Transformation of Methyl Linoleate to its Conjugated Derivatives with Simple Pd(OAc)<sub>2</sub>/Lewis Acid Catalyst

Senan, Ahmed M.; Zhang, Sicheng; Qin, Shuhao; Chen, Zhuqi; Yin, Guochuan

doi:10.1007/s11746-017-3052-5

Cited by 3 publications

(4 citation statements)

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“…It has been reported for Brookhart type nickel complexes, that terminal dienes completely deactivate the polymerization catalyst for ethylene and α ‐olefin polymerization . In the isomerization of MeL by a Pd(II)/Lewis acid system a selective formation of the four conjugated isomers was observed with no terminal isomers being mentioned . Therefore, we assume that the isomerization catalyst is deactivated by the polyunsaturated substrate and cannot deliver the terminal isomer of the unsaturated substrate suitable for incorporation into the polymer chain with the same efficiency.…”

Section: Resultsmentioning

confidence: 99%

One‐Pot Catalytic Copolymerization of Unsaturated Plant Oils or Fatty Acid Methyl Esters with Ethylene

Fleckhaus

Fokou

Klaassen

et al. 2018

Euro J Lipid Sci & Tech

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Until now natural fatty acid esters with their internal CC‐bonds cannot be used as substrates for catalytic polymerization reactions. It is always necessary to convert them to terminal unsaturated fatty acid esters first. Therefore, we now developed a two‐catalyst system consisting of an isomerization catalyst and a Brookhart polymerization catalyst. With this system of isomerizing copolymerization (IsoCoP) it is possible to copolymerize high oleic plant oils or fatty acid methyl esters with ethylene in a one‐pot reaction. The resulting polymers have molecular weights above 30 kDa and can contain more than 20 weight percent plant oils. The copolymers of fatty acid methyl esters are soluble in organic solvents. The predominant part of the copolymers from plant oils is usually soluble. The insoluble fraction is soluble after hydrolysis indicating a rare cross‐linking of polyolefin chains by triglycerol units. The catalytic system is effective yielding polymers with a productivity of up to 100 kg polymer per mole catalyst and pretty robust. Plants oils need to be purified only by a simple filtration over alumina before copolymerization. Practical Application: The possibility to copolymerize plant oils with ethylene leads to a new class of polymers and may enhance the usage of plant oils for plastics greatly. The new polymers might be used, e.g., for tackifiers or primers. High oleic plant oils as well as unsaturated fatty acid methyl esters can be directly copolymerized with ethylene by a combination of an isomerization catalyst with a Brookhart polymerization catalyst.

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Section: Resultsmentioning

confidence: 99%

One‐Pot Catalytic Copolymerization of Unsaturated Plant Oils or Fatty Acid Methyl Esters with Ethylene

Fleckhaus

Fokou

Klaassen

et al. 2018

Euro J Lipid Sci & Tech

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“…Additional file 1 : Figure S3 shows the mixture of products of methyl linoleate hydroxylation 95.3 ± 3.2% yield and, it is worth mentioning that the products mixture of hydroxy-methyl linoleate (CHML) which was further evidenced by MALDI-ToF mass spectrometry. Reading the results of conjugated hydroxy methyl linoleate CHML from Additional file 1 : Figure S7, almost no unreacted substrate ML could be detected, and a new mass peaks with an m/z value of 294.39 [(9 E , 11 E )-CML, confirmed by 1 H NMR analysis] [ 13 ]. M 330.32, 338.33, and 354.28 were observed, which matches the calculated molecular mass of CHML isomers (294.39 Da for [M] + ).…”

Section: Resultsmentioning

confidence: 99%

“…In this catalytic system of internal double bond hydroxylation, it contributed to oxidative/reductive-hydroxylation following [ 1 , 3 ]-hydrogen shift mechanism, and may not be realized (S 2 O 8 ) 2− moieties to initialize the [9,11]-hydrogen shift mechanism (Scheme 2 b), Fe(II)-species coordinated to C=C bond either from the 9-position or the 12-position, the F(III)/S 2 O 8 2− species next activates the methylene protons which have the chemical shift around 300 nm [ 13 , 38 ].…”

Section: Resultsmentioning

confidence: 99%

“…However, there have been continued shifts from food to industrial consumption [ 7 – 12 ]. In our previous studies, we reported that the transformation process of fatty acid is based on the reaction of isomerization and/or oxidation to corresponding keto-fatty acids/esters isomers with Pd(II)/Lewis acid catalyst [ 13 , 14 ]. However, the hydroxy fatty acids containing one or more than one hydroxyl (–OH) groups are remarkable owing to their essential chemical and physical properties.…”

Section: Introductionmentioning

confidence: 99%

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Efficient and selective catalytic hydroxylation of unsaturated plant oils: a novel method for producing anti-pathogens

et al. 2021

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With the increasing demand for antimicrobial agents and the spread of antibiotic resistance in pathogens, the exploitation of plant oils to partly replace antibiotic emerges as an important source of fine chemicals, functional food utility and pharmaceutical industries. This work introduces a novel catalytic method of plant oils hydroxylation by Fe(III) citrate monohydrate (Fe3+-cit.)/Na2S2O8 catalyst. Methyl (9Z,12Z)-octadecadienoate (ML) was selected as an example of vegetable oils hydroxylation to its hydroxy-conjugated derivatives (CHML) in the presence of a new complex of Fe(II)-species. Methyl 9,12-di-hydroxyoctadecanoate 1, methyl-9-hydroxyoctadecanoate 2 and methyl (10E,12E)-octadecanoate 3 mixtures is produced under optimized condition with oxygen balloon. The specific hydroxylation activity was lower in the case of using Na2S2O8 alone as a catalyst. A chemical reaction has shown the main process converted of plantoils hydroxylation and (+ 16 Da) of OH- attached at the methyl linoleate (ML-OH). HPLC and MALDI-ToF-mass spectrometry were employed for determining the obtained products. It was found that adding oxidizing agents (Na2S2O8) to Fe3+ in the MeCN mixture with H2O would generate the new complex of Fe(II)-species, which improves the C-H activation. Hence, the present study demonstrated a new functional method for better usage of vegetable oils.Producing conjugated hydroxy-fatty acids/esters with better antipathogenic properties. CHML used in food industry, It has a potential pathway to food safety and packaging process with good advantages, fundamental to microbial resistance. Lastly, our findings showed that biological monitoring of CHML-minimum inhibitory concentration (MIC) inhibited growth of various gram-positive and gram-negative bacteria in vitro study. The produced CHML profiles were comparable to the corresponding to previousstudies and showed improved the inhibition efficiency over the respective kanamycin derivatives.

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Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies

Xue

Zhang

et al. 2019

J. Org. Chem.

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Exploring new catalysts for efficient organic synthesis is among the most attractive topics in chemistry. Here, using Ni(OAc)2/LA as catalyst (LA: Lewis acid), a novel catalyst strategy was developed for oxidative coupling of thiols and phosphonates to phosphorothioates with oxygen oxidant. The present study discloses that when Ni(OAc)2 alone was employed as the catalyst, the reaction proceeded very sluggishly with low yield, whereas adding non-redox-active metal ions such as Y3+ to Ni(OAc)2 dramatically promoted its catalytic efficiency. The promotional effect is highly Lewis acidity dependent on the added Lewis acid, and generally, a stronger Lewis acid provided a better promotional effect. The stopped-flow kinetics confirmed that adding Y(OTf)3 can obviously accelerate the activation of thiols by Ni(II) and next accelerate its reaction with phosphonate to generate the phosphorothioate product. ESI-MS characterizations of the catalyst disclosed the formation of the heterobimetallic Ni(II)/Y(III) species in the catalyst solution. Additionally, this Ni(II)/LA catalyst can be applied in the synthesis of a series of phosphorothioate compounds including several commercial bioactive compounds. This catalyst strategy has clearly supported that Lewis acid can significantly improve the catalytic efficiency of these traditional metal ions in organic synthesis, thus opening up new opportunities in their catalyst design.

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Transformation of Methyl Linoleate to its Conjugated Derivatives with Simple Pd(OAc)₂/Lewis Acid Catalyst

Cited by 3 publications

References 46 publications

One‐Pot Catalytic Copolymerization of Unsaturated Plant Oils or Fatty Acid Methyl Esters with Ethylene

One‐Pot Catalytic Copolymerization of Unsaturated Plant Oils or Fatty Acid Methyl Esters with Ethylene

Efficient and selective catalytic hydroxylation of unsaturated plant oils: a novel method for producing anti-pathogens

Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies

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Transformation of Methyl Linoleate to its Conjugated Derivatives with Simple Pd(OAc)2/Lewis Acid Catalyst

Cited by 3 publications

References 46 publications

One‐Pot Catalytic Copolymerization of Unsaturated Plant Oils or Fatty Acid Methyl Esters with Ethylene

One‐Pot Catalytic Copolymerization of Unsaturated Plant Oils or Fatty Acid Methyl Esters with Ethylene

Efficient and selective catalytic hydroxylation of unsaturated plant oils: a novel method for producing anti-pathogens

Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies

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Transformation of Methyl Linoleate to its Conjugated Derivatives with Simple Pd(OAc)₂/Lewis Acid Catalyst