Thiol–yne reaction of alkyne-derivatized fatty acids: biobased polyols and cytocompatibility of derived polyurethanes

González-Paz, Rodolfo J.; Lligadas, Gerard; Ronda, Juan C.; Galià, Marina; Cádiz, Virgínia

doi:10.1039/c2py20273e

Cited by 37 publications

(34 citation statements)

References 32 publications

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“…Although it has reported that α-selectivity is improved by the increasing temperature, chemical yields of this reaction might be decrease probably due to deprotection of PMB group in the presence of TfOH. 25) Regarding a o-carborane unit, reaction of decaborane (B 10 H 14 ) with methyl 10-undecynoate 20, 26) which was prepared from 10-undecynoic acid 19, in the presence of 1-butyl-3-methyl imidazolium chloride 27) (bmimCl) afforded 21 (Chart 6). Removal of the methyl esters of 21 by hydrolysis with HCl provided the carborane-containing acid 22.…”

Section: Resultsmentioning

confidence: 99%

“…The filtrate was concentrated under reduced pressure and the remaining residue was purified by silica gel column chromatography (hexanes-AcOEt=10 : 1) and HPLC (Senshu Pak PEGASIL-B 20ϕ×250 nm, MeOH/H 2 O (0.1% TFA)=90/10, flaw rate 10 mL/min) to give α-18 (215 mg, 63%) and β-18 (47.8 mg, 14%) as colorless syrups. 26) (245 mg, 1.25 mmol, prepared from 19 as indicated in Chart 6 in this work) and 1-butyl-3-methylimidazolium chloride (bmimCl) (59.4 mg, 0.34 mmol) were added. The resulting solution was stirred at reflux condition for 3 h. After evaporation, the resulting residue was purified by silica gel column chromatography (hexanes-AcOEt=10 : 1) to afford 21 as a colorless amorphous (65.8 mg, 21% yield Sodium 1-O-(2,3,4-Tri-O-benzyl-6-sulfo-α-D-quinovopyranosyl)-3-O-p-methoxybenzyl-propane-1,3-diol (23) Oxone ® was added to a suspension of α-18 (161 mg, 0.23 mmol) and sodium acetate (390 mg, 0.48 mmol) in acetic acid (3.4 mL) and the resulting mixture was stirred at room temperature for 24 h. The mixture was then diluted with AcOEt and washed with saturated NaHCO 3 aq., and brine, dried over Na 2 SO 4 , filtered and concentrated under reduced pressure.…”

Section: Methodsmentioning

confidence: 99%

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Concise and Versatile Synthesis of Sulfoquinovosyl Acyl Glycerol Derivatives for Biological Applications

Tanaka

Sawamoto

Aoki

2017

CHEMICAL & PHARMACEUTICAL BULLETIN

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Sulfoquinovosyl acylpropanediol (SQAP), a chemically modified analogue of sulfoquinovosyl acylglycerol (SQAG) that occurs in sea algae, has been reported to show a variety of biological activities, including accumulation in tumor cells and the inhibition of tumor cell growth. We report herein on a new concise and versatile synthesis of SQAP itself and derivatives bearing iodoaryl groups and boronclusters. This method should be useful for the design and synthesis of SQAG/SQAP derivatives for diagnosis and the treatment of cancer and related diseases.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Concise and Versatile Synthesis of Sulfoquinovosyl Acyl Glycerol Derivatives for Biological Applications

Tanaka

Sawamoto

Aoki

2017

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…In a significant contribution, the same group demonstrated the use of thiol-yne reaction for the synthesis of polyols and in particular diols for PUs (González-Paz et al, 2012). These diols were synthesized in two steps, the first being an alkyne derivatization of fatty acids by bromation and dehydrobromation of the double bond and the second being a thiol-yne addition with 2-mercaptoethanol D508, page 7 of 10 Dossier L. Maisonneuve et al: OCL 2016, 23(5) D508 Fig.…”

Section: Diols Containing Thio-ether Linkagesmentioning

confidence: 99%

Vegetable oils: a source of polyols for polyurethane materials

Maisonneuve

Chollet

Grau

et al. 2016

OCL

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-This manuscript is dedicated to the literature on vegetable oil-based polyurethanes via the isocyanate/alcohol route. A lot of efforts have been made to replace petroleum-based resources. Among renewable resources, vegetable oils present various advantages going from their availability to the large range of possible chemical modifications they permit. Firstly, the vegetable oil chemical composition and the main commercially available vegetable oil precursors are exposed. Concerning vegetable oils-based polyurethanes, research groups first focused on cross-linked systems directly from triglycerides then on thermoplastic ones from fatty acids or fatty acid methyl esters. This manuscript focuses on thermoplastic PUs and underlines the literature about the introduction of hydroxyl groups and isocyanate functions onto triglycerides and fatty acid derivatives. Besides, in a view to the isocyanate/alcohol approach, vegetable oil-based thermoplastic PUs and corresponding diols and diisocyanates are described in details.Keywords: Polyurethanes / bio-based / vegetable oils / fatty acid / diol / di-isocyanate Résumé -Huiles végétales : une source de polyols pour les matériaux en polyuréthane. Cet article fait un état de l'art de la synthèse de polyuréthanes issus des huiles végétales par la voie alcool/isocyanate. De nombreux efforts ont été réalisés pour remplacer les ressources pétrolières. Parmi les ressources renouvelables, les huiles végétales représentent de nombreux avantages liés à leur disponibilité et aux nombreuses possibilités de modification chimique qu'elles offrent. Dans cet article, les principales huiles, leur composition, et les principaux précurseurs commercialisés issus des huiles végétales sont d'abord présentés. Concernant les PUs issus des huiles végétales, les travaux portent d'une part sur des réseaux tridimensionnels directement à partir des triglycérides et, d'autre part, sur des PUs thermoplastiques à partir des acides gras et de leurs dérivés. Les méthodes d'introduction de fonctions alcool et isocyanate sur les triglycérides et acides gras sont présentées puis la synthèse de PUs thermoplastiques par la voie alcool/isocyanate est discutée de façon détaillée. Mots clés :Polyuréthanes / bio-sourcé / huiles végétales / acide gras / diol / di-isocyanate.

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“…15 In order to enhance the alcohol density in polyol structure without dangling chain, Cadiz et al reported the thiol-yne functionalization of 10-undecynoic and 9-octadecynoic acids after bromation of double bond, deshydrobromation into alkenic bond followed byesterification of acid group. 25 The resulting PU thermosets have a Tg value up to 59 °C. In our methodology, even if we kept TYC approach, a shorter strategy was used to incorporatean alkenyl group in fatty acid (PFE) and diacid (PFD) structures.…”

Section: Methodsmentioning

confidence: 99%

“…By this methodology, propargylic fatty acid (PFE) and diacid (PFD) were converted into lipidic polyols (OH1) and (OH2), respectively.Cadiz et al havealreadysynthesized lipidic polyols by thiol-yne coupling after bromination, dehydrobromination of 10-undecenoic and 9-octadecenoic acids. 25,26 However the ethynyl group is in internal position, along the fatty chain whereas in our case itis in terminal position via propargylic precursor. Different experiments were heated at 10 °C.min -1 .…”

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confidence: 99%

Lipidic polyols using thiol‐ene/yne strategy for crosslinked polyurethanes

Pham

Lapinte

Raoul³

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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Oleic acid and α,ω‐diacid were converted into propargylic esters followed by thiol‐ene/yne coupling (TEC/TYC) functionalization in presence of mercaptoethanol. The multiradical addition on fatty esters leads to the formation of lipidic polyols (OH1 and OH2), as judged by 1H NMR and mass spectroscopies as well as by size exclusion chromatography. The crosslinking reaction between TEC/TYC‐based polyols and 4,4′‐methylene bis(phenylisocyanate) isocyanate reactant was monitored by FTIR experiment and reaction parameters were optimized. By differential scanning calorimetry, relatively high glass transitions are measured corresponding to structure with little or without dangling chain. Moreover, the thermal stability of the resulting plant oil‐based polyurethane materials (PU1 and PU2) were found to be fully consistent with that of other lipidic PUs respecting a three‐step process. Thanks to TYC methodology, fatty α,ω‐diacid produces lipidic polyol without dangling chain and lipidic thermoset PU with relatively high Tg. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1597–1606

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Thiol–yne reaction of alkyne-derivatized fatty acids: biobased polyols and cytocompatibility of derived polyurethanes

Cited by 37 publications

References 32 publications

Concise and Versatile Synthesis of Sulfoquinovosyl Acyl Glycerol Derivatives for Biological Applications

Concise and Versatile Synthesis of Sulfoquinovosyl Acyl Glycerol Derivatives for Biological Applications

Vegetable oils: a source of polyols for polyurethane materials

Lipidic polyols using thiol‐ene/yne strategy for crosslinked polyurethanes

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