ or D3O+ as sources of hydrogen or deuterium. Good yields and excellent stereoselectivities (Z/E up to 20 : 1) were obtained under very mild reaction conditions. The reaction proceeded with terminal and nonterminal alkynes, and also with alkynes containing easily reducible functional groups, such as carbonyl groups, as well as aryl chlorides, bromides, and even iodides. The nickel-foam electrocatalyst could be recycled up to 14 times without any change in its catalytic properties.
- Valiente, Alejandro,Martínez-Pardo, Pablo,Kaur, Gurpreet,Johansson, Magnus J.,Martín-Matute, Belén
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- Algicidal hydroxylated C18 unsaturated fatty acids from the red alga Tricleocarpa jejuensis: Identification, synthesis and biological activity
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Bioassay-guided separation of a methanol extract of Tricleocarpa jejuensis by monitoring algicidal activity against the red tide phytoplankton Chattonella antiqua led to the isolation of an active fraction consisting of a mixture of four isomeric compounds. The active compounds were identified as (E)-9-hydroxyoctadec-10-enoic acid (1), (E)-10-hydroxyoctadec-8-enoic acid (2), (E)-11-hydroxyoctadec-12-enoic acid (3) and (E)-12-hydroxyoctadec-10-enoic acid (4) by NMR, IR and mass spectral data. The structures were confirmed by comparison of the NMR and MS data with those of authentic samples of 1–4 obtained by unambiguous syntheses. Synthesized hydroxy acids 1–4 and related compounds were assessed for algicidal activity against C. antiqua and it was found that all of 1–4 had high activity (>80% mortality at 24 h) at a concentration of 20 μg/mL. A structure–activity relationship study using 11 related compounds revealed that the presence of the hydroxyl group is important for the activity and the double bond may be replaced with a triple bond.
- Ishibashi, Fumito,Kuwano, Kazuyoshi,Shibahara, Tomohiro,Zha, Shijiao
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- Production of ethylene glycol from direct catalytic conversion of cellulose over a binary catalyst of metal-loaded modified SBA-15 and phosphotungstic acid
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This study presents the utilization of a binary catalyst composed of metal-loaded modified SBA-15 (M/SBA-15) and phosphotungstic acid (H3PW12O40) for ethylene glycol (EG) production from direct catalytic conversion of cell
- Yu, Shitao,Cao, Xincheng,Liu, Shiwei,Li, Lu,Wu, Qiong
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p. 24857 - 24865
(2018/07/29)
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- METHOD FOR SYNTHESISING BIOBASED UNSATURATED ACIDS
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The invention relates to a method for preparing a compound of formula (I), wherein n is an integer from 1 to 21,said method comprises reacting a light olefin fraction, in the presence of a metathesis catalyst, with a compound having from 10 to 24 carbon atoms, of the following formula (II): wherein, n is an integer from 1 to 21,R corresponds to a hydrogen atom or an alkyl or alkenyl chain from 1 to20 carbon atoms optionally substituted by at least one hydroxyl group, said compound of formula (II) being used alone or in a mixture of compounds of formula (II).
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Paragraph 0093-0099
(2015/12/07)
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- COMPOUNDS AND METHODS OF TREATING OBESITY
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The present invention relates to novel fatty acid derivatives, methods for their preparation, pharmaceutical compositions including such compounds, and methods of using these compounds and compositions, especially as agents for the treatment of obesity and related disorders, and for improving cognition.
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Page/Page column 56
(2009/10/22)
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- Method of producing dicarboxylic acids
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A method of producing dicarboxylic acids (e.g., α,ω dicarboxylic acids) by reacting a compound having a terminal COOH (e.g., unsaturated fatty acid such as oleic acid) and containing at least one carbon-carbon double bond with a second generation Grubbs catalyst in the absence of solvent to produce dicarboxylic acids. The method is conducted in an inert atmosphere (e.g., argon, nitrogen). The process also works well with mixed unsaturated fatty acids obtained from soybean, rapeseed, tall, and linseed oils.
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Page/Page column 11; 13
(2009/05/29)
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- Process for the preparation of saturated or unsaturated primary fatty amines
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Process for the preparation of unsaturated and saturated primary fatty amines comprising the steps of chlorination, treatment by ammonia, reduction and purification
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Page/Page column 5
(2008/06/13)
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- Stereoselective debromination and selective reduction of vic-dibromides with nickel boride
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A simple procedure is reported for the stereoselective debromination of vic-dibromides with nickel boride at ambient temperature. Debromination with concomitant reduction of vic-dibromides to give dihydro products in a one-pot reaction is also reported. α,β-Dibromoketones can also be converted to their corresponding alcohols.
- Khurana, Jitender M.,Kandpal, Bhaskar M.,Kukreja, Gagan,Sharma, Purnima
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p. 1019 - 1023
(2007/10/03)
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- Process
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A process for producing a conjugated di- or poly-unsaturated fatty acid having from 12 to 24 carbon atoms, or a salt or ester thereof, comprises reacting a non-conjugated free fatty acid, or a salt or ester thereof with a base in the presence of a solvent comprising a monohydric alcohol having from 1 to 6 carbon atoms, wherein the reaction is carried out at a temperature of from 120° C. to 200° C. in the presence of water in an amount of at least 4% by weight based on alcohol.
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Page/Page column 4-5
(2008/06/13)
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- The kinetics of thiyl radical-induced reactions of monounsaturated fatty acid esters
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The time-dependent isomerizations and thiol additions of several Z- and E-monounsaturated fatty acid methyl esters catalyzed by alkanethiyl radicals during γ-radiolysis of tert-butyl alcohol solutions are analyzed on the basis of the radiation chemical yield of radicals and established rate data. This provides room-temperature rate constants for the reversible thiyl addition. Within experimental errors, they do not depend on the double bond position in the alkyl chains. Particularly noteworthy is the very fast β-elimination of thiyl radicals from alkyl radicals which carry a second β-substituent. It is supported by additional evidence obtained with a radical clock methodology, and the large preference of fragmentation to the E-isomers is attributed to different barriers for the formation of the E- and Z-transition states from the equilibrium radical structure.
- Chatgilialoglu, Chryssostomos,Altieri, Alessio,Fischer, Hanns
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p. 12816 - 12823
(2007/10/03)
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- Simple method of preparation of methyl trans-10,cis-12- and cis-9,trans-11-octadecadienoates from methyl linoleate
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Pure conjugated isomers of linoleic acid were prepared on a large scale by alkali-isomerization of purified methyl linoleate. The methyl esters of alkali-isomerized linoleic acid contained mainly the methyl cis-9,trans-11- and trans-10,cis-12-octadecadienoates (44 and 47%, respectively). These two isomers were then separated and purified by a series of low-temperature crystallizations from acetone. The isomeric purity obtained for the cis-9,trans-11-octadecadienoate isomer was >90% and that of the trans-10,cis-12-octadecadienoate isomer was 89 to 97%. The isolated yield of the two isomers corresponded to 18 and 25.7%, respectively, of the starting material. The structure of the two isomers was confirmed using partial hydrazine reduction, silver nitrate-thin-layer chromatography of the resulting monoenes and gas chromatography coupled with mass spectrometry of the 4,4-dimethyloxazoline derivatives. Fourier transform infrared spectroscopy of the monoenes gave the confirmation of the geometry of each double bond.
- Berdeaux,Voinot,Angioni,Juaneda,Sebedio
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p. 1749 - 1755
(2007/10/03)
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- 1H-Nuclear magnetic resonance spectroscopic studies of saturated, acetylenic and ethylenic triacylglycerols
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The 1H-NMR spectroscopic properties of 15 synthetic homologous saturated triacylglycerols of type AAA and 16 mixed saturated triacylglycerols of type ABA and AAB have been studied. Triacylglycerols containing short-chain fatty acids (2:0-6:0) are readily identified. Triacylglycerols containing medium- and long-chain fatty acid components are not differentiated. From the analysis of 19 acetylenic triacylglycerols of type AAA, ABA and AAB (containing positional isomers of acetylenic fatty acids), it is only possible to characterize triacylglycerols with acyl groups containing the acetylenic bond at the Δ2-Δ5 position. 1H-NMR analysis could not confirm the positions (α- or β-acyl) of the acetylenic acids in mixed triacylglycerols. In the study of 22 ethylenic triacylglycerols of type AAA containing positional isomers of (Z)- or (E)-ethylenic acids, molecules containing an ethylenic bond in the Δ2 position of the acyl chains were readily characterized, as the ethylenic protons in the α- and β-acyl chains were fully resolved. Triacylglycerols containing an unsaturated center at the position were characterized by the shifts of the 2-H protons. The spectra of the remaining triacylglycerol molecules were very similar and the position of the ethylenic system could not be determined by this technique.
- Lie Ken Jie, Marcel S.F.,Lam
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p. 155 - 171
(2007/10/03)
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- Phosphonium Iodide in Organic Synthesis
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Phosphonium iodide is found useful in the stereospecific conversion of some vicinal diols to olefins.Synthesis of cis-hexadec-9-enolide has been achieved.
- Chatterjea, J. N.,Majee, R. N.,Mukherjee, S. N.
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p. 733 - 735
(2007/10/02)
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- Reaction of Organic Halides with Chlorotris(triphenylphosphine)cobalt(I)
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Reaction of various types of organic halides with a monovalent cobalt complex, chlorotris(triphenylphosphine)cobalt(I) is described.Reaction of benzylic monohalides, dihalides and trihalides with CoCl(Ph3P)3 gave a coupling product with formation of a carbon-carbon single bond, double bond and triple bond, respectively, under mild and non-basic conditions.Dehalogenation of non-benzylic vicinal dihalides with the reagent took place cleanly to give an olefin in high yield.Reductive coupling of allylic halides using the reagent afforded regioselectively a 1,5-diene with retention of the stereochemistry of the carbon-carbon double bond of the allylic halides used.By using this reaction, (E,E,E,E)-squalene was stereospecifically synthesized from (E,E)-farnesyl bromide.Reaction of halohydrins with CoCl(Ph3P)3 gave exclusively a ketone in the presence of an amine or olefin through an alkylcobalt intermediate.A 1,2-hydrogen shift is involved in this reaction.Keywords - chlorotris(triphenylphosphine)cobalt(I); coupling reaction; benzylic halides; allylic halides; synthesis of 1,5-diene; squalene; halohydrin; ketone synthesis.
- Momose, Den-ichi,Iguchi, Kazuo,Sugiyama, Toshikazu,Yamada, Yasuji
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p. 1840 - 1853
(2007/10/02)
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- An Electron Spin Resonance Study of Fatty Acids and Esters. Part 1. Hydrogen Abstraction from Olefinic and Acetylenic Long-chain Esters
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The radicals generated from unsaturated fatty acid esters by hydrogen abstraction with photochemically formed t-butoxyl radicals have been investigated by e.s.r. spectroscopy.The substituted allyl and pentadienyl radicals generated from monoenoic and dienoic esters were conformationally stable under the conditions of the experiments.The main species observed on hydrogen-abstraction from monoynoic esters were substituted propynyl radicals, and the same radical type was generated from diynoic esters with more than one methylene unit separating the triple bonds.Substituted penta-1,4-diynyl and penta-1,3-diynyl radicals were identified on hydrogen-abstraction from methylene-interrupted and conjugated diynoic esters.Hydrogen abstraction from triacylglycerols containing one or more double bonds was also examined.Most of the unsaturated esters also gave rise to secondary radicals produced by hydrogen-abstraction from the chain methylene groups.From the measured concentrations of the secondary and delocalised radicals the following approximate relative rates of hydrogen-abstraction by t-butoxyl radicals from the different sites were obtained: secondary: propynylic: allylic: bisallylic = 1:18:36:116 at 293 K.
- Bascetta, Emanuele,Gunstone, Frank D.,Walton, John C.
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p. 603 - 614
(2007/10/02)
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- RETENTION OF CONFIGURATION IN DOUBLE BOND PROTECTION-DEPROTECTION BY BROMINATION-CATHODIC DEBROMINATION
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The double bond can be mildly protected by bromination with PyHBr3; deprotection is achieved by cathodic reduction at -1.4 V.The overall yields range from 68 to 99 percent, the configuration of the double bond is retained with at least 96 percent.
- Husstedt, Urda,Schaefer, Hans J.
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p. 623 - 624
(2007/10/02)
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