- Synthesis of Ether-Diols with Low Polarity from Long-Chained Fatty Alcohols for Use in Block Copolymers
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Diol-terminated polyethers are important intermediates for the manufacturing of block copolymers, but only a few polyethers other than polyethylene glycols are available on a technical scale. Most of them are highly polar. Natural fatty alcohols—converted to similar polyethers—should have a grossly reduced polarity because of a large separation of the oxygen atoms in the C18 chain. A synthesis sequence of polyethers with a longer carbon chain compared to the ethylene glycol-derived ethers based on commercially available fatty alcohols was designed for a future examination of the hydrophobic properties. Palladium-catalyzed cleavage of olefinic dialkyl carbonates results in carbon dioxide elimination and subsequent formation of ethers from an allyl-palladium cation. It could be shown that this process with fatty alcohols like undec-10-en-1-ol or oleyl alcohol can be run with appreciable yield. Although carbonates were obtained here using expensive chloroformates as starting materials, transesterification of dimethylcarbonates can be used similarly. Ruthenium-catalyzed acyclic diene metathesis (ADMET) at both chain terminations then was applied to polymerize the ethers. Depending on the alkenyl chain, short oligomers with a degree of polymerization (DP) of about 5–8 seem to be formed according to gel permeation chromatography (GPC).
- Huber, Veronika Ramona,Riepl, Herbert Mathias
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Read Online
- Tailored Ru-NHC heterogeneous catalysts for alkene metathesis
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The preparation of highly active and stable Ru-NHC (ruthenium-N-heterocyclic carbene ligands) alkene metathesis catalysts through surface organometallic chemistry on hybrid mesostructured materials was reported. Two types of mesoporous hybrid materials we
- Karame, Iyad,Boualleg, Malika,Camus, Jean-Michel,Maishal, Tarun K.,Alauzun, Johan,Basset, Jean-Marie,Coperet, Christophe,Corriu, Robert J. P.,Jeanneau, Erwan,Mehdi, Ahmad,Reye, Catherine,Veyre, Laurent,Thieuleux, Chloe
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- Contra-thermodynamic Olefin Isomerization by Chain-Walking Hydroboration and Dehydroboration
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We report a dehydroboration process that can be coupled with chain-walking hydroboration to create a one-pot, contra-thermodynamic, short-or long-range isomerization of internal olefins to terminal olefins. This dehydroboration occurs by a sequence comprising activation with a nucleophile, iodination, and base-promoted elimination. The isomerization proceeds at room temperature without the need for a fluoride base, and the substrate scope of this isomerization is expanded over those of previous isomerizations we have reported with silanes.
- Bloomer, Brandon,Butcher, Trevor W.,Ciccia, Nicodemo R.,Conk, Richard J.,Hanna, Steven,Hartwig, John F.
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supporting information
p. 1005 - 1010
(2022/02/10)
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- ACYCLIC CARBENE LIGAND FOR RUTHENIUM COMPLEX FORMATION, RUTHENIUM COMPLEX CATALYST, AND USE THEREOF
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Provided are a novel acyclic carbene ligand for ruthenium complex formation; a ruthenium complex catalyst using the ligand; a method of using the complex as a catalyst in an ethylene-metathesis ethenolysis reaction; a method of preparing the ruthenium complex catalyst; and a method of preparing a linear alpha-olefin, the method including the step of reacting a linear or cyclic alkene compound in the presence of the ruthenium complex catalyst. The acyclic carbene ligand of the present invention and the ruthenium complex catalyst using the same have high selectivity and turnover number for terminal olefin formation in an ethylene-metathesis ethenolysis reaction, and thus linear α-olefins may be prepared with a high yield.
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Paragraph 0124-0130
(2021/05/14)
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- Oxo 2-Adamantylidene Complexes of Mo(VI) and W(VI)
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Molybdenum and tungsten oxo 2-adamantylidene (Adene) complexes that contain two nonafluoro-tert-butoxide (ORF9) ligands have been prepared through addition of 2-methylene-or 2-ethylideneadamantane to neophylidene or neopentylidene complexes. The isolated oxo complexes include W(O)(Adene)(ORF9)2(PPh2Me) (1W), W(O)(Adene)(ORF9)2 (2W), W(O)(Adene)(2,5-dimethylpyrrolide)2 (3W), W(O)(Adene)(2,5-dimethylpyrrolide)(2,6-dimesitylphenoxide) (4W), Mo(O)(Adene)(ORF9)2(PPhMe2) (1Mo), and Mo(O)(Adene)(ORF9)2 (2Mo). Compound 2W is a dimer that contains unsymmetrically bridging oxo ligands; it dissociates readily and reversibly into monomers, especially in the presence of a donor such as THF. In contrast, 2Mo is a monomer. Both 2W and 2Mo are remarkably stable thermally. The pale-blue complexes Mo(Adene)(ORF9)2Cl2 (5Mo) and W(Adene)(ORF9)2Cl2 (5W) are formed upon addition of PCl5 to 2Mo and 2W, respectively. The oxo complexes are reactive olefin metathesis initiators, while 5Mo and 5W are relatively poor initiators. We ascribe the thermal stability of 2Mo and 2W to resistance of the 2-adamantylidene ligands to couple bimolecularly, to the absence of an α-hydrogen in the alkylidene, or both.
- Boudjelel, Maxime,Zhai, Feng,Schrock, Richard R.,Hoveyda, Amir H.,Tsay, Charlene
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supporting information
p. 838 - 842
(2021/04/09)
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- Continuous Flow Z-Stereoselective Olefin Metathesis: Development and Applications in the Synthesis of Pheromones and Macrocyclic Odorant Molecules**
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The first continuous flow Z-selective olefin metathesis process is reported. Key to realizing this process was the adequate choice of stereoselective catalysts combined with the design of an appropriate continuous reactor setup. The designed continuous process permits various self-, cross- and macro-ring-closing-metathesis reactions, delivering products in high selectivity and short residence times. This technique is exemplified by direct application to the preparation of a range of pheromones and macrocyclic odorant molecules and culminates in a telescoped Z-selective cross-metathesis/ Dieckmann cyclisation sequence to access (Z)-Civetone, incorporating a serial array of continually stirred tank reactors.
- Browne, Duncan L.,Colombel-Rouen, Sophie,Crévisy, Christophe,Curbet, Idriss,Mauduit, Marc,McBride, Tom,Morvan, Jennifer,Roisnel, Thierry
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supporting information
p. 19685 - 19690
(2021/08/06)
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- Vortex Fluidic Ethenolysis, Integrating a Rapid Quench of Ruthenium Olefin Metathesis Catalysts
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Ruthenium-catalysed ethenolysis occurs in a vortex fluidic device (VFD)-a scalable, thin-film microfluidic continuous flow process. This process takes advantage of the efficient mass transfer of gaseous reagents into the dynamic thin film of liquid. Also reported is the rapid quenching of the ruthenium-based olefin metathesis catalyst by the addition of a saturated solution of N-acetyl-l-cysteine in MeCN, as a convenient alternative to previously reported quenching methods.
- Pye, Scott J.,Chalker, Justin M.,Raston, Colin L.
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p. 1138 - 1143
(2020/08/27)
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- In a Quest for Selectivity Paired with Activity: A Ruthenium Olefin Metathesis Catalyst Bearing an Unsymmetrical Phenanthrene-Based N-Heterocyclic Carbene
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Robust, selective, and stable in the presence of ethylene, ruthenium olefin metathesis pre-catalyst, {[3-benzyl-1-(10-phenyl-9-phenanthryl)]-2-imidazolidinylidene}dichloro(o-isopropoxyphenylmethylene)ruthenium(II), Ru-3, bearing an unsymetrical N-heterocyclic carbene (uNHC) ligand, has been synthesized. The initiation rate of Ru-3 was examined by ring-closing metathesis and cross-metathesis reactions with a broad spectrum of olefins, showing an unprecendented selectivity. It was also tested in industrially relevant ethenolysis reactions of olefinic substrates from renewable feedstock with very good yields and selectivities.
- D?browski, Micha?,Grela, Karol,Trzybiński, Damian,Wo?niak, Krzysztof,Wyr?bek, Przemys?aw
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- Synthesis and Activity of Six-Membered Cyclic Alkyl Amino Carbene-Ruthenium Olefin Metathesis Catalysts
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Ru-cyclic alkyl amino carbene (Ru-CAAC) olefin metathesis catalysts perform extraordinarily in metathesis macrocyclization and ethenolysis, but previous studies have been limited to the use of five-membered CAAC (CAAC-5) ligands. In this work, we synthesized a different group of ruthenium catalysts with more σ-donating and π-accepting six-membered CAAC (CAAC-6) ligands, and their metathesis activity was probed through initiation studies, ring-closing metathesis (RCM), cross-metathesis, and ethenolysis. These catalysts display higher initiation rates than analogous Ru-CAAC-5 complexes but demonstrate lower activity in RCM and ethenolysis.
- Grubbs, Robert H.,Samkian, Adrian E.,Virgil, Scott C.,Xu, Yan,Yoon, Ki-Young
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supporting information
(2020/02/27)
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- Integrating Activity with Accessibility in Olefin Metathesis: An Unprecedentedly Reactive Ruthenium-Indenylidene Catalyst
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Access to leading olefin metathesis catalysts, including the Grubbs, Hoveyda, and Grela catalysts, ultimately rests on the nonscaleable transfer of a benzylidene ligand from an unstable, impure aryldiazomethane. The indenylidene ligand can be reliably installed, but to date yields much less reactive catalysts. A fast-initiating, dimeric indenylidene complex (Ru-1) is reported, which reconciles high activity with scaleable synthesis. Each Ru center in Ru-1 is stabilized by a state-of-the-art cyclic alkyl amino carbene (CAAC, C1) and a bridging chloride donor: the lability of the latter elevates the reactivity of Ru-1 to a level previously attainable only with benzylidene derivatives. Evaluation of initiation rate constants reveals that Ru-1 initiates >250× faster than indenylidene catalyst M2 (RuCl2(H2IMes)(PCy3)(Ind)), and 65× faster than UC (RuCl2(C1)2(Ind)). The slow initiation previously regarded as characteristic of indenylidene catalysts is hence due to low ligand lability, not inherently slow cycloaddition at the Ru=CRR′ site. In macrocyclization and "ethenolysis" of methyl oleate (i.e., transformation into α-olefins via cross-metathesis with C2H4), Ru-1 is comparable or superior to the corresponding, breakthrough CAAC-benzylidene catalyst. In ethenolysis, Ru-1 is 5× more robust to standard-grade (99.9%) C2H4 than the top-performing catalyst, probably reflecting steric protection at the quaternary CAAC carbon.
- Nascimento, Daniel L.,Gawin, Anna,Gawin, Rafa?,Guńka, Piotr A.,Zachara, Janusz,Skowerski, Krzysztof,Fogg, Deryn E.
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supporting information
p. 10626 - 10631
(2019/08/28)
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- Integrated extraction and catalytic upgrading of microalgae lipids in supercritical carbon dioxide
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Fatty acids from microalgae are attractive compounds for catalytic upgrading to chemicals, but their extraction often requires multi-step procedures and the use of various organic solvents. To relieve this bottleneck, we propose a straightforward approach of combined extraction and catalytic functionalization via olefin cross-metathesis (ethenolysis and butenolysis) in supercritical CO2 (scCO2). This is demonstrated for Phaeodactylum tricornutum microalgae biomass. ScCO2 at optimum conditions (90 °C, 620 atm, ρ(CO2) = 0.90 g mL-1) extracted the lipids selectively and quantitatively from previously disrupted cells, while organic solvent extraction for comparison additionally extracted polar diacylglycerides and chlorophylls. In a one-pot approach, olefin cross-metathesis of the unsaturated fatty acids (FA16:1, FA18:1 and FA20:5) by alkenolysis yielded the desirable mid-chain olefin and unsaturated ester products. The product spectrum compares to alkenolysis of individual model compounds in scCO2 as well as of separately scCO2 extracted microalgae oil. Both these ethenolysis and butenolysis proceed with conversions of more than 81% and high selectivities to the desired products. This biorefinery approach was further illustrated by the simultaneous extraction and catalytic isomerizing alkoxycarbonylation in scCO2.
- Zimmerer, Julia,Pingen, Dennis,Hess, Sandra K.,Koengeter, Tobias,Mecking, Stefan
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supporting information
p. 2428 - 2435
(2019/05/21)
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- In Situ Generation of Ru-Based Metathesis Catalyst. A Systematic Study
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A systematic study for the in situ generation of Ru-based metathesis catalysts was described. Assembly of commercially available and inexpensive reagents [Ru(p-cymene)Cl2]2, SIPr·HCl, and n-BuLi led to the formation of 18 electron arene-ruthenium complexes that, in the presence of additives such as alkynes, cyclopropenes, and diazoesters, generated highly selective and efficient catalytic systems applicable to a variety of olefin metathesis transformations. Notably, we were able to achieve a productive TON of 4500 for the self-metathesis of methyl oleate, a reaction which could be easily upscaled to 2 kg.
- Müller, Daniel S.,Raoul, Yann,Le N?tre, Jér?me,Baslé, Olivier,Mauduit, Marc
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p. 3511 - 3518
(2019/04/01)
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- A Gentler Touch: Synthesis of Modern Ruthenium Olefin Metathesis Catalysts Sustained by Mechanical Force
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Mechanochemical synthesis of nine contemporary ruthenium catalysts used for olefin metathesis is described, being the first reported example of formation of Ru carbene organometallic complexes in solid state. Three key organometallic transformations commonly used in the synthesis of the second and third generations of Ru catalysts in solution—phosphine ligand (PCy3) exchange with in situ formed N-heterocyclic carbene (NHC) ligand, PCy3 to pyridine ligand replacement, and benzylidene ligands interchange—were proved to work under mechanochemical conditions, affording the targets in high purity. Mechanochemical approach not only requires less amounts of organic solvent (null for synthesis, only for purification) and is scalable, but also allows for transformations that were reported impossible in the solution phase.
- Mukherjee, Nirmalya,Marczyk, Anna,Szczepaniak, Grzegorz,Sytniczuk, Adrian,Kajetanowicz, Anna,Grela, Karol
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p. 5362 - 5369
(2019/11/11)
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- METATHESIS CATALYSTS
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This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals and pharmaceuticals.
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Paragraph 000118; 000119
(2018/03/09)
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- Carboxyl Graphene as a Superior Support for Bulky Ruthenium-Based Olefin Metathesis Catalyst
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A Hoveyda-type catalyst decorated with two quaternary ammonium tags was synthesized and noncovalently grafted on SiO2, SBA-15, and on carboxyl graphene. A comparative study showed that the efficiency of the dual-anchored heterogeneous catalysts was highly dependent on the properties of the supporting material with graphene outperforming silicate supports. The graphene-immobilized complex exhibited excellent efficiency reflected in turnover numbers obtained in ring-closing metathesis and in self-metathesis of 1-decene. Importantly, the solid-supported catalyst assured increased recyclability with no ruthenium leaching as confirmed by inductively coupled plasma mass spectrometry.
- Kaczanowska, Katarzyna,Chwalba, Micha?,Pastva, Jakub,Kub?, Martin,Ruszczyńska, Anna,Bulska, Ewa,Balcar, Hynek,Skowerski, Krzysztof
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p. 1837 - 1844
(2018/07/05)
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- Syntheses of Molybdenum(VI) Imido Alkylidene Complexes That Contain a Bidentate Dithiolate Ligand
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Zn(DCTC) (DCTC = 3,6-dichlorodithiacatecholate) reacts with Mo(NAd)(CHCMe2Ph)Cl2(PPh2Me) (Ad = 1-adamantyl) to give Mo(NAd)(CHCMe2Ph)(DCTC)(PPh2Me). The reactions between Zn(DCTC) and Mo(NAd)(CH-t-Bu)(OTf)2(dme) or Mo(NAr)(CHCMe2Ph)(OTf)2(dme) (Ar = 2,6-i-Pr2C6H3; OTf = triflate; dme = 1,2-dimethoxyethane) produce [Mo(NAd)(CH-t-Bu)(DCTC)]2 and [Mo(NAr)(CHCMe2Ph)(DCTC)]2, respectively. Complexes that contain a 3,3′,5,5′-tetrasubstituted dithiabiphenolate were prepared in a reaction between Mo(NAr)(CHCMe2Ph)(Me2pyr)2 (Me2pyr = 2,5-dimethylpyrrolide) and the 3,3′,5,5′-tetrasubstituted dithiabiphenols, (3,3′,5,5′-tetrachlorodithiabiphenol (H2Cl4S2), 3,3′,5,5′-tetrabromodithiabiphenol (H2Br4S2), and 3,3′,5,5′-tetra-t-Bu-dithiabiphenol (H2Bu4S2)). The isolated complexes include Mo(NAr)(CHCMe2Ph)(Cl4S2)(pyridine), Mo(NAr)(CHCMe2Ph)(Br4S2)(pyridine), Mo(NAr)(CHCMe2Ph)(Bu4S2)(PMe3), and [Mo(NAr)(CHCMe2Ph)(Cl4S2)]2. Only the dithiabiphenolate derivatives (in the presence of B(C6F5)3) show activity for the metathesis of 1-decene, and although that reaction is limited by a sensitivity of the alkylidene complexes to ethylene, as suggested by the reaction between ethylene and Mo(NAr)(CHCMe2Ph)(Bu4S2) to give the ethylene complex, Mo(NAr)(C2H4)(Bu4S2). Mo(NAr)(C2H4)(Bu4S2) was unstable with respect to loss of ethylene and formation of an ethylene-free dimer. Mo(NAd)(CHCMe2Ph)(DCTC)(PPh2Me), [Mo(NAr)(CHCMe2Ph)(DCTC)]2, and [Mo(NAr)(CHCMe2Ph)(Cl4S2)]2 were characterized crystallographically.
- Tafazolian, Hosein,Tsay, Charlene,Schrock, Richard R.,Müller, Peter
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p. 4024 - 4030
(2018/10/31)
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- NOVEL RUTHENIUM COMPLEX, METHOD OF ITS PRODUCTION AND ITS USE IN REACTION OF OLEFINE METATHESIS
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The invention relates to novel ruthenium complexes of formula (9). The invention also relates to the method for preparation of novel metal complexes of formula (9) and their use in olefin metathesis reactions.
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Page/Page column 29-30
(2018/06/22)
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- Stable ruthenium olefin metathesis catalysts bearing symmetrical NHC ligands with primary and secondary: N -alkyl groups
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Four novel stable Hoveyda-Grubbs-type catalysts containing N,N′-dineopentyl- and N,N′-dicyclohexyl-substituted N-heterocyclic carbene (NHC) ligands with syn and anti phenyl groups on the ring backbone were synthesized and fully characterized. The catalytic potential of these complexes was investigated in metathesis reactions of both standard and renewable substrates. Compared to the Hoveyda-Grubbs second generation catalyst (HGII), all of the new catalysts showed high performances in most of the examined metathesis transformations. In particular, N,N′-dicyclohexyl catalysts gave improved results in the challenging ring-closing metathesis (RCM) reaction to form tetrasubstituted olefins, while catalysts with neopentyl N-groups were found to be more active and Z-selective in cross-metathesis (CM) reactions. Modest enantioselectivities in the asymmetric ring-closing metathesis (ARCM) of achiral trienes with different steric hindrance were observed in the presence of catalysts bearing chiral C2-symmetric NHC ligands.
- Ambrosio, Chiara,Paradiso, Veronica,Costabile, Chiara,Bertolasi, Valerio,Caruso, Tonino,Grisi, Fabia
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supporting information
p. 6615 - 6627
(2018/05/23)
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- Bis(Cyclic Alkyl Amino Carbene) Ruthenium Complexes: A Versatile, Highly Efficient Tool for Olefin Metathesis
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The state-of-the-art in olefin metathesis is application of N-heterocyclic carbene (NHC)-containing ruthenium alkylidenes for the formation of internal C=C bonds and of cyclic alkyl amino carbene (CAAC)-containing ruthenium benzylidenes in the production of terminal olefins. A straightforward synthesis of bis(CAAC)Ru indenylidene complexes, which are highly effective in the formation of both terminal and internal C=C bonds at loadings as low as 1 ppm, is now reported.
- Gawin, Rafa?,Kozakiewicz, Anna,Guńka, Piotr A.,D?browski, Pawe?,Skowerski, Krzysztof
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supporting information
p. 981 - 986
(2017/01/18)
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- Hoveyda-Type Quinone-Containing Complexes – Catalysts to Prevent Migration of the Double Bond under Metathesis Conditions
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Three new quinone-containing Hoveyda-type complexes have been synthesised and fully characterised. Their ability to suppress undesired double-bond migration along the carbon chain during metathesis reactions was examined. It was proved that these catalysts decrease the amounts of undesired side-products with a shifted double bond in the reaction mixture.
- Kajetanowicz, Anna,Milewski, Mariusz,Rogińska, Joanna,Gajda, Roman,Wo?niak, Krzysztof
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supporting information
p. 626 - 638
(2017/02/05)
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- Hydroformylation-hydrogenation and hydroformylation-acetalization reactions catalyzed by ruthenium complexes
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In this work, the catalytic activity of ruthenium II and III complexes containing chloride, pyridine, phosphine and CO ligands was investigated in the hydroformylation – hydrogenation and hydroformylation – acetalization reactions. The complexes mer-[RuCl3(dppb)(H2O)](1), mer-[RuCl3(dppb)(4-Vpy)](2), mer-[RuCl3(dppb)(4-tBupy)](3), mer-[RuCl3(dppb)(py)](4), mer-[RuCl3(dppb)(4-Phpy)](5), mer-[RuCl3(dppb)(4-Mepy)](6), cis-[RuCl2(CO)2(dppb)](7), trans-[RuCl2(CO)2(dppb)](8), RuCl3·xH2O(9), [RuCl2(PPh3)3](10) and [RuCl2(PPh3)2(dppb)](11) were used as supplied or synthesized as previously described in the literature {Where PPh3?=?triphenylphosphine, dppb?=?1,4-bis(diphenylphosphino)butane, py?=?pyridine, 4-Mepy?=?4-methylpyridine, 4-Vpy?=?4-vinylpyridine, 4-tBupy?=?4-tert-butylpyridine and 4-Phpy?=?4-phenylpyridine}. These complexes were used as a pre-catalysts in a hydroformylation catalytic system to produce C[sbnd]C, C[dbnd]O and C[sbnd]O bonds, where 1-decene resulted in a formation of respective alcohol and dimethyl acetals. Several reactions were performed in order to find the best reaction conditions presenting the best conversion (64% after 24?h). The 1-decene was also used as a substrate in two type tandem reactions labeled as: hydroformylation – hydrogenation (HH) and hydroformylation – acetalization (HA) reactions. The relationship between Ru – catalyst/substrate was 1:100, without free ligands or additives, in a controlled temperature and pressure. All the products of catalytic reactions HH and HA were analyzed by CG-FID with good yields.
- Rodrigues, Claudia,Delolo, Fabio G.,Norinder, Jakob,B?rner, Armin,Bogado, André L.,Batista, Alzir A.
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p. 586 - 592
(2016/12/16)
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- Expanding the Family of Hoveyda-Grubbs Catalysts Containing Unsymmetrical NHC Ligands
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A series of Hoveyda-Grubbs second-generation catalysts containing N-alkyl/N′-aryl N-heterocyclic carbene (NHC) ligands were synthesized and investigated in representative olefin metathesis reactions. Steric perturbations of unsymmetrical NHCs were achieved through modulation of the hindrance of alkyl (neopentyl, neophyl, cyclohexyl) and aryl (2-isopropylphenyl, mesityl) substituents at the nitrogen atoms in combination with different backbone configurations (syn and anti). The NHC substitution patterns strongly influence the stability and reactivity of the corresponding complexes. In general, complexes bearing an anti NHC backbone are more stable and more active than their corresponding syn isomers. In both the series, the presence of bulky, highly branched N-alkyl groups tends to give reduced catalytic differences between syn and anti isomers, whereas the nature of the N′-aryl substituent (2-isopropylphenyl or mesityl) gives rise to different activity and/or selectivity. Of note, an N′-mesityl catalyst with anti backbone was found to be highly competent in the ethenolysis of ethyl oleate, achieving up to 90% selectivity for the formation of terminal olefins.
- Paradiso, Veronica,Bertolasi, Valerio,Costabile, Chiara,Caruso, Tonino,D?browski, Micha?,Grela, Karol,Grisi, Fabia
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p. 3692 - 3708
(2017/10/13)
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- Bleaching Earths as Powerful Additives for Ru-Catalyzed Self-Metathesis of Non-Refined Methyl Oleate at Pilot Scale
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A practical and cost-effective ruthenium-catalyzed self-metathesis of non-refined methyl oleate (85 %) derived from very high oleic sunflower oils was demonstrated at pilot scale using a robust and kg-scale commercially available SIPr-M71 pre-catalyst. The simple addition of 1 wt % bleaching earths (Tonsil 110FF) to a thermally pretreated oil could efficiently prevent catalyst deactivation. Remarkably, without the need for filtration, the catalytic system was able to achieve a turnover number (TON) of more than 744 000 at a catalyst loading of only 1 ppm. At large scale (up to 200 kg), the equilibrium of the self-metathesis reaction was reached within 1 hour at 50 °C under neat conditions at a very low 5 ppm catalyst loading to produce the expected primary metathesis products (PMP), that is, 9-octadecene and dimethyl-9-octadecenoate, with a productive TON of 94900.
- Allard, Jessica,Curbet, Idriss,Chollet, Guillaume,Tripoteau, Fabien,Sambou, Sophie,Caijo, Frédéric,Raoul, Yann,Crévisy, Christophe,Baslé, Olivier,Mauduit, Marc
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supporting information
p. 12729 - 12734
(2017/09/25)
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- Fishing for the right catalyst for the cross-metathesis reaction of methyl oleate with 2-methyl-2-butene
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The activity of various Ru-alkylidene olefin metathesis catalyst types on the outcome of cross-metathesis of methyl oleate with 2-methyl-2-butene was studied.
- Sytniczuk,Kajetanowicz,Grela
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p. 1284 - 1296
(2017/05/05)
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- Remarkably Efficient Microwave-Assisted Cross-Metathesis of Lipids under Solvent-Free Conditions
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Catalytic transformation of renewable feedstocks into fine chemicals is in high demands and olefin metathesis is a sophisticated tool for biomass conversion. Nevertheless, the large-scale viability of such processes depends on the conversion efficiency, energy efficiency, catalytic activity, selective conversion into desired products, and environmental footprint of the process. Therefore, conversions of renewables by using simple, swift, and efficient methods are desirable. A microwave-assisted ethenolysis and alkenolysis (using 1,5-hexadiene) of canola oil and methyl esters derived from canola oil (COME) and waste/recycled cooking oil (WOME) was carried out by using ruthenium-based catalytic systems. A systematic study using 1st and 2nd generation Grubbs and Hoveyda–Grubbs catalysts was carried out. Among all ruthenium catalysts, 2nd generation Hoveyda–Grubbs catalyst was found to be highly active in the range of 0.002–0.1 mol % loading. The conversions proved to be rapid providing unprecedented turnover frequencies (TOFs). High TOFs were achieved for ethenolysis of COME (21 450 min?1), direct ethenolysis of canola oil (19 110 min?1), for WOME (15 840 min?1) and for cross-metathesis of 1,5-hexadiene with COME (10 920 min?1). The ethenolysis of commercial methyl oleate was also performed with a TOF of 8000 min?1 under microwave conditions.
- Ullah, Aman,Arshad, Muhammad
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p. 2167 - 2174
(2017/05/26)
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- ACTIVE INGREDIENT COMPRISING A MIXTURE OF UNSATURATED DICARBOXYLIC FATTY ACIDS, COMPOSITIONS COMPRISING SAID INGREDIENT AND COSMETIC OR DERMATOLOGICAL USES
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The ingredient comprises a mixture of unsaturated dicarboxylic acids comprising the Z and E isomers of at least one mono-unsaturated dicarboxylic C12-C24 acid, the concentration of the E isomer being of at least 25% by weight based on the total weight of Z and E isomers The ingredient can be used to form cosmetic or dermatological compositions, in particular for lightening the skin, improving the clarity and unification of the skin complexion.80
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Page/Page column 6; 19
(2016/02/12)
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- PROCESS FOR COMPOUND TRANSFORMATION
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Embodiments of the present disclosure provide for methods of using a catalytic system to chemically transform a compound (e.g., a hydrocarbon). In an embodiment, the method does not employ grafting the catalyst prior to catalysis. In particular, embodiments of the present disclosure provide for a process of hydrocarbon (e.g., C1 to C20 hydrocarbon) metathesis (e.g., alkane, olefin, or alkyne metathesis) transformation, where the process can be conducted without employing grafting prior to catalysis.
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Page/Page column 7-9
(2017/04/11)
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- Synthesis and catalytic activity of ruthenium indenylidene complexes bearing unsymmetrical NHC containing a heteroaromatic moiety
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New robust and air stable ruthenium(ii) indenylidene second generation olefin metathesis catalysts with unsymmetrical N-heterocyclic carbene (NHC) ligands were synthesized. Model metathesis reactions were performed in the presence of newly-developed complexes in commercial grade toluene under air, leading to high conversions and good selectivities.
- Smoleń, Micha?,Ko?nik, Wioletta,Loska, Rafa?,Gajda, Roman,Malińska, Maura,Wo?niak, Krzysztof,Grela, Karol
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p. 77013 - 77019
(2016/08/30)
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- N-Trifluoromethyl NHC Ligands Provide Selective Ruthenium Metathesis Catalysts
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We report the synthesis of ruthenium metathesis catalysts containing unsymmetrical N-trifluoromethyl NHC ligands. These complexes have been fully characterized, and a Ru-F interaction has been identified in the solid state by X-ray crystallographic analysis for three catalysts with Ru-F distances between 2.629(2) and 2.652(2) ?. The influence of the N-trifluoromethyl NHC ligands on the initiation rates and activation parameters was studied. The activity of these catalysts was evaluated in benchmark olefin metathesis reactions and compared to the standard second-generation Grubbs catalyst. Remarkably, N-trifluoromethyl catalysts display an unusually high selectivity for the formation of terminal olefins (up to 90%) in the ethenolysis of ethyl oleate. Much improved selectivity is demonstrated for alternating copolymerization of cyclooctene and norbornene as well. These results underline the importance of electronic effects exerted by the NHC ligand.
- Engl, Pascal S.,Fedorov, Alexey,Copéret, Christophe,Togni, Antonio
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p. 887 - 893
(2016/04/19)
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- High Trans Kinetic Selectivity in Ruthenium-Based Olefin Cross-Metathesis through Stereoretention
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The first kinetically controlled, highly trans-selective (>98%) olefin cross-metathesis reaction is demonstrated using Ru-based catalysts. Reactions with either trans or cis olefins afford products with highly trans or cis stereochemistry, respectively. This E-selective olefin cross-metathesis is shown to occur between two trans olefins and between a trans olefin and a terminal olefin. Additionally, new stereoretentive catalysts have been synthesized for improved reactivity. (Chemical Equation Presented).
- Johns, Adam M.,Ahmed, Tonia S.,Jackson, Bradford W.,Grubbs, Robert H.,Pederson, Richard L.
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supporting information
p. 772 - 775
(2016/03/01)
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- Valorisation of vegetable oils via metathesis reactions on solid catalysts: Cross-metathesis of methyl oleate with 1-hexene
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Abstract The activity and selectivity of silica-supported Hoveyda-Grubbs (HG) complex for the cross-metathesis of methyl oleate with 1-hexene to obtain 1-decene, methyl 9-tetradecenoate, 5-tetradecene and methyl 9-decenoate were studied in a batch reactor. The HG complex loading was varied between 0.87 and 11.6 wt%. Competitive secondary reactions were the self-metathesis of methyl oleate and the self-metathesis of 1-hexene. The yield to cross-metathesis products (ηC-M) was 47% when a 1-hexene/methyl oleate reactant ratio (RC6/MO) of one was employed. The ηC-M value increased with increasing 1-hexene initial concentration, reaching 87% for RC6/MO = 7. The selectivity to terminal olefins also increased at the expense of internal olefins among the cross-metathesis products when the concentration of 1-hexene was increased.
- Zelin,Nieres,Trasarti,Apesteguía
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p. 410 - 417
(2015/07/28)
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- Comparison of reactivity in the cross metathesis of allyl acetate-derivatives with oleochemical compounds
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The metathesis of unsaturated oleochemicals is an excellent tool for generating α,ω-difunctional substrates, which are useful intermediates for polymer synthesis. This article describes the cross metathesis of allyl acetate and cis-1,4-diacetoxy-2-butene with methyl 10-undecenoate and methyl oleate, which are oleochemical key substrates. Detailed optimizations led to high conversion rates and yields of the desired products under mild reaction conditions by using a low concentration of commercially available homogeneous ruthenium catalysts.
- Behr, Arno,Toepell, Stephanie
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p. 603 - 611
(2015/03/04)
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- Divergent Approach to a Family of Tyrosine-Derived Ru-Alkylidene Olefin Metathesis Catalysts
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A simple and generic approach to access a new family of Ru-alkylidene olefin metathesis catalysts with specialized properties is reported. This strategy utilizes a late stage, utilitarian Hoveyda-type ligand derived from tyrosine, which can be accessed via a multigram-scale synthesis. Further functionalization allows the catalyst properties to be tuned, giving access to modified second-generation Hoveyda-Grubbs-type catalysts. This divergent synthetic approach can be used to access solid-supported catalysts and catalysts that function under solvent-free and aqueous conditions.
- Gleeson, Ellen C.,Wang, Zhen J.,Jackson, W. Roy,Robinson, Andrea J.
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p. 7205 - 7211
(2015/07/28)
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- Cross-metathesis of biosourced fatty acid derivatives: A step further toward improved reactivity
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The improved catalytic conversion of bioresources, namely unsaturated fatty acid derivatives, is presented. The targeted reaction is ruthenium-catalyzed cross-metathesis with functionalized olefins (α,β-unsaturated esters), that affords shorter diesters. These can be used as biosourced (pre)monomers for the production of polyesters. It is demonstrated that switch from terminal to internal cross-metathesis partners (that is, from methyl acrylate to methyl crotonate) allows use of ppm-level catalyst loadings, while retaining high productivity and selectivity. This was exemplified on a commercial biosourced fatty acid methyl esters mixture, using minimal purification of the substrate, on a 50 g scale. We propose that this improved catalytic behavior is due to the sole presence of more stable alkylidene intermediates, as the notoriously unstable ruthenium methylidene species are not formed using an internal functionalized olefin.
- Vignon, Paul,Vancompernolle, Tom,Couturier, Jean-Luc,Dubois, Jean-Luc,Mortreux, André,Gauvin, Régis M.
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p. 1143 - 1146
(2015/04/22)
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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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- Ionic-tagged catalytic systems applied to the ethenolysis of methyl oleate
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A novel high selective ionophilic Hoveyda-type complex for the methyl oleate ethenolysis was prepared from Grubbs first generation catalyst. Ethenolysis under classical biphasic systems in ionic liquids showed to be mass-transference limited. This drawback was successfully solved by the catalyst dispersion on high specific surface area inorganic supports through a thin layer of ionic liquids (ILs). The supported ionic liquid phase (SILP) catalyst properties were patterned by the support type, IL cation and support/IL mass ratio. The SILP prepared with the IL 1-isopentyl-3-methylimidazole hexafluorophosphate and silica showed a turnover number higher (up to 2350) than that of biphasic systems (up to 1045).
- Aydos, Guilherme L.P.,Leal, Bárbara C.,Perez-Lopez, Oscar W.,Dupont, Jairton
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- Synthesis of α,β-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs' catalysts
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A series of α,β-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs' catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (≥90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids.
- Rountree, Sandra M.,Taylor, Sarah F.R.,Hardacre, Christopher,Lagunas, M. Cristina,Davey, Paul N.
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- USE OF SOLUBLE METAL SALTS IN METATHESIS REACTIONS
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The present invention describes the use of soluble metal salts to reduce impurities and metathesis catalysts poisons from olefinic feedstocks to improve olefin metathesis efficiency. The soluble metal salts were added to the olefinic feedstocks to prevent peroxides and catalyst poisons from inhibiting the metathesis catalyst. The soluble metal salts remain in the olefinic feedstocks and are used without further purification in the olefin metathesis reactions. The key to this invention is the soluble metal salt compounds do not inhibit the olefin metathesis catalysts but unexpectedly increase olefin metathesis catalyst efficiency while prior art heterogeneous metal complexes sequester the olefin metathesis catalyst, preventing olefin metathesis.
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Paragraph 000182; 000183
(2014/10/04)
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- Triacylglycerol self-metathesis over highly chemoselective methyltrioxorhenium supported on ZnCl2-promoted mesoporous alumina
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Since triolein is the main constituent of most oils such as olive and high oleic sunflower oils, self-metathesis of this triacylglycerol at mild reaction conditions was investigated via a heterogeneous approach, in the presence of ZnCl2-modified mesoporous alumina supported methyltrioxorhenium (MTO) as a catalyst. Both intra and intermolecular metathesis reactions were observed. While, 9-octadecene, dimers and trimers of the triacylglycerol were isolated, intermolecular cyclization metathesis products were also obtained. The MTO-based catalyst was found to be highly chemoselective affording only desired metathesis product formation. In contrast, more than 50% of triolein was converted to undesired solid product in the presence of the homogeneous Grubbs 2nd generation catalyst. Triolein metathesis products were effectively separated by chromatographic techniques and identified using mass spectrometric and NMR analyses. The reported results show that 3%MTO/ZnCl2-Al 2O3-meso is an efficient and selective heterogeneous catalyst for bulky functionalized olefins metathesis such as triacylglycerols and edible oils, avoiding the use of costly homogeneous catalysts, or the use other rhenium-based catalysts with toxic promoters such as R4Sn.
- Pillai, Subha Kumaraswamy,Abidli, Abdelnasser,Belkacemi, Khaled
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p. 121 - 133
(2014/05/20)
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- CLEANSING COMPOSITION FOR SKIN OR HAIR
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Provided is a cleansing composition for skin or hair capable of bringing about a good rinse feel and, in regard to hair, imparting softness to hair during rinsing and after towel drying, and further, imparting a sufficient moist feeling also to skin after application. A cleansing composition for skin or hair, comprising the following (A) and (B): (A) an internal olefin sulfonate having 12 or more and 24 or less carbon atoms; and(B) a cationic polymer or an amphoteric polymer.
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Paragraph 0179
(2014/04/03)
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- INTERNAL OLEFINIC SULFONATE COMPOSITION AND CLEANSING COMPOSITION CONTAINING THE SAME
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Provided is an internal olefin sulfonate composition which is capable of exerting good foamability at the same time with foam quality, foam dissipation property, and less irritation to the skin at high levels, and a cleansing composition containing the same. The internal olefin sulfonate composition of the present invention comprises (A) an internal olefin sulfonate having 16 carbon atoms and (B) an internal olefin sulfonate having 18 carbon atoms, wherein a mass content ratio (A/B) of component (A) to component (B) is from 75/25 to 90/10.
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Paragraph 0056
(2014/04/03)
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- CLEANSING COMPOSITION FOR SKIN OR HAIR
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There is provided a cleansing composition for skin or hair which can provide a good rinse feel, enhance combing property of the hair during rinsing to impart softness to the hair, and impart a refreshing feeling upon application to the skin without causing stickiness. A cleansing composition for skin or hair contains the following (A) and (B): (A) an internal olefin sulfonate having 12 or more and 24 or less carbon atoms; and(B) an anionic surfactant having no sulfate group except the internal olefin sulfonate (A) and an anionic surfactant having two or more carboxylic acid groups.
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Paragraph 0125
(2014/04/03)
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- AQUEOUS HAIR CLEANSING AGENT
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The invention relates to an aqueous hair cleansing agent comprising the following components (A), (B), (C), and water and having a pH of 2 to 5 at 25° C. when diluted 20-fold by mass with water: (A) an internal olefin sulfonate, (B) an organic solvent selected from the group consisting of the following (B1) to (B5): (B1) an aromatic alcohol,(B2) a polypropylene glycol,(B3) a N-alkyl pyrrolidone,(B4) an alkylene carbonate,(B5) a lactone or a cyclic ketone, and (C) an organic carboxylic acid selected from the group consisting of a hydroxymonocarboxylic acid and dicarboxylic acid.
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Paragraph 0119; 0120; 0121
(2014/04/03)
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- CLEANSING COMPOSITION FOR SKIN OR HAIR
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The present invention provides a cleansing composition for skin or hair which can provide a good rinse feel, give good combability and softness from rinsing to drying when the cleansing composition is applied to hair, and give good moist feeling to skin when the cleansing composition is applied to skin. The cleansing composition for skin or hair is a cleansing composition comprising an internal olefin sulfonate (A) having 12 or more and 24 or less carbon atoms.
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Paragraph 0155
(2014/04/03)
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- SKIN CLEANSING COMPOSITION
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The present invention provides a skin cleansing composition comprising the following components (A), (B), and (C): (A) (a1) an alkenylsulfonic acid having 12 to 22 carbon atoms or its salt, (a2) an alkylsulfonic acid having 12 to 22 carbon atoms or its salt, or a mixture of them,(B) an alkyl ether carboxylic acid represented by the following formula (1) or its salt: [in-line-formulae]R1—O—(CH2CH2O)n—CH2—COOX??(1)[/in-line-formulae] wherein R1 represents an alkyl group having 4 to 22 carbon atoms, n denotes a number from 0 to 20, X represents a hydrogen atom, an alkali metal, an alkali earth metal, ammonium, or organic ammonium, and n denotes a number of 0.5 or more and less than 4 on average; and (C) water.
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Paragraph 0084
(2014/04/03)
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- CLEANSING COMPOSITION FOR SKIN OR HAIR
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Provided is a cleansing composition for skin or hair which can provide a good rinse feel and can enhance the combing property of hair after rinsing and the manageability after drying in application to the hair and can impart a sufficient moist feeling to skin in application to the skin. A cleansing composition for skin or hair, comprising the following (A) and (B): (A) an internal olefin sulfonate having 12 or more and 24 or less carbon atoms; and(B) an oil solution having a solubility of from 0 to 1 g in 100 g of water at 20° C.
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Paragraph 0135
(2014/04/03)
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- Metathesis of renewable raw materials - Influence of ligands in the indenylidene type catalysts on self-metathesis of methyl oleate and cross-metathesis of methyl oleate with (Z)-2-butene-1,4-diol diacetate
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The influence of different N-heterocyclic carbene (NHC) and other neutral ligands on the outcome of the cross-metathesis reaction of methyl oleate with (Z)-2-butene-1,4-diol diacetate and self-metathesis of methyl oleate was studied for a series of indenylidene type Ru catalysts.
- Kajetanowicz, Anna,Sytniczuk, Adrian,Grela, Karol
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supporting information
p. 1579 - 1585
(2014/03/21)
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- Hoveyda-Grubbs first generation type catalyst immobilized on mesoporous molecular sieves
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New heterogeneous, reusable catalysts for olefin metathesis have been prepared by immobilizing the Hoveyda-Grubbs first generation type alkylidene (commercially available as the Zhan catalyst-1C) on siliceous mesoporous molecular sieves with different pore sizes and architectures (SBA-15, SBA-16, MCM-41 and MCM-48) having the surface modified with molecules bearing dicyclohexylphosphine (PCy2) end groups. Resulting novel heterogenized catalysts proved high activity in ring-closing metathesis (RCM) of 1,7-octadiene, diethyl diallylmalonate, tert-butyl N,N-diallylcarbamate and N,N-diallyl-2,2,2-trifluoroacetamide, in homometathesis of 1-decene, 5-hexenyl acetate and methyl 10-undecenoate, and in cross-metathesis (CM) of allylbenzene with cis-1,4-diacetoxy-2-butene. The catalytic activity decreased with decreasing pore size of supports in the order SBA-15 > MCM-48 > SBA-16 and MCM-41. Filtration test suggested that the solid catalyst was responsible for the catalytic activity. Catalysts were easily separated from the reaction mixtures and products of low levels of Ru concentration were obtained.
- Pastva, Jakub,?ejka, Ji?í,?ilková, Nadě?da,Mestek, Oto,Rangus, Mojca,Balcar, Hynek
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p. 184 - 192
(2013/08/23)
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- Hydroxy- and aldehyde functional compounds
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The invention relates to a method for producing a mixture containing hydroxy- and aldehyde functional compounds by a cross-metathesis reaction of at least one at least monounsaturated fatty acid or at least one at least monounsaturated fatty acid derivative with an olefinic compound having at least one hydroxy group and at least one C—C double bond, in the presence of a metathesis catalyst at a maximum temperature of 180° C.
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Page/Page column 14; 15
(2013/06/26)
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- Ruthenium-catalyzed olefin metathesis accelerated by the steric effect of the backbone substituent in cyclic (alkyl)(amino) carbenes
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Three ruthenium complexes bearing backbone-monosubstituted CAACs were prepared and displayed dramatic improvement in catalytic efficiency not only in RCM reaction but also in the ethenolysis of methyl oleate, compared to those bearing backbone-disubstitut
- Zhang, Jun,Song, Shangfei,Wang, Xiao,Jiao, Jiajun,Shi, Min
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p. 9491 - 9493
(2013/10/01)
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- Self-metathesis of methyl oleate on silica-supported Hoveyda-Grubbs catalysts
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The self-metathesis of methyl oleate (MO) to yield 9-octadecene and 9-octadecene-1,18-dioate (9-OD) was studied in liquid-phase on silica-supported Hoveyda-Grubbs complex catalysts (HG/SiO2) containing 0.43-6.0 wt.% HG. The reaction was carried out in a batch reactor at 303-343 K and 101.3 kPa, using cyclohexane as solvent. HG/SiO2 catalysts were active and highly selective for the MO metathesis reaction; equilibrium values of MO conversion and 9-OD yield were reached in 80 min. No catalyst leaching took place in cyclohexane. Catalysts containing HG > 0.87 wt.% showed no significant deactivation after two consecutive catalytic tests.
- Zelin, Juan,Trasarti, Andrés F.,Apesteguía, Carlos R.
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