- Phosphonium-based ionic liquids: Economic and efficient catalysts for the solvent-free cycloaddition of CO2 to epoxidized soybean vegetable oil to obtain potential bio-based polymers precursors
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A series of phosphonium-based ionic liquids have been prepared in one step in a simple way from inexpensive feedstocks. The prepared ionic liquids have been successfully tested as catalysts in the solvent-free cycloaddition reaction of CO2 to an epoxidized soybean oil to obtain carbonated soybean oil that can be potentially employed as bio-monomer in the synthesis for bio-based polymers. The catalytic performance of these ionic liquids was compared to the widely used and benchmark catalyst in CO2 cycloaddition to epoxides reaction, namely tetrabutylammonium bromide at different reaction conditions. The influence of some reaction parameters such as temperature, CO2 pressure, reaction time and catalyst amount was studied. It has been found that the solubility of the prepared ionic liquids in the reaction media (epoxidized soybean oil) is a key factor that limits the catalytic performance of some of the synthesized ionic liquids. All prepared ionic liquids have shown higher thermal stability that the benchmark catalyst and three of them have shown superior catalytic performance. The best results in terms of conversion and selectivity have been obtained with dodecyltriphenylphosphonium bromide (5) achieving almost full conversion (99.8%) and excellent selectivity (84.0%) after 5 h reaction at 160 oC and 40 bar of CO2. Outstanding results compared to those reported in the literature with similar catalysts in the solvent-free CO2 cycloaddtion to an epoxidized soybean oil to obtain the corresponding carbonated oil have been achieved. Considering the facile synthesis of catalyst 5, the large availability and non-expensive of the feedstocks and its catalytic performance it can be considered a valuable and green alternative for CO2 fixation to epoxidized vegetable oil.
- Centeno-Pedrazo, A.,Freixa, Z.,Garcia-Suarez, E. J.,Perez-Arce, J.,Prieto-Fernandez, S.
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- Synthesis, Surface Activity, and Biological Activities of Phosphonium and Metronidazole Salts
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A series of phosphonium amphiphilic compounds was synthesized. Cationic parts of molecules contain triphenylphosphonium moieties. Lipophilic parts of compounds are represented by straight alkyl chain or the alkyl chains which are ornamented by benzyl or metronidazole. The physicochemical properties of phosphonium amphiphilic compounds were investigated by the measurements of surface tension and conductivity. The critical micelle concentration (cmc), the surface tension value at the cmc (γcmc), the surface area at the surface saturation per head group (Acmc) were determined. The lowest cmc value was determined for phosphonium salts with straight dodecyl alkyl chain. Its value was 1.5 × 10?3 mol dm?3. Surface tension at the cmc decreases with the addition of bulky moieties (benzyl, radical from metronidazol) at the end of alkyl chains. Biological activities of compounds were studied on human erythrocytes and strains of Acanthamoeba lugdunensis and Acanthamoeba quina. Dodecyltriphenylphosphonium bromide showed the highest activity against Acanthamoeba. To the best of our knowledge, it is the first compound of the group of phosphonium amphiphiles, which exhibited high activity against Acanthamoeba. The determined structure–activity relationship indicated nonspecific trophocidal and hemolytic activity that depends on physicochemical properties of the studied compounds.
- Luká?, Milo?,Pisár?ik, Martin,Garajová, Mária,Mrva, Martin,Du?eková, Aneta,Vrták, Andrej,Horáková, Renáta,Horváth, Branislav,Devínsky, Ferdinand
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p. 1025 - 1032
(2020/07/27)
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- Ionic liquid functionalized acid orange for organic solvent and preparation method thereof
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The invention relates to ionic liquid functionalized acid orange for an organic solvent and a preparation method thereof. The preparation method for the ionic liquid functionalized acid orange for theorganic solvent provided by the invention comprises the following steps: first, first, reacting triphenylphosphine and slightly excessive bromoalkane, and washing and purifying by using ethyl acetateto prepare alkyl triphenyl bromide; performing neutral reaction on acidified acid orange and silver carbonate, and washing and drying to prepare acid orange silver salt; then, respectively performingion exchange on the prepared acid orange silver salt and different alkyl triphenyl bromide to prepare a series of novel ionic liquid functionalized acid orange which can be dissolved in a plurality of organic solvents. The synthesis reaction conditions are mild and the post-treatment is simple. The type of ionic liquid functionalized acid orange has good solubility in the plurality of the organicsolvents, and is an azo dye and an acid base indicator which can be used for the organic solvent.
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Paragraph 0051-0054
(2019/08/20)
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- Identification and synthesis of the male-produced sex pheromone of the soldier beetle chauliognathus fallax (Coleoptera: Cantharidae)
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Chauliognathus fallax Germar 1824 (Coleoptera: Cantharidae) occurs in North and South America and Australia. Gas chromatographic (GC) analyses of volatiles released by adults showed the presence of a male specific compound. GC coupled with electroantennographic detection (GC-EAD) showed that this compound is exclusively bioactive on female antennae, suggesting it to be a sex pheromone. GC coupled with mass spectrometry (GC-MS) and Fourier transform infrared spectroscopy (GC-FTIR), as well as dimethyl disulfide (DMDS) derivatization and hydrogenation, suggested the target compound to be (Z)-tricos-11-ene. Unambiguous structural proof was achieved by independent synthesis, whereas the biological significance of the compound as a sex pheromone was confirmed by field bioassays.
- Vidal, Diogo M.,Fávaro, Carla F.,Guimar?es, Matheus M.,Zarbin, Paulo H. G.
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p. 1506 - 1511
(2016/08/10)
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- Synthesis and inhibitory activities against colon cancer cell growth and proteasome of alkylresorcinols
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We have identified alkylresorcinols (ARs) as the major active components in wheat bran against human colon cancer cell growth (HCT-116 and HT-29) using a bioassay-guided approach. To further study the structure-activity relationships, 15 ARs and their intermediates (1-15) were synthesized expediently by the modified Wittig reaction in aqueous media, and six 5-alkylpyrogallols and their analogues (16-21) were prepared by the general Grignard reaction. The synthetic AR analogues were evaluated for activities against the growth of human colon cancer cells HCT-116 and HT-29 and the chymotrypsin-like activity of the human 20S proteasome. Our results found that (1) AR C13:0 and C15:0 (13 and 14) had the greatest inhibitory effects in human colon cancer cells HCT-116 and HT-29, while decreasing or increasing the side chain lengths diminished the activities; (2) two free meta-hydroxyl groups at C-1 and C-3 on the aromatic ring of the AR analogues greatly contributed to their antitumor activity; (3) the introduction of a third hydroxyl group at C-2 (20 and 21) into the aromatic ring of the AR analogues yielded no significant enhancement in activity against HCT-116 cells and decimated the effects against HT-29 cells, but dramatically increased the activity against the chymotrypsin-like activity of the human 20S proteasome; and (4) AR C11:0 (12) was found to have the greatest effect in a series of AR C9:0-C17:0 against the chymotrypsin-like activity of the human 20S proteasome.
- Zhu, Yingdong,Soroka, Dominique N.,Sang, Shengmin
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p. 8624 - 8631
(2012/11/13)
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- Design, synthesis, and in vitro testing of α-methylacyl-CoA racemase inhibitors
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The enzyme α-methylacyl-CoA racemase (AMACR) is overexpressed in prostate, colon, and other cancers and has been partially validated as a potential therapeutic target by siRNA knockdown of the AMACR gene. Analogs of the natural substrate branched chain α-methylacyl coenzyme A esters, possessing one or more β-fluorine atoms, have been synthesized using Wittig, conjugate addition, and asymmetric aldol reactions and found to be reversible competitive inhibitors. Each diastereomer of the previously reported inhibitor ibuprofenoyl-CoA was also tested. The compounds had Ki values of 0.9-20 μM and are the most potent inhibitors yet known. The presence of β-fluorine on the α-methyl group or the acyl chain results in a significant lowering of the Ki value compared with nonfluorinated analogs, and this is attributed to a lowering of the pK a of the α-proton, facilitating enolization and binding. Several of the CoA ester inhibitors were formed by incubating the free carboxylic acid precursors with cell free extracts and CoA. α- Trifluoromethyltetradecanoic acid, the precursor to the most potent inhibitor, was shown to inhibit growth of cancer cell lines PC3, CWR22 Rv1, and Du145 in a dose-dependent manner and could be related to the expression level of AMACR.
- Carnell, Andrew J.,Hale, Ian,Denis, Simone,Wanders, Ronald J. A.,Isaacs, William B.,Wilson, Brice A.,Ferdinandusse, Sacha
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p. 2700 - 2707
(2008/02/07)
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- VO(acac)2-catalyzed oxidative coupling reactions of phosphonium salts
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A novel eco-safer protocol for the preparation of symmetric or unsymmetric olefins directly from phosphonium salts under oxygen atmosphere in the presence of VO(acac)2 (1.0 mol%) was developed.
- Shi, Min,Xu, Bo
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p. 294 - 297
(2007/10/03)
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- Amides of some biologically active acids with(2S,3S)-2-amino-3-O-acetyl-1-O-(2,3,4,6-tetra-O-acetyl-β-D- glucopyranosyl)octadecane-1,3-diol, a model of natural lysocerebrosides
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(2S,3S)-3-O-Acetyl-2-amino-1-O-(2,3,4,6-tetra-O-acetyl-β-D- glucopyranosyl)octadecane-1,3-diol was synthesized starting from (4S,5R)-4-acetoxy-5-hydroxy-6-(2,3,4,6-tetra-O-acetyl-β-D- glucopyranosyloxy)hex-2-enal and used as a chiral amino component for building the amides (glucosylceramides) of β-glycyrrhizic acid and (5Z,13E)-16-(3-chlorophenoxy)-9α,11α,15α-trihydroxy-17,18,19, 20-tetranor-5,13-prostadienoic acid (chloprostenol).
- Tolstikov,Tolstikova,Khlebnikova,Tolstikov
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p. 199 - 204
(2007/10/03)
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- Asymmetric synthesis of solenopsins A, B and C
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Solenopsins A, B and C have been synthesized in enantiomerically pure forms from the corresponding anti-1,5-diols which have been obtained from glutaric anhydride by an asymmetric synthesis induced by chiral sulfoxides.
- Solladie, Guy,Huser, Nathalie
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p. 153 - 156
(2007/10/02)
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- A CONVENIENT SYNTHESIS OF LONG-CHAIN 3-n-ALKYLTHIOPHENES AND 3-n-ALKYLFURANS
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The syntheses of 3-substituted long-chain furans and thiophenes by a Wittig reaction are described. 1H-NMR and UV data of these compounds are reported.
- Shabana, R.,Amer, Adel,Mark, H. B.,Zimmer, Hans
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p. 299 - 306
(2007/10/02)
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- Preparation of Crown Compounds Containing Allyloxymethyl or Butenyl Groups for Attachment to Silica Gel or Containing Long Chain Lipophilic Groups for Use in Liquid Membrane Systems
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Several new macrocyclic polyether ligands have been prepared for use in the separation of metal ions from aqueous solutions.Four of the crown ethers reported contain 1,2,4-triazole or 4-pyridone protonionizable subcyclic units and lipophilic groups.The remaining crown ethers are not proton-ionizable but contain alkene groups and were prepared for attachment to silica gel.The crowns were prepared by reacting the appropriate glycols with the appropriate ditosylates or dichloride in the case of the 1,2,4-triazole subcyclic unit.The crowns with proton-ionizable and lipophilic substituents were tested in liquid membrane transport systems and some of the crowns with allyloxymethyl or butenyl substituents were attached to silica gel.The log K values for the interaction of these silica gel-bound macrocycles with certain metal ions were nearly the same (+/-10percent) as those for the association of the unbound macrocycles with the same metal ions.
- McDaniel, Christopher W.,Bradshaw, Jerald S.,Krakowiak, Krzysztof E.,Izatt, Reed M.,Savage, Paul B.,et al.
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p. 413 - 419
(2007/10/02)
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- OZONOLYSIS OF ALKENES AND INVESTIGATION OF THE REACTIONS OF POLYFUNCTIONAL COMPOUNDS. XXIII. A NEW SYNTHESIS OF DIASTEREOMERIC (+/-)-13,17,21-TRIMETHYLTRI-, (+/-)-13,17,21-TRIMETHYLPENTA-, AND (+/-)-13,17,21-TRIMETHYLHEPTATRIACONTANES
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A three-stage synthesis of the hydrocarbons 13,17,21-trimethyltri-, 13,17,21-trimethylpenta-, and 13,17,21-trimethylheptatriacontanes, isolated from the eggs of the tobacco worm (Manduc Sexta L.), was realized from (E,E)-4,8-dimethyl-1,12-dioxo-4,8-tridecadiene.
- Odinokov, V. N.,Akhmetova, V. R.,Tolstikov, G. A.,Moiseenkov, A. M.,Semenovskii, A. V.
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p. 443 - 447
(2007/10/02)
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