17018-07-4Relevant articles and documents
Synthesis method of diallyl glyceryl ether
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Paragraph 0031; 0032; 0033; 0034; 0035; 0036; 0037-0039, (2017/08/25)
The invention discloses a synthesis method of diallyl glyceryl ether. Strong acid ion exchange resin supported SnCl4 is used as a catalyst, allyl glycidyl ether and excessive allyl alcohol undergo an open-loop reaction, the catalyst is recovered by filtering, the excessive allyl alcohol is recovered by distillation, and a target product, diallyl glyceryl ether, is obtained by reduced pressure distillation. Compared with the traditional process, the synthesis method of diallyl glyceryl ether has the advantages that the process flow is short, the reaction condition is mild, and the operation is simple and convenient; the raw materials are readily available, and the product yield is high; the catalyst has low corrosion and can be recycled, and the process is clean and can be put into industrialization easily.
Pd-catalyzed reaction of allyl carbonate with polyols: The role of CO 2 in transesterification versus etherification of glycerol
Gordillo, Alvaro,Lloyd-Jones, Guy C.
supporting information; experimental part, p. 2660 - 2665 (2012/04/11)
An intermolecular Pd/PPh3-catalyzed transesterification of diallyl carbonate with glycerol to generate glycerol carbonate has been developed. Analysis of the reaction kinetics in THF indicates a first-order dependence on Pd and diallyl carbonate, that the Pd bears two phosphines during the turnover limiting event, and that increasing the glycerol concentration inhibits reaction, possibly via change in the polarity of the medium. 13C isotopic labeling studies demonstrate that the Pd-catalyzed transesterification requires at least one allyl carbonate moiety and that there is rapid equilibrium of the allyl carbonate with CO2 in solution, even when present only at low concentrations. A mechanism that is consistent with these results involves oxidative addition of the allyl carbonate to Pd followed by reversible decarboxylation, with the intermediate I·1- and I·3-allyl Pd alkoxides mediating direct and indirect transesterification reactions with the glycerol. Using this model, successful simulations of the kinetics of reactions conducted under atmospheres of N2 or CO2 could be achieved, including switching in selectivity between etherification and transesterification in the early stages of reaction. Reactions with the higher polyols threitol and erythritol are also efficient, generating the terminal (1,2) monocarbonates with high selectivity. It's a gas: A Pd-catalyzed transesterification of diallyl carbonate with polyols has been developed. The CO2 concentration is shown to control the relative rates of etherification and transesterification. Kinetic and isotopic labeling studies suggest that intermediate I·1-allyl Pd alkoxides mediate indirect intermolecular transesterification. The higher polyols erythritol and threitol selectively generate monocarbonates. Copyright
Synthesis of bi- and tetracatenar highly fluorinated compounds for grafting on silicone materials
Malfait, Stéphane,Gérard, Stéphane,Plantier-Royon, Richard,Mignani, Gérard,Portella, Charles
scheme or table, p. 760 - 766 (2011/10/05)
A series of highly fluorinated compounds bearing two or four perfluoroalkyl (RF) chains, with a flexible or rigid core have been synthesized. Radical additions, nucleophilic addition or condensation reactions were implemented for these synthesi
Silica sulfuric acid; an efficient and reusable catalyst for regioselective ring opening of epoxides by alcohols and water
Salehi, Peyman,Dabiri, Minoo,Zolfigol, Mohammad Ali,Fard, Mohammad Ali Bodaghi
, p. 1113 - 1121 (2007/10/03)
The nucleophilic ring opening reactions of epoxides by aliphatic alcohols and water are achieved efficiently in the presence of catalytic amounts of silica sulfuric acid with high degree of regioselectivity. The catalyst is reusable and can be applied several times without any decrease in the yield of reactions.
Magnesium hydrogensulfate: A cheap and efficient catalyst for the conversion of epoxides into β-alkoxy alcohols, vicinal-diols, and thiiranes
Salehi, Peyman,Khodaei, Mohammad Mahdi,Zolfigol, Mohammad Ali,Keyvan, Afsaneh
, p. 3041 - 3048 (2007/10/03)
The nucleophilic ring opening reactions of epoxides by aliphatic alcohols and water are achieved efficiently in the presence of catalytic amounts of magnesium hydrogensulfate, Mg(HSO4)2, with high degree of regioselectivity. The reactions are chemoselective and many of the other functional groups such as ethereal carbon oxygen bonds as well as carbon-carbon double bond remain intact under the reaction conditions. Epoxides also react with thiourea or ammonium thiocyanate in the presence of Mg(HSO 4)2 to afford the corresponding thiiranes in good to excellent yields.
Original synthesis of linear, branched and cyclic oligoglycerol standards
Cassel, Stephanie,Debaig, Catherine,Benvegnu, Thierry,Chaimbault, Patrick,Lafosse, Michel,Plusquellec, Daniel,Rollin, Patrick
, p. 875 - 896 (2007/10/03)
A variety of authentic standards of linear, branched and cyclic oligomers of glycerol, with well-defined structures and degrees of polymerisation from 2 to 5, have been efficiently synthesised. Linear oligomers were obtained by means of a convergent approach based on regioselective opening of bis(epoxides) with solketal; branched compounds were synthesised using oxidative cleavage of the corresponding anhydrohexitols as the key step. A 6-exo-trig halocyclisation reaction involving heteroatom-tethered unsaturated alcohols permitted an efficient synthesis of the precursors of selected cyclic dimers; larger cyclic oligomers were prepared by two one-pot Williamson reactions using a ditriflate derived from diglycerol. All these methodologies permitted further scaling up.
